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Title:
COATINGS CONTAINING POLYESTER MACROMERS CONTAINING 1,1-DICARBONYL-SUBSTITUTED 1 ALKENES
Document Type and Number:
WIPO Patent Application WO/2017/210415
Kind Code:
A1
Abstract:
Compositions comprising a) one or more polyester macromers containing one or more chains of the residue of one or more diols and one or more diesters wherein the residue of the one or more diols and the one or more diesters alternate along the chain and a portion of the diesters are 1,1-diester-1-alkenes and at least one terminal end comprises the residue of one of the 1,1-diester-1 alkenes and wherein one or more terminal ends may comprise the residue of one or more diols; and b) one or more polymers having pendant Michael Addition donor groups. Disclosed are coating prepared from these compositions.

Inventors:
PALSULE ANIRUDDHA S (US)
SULLIVAN JEFFREY M (US)
VANDERPOOL KATHERINE E (US)
HOLZER ALEXANDER R (US)
DESHPANDE ANUSHREE (US)
KLIER JOHN (US)
Application Number:
PCT/US2017/035422
Publication Date:
December 07, 2017
Filing Date:
June 01, 2017
Export Citation:
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Assignee:
SIRRUS INC (US)
International Classes:
C09D5/24; C08F290/06; C08F299/02; C08G63/52; C08G63/553; C08G63/676; C08G65/329; C08G65/332; C09D167/02; C09D171/02
Foreign References:
US20150104660A12015-04-16
Attorney, Agent or Firm:
SIMS, Norman L. et al. (P.C.29 W. Lawrence Street, Ste. 21, Pontiac MI, US)
Download PDF:
Claims:
CLAIMS

Ciaim 1 , A composition comprising a) a polyester maororner composition comprising one or more polyester macromers containing one or more chains of the residue of one or more diois and one or more diesters wherein the residue of the one or more diois and the one or more diesters aitemate aiong the chain and a portion of the diesters are il -diester-1-alkenes and at least one terminal end comprises the residue of one of the 1 , 1 -diester-1 a!kenes and wherein one or more terminal ends may comprise the residue of one or more dio!s; and b) one or more polymers having pendant Michael Addition donor groups.

Ciaim 2. A composition according to Ciaim 1 wherein the pendant Michael Addition donor groups comprise functional groups containing active hydrogen atoms.

Claim 3. A composition according to Ciaim 1 or 2 wherein the pendant Michael Addition donor groups comprise amines, hydroxy!, thiol, or mixtures thereof.

Ciaim 4. A composition according to any one of Claims 1 to 3 wherein the composition contains one or more alternating chains of the residue of one o more diois and one or more diesters wherein each of the chains are bonded at one end to an oxygen of the residue of a polyoi having three or more of the oxygen atoms.

Claim 5. A composition according to any one of Claims i to 4 wherein the polyester

wherein Z is separately in each occurrence ~R2GH or -R1;

1 is separately in each occurrence a hydrocarbyi group which may contain one or more heteroatoms;

R2 is separately in each occurrence a hydrocarbylene group having two or more bonds to oxygen atoms wherein the hydrocarbylene group may contain one or more heteroatoms;

c is an integer of 1 or more; and

n is an integer of about 1 to 3. Ciaim 8. A composition according to any one of Claims 5 wherein c is an integer of about 3 to about 8.

Ciaim 7. A composition according to any one of the preceding claims wherein the one or more polymers having pendant Michael Addition donor groups comprise one or more of acryiic poiyo!s, amine modified acryiic polyols, polycarbonate polyols, modified acrylic copolymer polyols, polyester polyols, polyether poSyols and siioxane po!yols.

Ciaim 8, A composition according to any one of Claims 1 to 7 wherein the one or more polymers having pendant Michael Addition donor groups comprise one or more acryiic polyois or amine modified acryiic polyols.

Ciaim 9. A composition according to any one of Cl ims 1 to 8 which comprises a) from about 40 to about 00 percent by weight of one or more polyester macf omers and from about 1.0 to 60 percent by weight of one or more one or more polymers having pendani IViichaei Addition donor groups wherein the amounts are based on th weight of the composition.

Ciaim; 10. A composition according to Claim 9 which contains a solvent which comprises one or more polar aprotic solvents.

Ciaim 1 1 A composition according to Claim 10 wherein the soiveni comprises one or more one or more aiky!ene giycoi ethers, acetate modified alkyiene giycoi ethers, or ketones, having a boiling point of about 80 °C to about 200 °C.

Ciaim: 12. A composition aceofding to any one of Claims 10 or 11 wherein trie solvent is present in an amount of about 5 to about 30 percent by weight wherein the amounts are based on the weight of the com osition,

Ciaim; 3. A composition according to any one of the preceding claims wherein the polyeste maeromer exhibits a number average mofecu!ar weight of about 600 to about 3000.

Ciaim 14. A composition according to any one of the preceding claims wherein the one or more chains of the polyester macromers comprise a residue of one or more dihydrocarbyl dicarboxylates. Ciaim 15. A composition according to Ciaim 14 wherein the one or more cBhydrocarbyl dicarboxyiates comprise one or more of aromatic dicarboxyiates, aliphatic dicarboxyiates and cycloaliphatic dicarboxyiates,

Ciaim: 8. A composition according to any one of the preceding claims wherein used to prepare the polyester macromers correspond to the formula;

the 1 ,1-diester-l-a!kenes correspond to the formula;

wherein the one or more dihydracarbyi dicarboxyiates correspond to the formula; wherein R1 is separately in each occurrence a hydroearbyi group which may contain one or more heteroatorns;

R2 is separateiy in each occurrence a hydrocarbyiene group having two or more bonds to oxygen atoms wherein the hydrocarbyiene group may contain one or more heteroatorns; and c is an integer of 2 or more;

R3 is separateiy in each occurrence a hydrocarbyiene group having two bonds to the carbonyi groups of the diester wherein the hydrocarbyiene group may contain one or more heteroatorns; and

c is an integer of 1 or more.

Claim 17. A composition according to any one of the preceding claims wherein

wherein D corresponds to the formu!a

Z is separately in each occurrence -R2GH or ~R1;

R1 is separately in each occurrence a hydrocarbyi group which may contain one or more heteroatoms;

R? is separately in each occurrence a hydrocarbyiene group having two or more bonds oxygen atoms wherein the hydrocarbyiene group may contain one or more heteroatoms;

3 is separately in each occurrence a hydrocarbyiene group having two bonds to the carbony! groups of the residue of the diesier wherein the hydrocarbyiene group may contain one or more heteroatoms:

c is an integer of 1 or more;

n is an integer of about 1 to 3:

p is an integer of 1 or more; and

q is an integer of 1 or more.

Claim 18. A composition according io any one of the preceding claims wherein from about 1 to about 4 dihydrocarbyl dicarbox iates are contained in each chain.

Claim 19. A composition according to any of the preceding c!aims wherein polyester macromer composition comprises:

i) a plurality of polyester maeroroers;

ii) one or more multifunctional monomers containing the residue of one or more poiyols and one or more 1s1-diester~1~aikenes, wherein the muitifunctionai mononiers have substantially ail of the hydroxy! groups of the poiyols replaced with the 1,1-diester-1- aikenes; and

iii) one or more 1,1-diester-l-a!kenes.

Ciaim 20. A composition according to Claim 9 wherein polyester macromer composition comprises

i) from about 10 to about 90 percent by weight of a plurality of polyester macromers; is) from about 1 to about 50 percent by weight of one or more multifunctional monomers; and iii) from about 1 to about 30 percent by weight of one or more 151~dieste -a!kenes wherein the percentages are based on the amounts of the ingredients listed.

Claim 21 A composition according to any one of the preceding claims wherein the polymers having pendant Michael Donor groups exhibit a hydroxy! number of about 50 to about 200.

Claim 22. A composition according to Ciaim 1 which is cured and in the form of a coating.

Claim 23. A composition according to according to Claim 22 wherein the composition is a coating having a thickness of about 1 to about 160 microns.

Claim 24. A composition according to any one of the preceding claims wherein the polyester macromers are eross!inked through the 1 ,1- aSkene groups and/or by Michael Addition of the Michael Addition Donors pendant from the polymers to the 1 alkene groups.

Ciaim 25, A composition according to Claims 22 to 24 wherein the cured coating exhibits one or more of the following properties of a gloss according to ASTM D523- 08 at 20 °, or 60°, or 85° of 40 GU or greater; a pencil hardness according to ASTM D3383-QQ of 3H or greater; a solvent resistance according to ASTM D5402-83 to 80 rubs of methyl ethyl ketone or greater; mandrel flexibility according to ASTM D522-93 of 80 percent or greater: cross hatch adhesion of 4B or higher and 100 percent according to ASTSvl D3353-Q9 and acid resistance up to 70 °C and base resistance at greater than 70 °C according to G W 14701. Ciaim 26. A method comprising contacting a composition according to any one of Claims 1 to 21 with a surface of a substrate wherein the surface is at least miidly nucieophiiic and forming a coating on the surface of the substrate comprising the composition containing the one or more polyester macromers.

Ciaim 27. A method according to Claim 26 wherein the substrate has a pigmented coating deposited on its surface wherein the pigmented coating is mildly basic or nucieophiiic.

Claim 28. A method according to Claim 26 which includes exposing the substrate with the composition containing one or more pofyesier macromers deposited on the substrate to a temperature of about 20 X to about 150 for about 10 minutes to about 120 minutes under conditions such that the coating containing one or more polyester macromers disposed on the surface of the substrate is crossiinked.

Claim: 29. A method according to Claims 28 wherein the coating or the surface of the substrate contains a cataiyst for Michael Addition.

Claim; 30. A method according to Claim 26 wherein the coating on the surface of the substrate contains an initiator for anionic polymerization .

Description:
COATINGS CONTAINING POLYESTER MAC OMERS CONTAINiNG 1,1- DiCARBO YL-SUSSTITUTED 1 At ENES

FIELD

[0013 Disclosed are novel compositions containing polyester macromers containing the residue of l,i~diester-l-aikene compounds and poiymers containing pendant Michael Addition donors. Further disclosed are coatings containing the compositions and methods for using the compositions as coatings.

BACKGROUND

[002] Polyesters are utilized in a number of applications due to their properties and their ease of synthesis. Exemplary uses include coatings, films, fibers, and resins. Due to their properties polyesters are also utilized in blends with other polymers to improve certain property limitations of the other poiymers, such polymers include polycarbonates, polyamides, styrenic poiymers, and poiyolefins, and the like. Polyesters are typically prepared by reacting diacids with dtalcohols, and generally are linear in structure, it is somewnat challenging to cross-link these polyesters due to the structure. Some crossiinking processes require special catalysts or high temperatures.

[003] 1,1 -diester- 1-alkenes, such as methylene maionates, contain two diester groups, and an alkylene group disposed between th two diester groups. Recent developments in synthesis of these compounds facilitate the synthesis of these compounds and their use in a variety of applications, see Maiofsky US 8,609,885; US 8,884,051 ; and US 9,108,914; incorporated herein by reference in their entireties for ail purposes. Processes for transesterifying these compounds have also been recently developed. Maiofsky et ai. WO 2013/059473 and US 2014/0329980, incorporated herein by reference in their entirety for all purposes, discioses the preparation of multifunctional methylene maionates by multiple synthetic schemes. One disclosed process involves reacting a methylene malonate with a polyol in the presence of a catalyst to prepare compounds wherein at least one of the ester groups on the methylene maionates undergoes transesterification to react with the polyol and form multifunctional compounds {multifunctional meaning the presence of more than one methylene malonate core unit). The use of enzyme catalysis is disclosed, SuiSvan, US 9,416,091 discloses transesterification of 1 ,1~disubstltuted~1~alkenes using certain acid catalysts, incorporated herein by reference in its entirety for ail purposes. [004] Commonly owned application titled POLYESTER MACROMERS CONTAINING 1 ,1 -DiCARBONYL-SUBSTSTUTED 1 AIKENES having a serial number 15/234,131 filed August 11, 2018 discloses compositions containing polyester macromers containing U-dicarhonyl-subsiituted 1 aikenes useful in preparing polyesters containing compositions which can be cfosslinked elegantly without the need for problematic catalysts and use relatively miid conditions . Disclosed are coatings prepared from such compositions that exhibit enhanced properties, where n such enhanced properties include flexibility, adhesion to substrates, pencil hardness, solvent resistance, abrasion resistance, ultraviolet radiation resistance, acid and base resistance, and the like. Processes that prepare the components for such coatings and the coatings are also disclosed. The compositions and processes disclosed provide significant improvements in coating technology, in order to meet customer expectations additional enhancement to this technology is desirable.

[005] What is needed are polyester macromers containing 1 ,1-dlcarbonyl- substitu-ted 1 aikenes compositions useful in preparing coating compositions which can be cross-linked etegantl without the need for problematic catalysts and use relativel mild condi-tions. What is also needed are coatings prepared from such compositions that exhibit enhanced properties, such as flexibility, adhesion to substrates, pencil hardness, solvent resistance, abrasion resistance, ultraviolet radiation resistance, high temperature acid and base resistance, fuel resistance. Processes that prepare the coatings are needed.

SUMMARY

[008J Disclosed are compositions comprising a) one or more polyester macromers containing one or more chains of the residue of one or more diols and one or more diesters wherein the residue of the one or more diols and the one or more diesters alternate along the chain and a portion of the diesters are 1 ,1-tiiester-1~ aikenes and at least one terminal ¾nd comprises the residue of one of the l,i~diester~ 1 -aikenes and wherein one or mor terminal ends may comprise the residue of one or more diols; and b) one or more polymers having pendsni Michael Additio donor groups. The pendant fvlichaei Addition donor groups may comprise functional groups containing active hydrogen atoms. The one or more polymers having pendant Michael Addition donor groups may comprise one or more of acrylic poiyois, amine modified acry!ic poiyois, poiycarbonate poiyois, modified acrylic copolymer poiyois, polyether amines, polyester poiyois, polyether poiyois and siloxane poiyois. The composition may contain three or more alternating chains of the residue of one or more diols and one or more diesters, wherein at least some of the diesters are i ,1-diester-1 -aikenes, and each of the chains are bonded at one end to an oxygen of the residue of a po!yo! having three or more of the oxygen atoms. The polyester macromers may correspond to Formula 1

wherein Z is separately in each occurrence -R J OH or -R ; R 1 is separately in each occurrence a hydrocarbyi group which may contain one or more heteroatoms; R 2 is separately in each occurrence a hydracarbylene group having two or more bonds to oxygen atoms, wherein the hydrocarbyiene group may contain one or more heteroatoms; c is an integer of 1 or more; and n is an integer of about 1 to 3, c may be an integer of about 2 to about 8 or about 3 to about 6. The polyester macromers may contain one chain of the residue of one or more dsois and one or more diesters, wherein at least some of the diesters are 1 ,1-diester-1-aikenes. The polyester macromers disclosed may exhibit number average molecular weights of about 400, about 600 or about 700 to about 3000.

[007] The one or more dsesters may comprise 1,.1-diester-1 -a!kenes. i n addition to the one or more 1 ,1-diester-l-alkenes, the one or more dsesters may comprise one or more dihydrocarbyl dicarboxylates. The polyester macromers contain the residue of one or more 1 s 1-diester-1~aikenes and may contain the residue of one or more dihydrocarbyl dicarboxylates. The one or more dihydrocarbyi dicarboxylates may comprise one or more of aromatic dicarboxylates, aliphatic dicarboxylates, cycioaiiphatic dicarboxylates and/or a dicarboxylaie containing two different hydrocarbyi groups selected from aromatic, aliphatic and cycioaiiphatic.

[008] Disclosed is a composition containing a polyester macromer composition comprising i) a plurality of poiyester macromers as described herein; ii) one or more multifunctional monomers containing the residue of one or more polyois and one or more 1 ,1~ !ester~1-alkenes, wherein the muitifunctionaf monomers have substantiai!y ail of the hydroxy! groups of the polyois replaced with the l .i-diester-l-alkenes; and iii one or more 1 ,1-diester-1~aSkenes. The one or more poiyo!s may be dio!s. The one or more multifunctional monomers may be difuneiionai monomers. This composition may be combined with one or more polymers having pendant Michael Addition donor groups.

