ESTERS USEFUL AS PVC PLASTICIZERS

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of Serial No. 61/227,116 filed July 21, 2009, the disclosure of which is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

[0002] The invention relates to keto acid esters based on branched alkyl groups, useful as plasticizers and viscosity depressants for a wide range of resins, particularly PVC resin.

BACKGROUND OF THE INVENTION

[0003] Plasticizers are incorporated into a resin (usually a plastic or elastomer) to increase the flexibility, workability, or distensibility of the resin. The largest use of plasticizers is in the production of "plasticized" or flexible polyvinyl chloride (PVC) products. Typical uses of plasticized PVC include films, sheets, tubing, coated fabrics, wire and cable insulation and jacketing, toys, flooring materials such as vinyl sheet flooring or vinyl floor tiles, adhesives, sealants, inks, and medical products such as blood bags and tubing, and the like.

[0004] Other polymer systems that use small amounts of plasticizers include polyvinyl butyral, acrylic polymers, poly(vinylidene chloride), nylon, polyolefms, polyurethanes, and certain fluoroplastics. Plasticizers can also be used with rubber (although often these materials fall under the definition of extenders for rubber rather than plasticizers). A listing of the major plasticizers and their compatibilities with different polymer systems is provided in "Plasticizers," A. D. Godwin, in Applied Polymer Science 21st Century, edited by C. D. Craver and C. E. Carraher, Elsevier (2000); pp. 157-175.

[0005] Plasticizers can be characterized on the basis of their chemical structure. The most important chemical class of plasticizers is phthalic acid esters, which accounted for about 85% worldwide of PVC plasticizer usage in 2002. However, in the recent past there as been an effort to decrease the use of phthalate esters as plasticizers in PVC, particularly in end uses where the product contacts food, such as bottle cap liners and sealants, medical and food films, or for medical examination gloves, blood bags, and IV delivery systems, flexible tubing, or for toys, and the like. For these and most other uses of plasticized polymer systems, however, a successful, general purpose substitute for phthalate esters has heretofore not materialized on a commercial scale.

[0006] One such suggested substitute for phthalates are esters based on cyclohexanoic acid. In the late 1990's and early 2000's, various compositions based on cyclohexanoate, cyclohexanedioates, and cyclohexanepolyoate esters were said to be useful for a range of goods from semi-rigid to highly flexible materials. See, for instance, WO 99/32427, WO 2004/046078, WO 2003/029339, WO 2004/046078, U.S. Application No. 2006-0247461, and U.S. 7,297,738.

[0007] Other suggested substitutes include esters based on benzoic acid (see, for instance, U.S. 6,740,254, and also co-pending, commonly-assigned, U.S. Provisional Application 61/040,480, polyketones, such as described in U.S. 6,777,514; and also co-pending, commonly-assigned, U.S. Provisional Application 12/058,397, and triglycerides, such as described in co-pending, commonly assigned, U.S. Provisional Application 61/040,490. Epoxidized soybean oil (ESO), which has much longer alkyl groups (C 16 to C 18) has been tried as a plasticizer, but is generally used as a PVC stabilizer in low concentrations. At higher concentrations, ESO exudaton can occur.

[0008] Typically, the best that has been achieved with substitution of the phthalate ester with an alternative material is a flexible PVC article having either reduced performance or poorer processability. Thus, heretofore efforts to make phthalate-free plasticizer systems for PVC have not proven to be entirely satisfactory, and this is still an area of intense research.

