WO2006007591A1 - Carboxylic acid compounds and polyester oligomers and polymers made therefrom - Google Patents

Carboxylic acid compounds and polyester oligomers and polymers made therefrom Download PDF

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Publication number
WO2006007591A1
WO2006007591A1 PCT/US2005/023741 US2005023741W WO2006007591A1 WO 2006007591 A1 WO2006007591 A1 WO 2006007591A1 US 2005023741 W US2005023741 W US 2005023741W WO 2006007591 A1 WO2006007591 A1 WO 2006007591A1
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Prior art keywords
composition
matter
group
acid
diol
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PCT/US2005/023741
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French (fr)
Inventor
Shuang Zhou
Tzyy Jan Han
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Cargill, Incorporated
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Priority to US11/629,745 priority Critical patent/US7687549B2/en
Publication of WO2006007591A1 publication Critical patent/WO2006007591A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones

Definitions

  • the invention relates to di- and tri- carboxylic acid compounds and polyester oligomers and polymers made therefrom.
  • the invention also includes curable compositions comprising the polyester oligomers and polyester polymers. Summary of the Invention
  • the invention relates to di- and tri-carboxylic acid compounds and polyester oligomers and polymers made therefrom.
  • the invention provides di- and tri-functional compounds that may be represented by formula (A): HOOC-Y-COOH
  • Y- is selected from the group consisting of:
  • R 1 - is a divalent aliphatic organic group
  • -X- is -O- or -NH- ;
  • R 3 — is a divalent organic group having at least one carbon-carbon double bond
  • -R 4 is a monovalent organic group having at least one carbon-carbon double bond
  • -R 5 is hydrogen or an alkyl group
  • R 6 - is a divalent aliphatic organic group.
  • the compounds may be used to prepare polyester oligomers and polyester polymers.
  • the polyester oligomers and polymers have improved properties.
  • the invention provides a composition of matter comprising a polyester oligomer or polyester polymer comprising the reaction product of:
  • polymer refers to a molecule made up of repeating monomer units wherein the molecule has a molecular weight of 7000 grams/mole or greater.
  • oligomer refers to a molecule made up of repeating monomer units wherein the molecule has a molecular weight of less than 7000 grams/mole.
  • the invention provides curable compositions that may be useful, for example, as coatings.
  • the curable compositions comprise a reactive diluent and a polyester polymer and/or oligomer of the invention.
  • the compositions may be cured (i.e., polymerized) by exposure to electron beam (i.e., e-beam) radiation.
  • the curable composition comprises a reactive diluent, a photoinitiator, and a polyester polymer or oligomer of the invention.
  • the compositions may be cured (i.e., polymerized) by exposure ultra-violet light.
  • the invention relates to di- and tri-functional carboxylic acid compounds that may be represented by formula (A).
  • Compounds of formula (A) may be used, for example to prepare polyester oligomers and/or polyester polymers.
  • the polyester oligomers and/or polymer have improved properties.
  • the di- and tri-functional compounds of the invention are represented by formula (A): HOOC-Y-COOH
  • -Y- is selected from the group consisting of:
  • -R 1 - is a divalent aliphatic organic group
  • -X- is -O- or -NH-;
  • -R 3 is a divalent organic group having at least one carbon-carbon double bond; -R is a monovalent organic group having at least one carbon-carbon double bond;
  • -R 5 is hydrogen or an alkyl group
  • -R 6 - is a divalent aliphatic organic group.
  • Compounds of formula (A) may be prepared, for example, by reacting: (1) a hydroxy-functional dicarboxylic acid, an amine-functional dicarboxylic acid, a hydroxy- functional anhydride, or an amine-functional anhydride with (2) a dicarboxylic acid having at least one carbon-carbon double bond, an anhydride having at least on carbon-carbon double bond, or a mono-carboxylic acid having at least one carbon-carbon double bond. Mixtures and combinations of the foregoing may also be used.
  • hydroxy-functional dicarboxylic acids include malic acid (e.g., /-malic acid, J-malic acid, and dj-m&lic acid), 3-hydroxy-3-methylglutaric acid, citramalic acid, and hydroxy aromatic dicarboxylic acids.
  • malic acid e.g., /-malic acid, J-malic acid, and dj-m&lic acid
  • 3-hydroxy-3-methylglutaric acid citramalic acid
  • citramalic acid hydroxy aromatic dicarboxylic acids.
  • a representative example of a hydroxy-functional anyhydride is 3-hydroxyphthalic anhydride.
  • Representative examples of amine-functional dicarboxylic acids include glutamic acid and amino aromatic acids (e.g., 3-aminophthalic acid).
  • Representative dicarboxylic acids having at least one carbon-carbon double bond- include itaconic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid.
  • Representative anhydrides having at least one carbon-carbon double bond include itaconic anhydride, maleic anhydride and citraconic anhydride.
  • Representative mono-carboxylic acids having at least one carbon-carbon double bond include methacrylic acid and its derivatives, crotonic acid and anhydride, unsaturated fatty acids such as oleic acid and linoleic acid.
  • itaconic anhydride is reacted with malic acid to form the tri-functional carboxylic acid compounds of formula (A) shown below.
  • the di- and tri- carboxylic acid compounds of the invention may be used to prepare polyester oligomers and/or polyester polymers by reacting the compounds with: (1) dihydric alcohols, or (2) dihydric alcohols and dicarboxylic acids. Accordingly, in another embodiment, the invention provides polyester oligomers and polyester polymers made from the di- and/or tri- carboxylic acid compound of the invention. Polyester oligomers and polymers of the invention may be synthesized in several routes, as described below. Route 1: Step l: In the first synthetic route, a diol and a dicarboxylic acid (or anhydrides) are reacted in known fashion to form a polyester diol. The diol is added in excess with respect to the dicarboxylic acid or anhydride in a ratio of diol to dicarboxlic acid of 1.01 : 1 to 100:1 on a molar basis.