[009] Disclosed is a composition containing a poiyester macromer composition comprising a) t) a plurality of polyester macromers as described herein; ii) one or more multifunctional monomers containing the residue of one or more polyois and one or more 1 ,1-diester-l-alkenes, wherein the multifunctional monomers have substantially all of the hydroxy! groups of the polyois replaced with the 1 ,1-diesier-1-alkenes; and i) one or more 1. 5 1-diest$r~1«alkenes b) a volatile solvent; e) an additional amount of one or more 1 ,1-dtester-l~alkenes if so desired; d) one or more leveling and wetting agents; e) one or more UV stabilizers f) one or more additives to improve abrasion resistance and g) one or more additives to provide surface slip and anticratering properties. The solvent may be an aikoxy aikanol or an aikoxy alkyi acetate. The wetting agent may be a poiyether modified polydtmethyi siioxane. UV stabilizer may be a benzotriazole based or a hindered amine based compound. The composition may contain an additive to improve scratch resistance which may be a nanometer sized silica filler. An additive to improve surface slip properties may be a poiyether modified poiydimethyl siioxane. This composition may be combined with one or more polymers having pendant Michael Addition donor groups.

[0010] Disclosed is a composition comprising one or more polyester macromers and one or more of the polyois endcapped with one or more 1 , -diester-l-aikenes or multifunctional monomers, that is the terminal ends of the chains contain the residue of one or more 1 ,1-dieste -aikenes and/or multifunctional monomers. The composition may contain a soivent. The one or more polyois may be one or more poiyether polyois, po!ysiloxane poiyols, polycarbonate polyois, polyester polyois, acrylic polyois, or pQiybutadtene poiyols. The one or more polyois may be one or more polycarbonate polyois. The one or more poiyols may be di or tri functional. The one or more poiyols may have Michael Donor groups, such as hydroxy!, thiol or amino groups, pendant from their backbone,

[0011] The compositions containing polyester macromer disclosed herein and one or more polymers having pendant Michael Addition donor groups may be fabricaied into film or coatings. The coatings or films may have a thickness of about 0.001 micrometers or greater, or about 10 micrometers or greater. The coatings or films may have a thickness of about 160 micrometers or less or about 140 micrometers or less. Compositions containing a plurality of one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups disclosed herein may be cured. Compositions containing a plurality of one or more polyester macromers disclosed herein may be crossiinked after cure.

[0012| Disclosed is a composition comprising a) a plurality of polyester macromers according to the preceding description and b) one or more polymers having pendant Michael Addition donor groups wherein a portion of or a!i of the polyester macromers are crossiinked through the 1 ,1- a!kene groups. Disclosed is a composition comprising a) a plurality of polyester macromers according to the preceding description and b) one or more polymers having pendant Michael Addtiion donor groups wherein a portion of or ail of the polyester macromers are cross!inked by Michael Addition of the Michael Addition Donors pendant from the polymers to the 1 aikene groups of the polyester macromers.

[0013] Disclosed is a composition comprising one or more poiyester macromers as disclosed herein in one part and in a second part one or more compounds having basic character sufficient to initiate anionic polymerization of the poiyester macromers; wherein when the two parts are combined the polyester macromers undergo curing. The one or more compounds having basic character may comprise one or more amines or po!yamines. The one or more compounds having basic character may comprise one or more poiya!kyleneimines. These compositions may be combined with one or more polymers having pendant Michael Addition donor groups,

[0014] Disclosed is an article having a coating containing one or more polyester mac-romers and one or more poiymers having pendant Michael Addition donor groups as part of the composition disposed on aii or a portio of one or more of the surfaces of the article. The article may have a base coat upon which the coating formulation is deposited. The base coat may contain pigments. The base coat may have a basic pH at the surface. The pigments may be basic. The base coat may have amine groups or hydroxy! groups on the surface that may help with the cure process and adhesion of the coating to the substrate. The polyester macromer coating may be clear. The poiyester macromer coating may contain pigments or other known ingredients used in coatings.

[0015J Disclosed is a method comprising contacting a composition containing one or more polyester macromers and one or more poiymers having pendant Michael Addition donor groups according to the preceding description with a surface of a substrate wherein the surface is at ieast mildly basic and forming a coating on the surface of the substrate comprising the composition containing the one or more polyester macromers. The substrate may be comprised of one or more of a material that is at least mildly basic, nuc!eophiiic and/or contains a plurality of Michael Addition donor groups on its surface.

[0016] Disclosed is a method comprising contacting a composition containing one or more polyester macromers as disclosed herein and one or more polymers having pendant Michael Addition donor groups with a surface of a substrate wherein the surface is at Ieast mildly basic, contains nucleophiles and/or Michaei Addition donors and forming a coating on the surface. The substrate may be comprised of material that is at least mildly basic, nuc!eophilic and/or contains Michaei Addition donors, A composition that contains a basic, nucleop iiiic, or a Michaei Addition donor compound that initiates anionic polymerization for 1 ,1~disubstituied a!kenes or Michael adds to the aikene groups of the poiyester macromers may be applied to the surface of the .substrate before applying the composition containing one or more polyester macromers and macromers and one or more polymers having pendant Michael Addition donor groups. Exemplary basic compounds comprise one or more amines, polyamine, basic pigments; po!yaSkyieneamine polyethylene amines and carboxy!ate salts. The methods for forming coatings may further comprise exposing the substrate with the composition containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups to a temperature of about 20 * G to about 150 a C for about 10 minutes to about 120 minutes under conditions such that the coating containing one or more poiyester macromers and one or more polymers having pendant Michael Addition donor groups disposed on the surface of the substrate is crossiinked. The coatings may aiso be cured with no heat input, at ambient temperatures, which requires greater cure times, or example up to about 24 hours,

[0017] The compositions containing polyester macromers and one or more polymers having pendant Michaei Addition donor groups can be used to prepare coating formulations that can be cured and crossiinked using relatively mild conditions. The poiyester macromers allow the tailoring of properties of polyester containing compositions, Specifically the polyester macromers aliow the preparation of polyester compositions that have improved mechanical properties and elasticity. The cured coatings disclosed exhibit one or more of the following properties of a gloss according to ASTM D523-0S at 20 * of 50 GU or greater; a pencil hardness according to ASTM D3383-00 of 4H or greater; a solvent resistance according to ASTM D5402-93 to 80 rubs of methyl ethyl ketone or greater; mandrel flexibility according to ASTM D522-93 of 80 percent or greater; cross hatch adhesion of 4B or higher and 100 percent according to ASTM D3359-Q9 and acid resistance up to 70 "C and base resistance at greater than 70 °C according to GM 14701. The methods of preparing coatings and films allow the preparation of coatings with the above-described enhanced properties in an efficient manner,

DETAILED DESCRIPTION

[0018] The explanations and illustrations presented herein are intended to acquaint others skilled in the art with the invention, its principles, and its practical application. The specific embodimenis of the present invention as set forth are not intended to be exhaustive or limiting of the Invention. The scope of the disclosure should be determined with reference to the appended ciaims, along with the full scope of equivalents to which such ciaims are entitled. The disclosures of ail articles and references, including patent applications and publications, are incorporated b reference for aii purposes. Other combinations are also possible as wiif be gleaned fromi the following claims, which are also hereby incorporated by referenc into this written description.

[0019] Unless defined otherwise, ai! technical a d scientific terms used herein have the meaning common!y understood by a person skilled in the art to which this disciosure belongs. The following references provide one of skill with a general definition of many of the terms used in this disciosure; Singleton ei a/., Dictionary of Microbiology and Molecular Biology (2nd ed. 1994); The Cambridge Dictionary of Science and Technology {Walker ed., 1988); The Glossary of Genetics, 5th Ed., R. Rieger et al. {eds.}, Springer Verlag (1991); and Hale & Marham, The Harper Collins Dictionary of Biology (1001 ). The following terms have the meanings ascribed to them below, unless specified otherwise.

[0020] Disclosed are compositions comprising a) polyester macromers containing in one or more chains the residue of one or more diols and one of more diesters wherein the residue of the one or more diols and the one or more diesters alternate along the chair* and a portion of the diesters are 1 , 1 -d tester- 1 -a!kenes and at least one terminal end comprises the residue of one of the 1 ,1-diester-i-a!kenes and wherein one or more terminal ends may comprise the residue of one or more diols and b) one or more poiymers having pendant Michael Addition donor groups. The macromers may have two or greater of such chains. The chains may include the residue or one or more dihydrocarbyi dicarboxylates. The chains may contain the residue of one or more diols and one or more diesters wherein the diesters comprise one or more 1 - diester- 1-a!kenes, the residue of the one or more diols and the one or more 1 , 1-diester- 1 alkertes and optionally one or more dihydrocarbyi dicarboxylates may be randomly disposed along the chains. The polyester macromers may be used to form polyesters, blended with polyesters and/or other polymeric compounds to provide enhanced properties. Disclosed are methods of preparing the polyester macromers and incorporating them in a variety of polyester containing com ositions. Further disclosed are methods of preparing structures from polyester m crom r containing compositions such as coatings,

[0021] As used herein, diester refers to any compound having two ester groups which can be subjected to transesterifscaiion. A 1 ,1 -diester- 1-aikene is a compound that contains two ester groups and a double bond bonded to a single carbon atom referred to as the one carbon atom. Dihydrocarbyi dicarboxylates are diesters having a hydrocarby!ene group between the ester groups wherein a double bond is not bonded to a carbon atom which is bonded to two carbonyl groups of the diester. [ΟΟ223 The term "monofunctionai" refers to the 1 ,1~dse$ier~1-alkenes having onl one core unit. The core unit comprises two carbonyl groups and a double bond bonded to a single carbon atom. The term "difunctional" refers to the 1 s 1~diesier~1-aikenes having two core units (each including the reactive alkene functionality) bound through a hydroearby!ene linkage between one oxygen atom on each of two core formulas. The term ''multifunctional" refers to the 1,1-diester-1~a!kenes having two or more core units {each core unit including the reactive alkene functionality} bound together through a hydrocarbylene linkage between one oxygen atom on each of two or more core formulas,

[ΟΟ233 Acid catalyst, as used herein, is an acidic species that catalyzes the transesterification reaction while minimizing or not contributing to side reactions. One or more as used herein means that at least one, or more than one, of the recited components may be used as disclosed. Nominal as used with respect to functionality refers to the theoretical functionality; generally this can be calculated from the stoiehiometry of the ingredients used. Heteroatom refer to atoms that are not carbon or hydrogen such as nitrogen, oxygen, sulfur, and phosphorus; heteroatoms may include nitrogen and oxygen. Hydrocarbyi, as used herein, refers to a group containing one or more carbon atom backbones and hydrogen atoms, which may optionally contain one or more heteroatoms. Where the hydrocarbyi group contains heteroatoms, the heteroatoms may form one or more functional groups well-known to one skilled in the art, Hydrocarbyi groups may contain eycioalsphaiic, aliphatic, aromatic, or any combination of such segments. The aliphatic segments can be straight or branched. The aliphatic and cycioaiiphatic segments may include one or more double and/or thp!e bonds. Included in hydrocarbyi groups are aiky!, aikeny!, aikynyf, aryi, cyc!oalkyl, cye!oalkenyl, alkaryi, and ara!kyl groups. Cycioaiiphatic groups may contain both cyclic portions and noncyciie portions. Hydrocarbylene means a hydrocarbyi group or any of the described subsets having more than one valence, such as alk lene, a!keny!ene, aikynylene, arytene, cyctoalkylene, cycloalkenylene, alkary!ene and aralkylene. As used herein percent by weight or parts by weight refer to, or are based on, the weight or the compounds or compositions described unless otherwise specified. Unless otherwise stated parts by weight are based 100 parts of the relevant composition.

[0024] The term "ketai" refers to a mo!ecuie having a ketai functionality; i.e., a molecule containing a carbon bonded to two -OR groups, where O is oxygen and R represents any alky! group or hydrogen. The terms "vofatiie" refers to compounds which are capable of evaporating readily at normal temperatures and pressures, "Nonvolatile * refers to compounds which are not capable of evaporating readily at norma! temperatures and pressures. The term "stabilized" (e.g., in the context of "stabilized" 1 ,1 -diester- 1- aikenes, or compositions comprising the same,) refers to the tendenc of the compounds (or their compositions) to substantially not polymerize with time, to .substantially not harden, form a gel, thicken, or otherwise increase in viscosity with time, and/or to substantially show minimal loss in cure speed (i.e., cure speed is maintained) with time. Residue with respect to an ingredient used to prepare the polyester macromers disclosed herein means that portion of the ingredient, such as a poiyo!, such as a did, a diester, such as a 1 ,1-dlesteM-a!kene and/or a dihydrocarbyi dicarboxySate, that remains in the compound after inclusion as a result of the methods disclosed herein. Substantially ali as used herein that greater than 95 percent of the referenced parameter, composition or compound meet the defined criteria, greater than 99 percent of the referenced parameter, composition or compound meet the defined criteria, or greater than 39.5 percent of the referenced parameter, composition or compound meet the defined criteria.

[0025] Disclosed are polyester macromers which contain one or more chains containing the residue of one or more diols and one or more diesters wherein a portion of the diesters comprise 1 ,1 -diester- 1 -aikenes. The residue of the diols and the diesters can alternate along the chains or can b disposed randomly along the chains. The diesters may further comprise any diester compound that will undergo transesterification with a potyoi or dioi. Among diester compounds are dihydrocarbyi decarboxylases. The polyester macromers may have three or more chains as described. The polyester macromers having three or mor chains contain the residue of a poiyoS originall having three or greater hydroxy! groups. The three or more chains propagate from each of the three or more hydroxy! groups. The po!yols having three or more chains function as initiators from which each of the chains of the polyesier macromers propagate, if the polyo! is a dioi a single chain is produced because the macromer formed is linear. Where a poiyol having three or more hydroxyls is used to prepare the macromer, it may have two or more chains as not all of the hydroxyls may propagate chains. The macromers may contain one or more chains, may contain two or mor chains, or may contain three or more chains. The macromers may contain eight or iess chai s, six or less chains, four or less chains or three or less chains. The chains may comprise the residue of one or more polyols, one or more diols and one or more diesters, Including one or more 1 ,1 -diester- 1- aikenes and optionally one or more dihydrocarbyi dicarboxylaf.es. The chains may comprise the residue of one or more diols and one or more diesters, including one or more 1 ,1~diester~1 -aikenes and optionally one or more dihydrocarbyi dicarboxyiates. The polyester macromers contain the residue of at least one 1-diester-1 -aikenes at the terminal end of one of the chains. The polyester macromers may further comprise one or more diols or dihydrocarbyl dicarboxy!ates at the terminal end of one or more of the chains.

Substantially all of the terminai ends of chains may be 1 ,l -diester-substituted alkenes, [0028] The polyester macromers may comprise sufficient amount of the residue of one or more polyols, in this context the polyois have 3 or greater hydroxy! groups, to initiate the desired number of chains. The residue of the pofyois in the polyester macromers may be about 20 moie percent or greater of the macromer; 30 mo!e percent or greater or about 40 moie percent or greater. The residue of the polyois in the polyester macromers may be about 50 mo!e percent or less; or about 40 mole percent or less. The polyester macromers may comprise sufficient amount of the residue of one or more diois, in this context the polyols have 2 hydroxy! groups, to prepare poiyester macromers having the desired chain length and number average molecular weight. The residue of the diois in the polyester macromers may be about 20 mole percent or greater of the macromer; 40 mole percent or greater or about 50 mole percent or greater. The residue of the diois in the polyester macromers may be about 50 mole percent or less; 40 mole percent or less or about 30 mole percent or less. The polyester macromers may comprise sufficient amou nt of the residue of the 1 ,1 -dlester- substituted-1-a!kenes to provide the desired crosslink density to compositions containing the polyester macromers. The residue of the 1 ,l-diester-substituted~1- alkenes in the poiyester macromers may be about 20 mole percent or greater of the macromer; 30 mole percent or greater or about 40 moie percent or greater. The residue of the 1 ,1-dtester-substiiuted-l -alkenes in the poiyester macromers may be about 60 moie percent or less of the macromer; about 50 moie percent or less of the macromer; about 40 moie percent or !ess or about 30 mole percent or less. The poiyester macromers may comprise sufficient amount of the residue of the dihydrocarbyl dicarboxylaies to provide the desired space between crosslinks to compositions containing the poiyester macromers to provide th desired flexibility and/or elasticity to the structures eoniaining the poiyester macromers. The residue of the dihydrocarbyl dtcarooxyfates in the polyester macromers may be about 10 moie percent or greater of the poiyester macromer; 20 mole percent or greater or about 30 mole percent or greater. The residue of the dihydrocarby! dicarboxy!ates in the poiyester macromers may be about 30 mol percent or less of the poiyester macromer; 20 mole percent or less or about 0 moie percent or !ess.

