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Title:
OXETANE BLOCK-CONTAINING COPOLYMERS
Document Type and Number:
WIPO Patent Application WO/2003/051959
Kind Code:
A1
Abstract:
A composition comprises an oxetane oligomer or polymer or copolymer block wherein each repeat group has at least one ether side chain which is terminated by a fluorinated aliphatic group and optionally with the proviso that at least two different repeat units of the oligomer or polymer or copolymer have different Rf groups. The oxetane block is connected to a hydrocarbon polymer block derived from a mono or polyhydroxyl initiator. The terminal fluorinated alkyl groups impart good stain resistance to the oligomer or polymer or copolymer. In another embodiment, a fluorinated aliphatic or alkyl alcohol is reacted with an amino dicarboxylic acid with the reaction product thereof being subsequently grafted to a maleated polyolefin or a maleated polymer derived from a vinyl substituted aromatic monomer. The fluorinated alcohol also imparts good stain resistance to the grafted copolymer. Both compounds can be utilized as an additive in polymers as for example various polyolefins.

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Inventors:
Medsker, Robert (2946 Aylesbury St. NW, North Canton, OH, 44720, US)
Thomas, Richard (4851 June Ave, Stow, OH, 44224, US)
Kausch, Charles (4312 Cobblestone Drive, Copley, OH, 44321, US)
Weinert, Raymond (8472 Bobolink Drive, Macedonia, OH, 44056, US)
Application Number:
PCT/US2002/038873
Publication Date:
June 26, 2003
Filing Date:
December 05, 2002
Export Citation:
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Assignee:
OMNOVA SOLUTIONS INC. (Law Department, 175 Ghent Road Fairlawn, OH, 44333-3300, US)
International Classes:
C08F2/00; C08G65/18; C08G65/22; C08L71/02; (IPC1-7): C08G65/18; C08G65/22
Attorney, Agent or Firm:
Burleson, David (Law Department, OMNOVA Solutions Inc. 175 Ghent Roa, Fairlawn OH, 44333-3300, US)
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Claims:
WHAT IS CLAIMED IS :
1. A polymeric composition comprising at least one polyoxetane block connected to at least one hydrocarbon block, said polyoxetane block comprising where R'is hydrogen or an alkyl having from 1 to 6 carbon atoms, n, independently, is from 1 to 6, DP is from about 2 to about 100, and wherein Rf is the same or different for each repeat unit and is independently a fluorinated aliphatic having from 1 to about 30 carbon atoms, and wherein Rf, independently, has at least 50% of the hydrogen atoms of said aliphatic replaced by a fluorine atom; and said at least one hydrocarbon block comprising an olefin polymer or copolymer derived from at least one olefin monomer having from 2 to about 8 carbon atoms ; or a hydrogenated diene polymer or copolymer derived from at least one conjugated diene monomer having from 4 to about 10 carbon atoms.
2. A polymeric composition according to claim 1, wherein Rf, independently, is an alkyl having from 3 to 24 carbon atoms, and wherein said Rf groups, independently, contain at least 75% of the alkyl hydrogen atoms replaced by a fluorine atom.
3. A polymeric composition according to claim 1, wherein said Rf groups, independently, contain at least 90% of the hydrogen atoms replaced by a fluorine atom, and wherein said olefin polymer or copolymer is derived from olefin monomers having 2 or 3 carbon atoms.
4. A polymeric composition according to claim 1 or 2, wherein said hydrogenated diene polymer or copolymer is butadiene having the structure wherein the ratio of said x group to said y groups is from about 0.10 to about 10.
5. A polymeric composition, fiber, or fabric comprising a blend of polyolefin and the composition of claim 1,2, 3, or 4.
6. A grafted polymer comprising: a) a maleated polyolefin derived from at least one olefin monomer, said maleated polyolefin having a plurality of maleated sites, or b) a maleated polymer derived from at least one vinyl substituted aromatic monomer, said maleated polymer having a plurality of maleated sites, and a fluorinated compound grafted to at least one of said maleated sites of said a) maleated polyolefin or said b) maleated polymer, said fluorinated compound derived from the reaction of a fluorinated alcohol and an amino dicarboxylic acid.
7. A grafted polymer according to claim 6, wherein said a) maleated polyolefin is derived from an olefin monomer having 2 carbon atoms, or 3 carbon atoms, or combinations thereof, and wherein said b) maleated polymer is derived from styrene, amethylstyrene, or combinations thereof.
8. A grafted polymer according to claim 6 or 7, wherein said fluorinated alcohol has the formula X (CX (CH2),OH wherein X is H or F, wherein X1, independently, is H or F for each repeat unit, wherein X2, independently, is H or F for each repeat unit, with the proviso that at least one of said X, said Xr or said X2 is F; wherein m is from 2 to about 30, and wherein n is from about 1 to about 6.
9. A fluorinecontaining block copolymer composition, comprising the reaction product of oxetane monomers having the formula where R is hydrogen or an alkyl having from 1 to 6 carbon atoms, n, independently, is from 1 to 6, and wherein Rf is independently a fluorinated aliphatic having from 1 to about 30 carbon atoms, with a mono or polyhydroxyl terminated hydrocarbon polymer comprising: an olefin polymer or copolymer derived from at least one olefin monomer having from 2 to about 8 carbon atoms; or a hydrogenated diene polymer or copolymer derived from at least one conjugated diene monomer having from 4 to about 10 carbon atoms.
10. A fluorinecontaining block copolymer composition according to claim 9, wherein said reaction product is a diblock or a triblock copolymer.
11. A block copolymer comprising one or more fluorinated oxetane block and a hydrocarbon block.
12. The block copolymer of claim 11 wherein the fluorinated oxetane block comprises ether side chains terminated by the same or different fluorine containing alkyl groups.
13. The block copolymer of claim 11 or 12 comprising fluorine containing alkyl groups having from 2 to 20 carbon atoms.
14. The block copolymer of claim 11,12, or 13 wherein the fluorinated oxetane block comprises repeating units having the formula where R'is hydrogen or an alkyl having from 1 to 6 carbon atoms, n, independently, is from 1 to 6, and Rf is the same or different for each repeat unit and is independently a fluorinated aliphatic having from 1 to about 30 carbon atoms.
15. The block copolymer of claim 11,12, 13, or 14 wherein the fluorinated oxetane block is derived from monomer comprising one or two pendant ether side chains terminated by a fluorinated aliphatic group.
16. The block copolymer of claim 15 wherein the monomer comprises oxetane monomer having the formula wherein n, independently, is from 1 to 6, and Rf is a linear alkyl having from 1 to about 30 carbon atoms.
17. The block copolymer of any of claims 1116 wherein the hydrocarbon block comprises polydiene or polyolefin.
18. The block copolymer of any of claims 1117 wherein the block copolymer is a diblock or a triblock copolymer.
19. Surfactant comprising block copolymer of any of claims 1118.
Description:
OXETANE BLOCK-CONTAINING COPOLYMERS The present invention relates to an oxetane oligomer or polymer or copolymer block the repeat groups of which contain ether side chains terminated by the same or different types of fluorine containing alkyl groups.