  • a catalyst such as sulfuric acid, sulfonic acid,/?- toluene sulfonic acid may be used, for example, in an amount ranging from about 0.05 to 5 % weight.
  • the reaction may be carried out at atmospheric pressure or, preferably, under reduced pressure of about 50 to about 500 mm Hg.
  • the reaction mixture is blanketed with an inert gas (e.g., carbon dioxide, nitrogen, or argon) to reduce side reactions with oxygen.
  • the reaction is typically carried out at temperature ranging from about 6O 0 C to about 25O 0 C for a time ranging from about 15 minutes to about 24 hours.
  • tetra(ethylene glycol) is reacted with succinic anhydride to form a polyester oligomer diol having the structure shown below.
  • a hydroxy-functional or amine-functional diacid is reacted with an unsaturated anhydride and/or an unsaturated diacid or unsaturated monoacid to form an unsaturated triacid or unsaturated diacid compound of formula (A).
  • the ratio of the unsaturated compound to the hydroxy-functional compound typically ranges from about 1.01:1 to 100:1 on a molar basis.
  • a catalyst such as tin powder, tin (II) chloride, tin (II) acetate, tin (II) oxide and lithium chloride may be used, for example, in an amount ranging from about 0.05% to 5% weight.
  • the carbon-carbon double bonds are protected by the addition of about 0.001 to about 1% weight of hydroquinone.
  • the reaction may be carried out at atmospheric pressure or, preferably, under reduced pressure of about 50 to about 500 mm Hg.
  • the reaction mixture is blanketed with an inert gas (e.g., carbon dioxide, nitrogen, or argon) to reduce side reactions with oxygen.
  • the reaction is typically carried out at a temperature ranging from about 6O 0 C to about 17O 0 C for a time ranging from about 15 minutes to about 24 hours.
  • malic acid is reacted with itaconic anhydride to form the compounds shown below.
  • the polyester oligomer diol or polyester polymer diol prepared in Step 1 and the triacid or diacid compounds of formula (A) that were prepared in Step 2 (and excess unsaturated compound) are reacted with each another.
  • the ratio of the total mole number of carboxylic acid (i.e., -COOH) groups to the total mole number of hydroxyl (i.e., -OH) groups in the reaction mixture typically ranges from about 1.01 : 1 to 2:1.
  • the reaction forms a polyester oligomer and/or polyester polymer having the structure shown below.
  • the reaction may be carried out at atmospheric pressure, or more preferably, the reaction is carried out at a reduced pressure ranging from about 50 to about 500 mm Hg.
  • the reaction mixture is blanketed by an inert gas (e.g., carbon dioxide, nitrogen, or argon) to reduce side reactions with oxygen.
  • an inert gas e.g., carbon dioxide, nitrogen, or argon
  • the reaction is typically carried out at temperatures ranging from about 6O 0 C to about 17O 0 C for a time ranging from about 15 minutes to about 24 hours.
  • the number average molecular weight (M n ) of the resulting polyester oligomer and/or polyester polymer ranges from about 300 to about 30,000 grams/mole.
  • Z — O-f(CH 2 CH 2 O) 4 -C-(CH 2 ) 2 -C- ⁇ ] ⁇ -(CH 2 CH 2 O) 4 -H or -OH
  • a hydroxy-functional or amine-functional diacid is reacted with an unsaturated compound, for example, an unsaturated anhydride, an unsaturated diacid, or an unsaturated monoacid to form a diacid or triacid compound of formula (A).
  • an unsaturated compound for example, an unsaturated anhydride, an unsaturated diacid, or an unsaturated monoacid to form a diacid or triacid compound of formula (A).
  • the ratio of unsaturated compound to the hydroxy-functional or amine- functional compound typically ranges from about 1.01:1 to 100:1 on a molar basis.
  • the carbon-carbon double bond is protected by the addition of about 0.001 to 1% weight of hydroquinone.
  • a catalyst such as tin powder, tin (II) chloride, tin (II) acetate or tin (II) oxide, may be added in an amount ranging from about 0.05% to 5% weight.
  • tin powder tin (II) chloride
  • tin (II) acetate tin (II) oxide
  • malic acid may be reacted with itaconic anhydride as shown above.
  • the ratio of the total mole number of carboxylic acid (i.e., -COOH groups) to the total mole number of hydroxyl groups (i.e., -OH groups) in the reaction mixture typically ranges from about 1.01 : 1 to 2: 1.
  • the components are then reacted to form a polyester oligomer and/or polyester polymer of the invention.
  • the reaction may be carried out at atmospheric pressure. More preferably, the reaction is carried out at a reduced pressure ranging from about 50 to about 500 mm Hg.
  • the reaction mixture is blanketed by an inert gas, including carbon dioxide, nitrogen, or argon to reduce side reactions with oxygen.
  • the reaction is typically carried out at a temperature ranging from about 6O 0 C to about 17O 0 C for a time ranging from about 15 minutes to about 24 hours.
  • tetra(ethylene) glycol and adipic acid are added to a compound of formula (A) sequentially to produce a polyester oligomer or polymer having a representative structure as shown below, where X, Y and Z are randomly distributed along the main chain of the oligomer or polymer.
  • R -OH; -0-X-(CH 2 CH 2 O) 4 -H or -0-Y-(CH 2 CH 2 O) 4 -H
  • a diol and a diacid (or anhydride) are reacted to form a polyester oligomer diol.