[00273 The polyester macromers may correspond to Formu!a 1

wherein Z is separatel in each occurrence ~R 2 QH or R- is separately in each occurrence a hydrocarbyi group which may contain one or more heteroatoms; R 2 is separately in each occurrence a hydrocarbyierte group having two or more bonds to oxygen atoms; c is an integer of 1 or more; and n is an integer of about 1 to 3. With respect to R 2 the bonds to oxygen atoms may include bonds to the oxygen of a poiyoL a diol, or a diester or the residue thereof depending on the context of use of R 2 .

[0028] The polyester macromers may coniain one chain of the residue of one or more diols and one or more diesters. These polyester macromers may correspond to Formula 2,

wherein Z, W and R 2 are as previously defined; and m is an integer of about 1 to 3.

[0029] The polyester macromers containing the residue of one or more 1 , 1 -diester- 1-aikenes and the residue of one or more dihydrocarbyi dicarboxyiates may

wherein D corresponds to the formuia

wherein Z, R\ R 2 and m are as prevtousiy defined; R 3 is separaiely in each occurrence a hydrocarbylene group having two bonds to the carbonyl groups of one or more of the diesters or to the residue of such ciiesters depending on the context, wherein the hydrocarbyiene group may contain one o more heteroaiorn ; c is an integer of 1 , or 2 or more; d is an integer of 0 or 1: e is an integer of 0 or 1; f is the integer 1; n is an integer of about 1 io 3; p is an integer of 2 or more; and ς is an integer of 1 or more; wherein each pair of d and e must equai 1. p may be an integer of 3 or greater, p ma be an integer of 8 or iess, 6 or iess or 3 less, q may be an integer of 4 or less or 3 or less.

[0031] The polyester macromers may contain in their backbone repeating units comprising the residue of at ieast one diester and one dioi. A significant portion of the diesters are 1 J-diester-substituied-1~a5kenes. A portion of the diesters may be 1,1- di ydrocarbyl dicarboxyiates. The backbone of polyester macromers contain a sufficient number of repeating units comprising the residue of at ieast one diester and one dioi to facilitate the use of the polyester macromers as disclosed herein such as in coatings. The number of repeating units comprising the residue of at least one diester and one dioi in polyester macromers may be 2 or greater, 4 or greater or 6 or greater. The number of repeating units comprising the residue of at least one diester and one dioi in polyester macromers ma be 8 or less, 6 or less, or 4 or less. The diesters in some polyester macromers can be ai! 1 ,1~diester~1~aikenes. The diesters in some polyester macromers can be 1 ,1 -diester- 1-alkenes and dihydrocarby! dicarboxylates. The moiar ratio of 1 ,1 -diester- 1-aikenes and dihydrocarby! dicarboxylates in some polyester macromers is selected to provide the desired degree of cross! inking in structures prepared from the poiyester macromers. The molar ratio of 1 ,1 -diester- 1-alkenes and dihydrocarby! dicarboxylates in some polyester macromers may be 1: 1 or greater, 8:1 or greater or 10:1 or greater. The moiar ratio of 1 ,l~diestersubstituted~1~alkenes and dihydrocarby! dicarboxylates in some polyester macromers may be 15: 1 or less, 10:1 or less, 6:1 or iess or4 :1 or less. The polyester macromers may exhibit a numbe average molecular weight of about 400 or greater, about 600 or greater, about 700 or greater, about 900 or greater, about 1000 or greater or about 12GQ or greater. The polyester macromers may exhibit a number average molecular weight of about 3000 or iess, about 2000 or less or about 1600 or !ess. Number average molecular weight as used herein is determined dividing totai weight of all the polymer molecules in a sample, by the total number of poiymer molecules in a sampie. The polydispersity of the polyester macromers may be about 1.05 or greater or about 1.5 or greater. The polydispersity of the polyester macromers may be about 2.5 or less or about 1.5 or iess. For calculating the poly-dispersity the weight average molecular weight is determined using gei permeation chromatography using polymethylmethacrylate standards. Polydispersity is calculated by dividing the measured weight average molecula weight (M v ) by the number average molecular weight (M n ), that is w M«,

[0032] The poiyester macromers disclosed may be prepared from -diester- - ai-kenes, diols, po!yols and/or difiydrocarfeyl dicarboxylates. The choice of specific ingredi-ents, ratios of ingredients and sequence of process steps impact the final structure and content of the poiyester macromers. The presence of polyo!s having greater than two hydroxy! groups function to initiate the chains and their use results in the formation of poly-ester macromers having more than two chains, that is the macromer exhibits branching and the poiymer is not linear. The 1 ,1-dlester- -a!kenes hel form the chains and introduce pendant a!kene groups capable of crosslinking via anionic and/or free radical polymerization and/or Michael addition. The dlois may initiate a single chain and chain extend the poiyester macromers. The dihydrocarby! dicarboxylaies hel form the chains and function to space the pendant a!kene groups from one another, thereby increasing the distance between crosslinks and the average molecuiar weight per crosslink.

[0033] The U-diester-1-aSkenes comprise a central carbon atom referred to as the 1 carbon atom. Bonded to the 1 carbon atom are the carbonyi groups of two ester groups and another carbon atom via a double bond. The double bond, due to it being bonded to two carbonyi groups, is highly reactive. The doubly bonded carbons may be part of an aikenyi group which is highly reactive. The aikenyi group may be a C 2.4 aikenyi group, or a methylene group (C=C). The esters contain hydrocarbyi groups bonded to the oxygen bonded to the carbonyi group wherein the hydrocarbyi groups may contain one or more heieroatoms, including heferoatom containing functional groups. The hydrocarbyi groups can be any hydrocarbyi groups that can undergo transesterification under the conditions disclosed herein. The hydrocarbyi groups on the ester may be separately in each occurrence aikyl, aikenyi, cycloaikyi, heterocyclyl, aiftyl heterocyclyi, aryl, araikyi, alkaryl, heteroaryl, or aikheteroaryi, or poiyoxyaikylene, or both of the hydrocarbyi groups may form a 5-7 membered cyclic or heterocyclic ring. The hydrocarbyi groups on the este may be separately in each occurrence C -Cis alkyi, C2-C15 aikenyi, C3-C9 cycloaikyi, G^o heterocyclyl, C¾.2o aikheterocyciyl, Ce-i$ aryl, C?.2s alkaryi, C 7.2s araikyi, C« is heteroaryl or Ce.25 afkyl heteroaryl, or poiyoxyaikylene, or both of the hydrocarbyi groups form a 5-7 membered cyclic or heterocyclic ring. The recited groups may be substituted with one or more substituenis, which do not interfere with the transesterification reaction. Exemplary substituenis include halo, aikyithio, aikoxy, hydroxy!, nitro, azido, cyano, acyloxy, carboxy, or ester. The hydrocarbyi groups on the este may be separately In each occurrence C1-C15 alkyi, Ca-Ce cycloaikyi, C+.ia heterocyclyi, C+.18 aikheterocyciyl, aryl, Cr-as alkaryl, C .2s araikyi, 0 n heteroaryl or C&.25 aikyl heteroaryl, or poiyoxyaikylene. The hydrocarbyi groups on the ester may be separately in each occurrence a CM aikyl. The hydrocarbyi groups on the ester may be separately in each occurrence methyl or ethyl. The hydrocarbyi groups on the ester may be the same for each ester grou on the 1 ,1-diester-1~aikene compounds. Exemp!ary compounds are dimethyl, diethy!, eihylmethyl, dipropyl, dibutyl, diphenyi, and ethyi-ethyigluconate ma!onates. The compounds may be dimethyl and diethyl methylene ma!onaie. The 1,1-diesier~1- alkenes can be prepared as disclosed in Ma!ofsky et al., US 8,609,885; 8,884,051 ; and US 9,108,914.

[00343 The 1 , 1 -diester-1 -aikene compounds may correspond io formula 7;

R 1 is separately in each occurrence a group that can undergo replacement or transesterification under the conditions of the methods disclosed herein. W may be separately in each occurrence alkyl, aikenyi, cycioalkyl, heterocyciy!, a!kyl heterocyciy!, aryi, ara!kyi, alkaryl, heieroary!, or aikheferoaryf, or poiyoxya!kylene, or both of the R*s form a 6-7 membered cyclic or heterocyclic ring, R 1 may be separately in each occurrence C1-C15 alkyl, C2-C15 aikenyi, C3-C9 cycloalkyl, C2-20 heterocyclyl, 03-20 alkheterocyclyi, ( ia aryi, Cr-as alkaryl, C 7^.5 aralkyi. CMS heteroaryl or Cs.25 alkyl heteroaryl or polyoxya!kyiene, or both of the i groups form a S-7 membered cyclic or heterocyclic, ring. The recited groups may be substituted with one or more substiiuents, which do not interfere with the transesterificafen reaction- Exemplary substituents Inciude halo a!ky!thto, aSkoxy, hydroxy!, nitre, azido, cyano, aoyioxy, carboxy, or ester. R " may be separately in each occurrence C1-C15 alkyl, Ca-Cs cycloalkyl, C S heterocyclyl, C -W alkheterocyclyi, Cs -?a aryi, C? 2& alkaryl, C7.25 aralkyi, CMS heteroaryl or C.¾.25 alkyl heteroaryl, or polyoxyalkyieoe. R 5 may be separately in each occurrence a C1 -4 alkyl. R 1 may be separately in each occurrence methyl or ethyl. R ; may be the same or different for each ester group on the 1 ,1-disubstituied a!kene compounds.

[0035] One class of 1 ,1-disubstituted aikeoe compounds are the methylene maionates which may correspond to formula 8:

wherein R 1 is as described herein before.

[00383 1 ,1-diester-aikenes may b prepared using a method which results in a sufficiently high purity so that they can be included into polyester macromers that can be polymerized and/or crossltnked. The purity of the 1 ,1-dieste -aikenes may be sufficientiy high so that 70 mole percent or more, 80 mo!e percent or more, 90 moie percent or more, 95 moie percent or more, or 99 moie percent or more of the polyester macromers containing 1 ,1-diester-1 -aikenes may be converted to polymer during a polymerization or curing process. The purit of the 1 ,1-dseste -a!kenes may be about 85 moie percent or more, about 90 mole percent or more, about 93 moie percent or more, about 95 mole percent or more, about 97 mole percent or more, or about 99 mole percent or more, based on the total moles of the 1 ,1-diesieM-alkenes. If the 1 ,1 - diesier-1-a!kenes includes the analogous 1,1-diester aikarie it may be about 10 mole percent or less or about 1 mote percent or less. The concentration of any impurities containing a dioxane group may be abou 2 moie pefcertt or iess, about 1 mole percent or less, about 0.2 moie percent or iess, or about 0.05 mole percent or less, based on the total moles of the 1 ,1-dieste -aikenes. The total concentration of any impuriiy having the alkene group replaced by an analogous hydroxyaikyi group (e.g., by a Michael addition of the alkene with water) may be about 3 mole percent or less, about 1 mole percent or less, about 0.1 mole percent or iess, or about 0.01 moie percent or less, based on the iota! moles in the 1 ,1-diester-1-alkenes. The 1 ,l-diester-1 - a!kenes may be prepared by a process including one or more (e.g., two or more) steps of distilling a reaction product or an intermediate reaction product (e.g., a reaction product or intermediate reaction product of a source of formaldehyde and a ma!onic acid ester).

[0037] Folyo!s useful in preparing polyester macromers disclosed herei are compounds having a hydrocarbyiene backbone with two or more hydroxy! groups bonded to the hydrocarbyiene backbone and which may be. capable of tfansestenfying ester compounds under the transesterification conditions disclosed herein. Po!yols useful herein fall in two groups. The first group are dio!s which have two hydroxyl groups bonded to a hydrocarbyiene backbone and which function both to initiate and extend the chains of the polyester macromers, Po!yols with greater than two hydroxy! groups bonded to the hydrocarbyiene backbone function to initiate more than two chains. Diols may also function to extend the mor than two chains. The polyo!s may have from 2 to 10 hydroxyl groups, from 2 to 4 hydroxy) groups or from 2 to 3 hydroxy! groups. The backbone for the polyo!s, inc!uding diois, may be aikylene, alkeny!ene, cycloa!kylene, heterocyciyiene, a!kyS heterocyclyiene, ary!ene, aralkyfene, aikary!ene, heteroaryiene, aikheteroary!ene, or pQiy-oxyaikylene. The backbone may be Ct-Cts. aikylene, aikenylene, Ca-Cs cycioaSky1~ene, C 2-20 heterocyclyiene, G alkheterocydyiene, CMS aryiene, C?^ a!karyiene, Cj.25 ara!kyiene, <¾.i 8 heteroaryiene, C -2s aiky! heteroaryiene or poiyoxya!ky!ene. The aikyiene sections may be straight or branched. The recited groups may be substituted with one or more substltuents which do not interfere with the transesterificaiion reaction. Exemplary substituents include ha!o aikyithio, a!koxy, hydroxy!, nitro, azldo, cyano, acyioxy, carboxy, or ester. The backbone may be C -w a!kyiene groups. The backbone may be a C ?,s aikyi-ene group, which may be straight or branched, such as ethylene, propylene, butyiene, pentylene, hexy!ene, 2-ethyl hexyiene, heptylene, 2,2-methyi, 1 ,3-propy!ene, 2-methy! 1 ,3 propylene or octylene. The diois having a methyl group at

18 the 2 position of an a!kyiene chain may be used. Exemplary dsols include ethane dioi, propane dioi, butane dioi, pentane dioi, hexane dioi, 2 ethyl hexane dioi, heptane dioi, octane dioi, neopentyi glycol (2,2-methyi, 1,3-pro arie dioi), 2-methyl 1,3 propane dioi, 2-butyt-1 ,3-propane dioi, 2-ethy1-1 ,3-propane dioi and 1 ,4- eyciohexanoL The poiyoi may correspond to formula 9 ^ ^ c ;

the dioi may correspond to formula 10: HO r2 o

wherein R 2 is separately in each occurrence a hydrocar ylene group having two or more bonds to the hydroxy! groups of a poiyoi. R 2 may be separatel i each occurrence aikylene, alkeny!ene, eycioafkyiene, heteroeycSylene, alkyi heterocyclylene, arylene, aralkyiene, a!karyiene, heieroarylene, alkheteroaryiene, or polyoxyalkyiene. R 2 may be separately in each occurrence d-Cis aikylene, Cj-Cts aikenyiene, C3-C9 cycioaikylene, C 2.20 heterocyclylene, C 3.20 alkheterocyclylene, C 6 ;s arylene, Cr^s a!karyiene, C7-25 aralkyiene, C5.18 heteroarytene, Ce^s lkyl heteroaryiene or polyoxyalkyiene. The recited groups may be substituted with one or more substituents which do not interfere with the transesterificaiion reaction. Exemplary substituents include halo aikylthio, alkoxy, hydroxy!, nitro, azsdo, cyano, acyioxy, carboxy, or ester. R z may be separately in each occurrence a C 2-8 aikylene group, such as ethylene, propylene, butylene, pentylene, hexyiene, 2-ethyl hexyiene, heptyiene, 2~methyi 1,3 propylene or octyiene. Exemplary C3-C3 cycloalkylenes include cye!ohexylene. Trie aikylene groups may be branched o straight and may have a methyl group on the 2 carbon. Among preferred afkarylene poly-ols are polyois with the structure of -aryl-alkyi-aryl- (such as -phenyi-meihyl-phenyl- o -phenyl- propy!-phenyi-} and the like. Among preferred alky! cycioaikylene poly-yls are those with the structure of -cycloalkyi-alkyl-cycioaikyl- (such as -cyciohexyi-methyl- eyoiohexyi- or -cyclohexyl-propyS-cyctohexy!-) and the like. The poSyalkyiene oxy groups may have aikylene groups of ethylene, propylene or butylene and the butylene groups may be derived from butylene oxides or tetrahydrofuran, c may be an integer of 8 or less, 6 or less, 4 or less or 3 or less, c may be an integer of 2 or greater or 3 or greater.