[0009] U.S. 2,233,513 teaches aroylbenzoic acid esters with nitrocellulose and acetylcellulose. Nitrocellulose and acetylcellulose are resins used in centuries-old technology and find only limited use today. These materials are very brittle without plasticizer. The most common plasticizer for these resins was camphor. In part because of the odor inparted to the final product caused by the use of camphor, there were constant efforts to find alternative plasticizers. In general for every polymer, you need to have a plasticizer with the correct balance of solvating properties, volatility, and so forth. In the case of nitrocellulose, most of these efforts to find replacement plasticizers were in the area of improving the processability, stability, and decrease the brittleness of rigid or semi-rigid nitrocellulose products. The first applications of nitrocellulose were for ivory substitutes in billiard balls, false teeth, and piano keys. Here the plasticizers help greatly in processing and to reduce the brittleness of these rigid products. Later applications of nitrocellulose were in the area of stiff brush or combs, which had, before the use of nitrocellulose, been made from natural products. Eventually nitrocellulose found use in motion picture film. However, while "plasticizing" such resins made them more impact resistant and durable, this technology was rapidly replaced, over the span of barely a decade, with the introduction of PVC-based resins. In contrast to the cellulosic resins, PVC may be made truly flexible by plasticizing with the appropriate materials. Accordingly, there is no reason to assume that a plasticizer used with cellulosic material can be used successfully with PVC. Camphor, for instance, is not a good plasticizer of PVC. The same is seen with plasticizers used in polyvinyl butryal (PVB) - generally successful plasticisers of PVB resin are not useful in PVC. Plasticizers used in these polymers are not necessarily good plasticizers.

[0010] Accordingly, the industry still seeks a general purpose non-phthalate plasticizer, particularly a plasticizer that has a suitable melting or pour point, increased compatibility with the resin, and providing a PVC composition having good performance and low temperature properties, wherein the plasticizer can be made by a process having a high throughput and using readily available raw materials.

[0011] In U.S. 2,372,947, alkyl esters of ortho-benzoyl benzoic acid are described as being useful in polyvinyl halide resins.

[0012] The present inventors have surprisingly discovered that keto acid esters have advantageous properties when used in PVC and furthermore can readily made by esterifying alcohols with keto acids, the keto acids preferably being derived by acylating an aromatic molecule with a cyclic anhydride.

SUMMARY OF THE INVENTION

[0013] The invention is directed to keto acid esters and their use as plasticizers with resins selected from PVC, PVC copolymers, acrylic polymers and copolymers, and polyurethanes.

[0014] In embodiments, the keto acid esters are derived by acylating an aromatic molecule, such as benzene, toluene, one or more xylenes, anisole and other aromatic ethers, or mixtures of aromatic molecules, in a Friedel-Crafts type reaction, with a cyclic anhydride, such as succinic anhydride, phthalic anhydride, and the like. The resulting keto acid is esterified using an alcohol.

[0015] In embodiments the alcohol are derived from C6 to C13 aldehydes obtained from a hydroformylation process.

[0016] In preferred embodiments, the process further comprises providing a feed for the hydroformylation process from dimerization of diverse feedstock, preferably dimerization of a C3 or C4 feedstock, or a mixture thereof. [0017] The invention is also directed to keto acid esters, particularly keto acid esters derived from branched C7 to C13 alcohols, and also to compositions including a resin, such as PVC, and a keto acid ester according to the invention.

[0018] In embodiments, the alcohols esterifϊed with the keto acids have an average branching of from about 0.8 to about 3.0 branches per molecule. In an embodiment, the average branching may range from about 1.0 to about 2.4. In another embodiment, the average branching of the C5 to C8 alkyl groups ranges from about 1.2 to about 2.2, preferably around about 1.2 to about 2.0, more preferably about 1.2 to about 1.8 branches per molecule. In embodiments the average branching will be from about 1.2 to about 1.6.

[0019] The invention is still further directed to an article comprising the composition according to the invention.

[0020] It is an object of the invention to provide a plasticizer suitable for diverse resins such as poly (vinyl chloride), acrylic polymers, and polyurethanes.

[0021] It is another object of the invention to provide a high throughput process for producing keto acid esters suitable for plasticizing resin, especially PVC.

[0022] It is yet another object of the invention to provide phthalate-free compositions and articles.