  • tetra(ethylene glycol) may be reacted with adipic anhydride to form a polyester oligomer diol having the structure shown below:
  • the reaction can be carried out at atmospheric pressure. More preferably, the reaction is carried out under reduced pressure ranging from about 50 to about 500 mm Hg. In some embodiments, the reaction mixture is blanketed by an inert gas, including nitrogen or argon. The reaction is typically carried out at the temperature ranging from about 60 0 C to about 250 0 C for a time ranging from about 15 minutes to about 24 hours. To enhance the reaction rate, a catalyst such as sulfuric acid, sulfonic acid, or p-toluene sulfonic acid may be added, for example, in an amount ranging from about 0.05 to 5 % weight.
  • a catalyst such as sulfuric acid, sulfonic acid, or p-toluene sulfonic acid may be added, for example, in an amount ranging from about 0.05 to 5 % weight.
  • polyester oligomer diol a hydroxy-functional or amine-functional diacid and an unsaturated anhydride or diacid or monoacid are then added.
  • the ratio of the total mole number of carboxylic acid groups (-COOH) to the total mole number of hydroxyl groups (-OH) typically ranges from about 1.01 : 1 to about 2:1.
  • the components are then reacted to form a polyester oligomer or polyester polymer.
  • the carbon-carbon double bond is protected by the addition of about 0.001 to 1 % weight of hydroquinone.
  • malic acid and itaconic anhydride are added to the polyester oligomer diol to provide a polyester oligomer and/or polyester polymer having a representative structure as shown below:
  • the polyester oligomer and/or polyester polymer typically has a number average molecular weight (M n ) ranging from about 300 to about 30,000 grams/mole.
  • Polyester oligomer/polymer compositions the invention include at least one diol.
  • diol refers to a molecule having two hydroxyl groups. Diols may be represented by the formula HO-R-OH, where -R- is a divalent organic group that optionally comprises O, P, S, N, and/or halogen. Suitable diols include straight chain alkane diols, branched chain alkane diols and ether diols. Straight chain alkane diols are represented by formula (B) and ether diols are represented by formula (C). Alkane diols:
  • straight chain alkane diols include 1,3 -propanediol; 1,4-butanediol; 1,5-heptanediol; 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol.
  • Branched chain hydrocarbon diols may also be used and include, for example, 1, 2-propane diol (i.e., HOCH 2 CH(CH 3 )OH) and 1, 3-butane diol (i.e., (HOCH 2 CH 2 CH(CH 3 )OH).
  • 1, 2-propane diol i.e., HOCH 2 CH(CH 3 )OH
  • 1, 3-butane diol i.e., (HOCH 2 CH 2 CH(CH 3 )OH.
  • Polyester oligomer and polymer compositions of the invention include a dicarboxylic acid or anhydride.
  • the dicarboxylic acid or anhydride reacts with a diol to form ester linkages in the polyester oligomer or polymer.
  • anhydride refers to a compound derived from an organic diacid by elimination of a molecule of water.
  • Suitable organic diacids may be represented by the general formula (D).
  • R 7 — is a divalent organic group including, for example, alkane (e.g., -(CH 2 ) n4 - ; where n4 is 2 to 8), alkene, a cycloaliphatic group, or an aromatic group.
  • alkane dicarboxylic acids include adipic acid, succinic acid, glutaric acid, and sebacic acid.
  • unsaturated dicarboxylic acids include itaconic acid, maleic acid and fumaric acid.
  • a representative example of a cycloaliphatic dicarboxylic acid is 1, 2-cyclohexanedicarboxylic acid.
  • aromatic dicarboxylic acids include phthalic acid and terephthalic acid. Suitable anhydrides may be represented by the general formula (E).
  • -R - is a divalent organic group including, for example, an alkane (e.g., -(CH 2 ) n5 - ; where n5 is 2 or 3), alkene, cycloaliphatic group or aromatic group.
  • alkane e.g., -(CH 2 ) n5 - ; where n5 is 2 or 3
  • alkene cycloaliphatic group or aromatic group.
  • anhydrides include succinic anhydride and glutaric anhydride.
  • Representative examples of unsaturated dicarboxylic anhydrides include itaconic anhydride and maleic anhydride.
  • Representative examples of cycloaliphatic dicarboxylic anhydrides include 1, 2-cyclohexanedicarboxylic anhydrides.
  • a representative example of an aromatic dicarboxylic anhydrides is phthalic anhydride.
  • the invention provides curable compositions comprising a reactive diluent, a photoinitiator and a polyester polymer or oligomer of the invention. The compositions may be suitable, for example, as coatings.
  • Curable compositions of the invention may be polymerized by exposure to electron beam, or polymerization can be initiated by exposure to ultra-violet (UV) light when the composition comprises a photoinitiator.
  • UV ultra-violet
  • photoinitiator refers to a material that functions to initiate polymerization when exposed to UV radiation of a suitable wavelength.
  • Representative examples of photoinitiators include 2,2-dimethoxy-2- phenylacetophenone, bezophenone, benzoin alkyl ether.
  • Reactive diluents are materials that include one or more double bonds that can be initiated by the radicals generated by the photoinitiator.
  • Representative examples of reactive diluents include 2-(2-ethoxyethoxy)ethyl acrylate, isodedcyl acrylate, ethoxylated neopentyl glycol diacrylate, polyethyleneglycol 400 diacrylate, tetra(ethylene glycol) diacrylate, tri(propylene glycol) diacrylate trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, and ethoxylated pentaerythritol tetraacrylate.
  • the number average molecular weight of the product was determined to be 2170 grams/mole from GPC (polystyrene as standard on a Water 2690 apparatus; columns, Styragel ® HR 0.5 and Styragel ® HR 2; eluent, THF; flow rate, 0.3 niL/min; column temperature, 35° C).