In the latter situation, the oligomer, polymer, or copolymer is derived from a mixture of oxetane monomers having ether side chains wherein different monomers are terminated by different fluorine containing aliphatic groups.

The oxetane block is made utilizing a mono or polyhydroxyl hydrocarbon polymer or copolymer initiator which results in the formation of the oxetane block connected to the hydrocarbon block. In an other embodiment, a fluorinated aliphatic or alkyl alcohol is reacted with an amino dicarboxcylic acid and the reaction product thereof is subsequently grafted to a maleated polyolefin or a maleated polymer derived from a vinyl substituted aromatic monomer. Such compositions are useful as melt additives for various polymers such as polyolefins.

Fluorochemicals, typically, have relatively low surface tensions.

Therefore, water and other common liquids tend to have a relatively high contact angle or"bead"when resting upon a fluorochemical surface. Fluoro- chemicals are, hence, referred to as repellent since they are not wetted by these fluids. Many commercially important fibers, fabrics, surfaces and materials are wetted by water and other common fluids. This wetting leads to unwanted effects such as water passing through an umbrella or coat or staining of a fabric by a liquid. It is desirable commercially to make these items repellent to water and/or common liquids. This can be accomplished by topical application of a waterborne fluorochemical emulsion or dispersion.

This technology has been practiced successfully for many years. Topical application of a water-borne repellent system has several disadvantages : (i) water must be removed in order for the repellent to work properly. The presence of water imparts a high thermal and time load on the manufacture of finished goods. Often, removal of water is the rate-limiting operation in the manufacture of goods containing repellents. The high temperatures and

high heat of vaporization required to remove water introduce large energy and equipment costs in manufacturing. Heating must be done carefully as to not exceed the deflection temperature of a given fabric, fiber or material ; (ii) there is a shift of fabrics to smaller deniers. This increases dramatically the surface area that needs to be coated by a fluorochemical repellent. The cost associated with providing repellency increases with decreasing fiber denier; (iii) the increased use of polyolefins has introduced challenges to topical application of waterborne fluorochemicals. Polyolefins, generally, have much lower surface tensions than materials used extensively in the past such as nylon. Successful application of a waterborne repellent package requires that the system wet the fiber to coat a substantial fraction of the surface. Water will not wet polyolefins well ; therefore, surfactants are used to lower the surface tension of water such that it will wet the polyolefin.

However, these surfactants remain with the fluorochemical coating and raise the surface tension of the final repellent package. This is detrimental to the performance of the fluorochemical as a repellent ; (iv) topical application of a fluorochemical repellent introduces unit operations into fabrication of finished goods and therefore increases manufacturing costs; and (v) topical fluoro- chemical treatment produces a relatively thick repellent coating on a surface.

Various oligomer, polymer, and copolymer oxetanes are described the repeat units of which have an ether side chain which in turn is end capped or terminated with a fluorinated aliphatic (Rf). Within the same oxetane oligomer or (co) polymer, generally the same fluorinated aliphatic groups and desirably alkyl groups exist having from about 1 to about 20 C atoms. Alternatively, the oxetane oligomer or (co) polymer can have repeat units wherein different repeat units are terminated by at least two different types of fluorinated alkyl groups having from about 2 to about 30 C atoms.

The repeat units containing different fluorinated alkyl groups are statistically arranged throughout the oligomer or polymer or copolymer. Regardless of the Rf embodiment, at least 50% of the hydrogen atoms have been replaced

by a fluorine atom. Preferably, the fluorinated alkyl groups are perfluorinated.

The oxetane oligomers, or polymers, or copolymers having the same, or a plurality of different Rf groups are derived from a mono or polyhydroxyl hydrocarbon polymer or copolymer initiators which results in the formation of an oxetane block connected to a hydrocarbon block.

In another embodiment, a fluorinated aliphatic or alkyl alcohol can be reacted with an amino dicarboxcyclic acid and the reaction product thereof is subsequently grafted onto maleated polyolefins or onto maleated polymers derived from vinyl substituted aromatic monomers.

Inasmuch as the fluorinated compounds are stain resistant, the block copolymers thereof or the maleated grafted copolymers, can be utilized in various polymers such as polyolefins to improve such properties thereof.

Since the block copolymer can be solid, they are advantageously blended with other polymers as by forming a master batch and/or coextruding.

The fluorinated thermoplastics of the present invention are derived from monomers having pendant ether side chains which in turn are terminated by a Rf group. The monomers can either have substantially the same Rf group, or there can be a mixture of monomers containing different Rf groups having different numbers of carbon atoms which are generally of an even number. The oxetane monomers generally have the structure as set forth in Formula I 1A Formula I 1 B wherein n, independently, is an integer of from 1 to about 6, desirably from 1 to about 4, and preferably 1 or 2, and where an R'is an alkyl having from 1 to 6 C atoms or H with methyl being preferred.

When the monomers all contain substantially the same Rf group (that is generally only 5,3, or 1 % or less by weight of the monomers have a different number of C atoms), the Rf group is a fluorinated aliphatic and desirably a linear alkyl group having from 1 to about 20 C atoms, desirably from about 3 to about 15 and preferably from about 6 to about 10 C atoms. When individual monomers contain different Rf groups, the Rf groups are a fluorinated aliphatic, desirably independently, linear or branched, alkyl groups having from about 2 or 4 to about 24 or 30 C atoms, desirably from about 6 to about 20 C atoms, and preferably from about 8 to about 16 C atoms. Whether a plurality of oxetane monomers all contain substantially, or the same Rf end group, or contain different Rf end groups, each Rf group, independently, generally contains at least 50%, desirably at least 75 or 90% and preferably at least 95% of the H atoms of the aliphatic or alkyl group replaced by a F atom.