[0023] These and other objects, features, and advantages will become apparent as reference is made to the following detailed description, preferred embodiments, examples, and appended claims.

DETAILED DESCRIPTION OF THE INVENTION

[0024] The invention is directed to keto acid esters and their use as plasticizers, particularly with PVC resins.

[0025] In embodiments, the keto acid esters are derived by acylating an aromatic molecule, such as benzene, toluene, one or more xylenes, anisole or other aromatic ethers, or mixtures of aromatic molecules, in a Friedel-Crafts type or condensation reaction, with a cyclic anhydride, such as succinic anhydride, phthalic anhydride, and the like. The resulting keto acid is esterifϊed using an alcohol.

[0026] In embodiments the alcohol are derived from C6 to C13 aldehydes obtained from a hydroformylation process.

[0027] In preferred embodiments, the process further comprises providing a feed for the hydroformylation process from dimerization of diverse feedstock, preferably dimerization of a C3 or C4 feedstock, or a mixture thereof. [0028] The invention is also directed to keto acid esters, particularly keto acid esters wherein the alcohol moiety is derived from branched C6 to C13 alcohols, and also to compositions including a resin, such as PVC, and a keto acid ester according to the invention.

[0029] The keto acid esters of the invention are derived by acylating an aromatic molecule such as benzene, toluene, anisole or other aromatic ethers, one or more xylenes, or mixtures of aromatic molecules. Typical aromatic molecules useful in this reaction include benzene, toluene, xylenes, propylbenzene, cumene, tert-butylbenzene, sec-butylbenzene, isobutylbenzene, isopentylbenzene, (l,2-dimethyl-propyl)-benzene, pentylbenzene, 1- phenylhexane, heptylbenzene, 1-phenyloctane, 1-phenylnonane, undecylbenzene, 1- phenylundecane, 1-phenyldodecane, 1-phenyltridecane, tetradecylbenzene, 1- phenyltetradecane, 1-phenylpentadecane, hexadecylbenzene, anisole, veratrole, naphthalene and substituted naphthalenes.

[0030] The cyclic anhydride may be selected from at least one of phthalic anhydride, succinic anhydride, maleic anhydride, cyclohexanedicarboxylic anhydride, methylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, hexahydro-4-methylphthalic anhydride, itaconic anhydride, norbornene-dicarboxylic anhydride, glutaric anhydride, dimethylglutaric anhydride, epoxy-tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, diglycolic anhydride, 2-phenylglutaric anhydride, homophthalic anhydride, and methylphthalic anhydride.

[0031] Acylation reactions with cyclic anhydrides are well-known per se (see Friedel- Crafts and Related Reaction, George Olah, Ed., Vol. 3 Part 1, Chapter XXXIV "Acylation with Di- and Polycarboxylic Acid Derivatives" by Andrew G. Peto, Interscience, 1964, for example). An aromatic keto acid is produced when an aromatic compound is reaction with a cyclic anhydride in the presence of an acidic catalyst. The catalyst may be a Lewis acid catalyst, such as AICI ₃ , a protonic acid or solid acid catalysts, such as zeolites or sulfated zirconia, among others.

[0032] In embodiments the alcohol are derived from C6 to C13 aldehydes obtained from a hydroformylation process, and in preferred embodiments, the process further comprises providing a feed for the hydroformylation process from dimerization of diverse feedstock, preferably oligomerization, such as dimerization or trimerization, of a feedstock selected from C3 to C6 olefins.

[0033] In embodiments, the alcohol with which the keto acid is esterified will have an average branching of from about 0.8 to about 3.0. In an embodiment, the average branching may range from about 1.0 to about 2.4. In another embodiment, the average branching will range from about 1.2 to about 2.2, preferably around about 1.2 to about 2.0 , more preferably about 1.2 to about 1.8 branches per molecule.