[0038] The one or more dihydrocarbyi dicarboxyiates are compounds with two ester groups having a hydrocarby!ene group disposed between the ester groups. The one or more dihydrocarbyi dicarfooxy!ates may comprise one or more of aromatic dicarboxylates, aliphatic dicarboxylates and cycioaiiphatic dicarboxylates or ma comprise one or more dihydrocarbyi dicarboxylates wherein one of the hydrocarbyl groups is aliphatic, cycioaiiphatic or aromatic and the other is selected from another class of aliphatic, cycioaiiphatic or aromatic groups. The one or more dihydrocarbyi dicarboxyiates ma comprise one or more of aromatic dicarboxyiates having 8 to 14 carbon atoms in the backbone, aliphatic dicarboxyiates having 1 to 12 carbon atoms in the backbone and cyeloalphatic dicarboxyiates having 8 to 12 carbon atoms in the backbone. The one or more dihydrocarbyi dicarboxyiates may comprise one or more malonates, tefephihalates, phthalates, iso-phihalafes, naphihaiene-2,8- dicarboxylaies, 1 ,3-pheny~!enedioxy diacetates, cycio-hexanedicarboxy!ates, cyciohexanediacetates, diphenyi-4,4'-dicarboxy)ates, succinates, giutarates, adipates, azeiates, sebacates, or mixtures thereof. The one or more dihydro-carbyi dicarboxyiates may comprise one or more maionates isophthalates, terephihaiates or sebacates. The one or more dihydrocarbyi dicarboxyiates may correspond to formula 11:

wherein R 1 is as previousl described; and

R a is separatel in each occurrence a hydrocarbyiene group having two bonds to the carbonyl groups of the diester wherein the hydrocarbyiene group may contain one or more heteroatoms. R A may be separately in each occurrence aryiene, cyc!oalky!ene, alkylene or alkenylene, R 3 may be separately in each occurrence C e-u aryiene, C s-12 cycioalkyiene, C ¾.« aikyiene or C alkenylene.

[00393 Some of the methods for the preparation of the poiyester macromers invoive the preparation of intermediate compounds. One ciass intermediate compounds is the multifunctional monomers. The muitifunctiona! monomers may be prepared from 1 s 1-diester-1-aSkenes and poiyols, including dso!s. Where the poiyoi has greater than two hydroxy! groups, preparation of a multifunctional monomer is desired before chain extension. Multifunctional monomers comprise a poiyoi wherein at least two of the hydroxy! groups are replaced bylhe residue of 1 ,1-djesler-1-aikenes. Where there are greater than two hydroxy! groups on the poiyoi it is possible that not all of the hydroxy! groups react with 1,1~diester~1-aikenes. it is desirable to react substantially ail of the hydroxy! groups with the 1,1-diester-1~a!kenes. The alternatives discussed hereinbefore for the poiyois and 1 ,1-diester-l-afkenes as far as structure are also applicable to the multifunctional monomers. Where a poiyoi with 3 or greater hydroxy! groups are used to prepare the multifunctional monomers they correspond to formula 12

where a dioi is used to initiate the multifunctional monomers they correspond to formula 13;

wherein R , R 2 and c are as defined hereinbefore. The multifunctional monomers can be prepared as disclosed hereinafter and as disclosed in Malofsky US 2014/0329980 and in Suiiivan US 9,416,091 both incorporated herein in their entirety for ali purposes, [0040J Another intermediate which may be used in the preparation of polyester macro-mers is one or more compounds comprising the one or more dihydrocarbyi dicarboxylaies having the residue of a poiyoi, such as a diol, bonded to each of the carbony! groups. These compounds may be referred to a poiyoi capped dihydrocarbyi dicarboxyiates. Some of them may be cai!ed dioi capped dihydrocarbyi dicarboxylaies. Each ester group of the dihydrocarbyi dicarboxyfates is subjected to transesterifica ' tion to replace the hydrocarbyi groups with polyo!s, such as diols. The resulting poiyoi capped dihydrocarbyi dicarboxyiates have terminai hydroxy! groups. The poiyoi capped dihydrocarbyi dicarboxyiates may correspond to formula 14;

the dioi capped dihydrocarbyi dicarboxylaies may correspond to formula 15;

wherein R 3 , R 3 and c are as described hereinbefore. In this context the hydroearby!ene of R 3 is bonded to the carbony! groups of the residue of a diester in the poiyoi capped dihydrocarbyi dicarboxyiates.

[0041] The polyester macromers may fee used in compositions that are usefui in preparing polymers and structures from the po!ymers. The compositions ma be assembled by blending the polyester macromers with desired components. The compositions may comprise or include mixtures of compounds formed in the preparation of the polyester macromers. Other ingredients may be added to the mixtures of corn-pounds formed in the preparation of the polyester macromers to form compositions which are designed to be used in the preparation of polymers containing the polyester macromers or structures formed from the polymers or polyester macromers. One corn-position comprises i) a plurality of polyester macromers disclosed herein: ii) one or more multifunctional monomers containing the residue of one or more pol o!s and one or more 1 , 1 -diester-1 -alkenes, wherein the multifunctional monomers have substantially al! of the hydroxy! groups of the po!yois replaced with the 1 ,1-diiester-l -alkenes; and i) one or more 1 ,1 -diester-1 -alkenes. Each of these ingredients are disclosed hereinbefore. This corn-position can be taken from the reaction mixture formed when the polyester macromers are prepared. The resulting reaction mixture can be subjected to a separation process, such as distillation to remove an excess one or more of the more volatile species, such as alcohols, po!yols or unreacted dihycrocarbyi dicarboxy!afes, to achieve the desired qon-eentrations of components. One or more of th recited compounds may be added to achieve the desired component concentrations. Plurality with respect to the polyester macromers mean that a number of poiyester macromer units which may be the same or different polyester macromers are present. The polyester macromers are present In suffi-cient amount to prepare the desired polymers and structures from the polymers and introduce a desired level of crosslnking. Any one or more of the poiyester macromers disclosed herein may be used in the compositions. Polyester macromers containing the residue of one or more dihydrocarbyl dicarboxy!ates in the backbon may be utilized. Poiyester macromers used in the compositions may comprise the residue of one or more polyo!s and one or more 1 , 1 -diester-1 -alkenes. The 1 , 1 -diester-1 -alkenes are present to function as reactive diluent and to facilitate forming a composition that exhibits a target viscosity. The 1 ,1 -diester-1 -alkenes may provide rapid reactivity to form: the polymer or structures prepared. The one or more multifunctional monomers are present to enhance crosslsnking of the polymer or structures prepared. The components are present in sufficient amounts to achieve their recited purpose. The plurality of polyester macromers are present in an amount of about 10 percent by weight or greate of the composition, about 30 percent by weight or greater or about 80 percent by weight or greater. The plurality of poiyester macromers are present in an amount of about 80 percent by weight or less of the composition, about 70 percent by weight or less or about 40 percent by weight or less. The multifunctional monomers are present in an amount of about 5 percent by weight o greater of the composition, about 10 percent by weight o greater, about 20 percent by weight or greater or 30 percent by weight or greater. The multifunctional mon-omers are present in an amount of about 50 percent by weight or iess of the composition, about 40 percent by weight or less, about 30 percent by weight or less or about 20 percent by weight or less. The 1 ,1-diester-t-aJkenes are present in an amount of about 0 percent by weight or greater of the composition, about 1 percent by weight or greater, about 5 percent by weight or greater, about 10 percent by weight or greater or about 20 percent b w ight or greater. The 1 ,1-diesteM-alkenes are present in an amount of about 40 percent by weight or iess of the composition, about 30 percent by weight or less or about 20 percent by weight or iess. The one or more po!yo!s may be diois. The multifunctional monomer may be a difunctiona! monomer,

[0042] The composition comprising i) a plurality of polyester macromers disclosed herein; ii) one or more multifunctional monomers containing the residue of one or more polyo!s and one or more 1 ,1- iester-1~a!kenes, wherein the multifunctional monomers have substantially ail of the hydroxy! groups of the polyofs replaced with the 1 ,1 - diesfer-1~aikenes; and iii) one or more i,1-dies?er-1-alkenes may be used as the basis for preparing additional compositions. This composition may be used in such other composi-tlons in sufficient amount to function as desired. This composition may be present in an amount of about 10 percent by weight or greater of the formed composition, about 20 percent by weight or greater, about 30 percent by weight or greater, about 60 percent by weight or greater or about 70 percent by weight or greater. This composition may present in an amount of about 30 percent by weight or less of the composition, about 60 percent by weight or less or about 30 percent by weight or less. Such compositions may contain a volatile solvent. The volatile solvent may be any solvent that does not react with the components or interfere in the curing of the compositions. The solvents may be volatiie at about 50 ,5 C or greater. The solvents may be volatile polar solvents. The solvent may be volatile polar aproiic solvents. The polar aprotic solvent may volatilize away from the other components once the coating is applied; to a substrate. Any polar aprotic solvent which volatilizes away from the other components once applied to the surface of a substrate may be utilized herein. The polar aprotic solvents may exhibit a boiling point of about 100 °C or greater, about 110 X or greater or about 130 *C or greater. The polar aprotic solvents may exhibit a boiling point of about 200 "C or less, about 190 °C or less or about 170 °C or less. The polar aprotic solvent may be an alkyiene glycol ether, an acetate modified aiky!ene glycol ether, a ketone, or a mixture of any of these solvents, and the like. The volatiie solvents are present in sufficient amount to facilitate use of the compositions as desired, that is the solvents facilitate delivery of the compositions and allow wet-out of the composition on the surface. The volatiie solvents are present in an amount of about 0 percent by weight or greater of the composition, about 1 percent by weight or greater, about 5 percent by weight or greater, about 10 percent by weight or greater or about 20 percent by weight or greater. The volatile solvents are present In an amount of about 50 percent by weight or less of the composition, about 40 perceni by weight or less of the composition, about 20 percent by weight or less or about 10 percent by weight or less. The compositions formed may contain an additional amount of 1 ,1 - diester-1 -alkenes. The additional 1 ,1-diester-l-alkenes are present in the compositions formed to function as reactive diluents and to accelerate polymerization. The additional 1 ,1-diester- -a!kenes may be present in an amount of 0 percent by weight or greater of the composition, about 1 percent by weight or greater, about S percent by weight or greater, about 10 percent by weight or greater or about 30 percent by weight or greater. The additional 1 ,1-dieste -aikenes may be present in an amount of about 50 percent by weight or iess of the composition, about 40 percent by weight or iess or about 30 percent by weight or !ess.

0043J The -formed compositions may further contain one or more wetting agents which facilitate the application of such compositions to substrates. Any wetting and or levelling agent which enhances the application of the compositions to a substrate may be used. Exemplary classes of wetting agents include polyether modified po!ydi- methy! siloxanes, fluorinated hydrocarbons and the like. The wetting agents may be poly-ether modified poiydimethy! siloxanes. The wetting and/or levelling agents are present in sufficient amount to facilitate application of the compositions to a substrates surface. The wetting agents may be present in an amount of about 0.01 percent by weight or greater of the composition, about 0.5 percent by weight or greater or about 1 percent by weight or greater. The wetting agents may be present in an amount of about 5 percent by weight or iess of the composition, about 2 percent by weight or iess or about 1 percent by weight or less. The formed compositions may further contain one or more UV stabilizers which inhibit th degradation of structures containing the polyester macromers. Any UV stabii-izer which inhibits degradation due to exposure to UV radiation ma be used. Exemplary classes of ultraviolet light sta ilizers include benzophenones, benzofriazo!es and hindered amines (commonly known as hindered amine Sight stabilizers (HALS). Exemplary UV light stabilizers include Cyasorb UV-531 2~hydroxy-4-n-octoxybenzophenone, Tinuvin 571 2~(2H-benzotriazof-2~y1)-6-dodecy1- 4-methylphenoi, branched and linear Tinuvin 1 ,2,3 bis-(1-oety!oxy-2,2 ; 6,6, tetramethyl- 4-piperidinyl) sebacate and Tinuvin 765, bis(1 ,2,2,6,6,-pentamethyl-4-pfperidinyl) sebacate. The UV light stabilizers are present In sufficient amount to enhance long- term durability of the compositions containing polyester macromers. The UV light stabilizers should be selected so as to not affect the stability or pot life of the composition by premature polymerization, either by initiating or catalyzing free radical polymerization, anionic polymerization or Michael addition across the aikene double bond. The UV light stabilizers may be present in an amount of about 0.01 percent by weight or greater of the composition, about 0,1 percent by weight or greater or about 0,2 percent by weight or greater. The UV Sight stabilizers may be present in an amount of about 5 percent by weight or less of the composition, about 3 percent by weight or less, about 2 percent by weight or less or about 1 percent by weight or less. The composition may further comprise def earners and/or deaerators. The compositions containing poly-ester macromers may foam during processing which can cause problems with respect to surface and appearance of the coating. Any defoamer and/or deaerator which prevents foaming or the formation of bubbles and which does not negatively impact the properties of the composition may be used. Exemplar defoamers are silicone defoamers, silicone free defoamers, po!yacry!ate defoamers, mixtures thereof and the tike. Exemplary de-foamers include FOAM BLAST™ 20F, FOAM BLAST™ 5 30 silicone defoaming compounds and FQ M BLAST m SSG poSyacrylate defoamers available from Emerald: TEGO At REX™ 920 polyacrylate defoamer and TEGO AIREX™ 980 from Degussa, SSLMER ACR™ DM0 and ACR™ Mo-8 poiydimethylsi!oxane acryiate copolymer from Si!tech Corporation, FOAM EX N™ or TEGO AiREX 900 silicone based defoamers available from Degussa or &YK m 1790 siiicone-free defoamer from BYK Chemie. The defoamer/deaerator is pre~sent in the polyester macromer compositions in a sufficient amount to prevent formation of bubbles and/or foam. If too much is used, adhesion to the desired surfaces and adhe- sives may be negatively impacted. The defoamer and/or deaerator may be present in an amount of about 0.01 percent by weight or greater based on the weight of the composition, about 0.06 percent by weight or greater or about 0.1 percent by weight or greater. The defoamer/deaerator may be present in an amount of about 2.0 percent by weight or less or about 1.0 percent by weight or less based on the weight of the composition,

[0044] These compositions may contain an additive to improve scratch resistance. Any additive which improves scratch resistance ma be utilized. Exemplary scratch resistance additives may include silicates, aluminas, zlrconias, carbides, oxides, nitrides or any other fillers with high hardness. Exemplary scratch resistance additives may include alumina {e.g., alpha alumina), silica, zirconia, boron carbide, silicon carbide, cerium oxide, glass, diamond, aluminum nitride, silicon nitride, yttrium oxide, titanium difooride, aiuminosiiicates (i.e. "Zeeospheres" from 3 ), titanium carbide, combinations thereof, and the Ike, Exemplary scratch resistance additives may be silicates and aluminas. Exemplary scratch resistance additives may include nanometer sized silica fillers. The scratch resistance additives may have a particle si∑e of about 10 micrometers or less or about 5 micrometers or less. The scratch resistance additives may be present in a sufficient amount to enhance the surface hardness and abrasion resistance of the coating and in an amount such that a homogeneous dispersion can be prepared. The scratch resistance additives may be present in an amount of about 0,1 percent by weight or greater of the composition or about 0.5 percent by weight or greater. The scratch resistance additives may be present in an amount of about 5 percent by weight or less of the composition, about 2 percent by weight or less or about 1 percent by weight or less.