  • step (1) and step (2) were combined under a blanket of nitrogen. After addition, the stirred reaction mixture was heated to 95° C for 15.5 hours. Subsequently, the reaction mixture was cooled to room temperature, yielding a light yellow viscous gel.
  • the number average molecular weight of the gel was determined to be 1650 grams/mole from GPC (polystyrene as standard on a Water 2690 apparatus; columns, Styragel ® HR 0.5 and Styragel ® HR 2; eluent, THF; flow rate, 0.3mL/min; column temperature, 35° C).
  • TMPTA trimethylolpropane triacrylate
  • Example 1 1.16 g of the product of Example 1 was added to the photoinitiator solution and was stirred until the mixture was uniform. A thin film of the mixture was applied to papefboard and the resulting film was cured under a 200 W/inch ultraviolet light in a nitrogen purged environment (cured under a portable 2" UV curing system commercially available under the trade designation "CON-TROL-CURE” from UV Process Supply, Inc.). The cured film was tack-free, transparent, and rigid.

Abstract

The invention relates to di- and tri-carboxylic acid compounds and polyester oligomers and polymers made therefrom. Curable compositions comprising the polyester oligomers and polymers are also described.

Description

CARBOXYLIC ACID COMPOUNDS AND POLYESTER OLIGOMERS
AND POLYMERS MADE THEREFROM
Field of the Invention
The invention relates to di- and tri- carboxylic acid compounds and polyester oligomers and polymers made therefrom. The invention also includes curable compositions comprising the polyester oligomers and polyester polymers. Summary of the Invention
The invention relates to di- and tri-carboxylic acid compounds and polyester oligomers and polymers made therefrom.
In one aspect, the invention provides di- and tri-functional compounds that may be represented by formula (A): HOOC-Y-COOH
(A) where:
— Y- is selected from the group consisting of:
Figure imgf000002_0001
-R1- is a divalent aliphatic organic group;
-R2 is -X-C(O) -R3-C(=O)OH or -X-C(=0) -R4 ; -X- is -O- or -NH- ;
— R3— is a divalent organic group having at least one carbon-carbon double bond; -R4 is a monovalent organic group having at least one carbon-carbon double bond; -R5 is hydrogen or an alkyl group; and
-R6- is a divalent aliphatic organic group.
The compounds may be used to prepare polyester oligomers and polyester polymers. In some embodiments, the polyester oligomers and polymers have improved properties. In another aspect, the invention provides a composition of matter comprising a polyester oligomer or polyester polymer comprising the reaction product of:
(a) a compound of formula (A) as described above;
(b) a diol; and (c) a diacid or anhydride.
As used herein the term "polymer" refers to a molecule made up of repeating monomer units wherein the molecule has a molecular weight of 7000 grams/mole or greater. As used herein the term "oligomer" refers to a molecule made up of repeating monomer units wherein the molecule has a molecular weight of less than 7000 grams/mole.
In another aspect, the invention provides curable compositions that may be useful, for example, as coatings. In one embodiment the curable compositions comprise a reactive diluent and a polyester polymer and/or oligomer of the invention. The compositions may be cured (i.e., polymerized) by exposure to electron beam (i.e., e-beam) radiation. In another embodiment, the curable composition comprises a reactive diluent, a photoinitiator, and a polyester polymer or oligomer of the invention. The compositions may be cured (i.e., polymerized) by exposure ultra-violet light. Detailed Description
The invention relates to di- and tri-functional carboxylic acid compounds that may be represented by formula (A). Compounds of formula (A) may be used, for example to prepare polyester oligomers and/or polyester polymers. In certain embodiments, the polyester oligomers and/or polymer have improved properties.
The di- and tri-functional compounds of the invention are represented by formula (A): HOOC-Y-COOH
(A) where:
-Y- is selected from the group consisting of:
Figure imgf000003_0001
-R1- is a divalent aliphatic organic group; -R2 is -X-C(=O) -R3-C(=O)OH or -X-C(=O) -R4 ; -X- is -O- or -NH-;
-R3— is a divalent organic group having at least one carbon-carbon double bond; -R is a monovalent organic group having at least one carbon-carbon double bond;
-R5 is hydrogen or an alkyl group; and -R6- is a divalent aliphatic organic group.
Compounds of formula (A) may be prepared, for example, by reacting: (1) a hydroxy-functional dicarboxylic acid, an amine-functional dicarboxylic acid, a hydroxy- functional anhydride, or an amine-functional anhydride with (2) a dicarboxylic acid having at least one carbon-carbon double bond, an anhydride having at least on carbon-carbon double bond, or a mono-carboxylic acid having at least one carbon-carbon double bond. Mixtures and combinations of the foregoing may also be used.
Representative examples of hydroxy-functional dicarboxylic acids include malic acid (e.g., /-malic acid, J-malic acid, and dj-m&lic acid), 3-hydroxy-3-methylglutaric acid, citramalic acid, and hydroxy aromatic dicarboxylic acids. A representative example of a hydroxy-functional anyhydride is 3-hydroxyphthalic anhydride.
Representative examples of amine-functional dicarboxylic acids include glutamic acid and amino aromatic acids (e.g., 3-aminophthalic acid). Representative dicarboxylic acids having at least one carbon-carbon double bond- include itaconic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid. Representative anhydrides having at least one carbon-carbon double bond include itaconic anhydride, maleic anhydride and citraconic anhydride. Representative mono-carboxylic acids having at least one carbon-carbon double bond include methacrylic acid and its derivatives, crotonic acid and anhydride, unsaturated fatty acids such as oleic acid and linoleic acid.