[0034] Branching may be determined by known NMR methods, such as employed in U.S. 6,437,170. Branching may also be attenuated by one of ordinary skill in the art by appropriate process conditions and reagents. In embodiments the branching in these alcohols may be almost exclusively methyl branches but some ethyl branches may also be present in small amounts.

[0035] In an embodiment, the process of the invention further comprises the production of branched aldehydes by hydro formylation of C5 to C13 olefins that in turn have been produced by oligomerization of propylene and/or butene over solid phosphoric acid or zeolite catalysts or nickel based dimerzation technologies or through the Dimersol process. These oligomerization processes are per se well-known. See, for instance, U.S. 7,253,330, and U.S.

7,145,049.

[0036] The resulting C6 to C13 aldehydes are then hydrogenated to yield the corresponding primary alcohols.

[0037] The plasticizers of this invention can then be prepared through the esterification of the keto acids with these C6 to C 13 alcohols.

[0038] The production of the keto acids and then corresponding esters, according to the invention may be conveniently exemplified by the following reactions, shown schematically.

These reaction schemes are depicted with mono-substituted aromatics but a wide range of aromatics may be used. For example, benzene (R=H), toluene (R=CH3, xylenes

(disubstituted with two R-CH3 groups). Similarly, ROH may cover a range of alcohols, such as described previously.

3 -aroy lpropanoate

3

[0039] In the case of the aroyl benzoic acid molecule derived from phthalic anhydride, shown in equation 2, the esterifϊcation can also yield another isomeric structure via rearrangement, as shown in equation 3. The final esterification product can be a mixture of the ester shown in equation 2 and the lactone shown in equation 3.

[0040] Another synthetic route to the keto acids of the invention is by the method illustrated below, wherein the alkyl groups on Rl may be selected from linear or branched alkyls, preferably having from 1 to 6 carbon atoms.

R = C 5 to C 13

R l = A lkyl [0041] Example 1. General procedure for synthesis of the plasticizer by esterifϊcation. Into a four necked 1000 ml round bottom flask equipped with an air stirrer, nitrogen inductor, thermometer, Dean-Stark trap and chilled water cooled condenser were added keto acid and Oxo alcohol in a mole ratio of 1 :2. The reaction mixture was heated to 220 ⁰ C with air stirring under a nitrogen sweep. The water evolved during the esterifϊcation reaction was collected in the Dean-Stark trap and was drained frequently and monitored until approximately theoretical weight was collected, indicating near complete reaction. The excess alcohol were removed by distillation or steam stripping. In some instances, titanium isopropoxide was used as a catalyst for the esterifϊcation reaction.

[0042] Table 1 summarizes the aroyl benzoates prepared from the reaction of an aromatic with phthalic anhydride. A general structure for the aroyl benzoates is shown below:

Table 1

[0043] Table 2 summarizes the aroyl propionates prepared from the reaction of an aromatic with succinic anhydride. A general structure for the aroyl propionates is shown below:

Table 2

Example 1 - Plasticization

[0044] Formulations corresponding to Table 3, were mixed at room temperature with moderate stirring, then placed on a roll mill at 340 ⁰ F and milled for 6 minutes. The flexible vinyl sheet was removed and compression molded at 350 ⁰ F.

[0045] Sample A DINP = di-isononylphthalate

[0046] Sample B TBA-9 = iso-nonyl toluoyl benzoate

[0047] Sample C TPA-9 = iso-nonyl toluoyl propionate

Table 3

Formulation -A -B -C

PVC 100 100 100

Plasticizer DINP TBA-9 TPA-9

Phr 50 50 50

ESO 3 3 3

CuZn Stabilizer J J 3

stearic acid 0.25 0.25 0.25

[0048] Comparison of the data for the formulations follows: Table 4

Mechanical Properties Comparison

Sample ID A B C

Original Mechanical Properties

Shore A Hardness (15 sec.) 78.0 79.2 71.6

95% Confidence Interval 0.5 0.6 2.3

Shore D Hardness (15 sec.) 26.1 28.5 21.0

95% Confidence Interval 0.3 0.5 0.3

100% Modulus Strength, psi 1668 2123 1233

95% Confidence Interval 26 30 33

Ultimate Tensile Strength, psi 2987 3351 3116

95% Confidence Interval 174 35 56

Ultimate Elongation, % 322 309 364

95% Confidence Interval 31 13 13

Aged Mechanical Properties: 7 Davs at 100 ⁰ C (AC/hour)