Most preferably Rf is a perfluorinated alkyl group. Optionally, from one to all of any remaining hydrogen atoms can be replaced by 1, Cl, or Br, or combinations thereof.

The individual oxetane monomers of the present invention are generally the same except for different Rf groups inasmuch as they are prepared from either the same fluorinated aliphatic or alkyl alcohol, or a mixture of different fluorinated aliphatic or alkyl alcohols. Such alkyl alcohols can generally be represented by the formula A X- (CXX2) m- (CH2) n-OH Formula A wherein X is H or F, preferably F, wherein X1, independently, is H or F for each repeat unit, preferably F, wherein X2, independently, is H or F for each repeat unit, preferably F, with the proviso that at least one of said X, said X'or said X2 is F; wherein m is from 2 to about 30, desirably from 4 to about 24, and preferably from about 6 to about 20 or about 8 to about 16, wherein m is often an even number, and wherein n is from 1 to about 6, desirably 1 or about 4, and preferably 1 or 2. Preferred compounds are thus perfluorinated alkyl methanol or ethanol. Such fluoroalcohols are often based upon various tetrafluoroethylene based telomer fluoroalcohols such as those commercially

available from Dupont as Zonyl, from Cariant as Fluowet, from Elf- Atochem as Foralkyl 6HN, and from Daikin as StFA.

The above oxetane monomers, whether Rf is the same or different, are generally prepared by reaction of the above noted fluoroalcohol with a halogenalkyl-3-alkyloxetane wherein the first"alkyl"group is represented by "n"and the second"alkyl"group is represented by Rl in formula 1A, in the presence of an alkali metal crown compound and a solvent with subsequent addition of an alkali hydroxide such as KOH, NaOH, or the like. The general reaction of the fluorinated alcohol with the oxetane compound is described in U. S. Patent Nos. 5,807, 977,5, 650,483, 5,668, 250, and 5,668, 251. Specific examples of the oxetane compound include 3-bromomethyl-3-methyloxetane or 3-iodomethyl-3-methyloxetane. The mixture of the fluoroalcohols with the oxetane compound is generally heated to a reaction temperature of from about 75° to about 100°C and preferably from about 80° to about 95°C. The alkali metal crown compound such as potassium 18-crown-6 is contained in the mixture along with the solvent and heated to the indicated temperature.

Subsequently the alkali hydroxide is generally added in increments while maintaining the reaction temperature. In order to eliminate water which is formed during the reaction, a Dean-stark trap can be utilized operating at temperature of from about 95° to 110°C. The presence of the crown compound increases the yield of the resulting monomer so that it is generally at least 70%, generally at least 80%, and preferably at least 90%. As known to the art, the alkali metal of the crown compound contains an alkali metal which can be K, Na, or Li and specific compounds include potassium 18- crown-6 which is preferred, sodium 15-crown-5, lithium 12-crown-4, and the like wherein the first number represents the total number of C and O atoms whereas the second number represents only the total number of O atoms in the compound. Generally the total number of carbon and O atoms can range from about 10 to about 20 whereas the total number of only O atoms can range from about 3 to about 8. The amount of said crown compound is generally from about 1 to about 15% by weight and desirably from about 1.0

or 1.5 to about 12% by weight and preferably from about 5 to about 10% by weight based upon the total weight of the halogenalkyl-alkyloxetane compound. The solvents include various fluoro solvents such as benzotrifluoride, or various hydrocarbon solvents such as various alkane, or aromatic solvents with specific examples including hexane, heptane, toluene, and the like.

When the fluoroalcohol utilized is a mixture of various different alcohols, the monomers will generally have the structure of Formula 1 with different monomers having a different number of carbon atoms in the Rf group such as C8F17, CioF2i, Ci2F25, Ci4F2g, 33, and the like. The amount of the different Rf groups will naturally generally vary with the amount of different types of fluorinated alcohols utilized in the fluorinated alcohol mixture.

When the monomer is that as shown by Formula 1 B, such monomers are commercially available from CIBA-GIEGY. These monomers can be made according to a manner as set forth in U. S. Pat Nos. 4,946, 992, 4,898, 981 and 5,097, 048. Alternatively, such monomers containing two Rf end capped ether side chains can be made in a manner similar to that set forth above with regard to the preparation of the monomers shown in Formula 1A wherein a bis (bromoalkyl) oxetane is utilized wherein the n alkyl group is the same as set forth above, that is it can have from 1 to 6 C atoms, desirably from 1 to 4 C atoms, and preferably 1 or 2 C atoms.

A specific example of the preparation of the monomers of the present invention is as follows : EXAMPLE M1 : Synthesis of oxetane-mixed Rf monomer Material Weight MW mmol Mole Ratio Daikin StFA 1500.00 495 3030.30 1.00 BrMMO* 525.35 165.02 3183.55 1.05 18-crown-6 37.50 322.37 116.33 0.038 KOH (86%) 217.44 56.11 3332.74 1.10 Benzotrifluoride 1789.45 146.11 12247.28 4.04 10% sulfuric acid 923.55 53.45 863.94 0.29 Water 1200 18.01 48981.12 16.16 Water Amount, g 241.58 Theoretical Yield, (g) 1049.2 Expected Yield, low (g) 786.9 Expected Yield, high (g) 996.8 Solids Loading, % 46.0 mL Volume after KOH addn. 2,902. 4 Volume after quench 3802.1 Volume after phase split 1248.5 Volume after wash 2130.6 * 3-bromomethyl-3-methyloxetane Daikin StFA is a mixture of fluoroalcohols as follows :

Alcohol Approximate Weight % of StFA Sample CioF2iCH=CH2 2.6 Cr2F25CH=CH2 1. 7 C8HF17C2H40H 50. 6 Ca0F2rC2H4OH 23. 5 C2F25C2H40H 9. 3 C14F29C2H40H 8. 4 Miscellaneous Alcohols 3.9

A 2 L three necked round bottomed flask was equipped with a mechanical stirrer, temperature probe, and heating mantle. The reactor was charged with StFA from Daikin (1.5 kg, 3.03 mol), 3-bromomethyl-3-methyl oxetane (525.35 g, 3.183 mol), 18-crown-6 (37.5 g), and 1.79 kg benzotri- fluoride was added and allowed to heat to 85°C. Ground solid potassium hydroxide (217.44 g, 3.33 mol) was added in 11 increments over 90 minutes maintaining a temperature of about 85° to about 92°C. Conversion was determined to be 90% by NMR. An additional 13.18 g of ground KOH was added, and the reaction was allowed to stir for one hour. The reaction mixture was quenched with deionized water, and the organic layer was washed with 10% sulfuric acid. A low boiling fraction was removed under vacuum at 711 mm Hg with a head temperature of 65° to 130°C. 1522.6 g of monomer was isolated (87% yield).