In one embodiment of the invention, itaconic anhydride is reacted with malic acid to form the tri-functional carboxylic acid compounds of formula (A) shown below.
HOOCCHCH2COOH mά HOOCCHCH2COOH
0-CCH2-CCOOH 0-C-CCH2COOH
Il Il Il Il O CH2 O CH2 In another embodiment, itaconic anhydride is reacted with glutamic acid to form the tri-functional carboxylic acid compounds of formula (A) shown below.
HOOCCHCH2COOH and HOOCCHCH2COOH
HN-CCH2-CCOOH HN-C-CCH2COOH
Il Il Il Il
O CH2 O CH2
The di- and tri- carboxylic acid compounds of the invention may be used to prepare polyester oligomers and/or polyester polymers by reacting the compounds with: (1) dihydric alcohols, or (2) dihydric alcohols and dicarboxylic acids. Accordingly, in another embodiment, the invention provides polyester oligomers and polyester polymers made from the di- and/or tri- carboxylic acid compound of the invention. Polyester oligomers and polymers of the invention may be synthesized in several routes, as described below. Route 1: Step l: In the first synthetic route, a diol and a dicarboxylic acid (or anhydrides) are reacted in known fashion to form a polyester diol. The diol is added in excess with respect to the dicarboxylic acid or anhydride in a ratio of diol to dicarboxlic acid of 1.01 : 1 to 100:1 on a molar basis.
To enhance the reaction rate, a catalyst such as sulfuric acid, sulfonic acid,/?- toluene sulfonic acid may be used, for example, in an amount ranging from about 0.05 to 5 % weight. The reaction may be carried out at atmospheric pressure or, preferably, under reduced pressure of about 50 to about 500 mm Hg. In some embodiments, the reaction mixture is blanketed with an inert gas (e.g., carbon dioxide, nitrogen, or argon) to reduce side reactions with oxygen. The reaction is typically carried out at temperature ranging from about 6O0C to about 25O0C for a time ranging from about 15 minutes to about 24 hours.
In a specific embodiment, tetra(ethylene glycol) is reacted with succinic anhydride to form a polyester oligomer diol having the structure shown below. O O
HO-f(CH2CH2O)4-C-(CH2)4-C-θ]^(CH2CH2O)4-H
Step 2:
Separately, a hydroxy-functional or amine-functional diacid is reacted with an unsaturated anhydride and/or an unsaturated diacid or unsaturated monoacid to form an unsaturated triacid or unsaturated diacid compound of formula (A). The ratio of the unsaturated compound to the hydroxy-functional compound typically ranges from about 1.01:1 to 100:1 on a molar basis. To enhance the reaction rate, a catalyst such as tin powder, tin (II) chloride, tin (II) acetate, tin (II) oxide and lithium chloride may be used, for example, in an amount ranging from about 0.05% to 5% weight. In some embodiments, the carbon-carbon double bonds are protected by the addition of about 0.001 to about 1% weight of hydroquinone.
The reaction may be carried out at atmospheric pressure or, preferably, under reduced pressure of about 50 to about 500 mm Hg. In some embodiments, the reaction mixture is blanketed with an inert gas (e.g., carbon dioxide, nitrogen, or argon) to reduce side reactions with oxygen. The reaction is typically carried out at a temperature ranging from about 6O0C to about 17O0C for a time ranging from about 15 minutes to about 24 hours.
In one embodiment, malic acid is reacted with itaconic anhydride to form the compounds shown below.
HOOCCHCH2COOH and HOOCCHCH2COOH
0-CCH9-CCOOH 0-C-CCH2COOH
Il " Il Il Il
O CH2 O CH2
Step 3:
In the last step, the polyester oligomer diol or polyester polymer diol prepared in Step 1 and the triacid or diacid compounds of formula (A) that were prepared in Step 2 (and excess unsaturated compound) are reacted with each another. The ratio of the total mole number of carboxylic acid (i.e., -COOH) groups to the total mole number of hydroxyl (i.e., -OH) groups in the reaction mixture typically ranges from about 1.01 : 1 to 2:1. The reaction forms a polyester oligomer and/or polyester polymer having the structure shown below. The reaction may be carried out at atmospheric pressure, or more preferably, the reaction is carried out at a reduced pressure ranging from about 50 to about 500 mm Hg. In some embodiments, the reaction mixture is blanketed by an inert gas (e.g., carbon dioxide, nitrogen, or argon) to reduce side reactions with oxygen. The reaction is typically carried out at temperatures ranging from about 6O0C to about 17O0C for a time ranging from about 15 minutes to about 24 hours. Typically, the number average molecular weight (M n) of the resulting polyester oligomer and/or polyester polymer ranges from about 300 to about 30,000 grams/mole.
Figure imgf000007_0001
O CH2 O
Il Il Il
Y= -C-CH2-C CO—
O O
Z= — O-f(CH2CH2O)4-C-(CH2)2-C-θ]^-(CH2CH2O)4-H or -OH
Route 2:
In the second synthetic route, a hydroxy-functional or amine-functional diacid is reacted with an unsaturated compound, for example, an unsaturated anhydride, an unsaturated diacid, or an unsaturated monoacid to form a diacid or triacid compound of formula (A). The ratio of unsaturated compound to the hydroxy-functional or amine- functional compound typically ranges from about 1.01:1 to 100:1 on a molar basis. In some embodiments, the carbon-carbon double bond is protected by the addition of about 0.001 to 1% weight of hydroquinone. To enhance the reaction rate, a catalyst, such as tin powder, tin (II) chloride, tin (II) acetate or tin (II) oxide, may be added in an amount ranging from about 0.05% to 5% weight. For example, malic acid may be reacted with itaconic anhydride as shown above.