Aged 100% Modulus Strength, psi 2114 2611 --

95% Confidence Interval 13 24 —

Ultimate Tensile Strength, psi 2822 2997 5869

95% Confidence Interval 86 88 336

Ultimate Elongation, % 265 214 28

95% Confidence Interval 20 17 11

Weight Loss, Wt% 5.9 6.2 20.7

95% Confidence Interval 0.28 0.12 0.28

Retained Properties: 7 Davs at 100 ⁰ C (AC/hour)

Retained 100% Modulus Strength, % 127 123 -

95% Confidence Interval 0.4 0.3 -

Retained Tensile Strength, % 94 89 188

95% Confidence Interval 0.4 0.3 0.7

Retained Elongation, % 82 69 8

95% Confidence Interval 1.7 1.4 0.9

Low Temperature

Clash Berg (Tf), C -21.9 3.8 -18.9

95% Confidence Interval 0.8 1.2 1.2

Samples were milled at 340 ⁰ F and molded at 350 ⁰ F to thickness. Conditioning was 7 days prior to testing

Table 4a

Mechanical Properties Comoamion

TSR # 0&-020 *Wet Bteod$ ^fl

Sample ID: D E

Formulations:

PVC (Oxy 240) 100 100 isodecylbenzoylbenzoate (BBA-10) 50

Jayflex DINP 50

ESO (Drapex 6.8) 3 3

CaZn stabilizer (Mark 1221 ) 2.5 2.5

Stearic Acid 0.25 0.25

Sample Prep & Observations:

Samples were milled at 330 ⁰ F and molded at 340 ⁰ F.

Low-moderate Low-moderate smoking; smoking; low odor low odor

Original Mechanical Properties

Shore A Hardness (15 sec.) 76.8 78.5

95% Confidence Interval 1.2 1.1

100% Modulus Strength, psi 2013 1674

95% Confidence Interval 67 22

Ultimate TensileStrength, psi 3319 3221

95% Confidence Interval 99 50

Ultimate Elongation, % 301 375

95% Confidence Interval 15 7

Aαed Mechanical Properties:

Aged 100% Modulus Strength, psi 2719 2249

Aged Ultimate TensileStrength, psi 162 85

Ultimate TensileStrength, psi 3082 3094

95% Confidence Interval 105 101

Ultimate Elongation, % 206 299

95% Confidence Interval 32 12

Weight Loss, Wt% 10 6.9

95% Confidence Interval 1.03 0.61

Retained P roper ties;

Retained 100% Modulus Strength, % 135 134

95% Confidence Interval 0.7 0.6

Retained Tensile Strength, % 93 96

95% Confidence Interval 0.3 0.3

Retained Elongation, % 68 80

95% Confidence Interval 1.7 0.8

Other:

Carbon Volatility (24 ϊioars at ?θ€*

Mean (3 specimens) 0.5 0.5

95% Confidence Interval 0 0.1

Low Temperature

Bell Brittleness (Tb), C -1.8 -30.2

95% Confidence Interval 2 2 Table 5

Mechanical Properties Comparison

TSR #09-021

f ^l P)a$tisol$*

Sample ID: F G

Formulations:

PVC Plastisol (GEON 124A) 100 100 iso-decyl benzoylbenzoate 70

Jayflex DINP 70

(ESO) Drapex 6.8 2 2

(Ca/Zn Stabilizer) Mark 1221 2.5 2.5

Sample Preo & Observations:

Samples were fused on WM Oven at 190°C and molded at 340°F to thickness.