[0045] These compositions may comprise an additive to improve surface slip properties. Any known composition that improves surface slip properties may be used. Exemplary surface slip additives may be a polyester modified polydsmethyl siioxanes, waxes and the iike. Exemplary waxes include those based on polyethylene, poiytetrafiuoroethyiene or polypropylene wax dispersions in acryiate monomers, such as the EVERGUOE™ or S-395 or SST serie of products from Shamrock Technologies, or polyam de particles such as ORGASGL™ from Ark ma, or montan wax with reactive acryiate groups, such as CERiOUST™ TP 5091 from C!ariant, or CERAFLOUR™ wax powders from Byk-Chemie. The wax may be in powder form having a particle size which is smaller than the desired thickness of the coating prepared from the composition. The maximum particle size may be about 30 microns or less, about 25 microns or iess, about 20 microns or less or about 15 microns or !ess. The wax may be highly crystalline. Exemplary waxes comprise a polyethylene, polypropylene, polyamide, polytetrafiuoro-ethy!ene, or b!ends and/ copolymers thereof. The wax may be crystalline polyethylene or poiytetrafiuoroethyiene or blends of polyethylene with poSyietraf!uoroethylene. The surface slip additives may be present in an amount of about 0.1 percent by weight or greater of the composition or about 0.5 percent by weight or greater. The surfac slip additives ma be present in an amount of about 5 percent by weight or less of the composition, about 2 percent by weight or less or about 5 percent by weight or less.

[00483 compositions disclosed herein contain one or more polymers having pen-dant Michaei Addition donor groups. Any polymers having pendant Michael Addition don~or groups that improve the properties of coatings prepared from compositions containing a plurality of polyester macromers may be used in the compositions disclosed herein, A Michael Addition donor is a functionai group that reacts with an e!ectrophiiic unsaturated group such as the aikene groups on the polyester macromers. The Mchaei Addition do-nors may be functional groups containing at least one active hydrogen atom. The Michael Addition donor groups may comprise amines, hydroxy! , thiol, or mixtures thereof. The Mi-chael Addition donor groups may comprise amines and/or hydroxy!. The polymer which contains the pendant Michael Addition Donor groups can be an polymer backbone that facilitates preparation of coatings with the desired properties, such as those described herein, it is desirable that the polymers enhance the gloss, flexibility and outdoor resis-tance in the form of improved UV and moisture resistance, of coatings prepared from polyester macromere compositions and polymers having pendant Michael Addition donor groups. The polymers having pendant Michael Addition donor groups may be acrylic, polycarbonate, styrene acrylonitrile, siloxane polyester or polyether backbones and the like. Exemplary polymers having pendant Michael Addition donor groups include one or more of acrylic poiyols, amine modified acrylic poiyols, polycarbonate poiyo!s, modified acrylic copolymer poiyo!s, seed oil poiyols, polyether poiyols, polyester poiyols and silox-ane poiyols. The one or more polymers having pendant Michael Addition donor groups comprise one or more acrylic poiyols or amine modified acrylic poiyols, and the like. Polymers containing pendant Michael Addition donor groups ma comprise compounds containing polyacry!ate backbones which are prepared from one or more acryiate containing compounds provided at least one of the acryiate containing compounds contain a Michael Addition donor, for instance a hydroxy!, amino, or thiol group. Such polymers may be prepared via free radical polymerization as is well known to those skilled in the art. Exemplary acryiate compounds containing Michael donor groups include hydroxyl-ethy! methacrylate, hydroxy butyiacrylate, hydroxyethyi acryiate, and the like. Styrene acrylonitriie based polymers containing Michael Addition Donors may be prepared by reacting styrene, acrylonitrile and a po!yalky!ene oxide containing an active hydrogen containing functional group such as an amine, hydroxy! or thiol group. The polya!kylene oxide may be a polypropylene oxide. The active hydrogen containing functional groups may be amino or hydroxy!, or may be hydroxy!. Polycarbonate based ol me containing Michael addition donors may be prepared by the steps of: {A) reacting (i) phosgene, (ii a branched-chain polyhydric alcohol having about 4 to 12 carbon atoms, and (iii) about 3 to 40 mole percent, based upon the total amount of polyhydric alcohol, of a straight-chain polyhydric a!coho! having about 5 to 20 carbon atoms in the presence of a solvent and in the absence of a catalyst at a temperature of about 60 ° C to 100 0 C, and (B) contacting the amorphous polycarbonate product in the reaction mixture with a catalytic amount of a tertiary amine at reflux temperature for a period of time of at least about 30 minutes.

[00473 Polymers containing pendant Michael Addition donor groups may have a hydroxy! number which enhances the properties of coatings prepared from the composi-tions disclosed. The hydroxy! number of the polymers containing pendant Michael Addition donor groups may be about 40 or greaier measured in terms of the KOH number, about 60 or greater or about 100 or greater. The hydroxy! number of the polymers contain-ing pendant Michael Addition donor groups may be about 220 or less measured in terms of the KOH number, about 200 or iess or about 50 or less. Hydroxy! number (OH) is the measure of the active hydrogen group content, such as hydroxy! group content, per gram of poiyoi. Hydroxy! value is measured by titrating a known mass of poiyoi against potas-sium hydroxide (KOH), and Is expressed as mg KOH/g. Lower hydroxy! values indicates lower active hydrogen content, hydroxy! content, and a higher molecular weight for the poiyoi. OH equivalent weight is the number of grams of a given product that contains one equivalent of hydroxy! groups (OH), Equivalent weight = 56100/OH. Molecuiar Weight is determined by multiplying the equivalent weight by the poiyoi functionality.

[0048] The composition comprising a) a composition containing a pluralit of polyester macromers and b) polymers containing pendant Michael Addition donor groups ma contain a sufficient amount of each so as to provide the desired properties of coatings prepared therefrom, as disclosed herein. Such compositions may contain an amoun of a composition containing a plurality of polyester macromers based on the total weight of a coating composition of about 40 perceni by weight or greaier, about 50 percent by weight or greater or about 80 percent by weight or greater. Such compositions may contain an amount of a composition containing a piuraSity of polyester macromers based on the total weight of a coating composition of about 90 percent by weight or less, about 70 percent by weight or less or about 50 perceni by weight or less. Such compositions may contain an amount of polymers containing pendant Michael Addition donor groups based on the total weight of a coating composition of about 10 percent by weight or greaier, about 30 percent by weight or greaier or about 40 percent by weight or greater. Such compositions may contain an amount of polymers containing pendant Michael . Addition donor groups based on the total weight of a coating composition of about 60 percent by weight or less, about 50 perceni by weight or less or about 40 percent by weight or less.

[0049] The composition comprising a) a composition containing a pluralit of polyester macromers and b) polymers containing pendant Michael Addition donor groups may further comprise c) one or more polar aprotic solvents. The po!ar aprotic solvent may vo!atiie!ze away from the other components once the coating is applied to a substrate. Any polar aprotic solvent which volatilizes away from the other components once applied to the surface of a substrate may be utilized herein. The polar aprotic solvents may exhibit a boiling point of about 00 °C or greater, about 110 "C or greater or about 130 °C or greater. The poiar aprotic solvents may exhibit a

28 boiling point of about about 200 °C or less, about 190 °C or less or about 170 C C or less. The polar aprotic solvent may be an al ylene glycol ether, an acetate modified alkylene glycol ether, a ketone, or a mixture of any of these solvents and th like. The polar aprotic solvent may be present in sufficient amount to adjust the viscosity of the composition to facilitate application of the -composition to a substrat and to allow appropriate wet-out of the composition on the surface to be coated. Such compositions may contain an amount of solvent based on the total weight of a coating composition of about 0 percent by weight or greater, about 1 percent by weight or greater or about 10 percent by weight or greater. Such compositions may contain an amount of solvents based on the total weight of a coaiing composition of about 30 percent by weight or less, about 20 percent by weight or less or about 15 percent by weight or less.

[0050] The polyester macrome compositions disclosed herein can be used to prepare coatings. Such structures may be cured and/or crosslinked. The crosslinked compositions -may be crosslinked through the a!kene groups pendant from the macromer chains. The crosslink may be a direct bond between the a!kene groups of adjacent macromer chains. The macromer chains may be included in prepo!ymer or polymer chains. The macromer chains may be crosslinked through any compound having unsaturation that polymerizes by anionic or free radical polymerization. The polyester macromer chains may be crosslinked through 1 ,1-diester a!kenes wherein the crosslinks comprise the residue of the 1,1-diester a!kenes. The polyester macromer chains may be crosslinked through multifunctional monomers wherein the crosslinks comprise the residue of the multifunctional monomers. The crosslinks between chains may be illustrated by formula 18:

wherein F is separately in each occurrence a direct bond, the residue of a compound that polymerizes with an unsaturated group by anionic polymerization or free radical polymer-ization. F may be separately in each occurrence a direct bond, the residue of a i,1-diester-1~alkene or a multifunctional monomer. The dotted lines refer to the backbone of the poly-merized macromer. The crosslink density of a crosslinked compositfon containing the poiyester macromers may be any such density that provides the desired properties of the composition. A portion of or all of the polyester macromers may be crosslinked by Michael Addition of the Michael Addition donors pendant from the polymers to the 1 a!kene groups of the polyester macromers. The crosslinks by Michael Addition of the Michael Addition donors pendant from the po!yols to the 1 alkene groups of the poiyester macromer may correspond to Formula 18

Wherein X is the residue of a Michaei Addition donor; and R x is the polymer or the substrate to which the residue of the Michael Addition donor is bonded. X may be independently in each occurrence O. R ? , or S. R* may be independently in each occurrence a poiymer comprising an acrylic polyoi, amine modified acrylic polyoi, polycarbonate poiyoi, modified acrylic copolymer polyoi, po!yether amines, polyester poiyols, polyether poiyo!s or siloxane polyoi or a substrate. R ' >' may be H or a hydroearbyi group as described hereinbefore. The polyester macromers may be crosslinked through the 1,1- a!kene groups and by Michael Addition of the Michael Addition donors pendant from the polymers to the 1 alkene groups. Alternatively, the polyester macromers may be crosslinked by unsaturated groups of compounds, including 1,1-disubstituted a!kenes and/or multifunctional monomers, via free radical or anionic addition processes as are well known to those skilled in the art.

[0051] The poiyester macromers and com ' ositions containing them may undergo polymerization when exposed to basic initiators. If applied to the surface of a substrate that is basic the polyester macromers will cure via anionic polymerization. Polyester macromers and compositions containing the poiyester macromers can undergo cure if contacted with a composition containing basic materials as a polymerization activator. The polymerization activator and methods of delivering the polymerization activator are disciosed in Malofsky US 9,181 ,365, incorporated herein by reference in its entirety for ail purposes. The polymerization activator may be at least one of a base, a base enhancer, a base creator, or a base precursor. The polymerization activator may comprise a basic materia! selected from a strong base (pH over 9), a moderately strong base (pH from 8-9), or a (mildly basic) weak base (pH from over 7 to 8), or a combination thereof. The polymerization activator may comprise a basic material selected from an organic material, an inorganic material or an organometa!iic materia!, or a combination thereof. The polymerization activator may be at ieasi one member selected from: sodium acetate; potassium acetate; acid salts of sodium,, potassium,, lithium, copper, and cobalt; tetrabutyl ammonium fluoride, chloride, and hydroxide; an amine whether primary, secondary or tertiary; an amide; salts of polymer bound acids; benzoate salts; 2,4~pentanedionate salts; sorbate salts; propionate salts; secondary aliphatic amines; piper-idine , plperazine, N-methylpiperazine, dibutylamine, morpho!ine, diethylamine, pyridine, tri-ethySa ine, tripropylamine, trieihy!enediamine, N,N-dimethylpiperazine, butyiamine, pentylamlne, hexy!amsne, hepiylamine, nony!amine, decylamine; salts of amines with organic monocarboxyiic acids; piperidine acetate; metal salt of a lower monocarboxyiic acid; copper(ll) acetate, cupric acetate monohydrate, potassium acetate, zinc acetate, zinc chioracetate, magnesium chioracetate, magnesium acetate; salts of acid containing polymers: salts of po!yacrylic acid co-poiymers, or pigments having a basic character. In certain embodiments, the po!ymerizatiGn activator is encapsulated in a wax, or is provided in inactive engagement with the polymerizable composition by chemical nactivation,

[00523 Disclosed is a polymerizable system com rising: a polymerizable composition containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups; and polymerization activator physically separated from the polymerizabie composition; wherein the polymerization activator is able to initiate polymerization upon contact with the polymerizable composition without substantia! mixing. The polymerization activator may be physically separated from the polymerizable composition, the physical separation is achieved by storing the activating agent and the polymerizable composition In separate locations within an applicator means. The appiicator means may be an aerosol spray device. The physical separation may be achieved by initially applying the polymerization activator to at least a portion of a substrate, followed b applying the polymerizable composition to the portion of the substrate. In still other embodiments, the physical separation may be achieved by providing the polymerization activator in or on at least a portion of a substrate. The polymerization activator may be physically separated from the polymerizable composition, the polymerization activator is In an inert state and wherein the polymerizabie system further comprises a converting agent abfe to convert the polymerization activator from the inert state to an activ state. The basic polymerization initiator ma be encapsulated in a composition that can be subjected to a process that releases the initiator. An encapsulated initiator particle includes an initiato matrix. The initiator matrix includes a first cured composition formed of one or more 1 ,1- disubstituied a!kene compounds and one or more polymerization initiators substantially encapsulated by the first cured composition. Exemplary compositions are disclosed in US 9,334,430 incorporated herein by reference in its entirety for all purposes,

[0053] Disclosed is a composition containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups as disclosed herein in one part and in a second part one or more com ounds having basic character sufficient to initiate anionic polymerization of the polyester macromers or one or more compound that catalyzes Michael Addition; wherein when the two parts are combined the polyester macromers undergo curing. Any of the basic materials disclosed herein may be used. The one or more compounds having basic character may be one or more ami es or poiyamJnes. The one or more compounds having basic character may be one or more polyalkyieneimines, such as po!yethyieneimines. Compounds that catalyze Michael Addition include acids and bases. Compounds that catalyze Michael Addition may be present in an amount of about 0,01 percent by weight or greater based on the weight of the formulation, about 0.06 percent by weight or greater, about 0.1 percent by weight or greater or about 0.3 percent by weight or greater. Compounds that catalyze Michael Addition may be present in an amount of about 1 percent by weight or less based on weight of the formulation, about 0,5 percent by weight or less or about 0.2 percent by weight or less,

[0054] The polyester macromers and compositions containing them ma be used in the preparation of polyester based structures including one or more polymers having pendant Michael Addition donor groups, such as coatings on substrates and the like. Disclosed are coatings containing polyesier macromers o the residue of the polyester macromers and one or more polymers having pendant Michael Addition donor groups. A coating containing polyeste macromers or the residue of the pofyester macromers and one or more polymers having pendant Michael Addition donor groups can be disposed on one or more surfaces or a portion thereof of a substrate. The coatings may be cured and/or crossiinked. The films or coatings may have a thickness of about 0. 01 micrometers or greater, about 0,04 micrometers or greater, about 0.1 micrometers or greater, or about 1 micrometers or greater. The coating may be cured and/or crossiinked. The coating may have a thickness of about 160 micrometers or less, about 140 micrometers o less, about 100 micrometers or less, about 60 micrometers or less, about 40 micrometers or less, about 10 micrometers or less, about 2 micrometers or less or about 1 micrometers or less. Disclosed are articles comprising a substrate with a coating comprising one or more polyesier macromers or a composition containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups applied to one or more surfaces. [00553 Disciosed are articles comprising substrates containing pigmented base coats on the substrates with coatings containing polyester macromers disclosed herein and one or more polymers having pendant Michaei Addition donor groups disposed on the base coats. The base coats may have a basic character which is sufficient to cure and/or cross-Sink the polyester macromers and one or more polymers having pendant Michael Addition donor groups. The coatings containing the polyester macromers and one or more po!y-mers having pendant Michaei Addition donor groups may be ciear and function as clear coats. The coatings disclosed ma contain an additional components utilized in coating such as pigments, adhesion promoters, fire retardants, and ingredients as disciosed herein and the iike. Coatings disciosed herein may contain pigments and function as stand-a!one coatings of base coats with a clear coat disposed above such base coats. Disciosed is a system which comprises a base coat and a clear coat containing a composition as disclosed herein, that is the composition contains one or more polyester macromers and one or more polymers having pendant Michaei Addition donor groups.