To the mixture described above, a diol and a diacid or anhydride are added sequentially. The ratio of the total mole number of carboxylic acid (i.e., -COOH groups) to the total mole number of hydroxyl groups (i.e., -OH groups) in the reaction mixture typically ranges from about 1.01 : 1 to 2: 1. The components are then reacted to form a polyester oligomer and/or polyester polymer of the invention. The reaction may be carried out at atmospheric pressure. More preferably, the reaction is carried out at a reduced pressure ranging from about 50 to about 500 mm Hg. In some embodiments, the reaction mixture is blanketed by an inert gas, including carbon dioxide, nitrogen, or argon to reduce side reactions with oxygen. The reaction is typically carried out at a temperature ranging from about 6O0C to about 17O0C for a time ranging from about 15 minutes to about 24 hours.
In a specific embodiment, tetra(ethylene) glycol and adipic acid are added to a compound of formula (A) sequentially to produce a polyester oligomer or polymer having a representative structure as shown below, where X, Y and Z are randomly distributed along the main chain of the oligomer or polymer.
HO-X-Y-Z-(CH2CH2O)4-H
O O
X = 4 r (CH2CH2O)4-C K -(CH2)4-C " -θjir
Figure imgf000008_0001
R = -OH; -0-X-(CH2CH2O)4-H or -0-Y-(CH2CH2O)4-H
Route 3:
In the third synthetic route, a diol and a diacid (or anhydride) are reacted to form a polyester oligomer diol. For example, tetra(ethylene glycol) may be reacted with adipic anhydride to form a polyester oligomer diol having the structure shown below:
O o r K 'I i
HO-f(CH2CH2O)4-C-(CH2)4-C-θ]^(CH2CH2O)4-H
The reaction can be carried out at atmospheric pressure. More preferably, the reaction is carried out under reduced pressure ranging from about 50 to about 500 mm Hg. In some embodiments, the reaction mixture is blanketed by an inert gas, including nitrogen or argon. The reaction is typically carried out at the temperature ranging from about 600C to about 2500C for a time ranging from about 15 minutes to about 24 hours. To enhance the reaction rate, a catalyst such as sulfuric acid, sulfonic acid, or p-toluene sulfonic acid may be added, for example, in an amount ranging from about 0.05 to 5 % weight. To the polyester oligomer diol, a hydroxy-functional or amine-functional diacid and an unsaturated anhydride or diacid or monoacid are then added. The ratio of the total mole number of carboxylic acid groups (-COOH) to the total mole number of hydroxyl groups (-OH) typically ranges from about 1.01 : 1 to about 2:1. The components are then reacted to form a polyester oligomer or polyester polymer. In some embodiments, the carbon-carbon double bond is protected by the addition of about 0.001 to 1 % weight of hydroquinone. In a specific embodiment, malic acid and itaconic anhydride are added to the polyester oligomer diol to provide a polyester oligomer and/or polyester polymer having a representative structure as shown below:
Figure imgf000009_0001
O O
X = — [(CH2CH2O)4-C-(CH2)4-C-θ4(CH2CH2O)4—
O CH2 O
Il Il Il
Y= -C-CH2-C CO-
Z = — O-X-H or —OH The polyester oligomer and/or polyester polymer typically has a number average molecular weight (M n) ranging from about 300 to about 30,000 grams/mole.
Materials used in preparing the polyester oligomers and polyester polymers of the invention are described in more detail below. Dihydric alcohol (diol):
Polyester oligomer/polymer compositions the invention include at least one diol. As used herein the term "diol" refers to a molecule having two hydroxyl groups. Diols may be represented by the formula HO-R-OH, where -R- is a divalent organic group that optionally comprises O, P, S, N, and/or halogen. Suitable diols include straight chain alkane diols, branched chain alkane diols and ether diols. Straight chain alkane diols are represented by formula (B) and ether diols are represented by formula (C). Alkane diols:
HO-(CH2)ni-OH (B) where nl is 2 to 10.
Representative examples of straight chain alkane diols include 1,3 -propanediol; 1,4-butanediol; 1,5-heptanediol; 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol. Ether diols:
HO -((CH2)n2-O)n3H
(C) where n2 is 2 to 4; and n3 is 2 to 10. Representative examples of ether diols include ethylene glycol (i.e., where n2 =2 and n3=2), propylene glycols (i.e., where n2= 3 and n3=2), and tetra(ethylene glycol) (i.e., where n2 = 2 and n3=4).
Branched chain hydrocarbon diols may also be used and include, for example, 1, 2-propane diol (i.e., HOCH2CH(CH3)OH) and 1, 3-butane diol (i.e., (HOCH2CH2CH(CH3)OH). Dicarboxylic acid or Anhydride:
Polyester oligomer and polymer compositions of the invention include a dicarboxylic acid or anhydride. The dicarboxylic acid or anhydride reacts with a diol to form ester linkages in the polyester oligomer or polymer. As used herein the term "anhydride" refers to a compound derived from an organic diacid by elimination of a molecule of water.
Suitable organic diacids may be represented by the general formula (D).
HOOC-R7-COOH (D) where — R7— is a divalent organic group including, for example, alkane (e.g., -(CH2)n4- ; where n4 is 2 to 8), alkene, a cycloaliphatic group, or an aromatic group.
Representative examples of alkane dicarboxylic acids include adipic acid, succinic acid, glutaric acid, and sebacic acid. Representative examples of unsaturated dicarboxylic acids include itaconic acid, maleic acid and fumaric acid. A representative example of a cycloaliphatic dicarboxylic acid is 1, 2-cyclohexanedicarboxylic acid. Representative examples of aromatic dicarboxylic acids include phthalic acid and terephthalic acid. Suitable anhydrides may be represented by the general formula (E).