Example M2 relates to the preparation of oxetane monomers containing mixed Rf groups obtained from Cariant.

EXAMPLE M2: Synthesis of oxetane-mixed Rf monomer Material Weight ht MW mmol Mole Ratio Fluowet ea-812-ac 1500.00 495 3030.30 1.00 BrMMO 525.35 165.02 3183.55 1.05 18-crown-6 37.50 322.37 116.33 0.038 KOH (86%) 217.44 56.11 3332.74 1.10 Benzotrifluoride 1789.45 146.11 12247.28 4.04 5% Ammonium Chloride 923.55 53.45 863.94 0.29 Water 1200.00 18.01 66629.65 21.99 Water Amount (g) 241.58 Theoretical Yield, (g) 1049.2 Expected Yield, low (g) 786.9 Expected Yield, high (g) 996.8 Solids Loading, % 46.0 FluowetT" ea-812-ac is a mixture of fluoroalcohols from Cariant as follows : Alcohol Approximate Weight % of Fluowet ea-812-ac Sample CioF2iCH=CH2 2.3 C12F25CH=CH2 1.7 C8HF17C2H4OH 50.0 C10F21 C2H4OH 23.2 C12F25C2H4OH 9.2 C14F29C2H40H 8.3 Miscellaneous Alcohols 5.3

A 4 L jacketed four necked round bottomed flask was equipped with a mechanical stirrer, temperature probe, and a reflux condenser equipped with a Dean-stark trap. The reactor was charged with fluowet ea-812-ac (1,500 g, 3.03 mol), 3-bromomethyl-3-methyl oxetane (525.35 g, 3.183 mol), 18- crown-6 (37.5 g), and 1789 g benzotrifluoride was added and allowed to heat to 85°C. Ground solid KOH (217.44 g, 3.33 mol) was added in 11 increments over 90 minutes maintaining a temperature of 85°-92°C.

Conversion was determined to be 90% by NMR. The reaction was heated to 95°C and a mixture of benzotrifluoride and water was removed using the Dean-stark trap. An additional 20.00 g of ground KOH was added, and the reaction was allowed to stir for 1 hour. The reaction mixture was quenched with deionized water, and the organic layer was washed with 10% sulfuric acid. A low boiling fraction was removed under vacuum at 711 mm Hg with a head temperature of 65°-130°C. 1522.6 g of monomer was isolated (87% yield).

Example M3 relates to preparation of oxetane monomers having two ether Rf terminated side chains.

EXAMPLE M3: Synthesis of Oxetane bis (same) Rf monomer Substance Weight (g) MW mmol Cheminox fa-8 100.00 461.1 216.87 BBrMMO 27. 77 243.92 113.86 18-crown-6 2.50 Benzotrifluoride 102.98 146.11 704.84 KOH (86%) 15.56 56.11 238.56 KOH 5.68 56.11 KOH 5.68 56. 11-- 10% H2SO4 69.56 53.46 1,301. 24 Theoretical Yield, g 125.57 Expected Yield (85%) 105.48 Solids Loading (%) 71.67% mL Initial Volume 175.21 Total Water 2.18 Volume + Quench 245.09 Volume + Wash 150.33 Cheminot fa-8 is approximately 97% by weight of CgFi7C2H40H and approximately 1.8% by weight CioF2iC2H40H from Nippon Mektron of Japan.

A 250 mL three necked round bottomed flask was equipped with a magnetic stirrer, temperature probe, reflux condenser equipped with a dean- stark trap. The reactor was charged with Cheminox fa-8 (100 g, 0.216 mol), 3,3'-bis (bromomethyl) oxetane (27.77 g, 0.113 mol), 18-crown-6 (2.5 g), and 103 g benzotrifluoride was added and allowed to heat to 85°C. Ground solid KOH (15.56 g, 3.33 mol) was added in 11 increments over 90 min. maintaining a temperature of 85°-92°C. Conversion was determined to be approximately 60% by NMR. The reaction was heated to 95°C and a mixture of benzotri- fluoride and water was removed using the Dean-stark trap. An additional 5.68 g ground KOH was added, and the reaction was allowed to stir for 12 hours at

85°C. The reaction mixture was filtered to remove wet KBr, and returned to the reaction vessel, and heated to 85°C. An additional 5.68 g KOH was added, and the reaction was allowed to stir at 95°C for 24 hours. The reaction mixture was washed with 10% sulfuric acid, dried, and the solvent was removed. A low boiling fraction was removed under vacuum at 711 mm Hg with a head temperature of 65°-130°C, 66.19 g of monomer was isolated (58% yield).

The 3,3'-bis (bromomethyl) oxetane of Example M3 was prepared in the following manner: EXAMPLE M3 (BBrMMO): Synthesis of 3, 3'-bisbromomethyloxetane Substance Weight (g) MW mol tribromoneopentyl alcohol 500 324.84 1.54 Water 288.50 18.01 16.02 tetrabutyl ammonium bromide 12.40 322.37 0.04 45% KOH 211.12 56.11 1.69 Di water quench 500 18.01 27.76 theoretical yield 375.46 Yield, Max 356.69 Yield, Min 281.60 mL Vol after KOH addition 664.90 Vol after Quench 1164.90 *Tribomoneopentyl alcohol used in this synthesis was purchased from Ameribrom, Inc. (Fort Lee, NJ).