[0056] The polyester macromers or compositions containing them may be added to any composition containing the ingredients to prepare polyesters so as to introduce aikene units into the backbone. The compositions comprise diols and diesters known to those skiied in the art of preparing polyesters. The poiyester macromers or compositions containing them may be added to bSends containing polyesters to add the aikene functionality. The compositions containing the polyester macromers or compositions containing them may be crosslinked as disciosed herein.

[0057J poiyester macromers may be prepared from poiyols, diols, and diesters. The di-esters include one or more 1 ,1-diester-t-aikenes and may include dihydfocarbyi dicarboxy!ates. The finai structure of the polyester macromers may be determined b the ratios of reactants and the sequence of synthesis of intermediates which are disciosed hereinbefore. The intermediates and the polyester macromers may be prepared b transesterification. The poiyols having greater than two hyd oxy! groups and diois function to initiate the polyester macromer chains. The diols also function to react with the diesters to form the macromer chains. The 1 ,1-diester-1 - aikenes react with the poiyols and dio!s to form the macromer chains and to introduce pendant aikene groups into the macromer chains. The dibydrocarbyi dicarboxy!ates function to react with the poiyols and diols to form the macromer chains and to spread out the pendant aikene groups on the macromer chains. The polyester macromers may be prepared by contacting the poiyoi, diols and diesters and subjecting them to transesterification conditions. The resulting polyester macromers may have somewhat random and uncontrolled structure, ft may be desirable to prepare intermediates and use the intermediates to prepare the polyester macromers as the use of intermediates allow for control of the final structure.

[0058] The multifunctional monomers may be prepared by contacting one or more poiyols with an equivalents excess of one or more 1,1-diester 1-alkenes in the presence of a transesterification catalyst under conditions such that one or more multifunctional monomers are formed wherein the multifunctional monomers contain the one or more poiyols having two or more of their hydroxy! groups replaced with the residue of the one or more 1,1-diester 1-alkenes. The ratio of equivalents of one or more 1 ,1-diester 1-alkenes to one or more poiyols maybe about 2:1 or greater or about 4:1 or greater. The ratio of equivalents of one or more 1 ,1-diester 1 -a!kenes to one or more poiyols maybe about 5:1 or less or about 3:1 o less. The multifunctional monomers may be used to control the number of chains in the polyester macromers and/or to form the polyester macromer chains in a contro!ied manner. The poiyoS capped dihydrocarbyl dicarboxylates may be prepared by contacting the one or more dihydroearbyi dicarboxyiates with an excess of one or more poiyols in the presence of a transesterification catalyst under conditions such that one or more dihydrocarbyl dicarboxylates having the residue of a polyo! bonded to each of the carbony! groups Is prepared. The ratio of equivaients of one or more dio!s to one or more dihydrocarbyl dicarboxylates maybe about 2:1 or greater. The ratio of equivaients of one or more diols to one or more dihydrocarbyl dicarboxySates maybe about 4:1 or less or about 3:1 or less.

[00593 Disclosed: is a method comprising: contacting one or more poiyols with an equivaients excess of one or more 1,1-diester 1-a!kenes in the presence of a transesterification catalyst under conditions such that one or more multifunctional monomers are formed wherein the multifunctional monomers contain the one or more poiyois having two or more of their hydroxy! groups replaced with the residue of the one or more 1,1-diester 1-alkenes; and contacting the multifunctional monomers with an additional amount of the one or more poiyols, with the proviso that the poiyols are diols, or with one or more second poiyols which are diols,. in the presence of a transesterification catalyst under conditions such that one or more polyester macromers are prepared which contain one or more chains of the residue of one or more dio!s and one or more 1,1-diester-l-a!kenes wherein the residue of the one or more diols and the one or more 1,1-diester- 1 alkenes alternate along the chain and at least one terminal end comprises the residue of one of the 1,1-diester-1 a!kenes and wherein one or more terminal ends may comprise the residue of one or more diols. The multifunctional monomers and an additional amount of the one or more poiyols or with one or more second poiyols are contacted with one or more compounds comprising one or more dihydroearbyi dicarfaoxyiates having the residue of a potyo! bonded to each of the carbony! groups such that one or more polyester macromers are prepared wherein at least some to the polyester macromers contain the residue of the one or more the dihydroearbyi diearboxyiates in their backbone. The one or more compounds comprising the one or more dihydrccarbyS dicarboxylaies having the residue of a poiyoi bonded to each of the carbony! groups is prepared b contacting the one or more dihydroearbyi dicarboxylates with an excess of one or more poiyols in the presence of a transesterification cataiyst under conditions such that one or more dihydroearbyi dicarboxylates having the residue of a poiyoi bonded to each of the carbonyi groups is prepared.

[0060] Disclosed a method comprising: contacting one or more dso!s, one or more 1 ,1-diester 1-aikenes, and one or more dihydroearbyi dicarboxylates in the presence of a transesterification catalyst under conditions that one or more polyester macromers are prepared which contain one or more chains of the residue of one or more diols, one or more dihydroearbyi dicarboxylates and one or more 1 -diester-1-a!kenes wherein the residues of each are disposed in a random manner along the chain and at least one terminal end comprises the residue of one of the 1,1-diester-1 a!kenes and wherein one or more terminal ends may comprise the residue of one or more diols and/or one or more dihydroearbyi dicarboxylates.

[0061] Disclosed is a method comprising: contacting one or more poiyols with an equivalents excess of one or more 1 ,1-diester 1-alkenes in the presence of a transesferifscation catalyst under conditions such thai one or more multifunctional monomers are formed wherein the multifunctional monomers contain the one or more poiyols having at least two of their hydroxy! groups replaced with the residue of the one or more 1,1-diester 1~alkenes: and contacting the one or more multifunctional monomers one or more diols, one or more 1 ,1-diester 1-aikenes, and one or more dihydroearbyi dicarboxylates in the presence of a transesierfication cataiyst under conditions that one or more polyester macromers are prepared which contain on or more chains of the residue of one or more diols,. one or more dihydroearbyi dicarboxylates and one or more 1 ,1-diester- 1-aikenes wherein the residues of each are disposed in a random manner along the chain and at least one terminal end comprises the residue of one of the 1,1-diester-l alkenes and wherein one or more terminal ends may comprise the residue of one or more diote and/or one or more dihydroearbyi dicarboxylates.

[00823 Disclosed is a method comprising: contacting one or more multifunctional monomers which contain the one or more poiyols having their hydroxyl groups replaced with the residue of the one or more 1 ,1-diester 1 -alkenes; one or more compounds comprising a dihydrocarbyi dicarboxyiates having the residue of a po!yo! bonded to each of the carbonyi groups; and one or more poiyols in the presence of a transesterification catalyst under conditions such that one or more polyester macromers are prepared which contain one or more chains of the residue of the one or more poiyo s, the one or more 1,1-di8Ster-1-aikenes, and the one or more compounds comprising a dihydrocarbyi dicarboxyiaies having the residue of a po!yoS bonded to each of the carbonyi groups and at feast one terminal end comprises the residue of one of the 1,1~diesier~1 aikenes and wherein one or more terminal ends may comprise the residue of one or more dsols and/or one or more dihydrocarbyi dicarboxyiaies,

[00833 in h methods disclosed wherein th one or more poiyois o second poiyols may be diois. The one or more dihydrocarbyi dicarboxyiaies comprise one or more of aromatic dicarboxyiaies, aliphatic dicarboxyiaies, cycloaiiphatic dicarooxyiates, or a dihydrocarbyi dicarboxyiates having different hydrocarbyl groups selected from aromatic, -aliphatic and cycloaiiphatic groups. The oxygens from the hydroxy! groups on the diois and poiyols are bonded to aliphatic carbon atoms.

[0064] Transesterification is an equilibrium process and is typicaliy performed under conditions to remove the byproduct formed during the exchange, meaning the product formed by the hydrocarbyl moieties leaving the esters undergoing transesterification. The hydrocarbyl moieties leaving the ester group of the ester compounds may be smaller than the hydrocarbyi moieties replacing them so as to make the byproducts more volatile ihan the transesterified ester compounds. The smaller byproducts will generally be more volatile than the transesierified esier compound, which facilitates removal of the byproduct due to thei volatile nature. The process disclosed can be used with any process conditions that remove the byproduct formed from the leaving hydrocarbyl moieties. Exemplary process conditions or steps that may be used to remove the byproduct formed from the leaving hydrocarbyl moietie may include one or more of the following: distillation, membrane transport, inert gas purge, and the like.

[00853 transesterification reactions may be performed in the presence of a catalyst, such as an acid, an ester of such acid or an enzyme. The transesterification catalyst may be an enzyme. The transesterification catalyst may be a lipase enzyme. A transesterification process utilizing an enzyme is disclosed in US 2014/0329980, incorporated herein by reference for aii purposes in its entirety.

[00883 The cata!ysi may be an acid or an esier thereof. The transesterification process using an acid or ester is disclosed in co-owned patent US 9,416,091, incorporated herein by reference for all purposes in its entirety. Any acid or ester thereof that catalyzes transesterification white minimizing side reactions ma be used. In some embodiments the acid or acid utilized to form an ester is an acid having a pKa in a polar aprotie solvent, such as acetoniiriie or dioxane, as disclosed hereinafter. The pKa may be chosen to efficiently catalyze the transesterification reaction while minimizing side reactions and the concentration of catalyst in a reaction mixture. The acid used may have a pKa of about -5 or greater, about -3 or greater, or about 1.0 or greater. The acid used may have a pKa of about 14 or less, about 11 or less, or about 9 or less. The acid can be a Bronsted acid having a pKa as disclosed. The catalyst may be a superacid or an ester thereof. Superacid means an acid having an acidic strength greater than the strength of 100 percent sulfuric acid. Ester thereof, in the context of the acid catalysts, refer to compounds wherein the hydrogen on the acid is replaced with a hydrocarbyl group, for example an a!kyl group. Superacids are acids having a strength greaier than the strength of 100 percent sulfuric acid, a pKa less than 100 percent sulfuric acid, that is less than 8, less than about 5, or less than about 2. The measurement of acid strength is based on Kutt et al. "Equilibrium Acidities of Super Acids;' Journal of Organic Chemistry Vol 76 pages 391 to 395, 2011 , published on the Web December 17, 2010, which is incorporated herein by reference. Exemplary super acids inc!ude trifSuoromefhanesu!fonic acid (triflic acid), sulfated tin oxide, inflated tin oxide, sulfated zirconia, triflated zirconia, and inflated HZSM-5. Exemplary super acids are triflic and fiuorosulfonic acid.

[0087] Exemplary acid catalysts include trffiic acid, fiuorosulfonic acid, and sulfuric acid. For reactions requiring monosubsiitution (only one hydroxy! group on the alcohol or one ester group on the second ester is being replaced by transesterification), weaker acids with pKa values equal to or higher than suifuric acid may be desired. Examples of such acids include suifuric acid or methanesulfonic acid. For reactions requiring disubstitution (two hydroxy! groups on the alcohoi or two ester groups on the second ester are being replaced b transesterification), stronger acids with pKa values equal to or lower than sulfuric acid ma be desired. Examples of such acids include sulfuric acid, fiuorosulfonic acid, and triflic acid. For reactions requiring po!ysubsliiution (more than 2 hydroxyl groups on the alcohol and more than 2 ester groups on another ester compound), choice of acid catalysts can be similar to that for disubstituiion reactions but reaction time may need to be increased. Esters of acids useful as catalysts include alky! triflates.

[0068] The catalyst can be mixed with the reactanis or can be supported on a substrate such as a membrane or an inert carrier such as a porous support structure (the catalysts can be heterogeneous). Catalysts which are not supported are commonly refer-red to as homogeneous. The catalyst can be used in any concentration that catalyzes the transesterification reaction. The amount of cataiyst utilized for the reaction depends on the type of cataiyst being chosen. The concentration of homogeneous cataiyst is about 1 mo!ar equivalents or !ess per equivalent ' of the ester compounds undergoing transesterification; about 0. 1 molar equivalents or less; about 0.05 molar equivalents or less; about 0.005 mola equivalents o iess. The concentration of catalyst is about 0.001 moiar equivalents or greater per equivalent of the ester compounds undergoing transesterification; or about 0.0015 molar equivalents or greaier. Higher concentrations of catalysts than recited may be utilized. As disclosed in Matofeky et a!., US 8,609,885; 3,884,051 ; and WO 2013/059473 the presence of acid in the 1 ,1-disufostituted aikene compounds recovered can present problems with respect to use of the compounds and lo concentrations of acid in the products in use is desired. If high levels of acid are contained in the final product, additional purification or removal steps may be required. The amounts recited achieve the balance between efficient catalysis and the need for Sow acid concentrations in the product far use. Irs embodiments when the catalyst is selected from sulfuric acid or those acids having pKa values iess than that of sulfuric acid, the concentration of such catalysts in the reaction mixture is preferably at the upper end of the ranges recited herein. The choice of poiyo! and/or diester compound and the relative moles of the poiyol and the diester will impact the product of the process.

[0069] Where the reactants are liquid under reaction conditions it is desired to contact the reactants and catalysts in neat form (i.e., without a solvent or dispersani). If the use of a solvent is desired, a solvent that does not react with the reactants or the catalyst is desired. Another consideration in the choice of solvents is the boiling point of the solvent chosen. It is desired that the solvent have a boiling point of about 15 °C or higher or about 20 °C or higher than the temperature at which the reaction is conducted, Aprottc solvents may be used and long chain alkanes having a boiling point above the reaction temperature as described herein may be used; exemplary solvents are decane or dodecane. The reactants are contacted at any temperature at which the fransesterification will proceed. Preferably the reactants are contacted at a temperature of about 80 °C or greater or about 100 °C or greaier. The reactants may be contacted at a temperature of about 160 °C or less, 140 °C or iess or about 130 °C or less. The reactants are contacted for a sufficient time to prepare the desired transestertfied product, it is preferred to perform th process such that the starting first ester compound, such as a 1 ,1-disubstituted aikene compound, is substantially completely reacted with the alcohol or a second ester compound to prepare the desired product. Preferably the reactants are contacted for about 1 hour or greater. The reactants are contacted may be 4 hours or less or about 2 hour or less.

38 [0070] it is desired to perform the process under conditions that enhance contact of the diesters and pofyoi to allow the replacement of the original hydroearby! moieties on the ester groups of the diester. Some form of agitation is desired to enhance this contact. Exemplary methods of agitation include the use of stirrers, sparging with an inert gas, and the like. Vigorous stirring and/or vigorous sparging with nitrogen may be used. The transesterification reaction is believed to be an equilibrium reaction. Performing the process under conditions to drive the reaction in the direction of the desired product is recommended. Exemplary ways to achieve this include adding an excess of one reactant, removing the alcohol formed by the leaving hydrocarbyi moiety, and the like. Where the compound formed from the leaving hydrocarbyi moiety is volatile it can be removed through the us of a vacuum, use of conditions at which the leaving alcohol can be distilled off and the other reaetants and products do not distill away.

[0071 ] The catalyst may be an enzyme. The transesterification reaction conditions comprise room temperature and atmospheric pressure; elevated temperature and atmospheric pressure; room temperature and under vacuum; elevated temperature and under vacuum; or any combination thereof. The transesterification step may be performed at a temperature of about 20 ,5 C or greater, about 35 or greater or about 40 °C or greater. The transesterification step may be performed at a temperature of about 85 8 C or less or about 70 ° C or less.