Figure imgf000011_0001
(E) where -R - is a divalent organic group including, for example, an alkane (e.g., -(CH2)n5- ; where n5 is 2 or 3), alkene, cycloaliphatic group or aromatic group.
Representative examples of anhydrides include succinic anhydride and glutaric anhydride. Representative examples of unsaturated dicarboxylic anhydrides include itaconic anhydride and maleic anhydride. Representative examples of cycloaliphatic dicarboxylic anhydrides include 1, 2-cyclohexanedicarboxylic anhydrides. A representative example of an aromatic dicarboxylic anhydrides is phthalic anhydride. In one embodiment, the invention provides curable compositions comprising a reactive diluent, a photoinitiator and a polyester polymer or oligomer of the invention. The compositions may be suitable, for example, as coatings. Curable compositions of the invention may be polymerized by exposure to electron beam, or polymerization can be initiated by exposure to ultra-violet (UV) light when the composition comprises a photoinitiator. As used herein the term "photoinitiator" refers to a material that functions to initiate polymerization when exposed to UV radiation of a suitable wavelength. Representative examples of photoinitiators include 2,2-dimethoxy-2- phenylacetophenone, bezophenone, benzoin alkyl ether.
Reactive diluents are materials that include one or more double bonds that can be initiated by the radicals generated by the photoinitiator. Representative examples of reactive diluents include 2-(2-ethoxyethoxy)ethyl acrylate, isodedcyl acrylate, ethoxylated neopentyl glycol diacrylate, polyethyleneglycol 400 diacrylate, tetra(ethylene glycol) diacrylate, tri(propylene glycol) diacrylate trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, and ethoxylated pentaerythritol tetraacrylate.
The invention will be further illustrated below with reference to the following Examples, which are intended to aid in the understanding of the present invention, but which are not to be construed as a limitation thereof.
EXAMPLES Material List
Chemical Name Source d, /-malic acid Sigma Aldrich Cat No. 240176
SnCl2 (Tin(II) chloride) Sigma Aldrich Cat No. 208256 hydroquinone Sigma Aldrich Cat No. 240125 itaconic anhydride Sigma Aldrich Cat No. 259926 adipic acid Sigma Aldrich Cat No. A5252 tetra(ethylene glycol) Sigma Aldrich Cat No. 110175 succinic anhydride Sigma Aldrich Cat No. 239690
2,2-dimethoxy-2-phenylacetophenone Sigma Aldrich Cat No. 196118 trimethylolpropane triacrylate (TMPTA) Sigma Aldrich Cat No. 246808 EXAMPLE 1 (Route 2) Synthesis of polyester oligomer.
0.537 g of d, /-malic acid, 0.0396 g Of SnCl2 and 0.0023 g of hydroquinone were added to 2.241 g of molten itaconic anhydride. The stirred mixture was heated under nitrogen at 90° C. for 1 hrs. Then 7.77 g of tetra(ethylene glycol) and 2.920 g of adipic acid were added to the above mixture under nitrogen sequentially. Then the temperature was raised to 95° C. and the mixture was stirred for 7 hours. The resulting reaction mixture was cooled to room temperature and was discharged. The product was light yellow viscous gel. The number average molecular weight of the product was determined to be 2170 grams/mole from GPC (polystyrene as standard on a Water 2690 apparatus; columns, Styragel® HR 0.5 and Styragel® HR 2; eluent, THF; flow rate, 0.3 niL/min; column temperature, 35° C).
EXAMPLE 2 (Route 1) Synthesis of polyester oligomer. Step (1):
0.134 g of d, I -malic acid was added to 0.672 g of itaconic anhydride and 0.001 g of hydroquinone under nitrogen at 120° C. The reaction mixture was stirred for 4.5 hours and D, L-malic acid was completely reacted with itaconic anhydride (HPLC monitoring using Shimadzu LC-I OAT, column, Aminex® HPX87H; eluent 0.01 N sulfuric acid solution; flow rate 0.5 rnL/min; column temperature 60° C). Step (2):
2.918 g of tetra(ethylene glycol) and 1 g of succinic anhydride were mixed at 120° C. The reaction mixture was stirred for 4.5 hours. Step (3):
The compounds prepared in step (1) and step (2) were combined under a blanket of nitrogen. After addition, the stirred reaction mixture was heated to 95° C for 15.5 hours. Subsequently, the reaction mixture was cooled to room temperature, yielding a light yellow viscous gel. The number average molecular weight of the gel was determined to be 1650 grams/mole from GPC (polystyrene as standard on a Water 2690 apparatus; columns, Styragel® HR 0.5 and Styragel® HR 2; eluent, THF; flow rate, 0.3mL/min; column temperature, 35° C).
EXAMPLE 3
UV curing of compound of Example 1. 0.060 g of 2,2-dimethoxy-2-phenylacetophenone photoinitiator was dissolved in
0.616 g of trimethylolpropane triacrylate (TMPTA) to provide a photoinitiator solution.
1.16 g of the product of Example 1 was added to the photoinitiator solution and was stirred until the mixture was uniform. A thin film of the mixture was applied to papefboard and the resulting film was cured under a 200 W/inch ultraviolet light in a nitrogen purged environment (cured under a portable 2" UV curing system commercially available under the trade designation "CON-TROL-CURE" from UV Process Supply, Inc.). The cured film was tack-free, transparent, and rigid.
Other embodiments of the invention will be apparent to those skilled in the art upon consideration of this specification or from practice of the invention disclosed herein. Various modifications and changes to the principles and embodiments described herein may be made by one skilled in the art without departing from the true scope and spirit of the invention which is indicated by the following claims. All patents, patent documents, and publications cited herein are hereby incorporated by reference as if individually incorporated.