A jacketed 3-necked round bottomed flask equipped with a temperature probe, reflux condenser, and addition funnel was heated to 85°C. Tribromoneopentyl alcohol (500 g, 1.54 mol), and a solution of tetrabutyl ammonium bromide (12.40 g, 0.04 mol) in deionized water (288.5 g) were added. A 45% solution of KOH in water (211.12 g, 1.69 mol) was

added over 45 minutes. The reaction was allowed to stir for 2 hours. The reaction was quenched with 500 grams of water, and the water layer was removed. The product was distilled at 151 °C at 711 mm of vacuum giving 239.83 g or 64%.

Monohydroxyl or polyhydroxyl terminated hydrocarbon polymer or copolymer initiators are utilized to polymerize the above-noted monomers whether they contain the same Rf group, or whether they contain a mixture of different Rf groups. Such initiators generally include mono or polyhydroxyl terminated olefin polymers or copolymers, or mono or polyhydroxyl terminated hydrogenated diene polymers, or copolymers, and the like. The block copolymers are of the type AB or ABA where A represents the oxetane block and B represents the hydrocarbon block.

A desirable class of mono or polyhydroxyl initiators are the various polyhydroxyl terminated olefin polymers or copolymers. These initiators are made from olefins generally having from 2 to 6 or 8 C atoms and preferably 2 or 3 C atoms. Examples of specific olefin monomers include ethylene, propylene, butylen and isobutylene, and the like. Preferred copolymers are those made from ethylene and propylene monomers. These polymers or copolymers are terminated with one or more hydroxyl groups as known to the literature and to those skilled in the art. Examples of specific preferred initiator compounds include polyethylene glycol, polypropylene glycol, a copolymer of ethylene and propylene having two terminated hydroxyl groups, and the like. The number average of molecular weight of such initiators is generally from about 200 or 400 to about 4000.

Another class of suitable initiators are polymers and copolymers of various hydrogenated dienes which are mono or polyhydroxyl terminated.

Such polymers, as well as the preparation thereof, are known to the art and to the literature. Typical diene polymers or copolymers are made from one or more conjugated dienes, having from 4 to 10 carbon atoms, such as 1,3- butadiene, isoprene, dimethyl butadiene, and the like. The polymerization of the diene monomer, typically, is via anionic initiation (e. g. with di-lithium

hydrocarbyl initiators) or via free-radical polymerization, e. g. by initiation with hydrogen peroxide, which also introduces hydroxy end groups. In case of anionic polymerization, OH-end groups are advantageously introduced by reaction of the polymeric carbanion chain ends with ethylene oxide. These techniques are generally well known to the literature. The hydroxy-functional polydienes are generally hydrogenated, for example, partially or substantially (i. e. , at least 50,70, or 90% of the unsaturated sites), and even completely hydrogenated, according to any conventional method known to the art and to the literature. Complete hydrogenation of various diene polymers such as 1,4- polyisoprene is equivalent to an alternating ethylene/propylene hydrocarbon polymer. The hydrocarbon polymers generally have a number average molecular weight from about 500 to 15,000 and preferably from about 1000 to about 8000. The polymers are desirably liquid at room temperature, but can have a melting point up to about 80°C. Preferred polymers are hydroxyl functional telechelic, hydrogenated diene polymers containing 2 to 6 and preferably 2 to 4 hydroxy end groups per polymeric molecule (polymer unit).

An especially preferred hydrogenated butadiene polymer or copolymer <BR> <BR> is commercially available as PolytailT" H and HA (Mitsubishi Kasei Corp. ) and has the very generalized structure: wherein X and Y are randomly distributed and the structure can contain additional-OH groups. In Polytail H, x is generally about 2 and y is about 8, whereas in Polytail HA, x is about 9 and y is about 1. Thus, the ratio of the two groups to one another can range from about 0.10 to about 10 of the branch repeat group (x) per one linear repeat group (y). Z is from about 1 to about 10 and desirably from about 2 to 4.

Inasmuch as the above initiators are a polymer or a copolymer, they form a block copolymer when reacted with an oxetane oligomer, polymer, or copolymer block.

The above noted oxetane monomers having the same Rf groups or a mixture of different Rf groups are reacted in the presence of the above mono or polyhydroxyl hydrocarbon polymer or copolymer initiators to produce an oxetane oligomer, polymer, or copolymer block chemically connected to the mono or polyhydroxyl hydrocarbon polymer or copolymer initiator block.

Such a block copolymer has at least one oxetane block portion generally represented by Formulas 2A and 2B with the overall block copolymer often represented by the structure as set forth in Formulas 3A and 3B when the initiator is a diol hydrocarbon polymer or copolymer.

Formula 2 CH2-0- (CH2) n-Rf CH2-O- (CH2) n-Rf reacted iniUator block of a H- (O-CH2-C-CH2) DP-O monoor polyhydroxyl-O- (-CH2-C-CH2-O-) Dp-H terminated hydrocarbon polymer or copolymer block RI R'--t R' Formula 3A

CH2-0- (CH2) n-Rf CH2-O- (CH2) n-Rf reacted initiator block of a H- (O-CH2-C-CH2) DP-0 monoorpolyhydroxy-O- (-CH2-C-CH2-O-) DP-H terminated hydrocarbon polymer or copolymer block CH2-0- (cH2) n-Rf CH2O (CH2) n-Rf Formula 3B wherein R'and n is the same as set forth above and DP is from about 2 to about 100, desirably from about 3 to about 50, and preferably from about 3, or 4, or 5 to about 15, or 20, or 30. It is to be understood that the above structures of Formula 3 are only representative in that the initiator can also contain 1, or 3 or 4 hydroxyl groups, and the like. When the oxetane oligomer, polymer, or copolymer of Formulas 2A and 2B contain different Rf groups within the various repeat units thereof, the amount of each particular type of Rf repeat unit can vary considerably as from about 1,3, or 5 to 95,97 or 99% and desirably from about 8 or 10 to about 50 or 60% by weight based upon the total weight of all the different Rf repeat units in the oxetane oligomer, polymer, or copolymer.

Formula 4 sets forth a particular representation of a fluorinated oxetane block having repeat units containing different terminal Rf groups such as C8F17, CroF21, C12F25, and C14F29.

Formula 4 wherein R'and n are the same as set forth herein above or R'independently is a pendent group the same as set forth in the top portion of the formula, e. g.,-CH2-0-(CH2) nCôF17, etc. Inasmuch as the oligomer, polymer, or copolymer block is a statistical entity, the order and length of the various units will vary statistically throughout the entity. Accordingly, the number of repeat units with respect to w, x, y, and z can vary throughout the polymer,

copolymer, etc. , and can be 1 or greater with many different such repeat groups existing either singularly or in large amounts.