[0072] The transesterification reaction may be performed in the presence of free radical stabilizers and anionic polymerization inhibitors as described in Maiofsky et ai., US 8,609,886; 8,884,051: and WO 2013/059473, relevant parts incorporated herein by reference. To prevent production of polymeric products, it is desirable to include an acid which inhibits polymerization but does not significantly participate in catalysis of the transesterification. The acid used to inhibit polymerization may have a pKa less than 100 percent sulfuric acid. According to certain embodiments, stabilizers can b included in compositions containing the transesterified products to increase and improve the shelf life and to prevent spontaneous polymerization. One or more anionic polymerization stabilizers and/or free-radical stabilizers may be added to the com ositions. Anionic polymerization stabilizers are generally e!ectrophiSic compounds that scavenge nucieophl!es from the composition or growing polymer chain. The use of anionic polymerization stabilizers can terminate additional polymer chain propagation. Exemplary anionic polymerization stabilizers ar acids, exemplary acids are carboxylic acids, sulfonic acids, phosphoric acids, and the like. Exemplary stabilisers include liquid phase stabilizers (e.g., methanesuifonic acid ("MSA"}} and vapor phase stabilizers (e.g., trif!uoroacetic acid ("TFA"}). it may be desirable to utilize relatively weak acids to inhibit polymerization. Generall such weak acids exhibit a pKa in acetonitriie of about -1.5 or about 2 or less. Exemplary acids used to inhibit anionic polymerization are alky! substituted aryi sulfonic acids, such as dodecyibenzenesuifonic acid, p-toluenesu!fonic add, and the like. As the catalyst in the method disclosed is an acid a second anionic polymerization inhibitor may not be required in performing the method disclosed herein, it is desired to include a free radical stabilizer or polymerization inhibitor in performing the method disclosed herein. The concentrations of the stabilizers, or polymerization inhibitors, useful in the method are disclosed hereinafter.

[0073] Free radical stabilizers preferab!y include phenolic compounds (e.g., 4- methoxyphenoi, mono methyl ether of hydroquinone {"MeHQ") buty!ated hydroxytoiuene {"8HT"}). Stabilizer packages for 1 ,1-disubstiiuted alkenes are disclosed in U.S. Patent No. 8,609,885 and U.S. Patent No. 8,884,051 , each incorporated by reference. Additional fre radical polymerization inhibitors are disclosed in U.S. Patent No, 6,458,956 and are hereby Incorporated by reference. Generally, only minimal quantities of a stabilizer are needed and, in certain embodiments only about 5000 parts-per-mUlion {"ppm") or less can be included. In certain embodiments, a blend of multiple stabilizers can be included; for example, a blend of anionic stabilizers (MSA) and free radical stabilizers ( eHQ),

[0074] The one or more anionic polymerization stabilizers are present in sufficient amount to prevent premature polymerization. The anionic polymerization stabilizers may be present in an amount of about 1 ppm or greater based on the weight of the first ester corn-pound (1 ,1-disubstiiuted aikene}, about 5 ppm by weight or greater, or about 10 ppm by weight or greater. The anionic polymerization stabilizers may be present in an amount of about 500 ppm by weight or less based on the weight of the ester com pound f!,1~disubstiiuted aikene), about 250 ppm by weight or less, or about 100 ppm by weight or less. The one or more free radical stabilizers are present in sufficient amount to prevent premature polymerization. The free radical polymerization stabilizers may be present in an amount of about 10 ppm or greater based on the weight of the ester compound (1 ,1~disub-stttuted aikene), about 1 ΘΘ ppm by weight or greater or about 1000 ppm by weight or greater. The free radical polymerization stabilizers may be present in an amount of about 10,000 ppm by weight or less based on the weight of the ester compound {1 ,1-disub-stitute aikene), about 8000 ppm by weight or lessor about 5000 ppm by weight or less.

[0075] Disclosed is a method comprising contacting a composition containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups with a surface of a substrate wherein the surface is at least mildly basic and forming a coating on the surface of the substrate comprising the composition containing the one or more poiyester macromers and one or more polymers having pendant Michael Addition donor groups. The substrate is comprised of material that is basic. The composition that contains a basic compound may be applied to the surface of the substrate before applying the composition containing one or more poiyester macromers. The composition that contains a basic compound may comprise any compound disclosed herein as an anionic polymerization inhibitor useful with l ,1-diester-1-alkenes. Exemplary basic compounds include an amine, po!yamine basic pigments or carboxylate salts. The composition that contains a basic compound may comprise a polya!kyieneimine. The method may further include exposing the substrate with the composition containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups to a temperature of about 20 °C or greater or about 50 "C or greater. The method may further include exposing the substrate to with a composition containing one or more poiyester macromers and one or more polymers having pendant Michael Addition donor groups to a temperature of about to 150 °C.or less . or about 120 "C or less. The time period for such exposure may be about 10 minutes or greater or about 20 minutes or greater. The time period for such exposure may be 120 minutes or less, about SO minutes or less or about 30 minutes or less. The exposure is performed under conditions such that the coating containing one or more poiyester macromers and one or more polymers having pendant Michael Addition donor groups disposed on the surface of the substrate is cured and/or cross!inked.

[0078J poiyester macromer containing coatings or films may cure and/o crosslink when exposed to certain conditions. When the coating or film are exposed to relatively strong bases and or elevated temperatures they cure and crosslink at the same time. If they are exposed to mildiy basic materials at relatively low temperatures, less than about 50 *C or less than about 40 *C they may not completely cure or crosslink. Such coatings or films may be cured by exposure to elevated temperatures to cure as disclosed herein.

0077j ^ e coatings prepared from one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups may exhibit one or more of the following properties listed below. A gloss according to ASTM D523-08 at 20 " of 40 GU or greater, 50 GU or greater or 60 GU or greater. A pencil hardness according to ASTM D3383-G0 of 3H o greater, 4H or greater or 5H or greater. A solvent resistance according to ASTM D5402-93 of about 80 double rubs of methyl ethyl ketone or greater, 100 rubs or greater or 200 rubs or greater. A mandrel flexibility according to ASTM D522-93 of 70 percent or greater, 80 percent of greater or 90 percent; A cross hatch adhesion of 4B or higher 100 percent according to ASTM D3359-09, An acid resistance according to G W 14701 up to 40 °G, up to 50 °C or up to 60 "C. A base resistance according to GMW 14701 40 * C or greater, 50 °C or greater or of 60 C or greater. Coatings are able to withstand 500 hours, 1000 hours, of Xenon arc UV/moisture exposure according to ASTM D788S with no loss in gioss or color and 500 hours of sa!t spray testing according to GMW 3286-11 with no change in gloss or no signs of blistering and corrosion.

[00783 The articies/composit!ons disclosed may further comprise any one or more of the features described in this specification in any combination, including the preferences and examples listed in this specification, and includes on or more of the following features: wherein the pendant Michael Addition donor groups comprise functional groups containing active hydrogen atoms; wherein the pendant Michael Addition donor groups comprise amines, hydroxy!, thiol, or mixtures thereof; wherein the Michaei Addition donor groups comprise amines and/or hydroxyi wherein the composition contains one or more alternating chains of the residue of one or more diols and one or more diesters wherein each of the chains are bonded at one end to an oxygen of the residue of a poiyoi having three or more of the oxygen atoms; wherein the polyester macromer corresponds to Formula 1 ; wherein c as used in a number of formuias may be an integer of about 3 to about 6; wherein the one or more po!ymers having pendant Michael Addition donor groups comprise one or more of acrylic polyols, amine modified acrylic polyols, polycarbonate po!yois, modified acrylic copolymer poiyols s polyester polyols, polyether poiyo!s and siloxane polyols; wherein the one or more polymers having pendant Michaei Addition donor groups comprise on or more acrylic polyols or amine modified acrylic polyois; a composition according to any one of the preceding claims which comprises a) from about 40 to about 90 percent by weight of one or more polyester macromers and from about 10 to 60 percent by weight of one or more one or more polymers having pendant Michael Addition donor groups wherein the amounts are based on the weight of the composition, which may optionally contain a solvent; the so!venf may comprise one or more poiar aprofic solvents; the solvent may comprise one or more one or more alky!ene glycol ethers, acetate modified aikyiene glycol ethers, or ketones, having a boiSing point of about 80 S C to about 200 !i C; the solvent is present in an amount of about 5 to about 40 percent by weight wherein the amounts are based on the weight of the composition; th polyester macromer may contain one chain of the residue of one or more diols and one or more diesters; the polyester macromers may correspond to Formula 2; the polyester macromers may exhibit a number average molecular weight of about 400 to about 3000; the oxygens from the hydroxyl groups on the diols and polyols of the polyester macromers may be bonded to aliphatic carbon atoms; the one or more chains of the polyester macromers may comprise a residue of one or more dihydrocarbyi dicarboxyi ies; the one or more dihydrocarbyi dicarboxyiates may comprise one or more of aromatic dicarboxyiaies having 8 to 14 carbon atoms in the backbone, aliphatic dicarboxyiates having 1 to 12 carbon atoms in the backbone and cycioaSiphatic dicarboxyiaies having 8 to 12 carbon atoms in the backbone; the one or more dihydrocarbyi dicarboxyiates may comprise one or more maionates, terephthalates, phthalates, isophthaiates, naphthaSene-2,6-d(carboxyiaies, 1 ,3-pheny!enedioxy diacetates, cvcSohexanedicarboxylates, cyctohexanediaceiates, diphenyl-4,4'- dicarboxyiaies, succinates, giutarates, adipates, azeiates,, sebacates, or mixtures thereof; the one or more dihydrocarbyi dicarboxyiates comprise one or more maionates, isophthaiates, terephthalates or sebacates; the poiyois used to prepare the polyester macromers correspond to Formula 9, the 1 ,1 -diester-1~aikenes correspond to Formula 7 and the one or more dihydrocarbyi dicarboxyiates correspond to Formula 11 ; c is 2 and the poiyois used to prepare the polyester macromers correspond to the formula HO — f^— H th i R 2 is as previously described; the poiyois used to prepare the polyester macromers may comprise one or more aliphatic backbones thai are branched; the one or more poiyois used to prepare the po!yester macromers may comprise one or more branched aliphatic chains having at least on branch on th 2 carbon atom and cycloa!iphatic backbones; the one or more poiyois may comprise pentane dioi, hexane dioi, neopentyi giyco!, 2-maiftyi~1 ,3-propane dioi, 2-butyi~1 ! 3- propane dioi, 2-ethy!-1 ,3~propane dioi or cyc!ohexane dimethanoi; the polyester macromers correspond to Formula 3; the polyester macromers correspond to Formula 4; the polyester macromers correspond to Formula 5; polyester mnacromers according to Formula 4 or 5 wherein the ratio of d to e in the macromer is about 1 1 to about 4:1 ; a polyester macromer having from about 1 to about 4 dihydrocarbyi dicarboxyiates are contained in each chain; the polyester macromers correspond to Formula 6; a composition comprising t) a plurality of polyester macromers described herein, if J ' one or more multifunctional monomers containing the residue of one or more poiyois and one or more 1 ,1-diester- -alkenes, wherein the multifunctional monomers have substantially ali of the hydroxy! groups of the poiyois replaced with the 1 ,1-diester-l- aikenes, and iii) one or more 1,1-diester-l-alkenes, wherein such composition may comprise I} from about 10 to about90 percent by weight of a plurality of polyester macromers, ii) from about 1 to about 50 percent by weight of one or more multifunctional monomers, and iii} from about 1 to about 30 percent by weight of one or more 1 ,1-diesier-1-alkenes wherein the percentages are based on the amounts of the ingredients iisted; the one or more poiyois used to prepare the polyester macromers may be dio!s; the one or more multifunctional monomers used to prepare the polyester macromers may be difunctionai monomers; a composition comprising a) a polyester macromer containing composition as disclosed herein, b} a volatile solvent, c) optsonaiiy, an addilionai amount of one or more 1 ,1-diesier-l-aikenes, d) one or more wetting and levelling agents, e) one or more UV stabilizers and/or UV absorbers, and, f) one or more defoamers, wherein such composition may comprise a) from about 10 to about 90 percent by weight of a a poiyester macromer containing composition as disclosed herein, b) from about 1 to about 50 percent by weight of a volatile solvent, c) from about 0 to about 40 percent by weight of one or more 1 ,1-diester-l-a!kenes, d) from; about 0.01 to about 2 percent by weight of one or more wetting and !eve!!ing agents, e) from about 0,01 to about 3 percent by weight of one or more UV stabilizers and/or UV absorbers, and, f) from about 0.01 to about 2 percent by weight of one or more defoamers, wherein the percentages are based on the weight of components a, b, e, d, e and f; a composition as disclosed herein which is cured and in the form of a coating; wherein the coating exhibits thickness of about 1 micrometers to about 100 micrometers; wherein the coating exhibits a thickness of about 2-180 microns; a composition containing a plurality of poiyester macromers wherein a portion of or all of the poiyester macromers are crosslnked through the 1 ,1- alkene groups; a composition wherein the crosslinks between chains may be illustrated by formula 17; a composition according to Formula 17 wherein F may be separately in each occurrence a direct bond, the residue of a 1 ,i-diester-l-a!kene or a multifunctional monomer; a composition wherein a portion of or a!! of the polyester macromers are crosslinked by Michael Addition of the Michael Addition Donors pendant from the polymers to the 1 alkene groups of the polyester macromers; composiiion wherein the crosslinks by Michaei Addition of the Michael Addition Donors pendant from the poiyois to the 1 alkene groups of the polyester macromer correspond to Formula 18; a composition according to Formula 18 wherein X is independerrtiy in each occurrence O, NR , or S; and R* is independently in each occurrence a .polymer comprising an acrylic poiyol, amine modified acryiic poiyol, polycarbonate poiyo!, modified acrylic copolymer poiyol, poiyester poiyol, poiyether poiyol or siioxane poiyol or a substrate; the polyester macromers are crosslinked through the 1 ,1- alkene groups and/or by Michaei Addition of the Michael Addition Donors pendant from the polymers to the 1 alkene groups; the cured coating exhibits one or more of the fo!!owing properties of a gloss according to ASTM D523-08 at 20 *, or 60°, or 85° of 40 GU or greater; a penci! hardness according to ASTM D3363-00 of 3H or greater; a solvent resistance according to ASTM D5402-93 to 80 rubs of methyl ethyl ketone or greater; mandrel flexibility according to AST D522-93 of 80 percent or greater; cross hatch adhesion of 48 or higher and 100 percent according to ASTM D3359-Q9 and acid resistance up to 70 °C and base resistance at greater than 70 °C according to G W 14701; the polymers having pendant Michael Donor groups exhibit a hydroxy! number of about 50 to about 200; and a composition as described herein which further comprises one or more of the following components: pigments, fillers, reinforcing agents, anti-slip additives, and additves to improve abrasion resistance.

[0079] The methods disclosed may further comprise any one or more of the features described in this specification in any combination, including the preferences and examples listed in this specification, and includes any one or more of the following features; the substrate Is comprised of one or more of a material that is at least mildly basic, nucieophilic and/or contains a pluralit of Michael Addition Donor groups on its surface; the pendant Michael Addition donor groups comprise functional groups containing active hydrogen atoms; the pendant Michael Addition donor groups comprise amines, hydroxy!, thiol, or mixtures thereof; the Michael Addition donor groups comprise amines and/or hydroxyl; the substrate has a pigmented coating deposited on its surface wherein the pigmented coating is mildly basic or nucteophic; the eoating comprising the composition containing the one or more polyesier macromers forms a clear coating; which includes exposing the substrate with the composition containing one or more polyester macromers deposited on the substrate to a temperature of about 20 °C to about 150 °C for about 10 minutes to about 120 minutes under conditions such that the coating containing on or more polyester macromers disposed on the surface of the substrate is cross!inked; wherein the coating or the surface of the substrate contains a catalyst for Michael Addition; and the coating or the surface of the substrate contains an initiator for anionic polymerization.

ILLUSTRATIVE EMBODIMENTS OF THE INVENTION

fOOSOj T e following examples are provided io illustrate the invention, but are not intended to limit the scope thereof. All parts and percentages are by weight unless otherwise indicated .

[0081] The reaction procedure is described as follows: a three neck 100 mL round bottom flask with a distillation head, thermometer, vacuum adapter, and collection flask are assembled using high vacuum grade grease a!ong with a heating mantle, thermocouple, and a magnetic stir bar. The reaction mixture is subjected to agitation typically ran ing from 400-800 rpm. Vacuum is used to remove subsequent byproducts from the reaction mixture and the various pressures are indicated be!ow along with the mix time in each case. In some cases, nitrogen gas is used to purge the mixture in lieu of vacuum and, if app!icab!e, is indicated below. In each case, the mole equiva!ent is relative to the diethyl methylene malonate ("DEMM") monomer used,

[0082] HMR spectroscopy is employed using a 300 MHz NIVI to analyze reaction mixtures. Samples ' are prepared using chloroform-d (CDC ) and hexamethy!disiioxane as an internal standard appearing at about 0 ppm. For ,1-disustttutect aikene compounds with symmetrica! substituents (e.g., DE ), the reactive aikene functionaiity (i.e., the double bond) appears at about 6.45 ppm. For 1 ,1-disubstituted aikene compounds with asymmetrical substituents, the reactive a!kene functionaiity appears as a doublet at about 8.45 ppm. In most cases, four NMR scans are run on each samples specimen with a 20 second delay between scans.