Claims

What Is Claimed Is:
1. A composition of matter comprising a compound of formula (A):
HOOC-Y-COOH
(A)
where
-Y- is selected from the group consisting of:
Figure imgf000015_0001
-R1- is a divalent aliphatic organic group;
-R2 is -X-C(O) -R3-C(=O)OH or -X-C(O) -R4 ; -X- is -O- or -NH- ;
-R3- is a divalent organic group having at least one carbon-carbon double bond;
-R4 is a monovalent organic group having at least one carbon-carbon double bond; -R5 is hydrogen or an alkyl group; and
-R6- is a divalent aliphatic organic group.
2. The composition of matter of claim 1, wherein -Y- is
R5 — R1— C— R6—
R2
3. The composition of matter of claim 1 , wherein -Y- is
R5 — R1— C—
R2
4. The composition of matter of claim 1 , wherein -Y- is
Figure imgf000016_0001
5. The composition of matter of claim 1, wherein -R2 is -X-C(=O) -R3-C(=O)OH, and -X- is -O-.
6. The composition of matter of claim 1 , wherein -R2 is -X-C(=O) -R3-C(=O)OH, and -X- is -NH-.
7. The composition of matter of claim 1, wherein -Rz is -X-C(=O) -R4, and
-X- is -O-
8. The composition of matter of claim 1, wherein -R2 is -X-C(=O) -R4, and -X- is -NH-.
9. The composition of matter of claim 1 , wherein the compound of formula (A) is selected from the group consisting of:
HOO
Figure imgf000016_0002
10. The composition of matter of claim 1 , wherein the compound of formula (A) is selected from the group consisting of:
HOOCCHCH2COOH and HOOCCHCH2COOH
HN-CCH2-CCOOH HN-C-CCH2COOH
Il Il Il Il O CH2 O CH2
11. A composition of matter comprising: a polyester oligomer or polyester polymer comprising the reaction product of: (a) a compound of formula (A): HOOC-Y-COOH
(A) where — Y— is selected from the group consisting of:
Figure imgf000017_0001
and where:
-R1- is a divalent aliphatic organic group;
-R2 is -X-C(=O) -R3-C(=O)OH or -X-C(=O) -R4 ;
-X- is -O- or -NH- ; -R3- is a divalent organic group having at least one carbon-carbon double bond;
— R4 is a monovalent organic group having at least one carbon-carbon double bond;
-R5 is hydrogen or an alkyl group; and -R6- is a divalent aliphatic organic group;
(b) a diol; and
(c) a diacid or anhydride.
12. The composition of matter of claim 11, wherein the diol is an alkane diol having the formula: HO-(CH2)nl-OH where nl is 2 to 10.
13. The composition of matter of claim 12, wherein the diol is selected from the group consisting of 1,3 -propanediol; 1,4-butanediol; 1,5-heptanediol; 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol.
14. The composition of matter of claim 11 , wherein the diol is an ether diol having the formula:
HO -((CH2)H2-O)nSH where n2 is 2 to 4; and n3 is 2 to 10.
15. The composition of matter of claim 14, wherein the diol is selected from the group consisting of ethylene glycol, propylene glycol, and tetra(ethylene glycol).
16. The composition of matter of claim 11, wherein the diol is 1, 2-propane diol or 1, 3-butane diol.
17. The composition of matter of claim 11 , wherein the diacid has the formula:
HOOC-R7-COOH where -R7- is a divalent organic group selected from the group consisting of alkanes, alkenes, cycloaliphatic groups, and aromatic groups.
18. The composition of matter of claim 17, where the diacid is selected from the group consisting of adipic acid, succinic acid, glutaric acid, sebacic acid, itaconic acid, maleic acid, fumaric acid, 1, 2- cyclohexanedicarboxylic acid, phthalic acid and terephthalic acid.
19. The composition of matter of claim 11, wherein the anhydride has the formula
[-C(=O)O(O=)C-i
I R8 1 where -R - is a divalent organic group selected from the group consisting of an alkanes, alkenes, a cycloaliphatic group and an aromatic group.
20. The composition of matter of claim 19, wherein the anhydride is selected from the group consisting of succinic anhydride, glutaric anhydride, itaconic anhydride, maleic anhydride, 1, 2- cyclohexanedicarboxylic anhydrides and phthalic anhydride.
21. A curable composition of matter comprising: a reactive diluent; and a composition of matter according to claim 11.
22. The composition of claim 21, wherein the composition has been cured by electron beam.
23. The curable composition of claim 21, wherein the reactive diluent is selected from the group consisting of 2-(2-ethoxyethoxy)ethyl acrylate, isodedcyl acrylate, ethoxylated neopentyl glycol diacrylate, polyethyleneglycol diacrylate, tetra(ethylene glycol) diacrylate, tri(propylene glycol) diacrylate, trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, and ethoxylated pentaerythritol tetraacrylate.
24. A curable composition of matter comprising: a reactive diluent; a photoinitiator; and a composition of matter according to claim 11.
25. The curable composition of claim 24, wherein the photoinitiator is selected from the group consisting of 2,2-dimethoxy-2-phenylacetophenone, bezophenone, and benzoin alkyl ether.
26. The curable composition of claim 24, wherein the reactive diluent is selected from the group consisting of 2-(2-ethoxyethoxy)ethyl acrylate, isodedcyl acrylate, ethoxylated neopentyl glycol diacrylate, polyethyleneglycol diacrylate, tetra(ethylene glycol) diacrylate, tri(ρropylene glycol) diacrylate, trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, and ethoxylated pentaerythritol tetraacrylate.
27. The curable composition of claim 24, wherein the composition has been cured by exposure to ultraviolet light.
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