In a current preferred embodiment, i. e. the use of Daikin StFA fluoroalcohols, the total amount of"w"repeat units which contain a C8F17 Rf group is generally from about 20 to about 80% by weight and preferably from about 35 to about 65% by weight based upon the total weight of the poly- oxetane block per se (i. e. without any non-oxetane polymer). The total number of x repeat units containing a C10F21 Rf group is approximately 10 to 50% and desirably from about 15 to 35% by weight based upon the total weight of the polyoxetane per se. The total number of repeat units y containing C12F25 Rf groups and the number of z repeat units containing C14F29 Rf groups are generally about the same and range from about 2 or 3 to about 25% and desirably from about 5 to 20% weight% based upon the total weight of the polyoxetane per se.

The preparation of the polyoxetane block from the above-noted oxetane monomers can generally be formed in the manner as set forth in U. S. Pat. Nos. 5,807, 977 ; 5, 668,250 ; 5,668, 251; and 5,650, 483. Generally, the mixtures of monomers and the desired mono or polyhydroxyl hydro- carbon polymer or copolymer initiator are added to vessel along with a suitable catalyst such as boron trifluoride. Since this compound is a gas, it is generally utilized in the form of a complex with a cyclic oxygen compound such as THF so that it is in the form of a liquid. Suitable reaction tempera- tures generally range from about 15° to about 80°C, 20° to about 70°C, with from about 25° to 50°C being preferred. The reaction temperature ranges are higher for the bis mixed monomer and generally range from about 30° to about 100°C and preferably from about 60° to about 90°C. The THF will also react with the oxetane monomers and form a statistical copolymer thereof. The amount of THF is small, i. e., generally less than 5%, and desirably less than 3% by weight based upon the total weight of the statistical copolymer. Various alkyl glycidyl ethers can be utilized to prevent cyclic formation within the polymers. The alkyl component of the glycidyl

ether generally has from about 4 to about 10 carbon atoms with about 4 carbon atoms being preferred.

The solvent utilized is generally the same as the solvent utilized for the monomer formation and hence includes fluorosolvents and hydrocarbon solvents such as benzotrifluoride, toluene, methylene dichloride, and the like.

The amount of the solvent is such that the formed composition generally contains from about 50 to about 90% by weight of solvent and hence from about 10 to about 50% by weight of solids containing the above noted block copolymers such as set forth in Formulas 3A and 3B.

EXAMPLE 1: Synthesis of PolyFox-Polytail H-PolyFox Triblock, Total DP 6 Compound Weight (g) MW Mol Mole Ratio Polytail H 100.746 2800.00 0.04 2.50 BF3 THF 2.013 139.90 0.01 1.00 Benzotrifluoride 150.000 146. 00---- Toluene 150.000 92.14 1.63 113.17 mixed Rf Monomer (Ex. M2) 125.000 579.00 0.22 15.01 HeloxyTM 61 * 1.619 150.00 0.01 0.30 Benzofluoride 200. 000------ Water 53.750 18.01 2.98 207.47 Water 106.250 18.01 5.90 410.11 Theoretical Yield (g) 226.78 Expected Yield, Low (g) 204.11 Expected Yield, High (g) 215.44 Solids Loading Reaction, % 60.29 Solids Loading Wash, % 31.30 * HeloxyT""61 is a mixture of C8 to C, alkyl glycidyl ethers.

A 500 mL 3-necked round bottomed flask was equipped with a condenser, temperature probe, magnetic stirrer, addition funnel, and water cooling bath. Polytail H (100.75 g, 0. 0414 mol), BF3 THF (2.013 g, 0.014

mol), 150 g benzotrifluoride, and 150 g toluene were added and allowed to stir for 30 minutes at 30°C. A solution of mixed Rf monomers from Example M2 (125 g, 0.22 mol) and Heloxy 61 glycidyl ethers (1.619 g, 0.0108 mol) in 200 g benzotrifluoride was prepared. The mixed monomer solution was added to the reactor over 1 hour. An exotherm was observed increasing the temperature to 43°C. The reaction was allowed to stir at 25°C for 10 hours.

The reaction was quenched with 1185 g of 5% sodium bicarbonate. The organic layer could not be separated, so the solvent was removed under reduced pressure. A yield of 208 g polymer with a degree of polymerization of 6 was observed. A triblock copolymer was formed with polytail H having the structure (fluorinated oxetane-THF)-Polytail H- (fluorinated oxetane-THF).

EXAMPLE 2: Poly-5-Fox-polytail H-Poly-5-Fox Triblock, Total DP 23 Compound Weight (g) MW Mol Mole Ratio Polytail H 179.364 2800.00 0.06 2.50 BF3 THF 3.585 139.90 0.03 1.00 Benzotrifluoride 480.000 146.11 3.29 128.21 Toluene 237.000 95.17 2.49 97.19 5-fox monomer 300.00 234.16 1.28 50.00 5% sodium bicarbonate 129.000 18.01 7.16 279.54 Water 255.000 18.01 14.16 552.58 Theoretical Yield (g) 481.21 Expected Yield, Low (g) 433.09 Expected Yield, High (g) 457.15 Solids Loading Reaction, % 67.08 Solids Loading Wash, % 40.25 A 1000 mL 3-necked round bottomed flask was equipped with a dondenser, temperature probe, magnetic stirrer, addition funnel, and Heating Mantle. Polytail H (179.36 g, 0.0640 mol), BF3 THF (3.59 g, 0.0257 mol), 480 g benzotrifluoride, and 237 g toluene were added and allowed to stir for 30

minutes at 68°C. 5-fox monomer (OMNOVA Solutions Inc. ; Mogadore, Ohio) (300 g, 1.28 mol) was added to the reactor over 1 hour. An exotherm was observed increasing the temperature to 75°C. The reaction was allowed to stir at 68°C for 10 hours. The reaction was quenched with 129 g of 5% sodium bicarbonate. The organic layer could not be separated, so the solvent was removed under reduced pressure. A yield of 457 g of a statistical oxetane-THF copolymer with a total degree of polymerization of 23 was observed. A triblock copolymer with polytail H was formed having the structure (fluorinated oxetane-THF)-Polytail H- (fluorinated oxetane-THF).