Ortq inal Mechani cal Properties

Shore A Hardness (15 sec.) 61 63

95% Confidence Interval 0.4 0.8

100% Modulus Strength, psi 980 975

95% Confidence Interval 24 14

Ultimate TensileStrength, psi 2389 2318

95% Confidence Interval 74 90

Ultimate Elongation, % 334 384

95% Confidence Interval 67 12

Aq ed Mechanical Properties:

Aged 100% Modulus Strength, psi 1794 1379

Aged Ultimate TensileStrength, psi 173 29

Ultimate TensileStrength, psi 2460 2114

95% Confidence Interval 209 40

Ultimate Elongation, % 232 253

95% Confidence Interval 27 9

Weight Loss, Wt% 14 11

95% Confidence Interval 0.43 0.28

Reta i Red Prope rties :

Retained 100% Modulus Strength, % 183 141

95% Confidence Interval 1.4 0.7

Retained Tensile Strength, % 103 91

95% Confidence Interval 0.5 0.3

Retained Elongation, % 70 66

95% Confidence Interval 1.6 0.7

Table 6

yechaπtcal Properties Gomoanson

TSR # 09-057

*Wet-δte«te*

Sample ID H I

Formulations:

Oxy 240 100 100 iso-nonyl benzoylpropionate 50

iso-nonyl benzoylbenzoate 50

Drapex 6.8 (ESO) 2.5 2.5

Mark 1221 (CaZn Stabilizer) 2.5 2.5

Stearic Acid (External Lubricant) 0.3 0.3

Sample Prep & Q|?$ervatiiQf*&:

Samples were milled at 330 ⁰ F and molded at 340 ⁰ F.

Moderate smoking; Low smoking; low

High odor odor

On qϊna I Me c han i ca I Properties

Shore A Hardness (15 sec.) 73 79

95% Confidence Interval 0.64 0.80

Shore D Hardness (15 sec.) 21 27

95% Confidence Interval 0.14 0.14

100% Modulus Strength, psi 1276 2011

95% Confidence Interval 35 32

Ultimate TensileStrength, psi 3148 3403

95% Confidence Interval 122 129

Ultimate Elongation, % 357 296

95% Confidence Interval 13 20

Aαed Mechanical Properties:

Aged 100% Modulus Strength, psi 1640 2146

95% Confidence Interval 109 30

Ultimate TensileStrength, psi 3131 3211

95% Confidence Interval 99 123

Ultimate Elongation, % 309 279

95% Confidence Interval 23 16

Weight Loss, Wt% 5 1

95% Confidence Interval 1.4 0.4

Retained Properties:

Retained 100% Modulus Strength, % 129 107

95% Confidence Interval 0.86 0.33

Retained Tensile Strength, % 99 94

95% Confidence Interval 0.40 0.38

Retained Elongation, % 87 94

95% Confidence Interval 1.4 1.7

Low Temperature

Clash Berg (Tf), C -20 -0.2

95% Confidence Interval 2.4 1.6

[0049] The plasticizers according to the invention may also be used with vinyl chloride- type resins, polyesters, polyurethanes, ethylene-vinyl acetate copolymer, rubbers, acrylics, polymer blends such as of polyvinyl chloride with an ethylene-vinyl acetate copolymer or polyvinyl chloride with a polyurethane or ethylene-type polymer.

[0050] All patents and patent applications, test procedures (such as ASTM methods, UL methods, and the like), and other documents cited herein are fully incorporated by reference to the extent such disclosure is not inconsistent with this invention and for all jurisdictions in which such incorporation is permitted.

[0051] When numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated. While the illustrative embodiments of the invention have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.

[0052] The invention has been described above with reference to numerous embodiments and specific examples. Many variations will suggest themselves to those skilled in this art in light of the above detailed description. All such obvious variations are within the full intended scope of the appended claims.