[0083] GC-MS is employed to determine conversion of starting materials to the desired transesterified product(s) and detect the presence of any byproducts. A helium gas {carrier gas) purge of about 1 mL/min is employed to aid the Ionized in sample reaching the MS detector. Typical sample injection volumes of 1-2 pL of about 2-5% of the reaction mixture in dicl ioromethane (OHaC¾) are used for injecting into the <3C- MS instrument. The GO-MS profile method involves maintaining the oven ai 100 °C, followed by a ramp of 15 °C min to 250 °C. Typical run times range from 18-23 minutes. Retention times of 1 ,1-disubstituted aikene compounds, based on the above mentioned method, range from 4.5-17 min and are strongly dependent on the substituents and the ease of ionization of the particular molecule in the GC chamber.

[0084] Gel permeation chromatography (GPC is used to determine the molecular weight of the polyester macromers formed after transesieriffcaiion. Polymethylmethacrylate standards (P MA), covering a range of 500 to 1 ,08 million in number average molecular weight (Mn) were used to plot the calibration curve. Samples were dissolved in THF and filtered before injection. A 10 pL injection volume was utiiized at I ml/mln. Columns were maintained at 35 *C and 75 bar pressure. A refractive index detector is utilized downstream and is also maintained at 75 bar pressure. The amount of different species in the composition were calculated based on the percent area of the molecular weight peak on the chromatogram.

[00853 ingredients and Products

Pentane Diol

DEM Diethyl malonate

DEMM Diethyl methylene malonate (diethyl l -meihyiene-l .l-dicarboxylate) MeHQ Mono methyl ether hydroquinone

MSA Methanesulfonic acid

Catalyst CALB Lipase Enzyme [0088] Testing and Test procedures « coatings prepared as described herein are tested for a number of properties according to the following procedures,

Crosshatch tape adhesion ASTM D3359-09

Specular gloss ASTM D523-08

Pencil hardness ASTM D3363-00

MEK rub resistance ASTfvl D54G2-93

Mandrel ASTM D522-93

Abrasion ASTM D4060-95 (modified for Linear Taber)

Moisture GM 14729

Acid/Base resistance GMW 14701

Weathering (UV + moisture) SAE J 2020

Sail spray GMW 3286-1 Neutral salt spray

[0087] Example 1 - Preparation of Di-functional Monomer from Pentane Dio! and

DEMM

A round bottom flask is charged with DEMM (172 g, 1 moi), perstanediof (26 §, 0.25 mot) and CALS lipase enzyme (8,8 g) (purchased from CLEA) 5 weight percent based on DEMM. The round bottom flask is placed on a roiovap preheated to 4S*C and pressure of 150 mm Hg is applied. After 1 hour the reaction is checked for completion by GCMS and HNMR, Once the pentanediol has been consumed, the reaction has gone to completion. The product mixture is about a 65/35 mixture of difunctionai monomer and DEMM according to GCMS analysis. The reaction mixture is filtered to remove enzyme. A 3 neck round bottom flask equipped with mechanical agitator, thermometer and a condenser is charged with the reaction mixture formed. The reaction mixture is distilled at 65°C and a pressure < 0.800 mm Hg for 2 hours or until the amount of difunctionai monomer is greater than 65 percent by weight of the solution. The typical product composition is: 67% DEMM-pentanedioi multifunctional monomer and 33% DEMM.

[0088] Example 2 - Endcapping Diethyl Maionate with Pentane Diol

A round bottom flask is charged with pentanediol (260 g 2.5 mo!), DEM (159 g, 1 moi) and CALB lipase enzyme (18 g) (purchased from CLEA) S 7 weighi percent based on pentanediol. The round bottom flask is placed on a rotovap and preheated to 45*0 and a pressure of 150 mm Hg is applied. After 1 hour the reaction is checked for com !etion by GCMS and HNMR. Once the DEM has been consumed, the reaction has gone to completion. The reaction mixture is filtered to remove enzyme, A 3 neck round bottom fiask equipped with mechanical agitator, thermometer and a condenser is charged with the reaction mixture which is distilled at 100 °C and less than 0,800 mmHg for 2 hours or until the amount of pentanediol is about 0 weighi percent of the reaction mixture (as determined b GC S). The typical product composition is about 90 percent b weight or pentanedioi capped diethyl malonaie and about 10 percent by weight pentanedioi.

[0089] Example 3 - Preparation of Polyester Macromer

A round: bottom flask is charged with DEMM-pentanedioi difunctional monomer {142 g, 0.4 mo!) and pentanedioi capped diethyl malonaie (27.6 g 0.1 mol), diethyl methylene ma!onate, (70 g, 0.4 mol), pentane dial (2,7g, 0.025 mol) and CA18 lipase enzyme (10 g) 7 weight percent based on DEMM-pentanedioi difunctiona! monomer. The round bottom flask is placed on a rotovap preheated to 45°C and at a pressure of 150 mm Hg, After 1 hour the reaction mixture is checked for completion (disappearance of pentanedioi- difunctiona! monomer) by GCMS, The reaction mixture is filtered to remove the enzyme. The resulting solution is examined by GPC. The product composition is generally comprised of the following: 80-75 weight percent of polyester macromer, 20-30 weight percent of pentanedioS-difunctionai monomer, 0-10 weight percent of PEMM, 100 ppm M HQ. and TQ ppm .MSA are added to the final product MSA is accurately measured out from a 1 percent by weight MSA; DEMM solution. This reaction is illustrated by the equation:

Mn - 1382 a/moi

Mw !a 1964 g mol

PD = J .2

Example 4 - Preparation of Polyester Macromer

A round bottom flask is charged with DEMM-pentanedioi difunctional monomer (142 g, 0.4 moi), diethyl methylene malonaie, (70 g, 0.4 mol), pentane dioi (10.8 g, 0.10 mol) and CALB lipase enzyme (10 g) 7 weight percent based on DEMM-pentanedioi difunctiona! monomer. The round bottom f!ask is placed on a rotovap preheated to 45 °C at a pressure of 150 mm Hg. After 1 hour the reaction mixture is checked for completion (disappearance of pentanedioi- difunctional monomer) by GCMS. The reaction mixture is filtered to remove the enzyme. The resulting solution is examined by GPC, The product composition is generally comprised of the following: 60-76 weight

48 percent of polyester macromer, 20-30 weight percent of pentanediol-difunctionai monomer, 0-10 weight percent of DE . 100 ppm MEHG and 10 ppm MSA are added to the final product. MSA is accurately measured out from a 1 percent by weight MSA

[00903 For most of the experiments the composition is 60-70% of polyester macromers having a molecular weight of 800, 30-35% DEMM-pentane diol Afunctional molecule and S-10% DEMM References to polyester composition refers to this general com osition. Any deviations from this will be specifically mentioned,

[0091] Example 6: Testing the polyester com position on cold rolled steel

[0032] The cold roiled steel panels are from Q-PaneS (4 * X 8" steel). The steel panels require an initiator to be used to adhere to the substrate, Pyridyl ethyl trirnethoxysilane (PETS), and Poiyethylenirnine branched (PEi) are used as initiators as 1 % solution in butyl ce!ioso!ve. The initiator solution is drawn down using a 2.5 Meyer rod and solvent is flashed off at 80 a C for 5 minutes. A solution of the polyester composition is drawn down using a 20 Meyer rod resulting in a wet film thickness of 40 microns. The cure temperature used is 80X. The coated panels are cured within 20-30 minutes. Properties of the resultant coating after full cure are summarized in Table 2, To pass the Cross Hatch test the result must be 58, To pass the mandrel test the sample must show no detected cracks at ail bend angles on the mandrel.

[0033] Table 2; Properties of the polyester com position on cold rolled steel i n itiated by 1% PEI (250 MW) in butyl ceiiosoive

[0094] The polyester composition, having a molecular weight of 800 is also cured using a branched PEI initiator with a molecular weight of 800. The results of the testing are summarized in Tab!e 3. The improved flexibility of this polyester composition on a Mandrel test is attributed to the higher molecular weight of this poiyester composition, [0095] Table 3: Properties of a polyester on cold roiled steel initiated by branched t% PEI (800 SVfW) in butyl ceiiosoive.

Example 7: Spray coating on base coated steel panels

[0097| BASF R-M Onyx HD™ base coat is professionally sprayed on the panels. There is some variation In the color of the coated base coats across different tests. This shows the robustness of the chemistry being able to cure on base coats of different colors.

[0098J ^e ciear coat is also sprayed on the base coated panels . Each formulation is sprayed using an automotive refsnish HVLP gun {Anest twata model number S- 400). Each round of spraying is conducted in a forced air laboratory hood with 100 ft/min air flow. Before first use, the gun is pacified by spraying a solution of 1 % methanesulfonic acid in acetone. The gun is connected to a shop compressed air sou ce of 90 psi which is stepped down with a regulator to 25 psi at the gauge. During spraying, the active pressure reading is 20psi. Spray coatings are applied in two coats with each pass overlapping the one above it 50%. After each formu!ation, the gun is cleaned by spraying acetone through if twice.

[0099] The poiyester composition is adjusted by formulation according to Table 4 below, BYK 333 is a polyether modified silicone additive which is used for improving wet out on base coats. 40% butyl ce!!oso!ve solvent is used to dilute the polyesier composition to improve spray capabilities and to assist with wet out. Formulation 1 using poiyester and soivent comprises the polyester composition having a mo!ecular weight of 80 weight percent; 0,1 wt% BYK 333 polyether modified silicone and 40 wf% Butyl celiosolve.

[00100] Tabie 5: Properties of the formulation on base coat

[001013 This demonstrates that the cure of the po!yester based formulation using the base coat at elevated temperatures results in good coating properties.

[001023 Exam le 8; Example 7 is repeated except the cure temperature chosen is S2 ': €, Properties of the resultant coating are not affected as shown in Table 6 below.

Table 6: Coatin ro erties for Formulation 1 after cure at 82 'C

[001033 Example 9: Replacing solvent with reactive diluent {DE M}

[001043 DEMM (dimethyl methylene malonate) is added at 20% to decrease the weight percentage of butyl ce!!osolve to 20 percent. DEMM reacts rapidly to form crosslinks with the di and multi-functional components at lower temperatures. The formulation comprises 80 weight percent of a polyester macromer having a molecular weight of SQQ, 0.1 wt% BYK 333 poiyether modified silicone, 20 wt% Butyl eeilosoive and 20 t% DEMM

[001053 " ^® coating procedure is similar to that described in Example 8. The Coatings are cured at 50 "C for 25 minutes and complete cure is obtained. Coatings appeared aesthetically pieasing and showed good properties as shown in Table 7.

[001073 This demonstrates that the coatings have good a id and base resistance after full crosslink ing where the only failures are occurring at elevated temperatures, [001083 Example 10: Formulations with polyester and acrylic poiyols

[001093 Acrylic po!yols are chosen to be used with polyesters in varying amounts to improve flexibility, resistance properties and long term aging characteristics. Acrylic poiyois made by BASF under the trade name Joncryi and those made b Dow under the trade name Para!oid are utilized. Severe! formulation attempts have been made to test the ratio of acrylic polyoi to polyester that provides the desired flexibility and to improve coating properties. Two ratios of polyester to acrylic po!yoi are chosen based on an -evaluation of the core speed and conditions and th properties of the coatings after cure. Formulations are sprayed on to steel panels coated with a base coat and cured as described above.

[00110] The formulation ma be curing using Anionic polymerization and Michael addition reactions. The hydroxy! groups present on the surface of the base coat and scattered across the chain length of the acryiic polyoi undergo Michael addition with the reactive methylene groups present in the polyoi, thus incorporating the polyoi into the erossiinked matrix.

[00111] Table 9: Formulation 3 utilizing polyester and acrylic polyoi

Formulation 4 is spray coated on a Car Star Base Coat. Formulation 4 demonstrates a lower flexibility on the Mandrel test.

[001153 Table 11 : Formulation 4 using poiyester and acryiic polyoi

[001 16] Table 13: Performance Data for Formulation 4

[00121] The spray and cure process is as described in the examples above, A longer cure time is needed and this is attributed to the reduced electron withdrawing capability of the methylene groups due to the spacing effect. Properties of the coating after full cure can be summarized in Tabie 14 below.

[00122] Table 14: Properties of Formulation 5

Fuel (Method B) GMW 14333 100% removed

Abrasion Wear Index 0,85

UV/ Moisture- i 68 hours 100% gloss retained

" Sal Spray- Ϊ 68 hours 100% gloss retained

[00123] Cure Time 25 minutes @ 60 * C followed by 15 min @ 120 * C

[001243 Formuiaiion 5 has much better flexibility on the Mandrel test due to the spaced structure of the base polyester. Si has a lower pencil hardness before aging. After UV/moisture and salt spray testing, this formulation is ab!e to maintain gloss, adhesion and flexibility. Thus spacing the methylene groups in the polyester may provide a useful strategy for improved fiexibiSity after resistance testing although initial testing may not reflect the best possible combination of properties,

[00125] Example 13: Coatings made with polyester having cyclic structures

[001283 inclusion of cyclic aliphatic ring in the dioi to make the polyester by using diois like cycJohexane dimethano! (CDM) reduces the free volume in the system, improves the overai! moisture resistance and UV resistance and imparts rigidity to the resultant polymer. The structure for the polyester is as shown in the formula provided below.

[00127] Table 15: Formulation 6

[00128] The spray and cure process is as described in the examples above. A longer cure time is needed and this was attributed to the reduced electron withdrawing capability of the methylene groups due to the CDM groups. Properties of the coating after full cure are summarized in Table 18 below.

[00129] Tabie 18: Properties of Formulation 6

[001303 Cure Time 25 minutes @ 60 ' C followed by 15 min @ 120'C

[00131] Formulation 6 demonstrates a lower flexibilit on the andre! test due to the cyclic structure of the base polyester, it has a higher pencil hardness before aging. After UV/moisture and salt spray testing, this formulation is able to maintain gloss and adhesion. Formulation is also able to maintain gloss 100% after exposure to 99% relative humidity in a humidity chamber for 3 weeks. This shows the improved moisture resistance due to the cyclic structures present in the polyester.

[00132] Parts by weight as used herein refers to 100 parts by weight of the composition specifically referred to. Any numerical values recited in the above application include all values from the lower value to the upper value in increments of one unit provided thai there is a separation of at least 2 units between any lower vaiue and any higher value. As an example, if it is stated that the amount of a component or a value of a process variable such as, for example, temperature, pressure, time and the like is, for example, from 1 to 90, preferably from 20 to 80, more preferabiy from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51 , 30 to 32, etc., are expressly enumerated in this specification. For va!ues which are iess than one, one unit is considered to be 0.0001, 0,001 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended and all possibl combinations of numerical values between the lowest value, and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner. Unless otherwise stated, all ranges include both endpoints and ali numbers between the endpoints. The use of "about" or "approximately" in connection with a range applies to both ends of the range. Thus, "about 20 to 30" is intended to cover "about 20 to about 30", inclusive of at least the specified endpoints. The term "consisting essentially of to describe a combination sha!! include the elements, ingredients, components or steps identified, and such other elements ingredients, components or steps that do not materially affect the basic and novel characteristics of the combination. The use of the terms "comprising" or Including * to describe combinations of elements, ingredients, components or steps herein also contemplates embodiments that consist essentially of the elements, ingredients, components or steps. Rural elements, ingredients, components or steps can be provided by a single Integrated element, ingredient, component or step. Alternatively, a single integrated element, ingredient, component or step might be divided into separat plura! elements, ingredients, components or steps. The disclosure of "a" or "one" to describe an element, ingredient, componeni or step is not intended to foreclose additional elements, ingredients, components or steps.