EXAMPLE 3: Synthesis of bis-FOX-polytail H-Bis-Fox Triblock, Total DP6 Compound Weight (g) MW Mol Mole Ratio polytail H 46.467 2800.00 0.0166 2.50 BF3 THF 2.013 139.9 0. 014-- benzotrifluoride 160.000 146.11 1.10 164.97 bis FOX monomer (Ex. M3) 100.000 1004.30 0.10 15.00 Heloxy 61 0.747 150.00 0.0050 0.75 Benzotrifluoride 80.000 146.11 0.5475 82.48 5% Sodium bicarbonate 43.000 84.01 0.03 3.86 Theoretical Yield (g) 146.95 Expected Yield, Low (g) 132.25 Expected Yield, High (g) 139.60 Solids Loading Reaction, % 64.82 mL Initial Volume 193.10 Solution density before wash 1.18 Volume after quench 371.12 Volume after wash 413.12 A 500 mL 3-necked round bottomed flask was equipped with a condenser, temperature probe, magnetic stirrer, addition funnel, and heating

mantle. Polytail H (46.47 g, 0.0166 mol), BF3 THF (2.013 g, 0.014 mol), 160 g benzotrifluoride, was mixed and allowed to stir for 30 minutes at 70°C. A solution of bis FOX monomer from Example M3 (100 g, 0.10 mol) and Heloxy 61 (0.747 g, 0.005 mol) in 80 g benzotrifluoride was prepared. The monomer solution was added to the reactor over 1 hour. An exotherm was observed increasing the temperature to 79°C. The reaction was allowed to stir at 75°C for 2 hours. The reaction was quenched with 43 g of 5% sodium bicarbonate.

The organic layer could not be separated, so the solvent was removed under reduced pressure. A yield of 135 g of statistical oxetane-THF copolymer with a degree of polymerization of 6 was observed. A triblock copolymer with polytail H was formed having the structure (fluorinated bis-oxetane-THF)-Polytail H- (fluorinated bis-oxetane-THF).

During polymerization of the above oxetane monomers with the above noted initiators, various other comonomers can optionally be added to form a copolymer. For example, a variety of comonomers having epoxy (oxirane) functionality can be used such as epichlorohydrin, propylene oxide, ethylene oxide, butyl glycidylether, and perfluorooctyl propylene oxide as well as alkyl substituted oxiranes having from 1 to about 15 or from about 7 to about 12 carbon atoms or mixtures thereof; monomers having a 4-membered cyclic ether group such as trimethylene oxide, 3,3-bis (chloromethyl) oxetane, 3,3- bis (bromomethyl) oxetane, and, 3, 3-bromomethyl (methyl) oxetane ; monomers having a 5-membered cyclic ether group such as tetrahydrofuran, tetrahydropyran, and 2-methyltetrahydrofuran ; and the like. Still other suitable monomers include 1,4-dioxane, 1,3-dioxane and 1, 3-dioxalane as well as trioxane and caprolactone. The copolymerization reaction is carried out generally under the same conditions as is the polymerization of the fluorooxetane monomers set forth hereinabove. The amount of the comonomer is from about 0.1 to about 55% by weight, desirably from about 0.25 to about 25 or 40% by weight, and preferably from about 0.5 to about 2, 5, or 10% by weight based upon the total weight of the one or more comonomers and the oxetane-Rf monomers.

The block copolymers of the present invention as well as the fluorinated alcohol grafted maleated polyolefin polymers or maleated polymers derived from vinyl substituted aromatic monomers are generally a solid, and have good physical properties such as low surface tension, thermal stability, and stain resistance, and can be utilized as additives to impart favorable properties to polymers such as polyolefins. The polyolefins are generally derived from one or more monomers having from 2 to about 6 or 8 carbon atoms and preferably 2 or 3 carbon atoms such as ethylene, propylene, and the like. Desirably, polyethylene, polypropylene, or copolymers thereof are utilized.

The block copolymers as well as the grafted polyolefins of the present invention can be added in a number of ways to existing polymers such as polyolefins as by melt coextrusion, preparation of a master batch, and the like.

For example, (I) a master batch of the block copolymer or the grafted polymers could be prepared by addition of the same to the polyolefin used to make a product such as a fabric. The master batch would then be coextruded with additional polyolefin. The blend would then be processed as any other polyolefin such as in sheet form, annular form such as a hose, fiber formed such as a melt spun fiber, or the like. (II) Alternatively, the block copolymer or the grafted polymers could be added directly by coextrusion to the polyolefin that is to comprise the fiber, sheet, annulus, or the like.

The block copolymer or grafted copolymers are typically used in the amount of from about 0.1 to about 5 or 10 parts by weight (pbw) and desirably <BR> <BR> from about 0.5 to about 1.5 or 3 pbw based upon 100 pbw of polyolefin (e. g. , a fiber) so that the blended polyolefin has from about 0.1 to about 2 or about 3 weight %, and desirably from 0.25 to about 0.75 weight % fluorine based on the total weight of polyolefin.

The invention will be better understood by reference to the following examples and data which serve to illustrate, but not to limit the invention.

Various block copolymers of an oxetane polymer, or copolymer (as with THF) and a polyhydroxyl terminated hydrogenated butadiene polymer was

melt blended with polypropylene having a melt index of about 18 in the amounts shown in Tables 1 and 2 and tested.

TABLE 1: Contact Angles on Various Sample Melt Additives in Polypropylenet The triblock copolymer of Sample 1 is made in a manner essentially very similar to Example 1 sefforth hereinabove. Samples 2 and 3 are controls of a single polyoxetane block. Sample Structure Hexadecane Weight % Contact Additive Advancing Contact Angle See Structure A, with x2, 8, z160, a+b6, n8 34. 83. 3 1. 21 OCH2CH2 (CF2) nF 2 1 8. 4 4. 0 0. 72 (Control) (Control) C8H I CH2 OH L ; H3 x x4. 5, n8 OCH2CH2 (CF2) nF 3 1 15. 6 0. 6 0. 68 (Control) CeHi7-0-CH2-C-CH2-OH CH3 x x ~ 1 8, n ~ 8 4 A fluorinated melt additive, i. e. FX-37. 5 3. 2 1. 0 (Control) 1801 from 3M. t Samples compounded using Brabender mixer at about 175°C and then compression molded into plaques. All samples contained 0.375 weight % fluorine based on weight of polypropylene.

Structure A = TABLE 2: Effect of PolyOxetane Block Length on Contact Angles of Additive in Polypropylene t Sample Structure Hexadecane Weight % Contact Additive Advancing Contact Angle (°) See Structure A, with x>2, y>8, z~160, a+b>6, n#8. _. See Structure A, with x>2, y>8, z~160, a+ b~ 18. 6, n>8 _.

tSamples compounded using Brabender mixer at about 175°C and them compression molded into plaques. Sample 1 was made in a manner essentially similar to that of Example 1 as set forth herein above. Sample 2 was made in a manner similar to Example 1.

As apparent from Table 1, the present invention, that is Example1, when tested with regard to contact angle showed vast improvement over Controls 2 and 3 which related to a fluorinated oxetane monool. Example 4 relates to a previously commercially available material from 3M.

Table 2 shows the effect on the contact angle with the length of the polyoxetane block. When the number repeat groups was generally at least 5 or 6 or greater, i. e., Table 1, Example 1 and Table 2, Example 2, high contact angles, i. e. , in excess of 20,25, or 30, were obtained.

The above fluorinated aliphatic or alkyl alcohols, such as those exemplified by Formula A, can be grafted onto existing polyolefins or polymerized vinyl substituted aromatics monomers which have been maleated. The polyolefins are derived from olefin monomers having from 2 to 8 C atoms with 2 or 3 C atoms being preferred or a copolymer of poly- (ethylene-propylene) copolymer being preferred. The preparation of such maleated polyolefins which have a plurality of maleated sites are well known to the literature as well as those skilled in the art and are commercially available such as from ExxonMobil Chemical as Exxelor. The vinyl substi- tuted aromatic monomers contain from about 8 to about 12 carbon atoms with specific examples including styrene, a-methylstyrene, and the like with

styrene being preferred. Polymers therefrom can also be maleated in a manner well known to the literature as well as to the art and also contain a plurality of maleated sites.

The above noted fluorinated alcohols such as set forth in Formula A wherein Rf of a plurality of alcohols, independently, can be either the same or different, are initially reacted with an amino dicarboxcylic acid having a total of from about 3 to about 15 C atoms and desirably from about 4 to about 6 C atoms and from 1 to 3 amino groups and preferably 1 amino group. Examples of such acids include glutamic acid, aspartic acid and the like. The amino acids are reactive with the fluorinated alcohols in the presence of a small amount of hydrocarbon solvents such as the various alkanes having from about 6 to about 8 C atoms such as hexane, heptane and the like. The reaction temperature is from about 150° to about 210°C and desirably from about 170° to about 190°C in the presence of a Lewis acid catalyst such as tetrabutyl titanate, e. g., Tyzor TBT made by DuPont.

Various conventional tin catalysts as well as HCI can also be utilized. A condensation reaction is conducted with water being collected.

The following example relates to the reaction between Glutamic acid and Cheminox fa-8.

EXAMPLE A Substance Weight (a) MW mmol Cheminox fa-8 50 461.1 108.44 Tyzor T"TBT 0.025 340 7. 35x10-5 Heptane 5 100.21 49.90 Glutamic acid 15.95 147.13 108.44 A 3-necked round bottomed flask was equipped with a temperature probe, condenser equipped with a dean stark trap, magnetic stirrer, and a heating mantle. CheminoxT" fa-8 (50 g, 108.44 mmol), Tyzor TBT catalyst (0.025 g), heptane (5 g), and Glutamic acid (15.95 g, 108.44 mmol) were added. The reaction was heated with stirring to 180°C, and the water and

heptane were distilled into the dean stark trap. The reaction was followed with proton-NMR for the disappearance of the OH group. After 5 hours the reaction reached a conversion of 90%, and the reaction was stopped.-60 g glutamic acid ester was isolated.

The fluorinated alcohol functionalized amino dicarboxcylic acids are subsequently grafted onto the maleated polyolefin or the maleated polymer derived from vinyl substituted aromatic monomers. The reaction is generally simply carried out at temperatures of from about 175° to about 225°C and desirably from about 190° to about 210°C. An amount of the amino dicarboxylic acid utilized is sufficient to graft generally at least 50%, desirably at least 70%, and preferably at least 90% of the maleated sites. Subsequently, the grafted copolymers can be blended with polyolefins having an Aristech D180M melt index of from about 15 to about 50.

The following example illustrates the grafting reaction and imidization of the maleated polyolefin.

EXAMPLE B A brabender mixer was heated to 175°C and Exxelor TM Po 1015 maleated polypropylene was added (6.87 g). The temperature was increased to 200°C, and Glutamic acid functionalized Cheminot fa-8 (0.42 g) from Example A was added, and mixed for 5 minutes. The temperature was decreased to 175°C, and a maleated polypropylene having an Aristech D180M 18 melt index was added and mixed for 5 more minutes. The mixed polymer was removed from the Brabender and molded into a flat sheet at 68.95 MPa pressure while still hot. The grafted polypropylene mixture was then molded into a thinner sheet between metal plates at 180°C, and 68.95 MPa pressure.

The blended polyolefins which contain the block copolymers or graft copolymers of the present invention therein can be utilized in a variety of applications or end uses such as in sheet form, as individual fibers, as fibers which are subsequently utilized as a non-woven or woven fabrics made from

such fibers, for example carpets, awnings, tents, and the like. Other uses include furniture, especially outdoor, fencing, and the like.

The solid melt additive process of the present invention has a number of advantages over topical application of water-borne fluorochemicals ; especially for treatment of polyolefin materials : (I) There is no water used in process and, therefore, none to remove. This could eliminate substantial energy and time costs associated with removal of water. (II) Many polymers are processed into fibers normally by extrusion and melt spinning. Materials such as antioxidants, colorants and processing aids, are often added to the melt during production into fiber. The addition of a block copolymer at this stage would not add any unit operations to fiber production. (III) No surface tension-lowering surfactants are necessary to wet the fabric or fiber. The fluorinated block copolymer "wetting"of the fiber surface occurs unaided during processing of fiber. The fluorinated block copolymer tends to exude by a diffusive process to the outer regions of the fiber where a mixture of the block copolymer and the polyolefin exists.