WO2011071674A1

WO2011071674A1 - Asymmetric cyclic diester compounds

Info

Publication number: WO2011071674A1
Application number: PCT/US2010/057334
Authority: WO
Inventors: John D. Bradshaw; George F. Schaefer; Larry J. Baldwin; Ronald J. Raleigh; Brenda Hollo
Original assignee: Ferro Corporation
Priority date: 2009-12-10
Filing date: 2010-11-19
Publication date: 2011-06-16
Also published as: US20100113664A1; TW201129539A

Abstract

Compounds useful as plasticizers and the synthesis thereof are disclosed. In general, the invention includes mixed alkyl/aryl asymmetric cyclic diesters where the aryl and alkyl ester moieties are attached to a cyclic structure at vicinal carbons. The invention also includes synthetic processes of making such compounds. Blends of these asymmetric cyclic diesters with other plasticizers are demonstrated to be of use in plasticizing polymers.

Description

ASYMMETRIC CYCLIC DIESTER COMPOUNDS

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Application Serial No. 12/635,267 filed

December 10, 2010 which is a Continuation-in-Part of U.S. Application Serial No. 12/421,728 filed 10 April 2009, which claims the priority of U.S. Provisional Application Serial No.

61/060,520, filed 1 1 June 2008, all of which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of Invention

[0002] The invention relates to plasticizers useful in plasticizing thermoplastic polymers, for example, polyvinyl chloride (PVC). In particular, the invention relates to asymmetric cyclic esters, having aryl and alkyl ester moieties attached to a cyclic structure at vicinal (consecutive) carbons. In many cases, this is carbons in a 1, 2 relationship.

2. Description of Related Art

|0003] Plasticizers are compounds or mixtures of compounds that are added to polymer resins to impart softness and flexibility. Phthalic acid diesters, also called phthalates, are the primary plasticizers for most flexible polymer products, especially polymer products formed from polyvinyl chloride (PVC) and other vinyl polymers. Examples of common phthalate plasticizers include: diisononyl phthalate (DINP), butyl benzyl phthalate (BBP), and di-2-ethylhexyl- phthalate (DEHP).

SUMMARY OF THE INVENTION

[0004] The invention relates to mixed alkyl/aryl diester compounds useful in plasticizing polyvinyl chloride (PVC) and other thermoplastic polymers. In particular, the mixed alkyl/aryl diesters of the invention are asymmetric cyclic esters where the aryl and alkyl ester moieties are attached to a cyclic structure at adjacent, or vicinal, carbons. Preferably the cyclic structure is a six-membered ring, such as a cyclohexyl group.

[0005] In particular, an embodiment of the invention is a compound including an asymmetric cyclic ester having the formula (I): R¹-0-C-Y-C-0— W— Ar

(I)

wherein Y is a C₅ to C₈ cyclic alkyl group, wherein R is a straight chain or branched C₂-Ci 8 alkyl group, wherein W is a straight chain or branched C1-C5 alkyl group, wherein Ar is a C₆-C i5 cyclic aryl group having at least three double bonds, and wherein R^!0(0=)C- and ArWO(0=)C- are attached to vicinal carbons of Y.

[0006] Another embodiment of the invention is a plastic composition comprising a polymer and a plasticizer blend comprising (a) a first plasticizer comprising an asymmetric cyclic ester having o o

the formula (I), (I) R¹— O-C-Y-C-O— w— Ar^ _wnerei_n Y is a C₅ to C₈ cyclic alkyl group, wherein R¹ is a straight chain or branched C₂-Q₈ alkyl group, wherein W is a straight chain or branched C1-C5 alkyl group, wherein Ar is a C₆-Ci₅ cyclic aryl group having at least three double bonds, and wherein R^O^C- and ArWO(0=)C- are attached to vicinal carbons of Y, and (b) a second plasticizer wherein the second plasticizer is other than that described in (a).

[0007] Still another embodiment of the invention is a plastic composition comprising a polymer and of a plasticizer blend comprising (a) a plasticizer comprising an asymmetric cyclic ester o o

having the formula (I): (I) ^{R ~} O-C-Y-C-O— W— Ar _? wherein Y is a C₅ to C cyclic alkyl group, wherein R¹ is a straight chain or branched C₂-Ci₈ alkyl group, wherein W is a straight chain or branched C₁-C5 alkyl group, wherein Ar is a C₆-Ci5 cyclic aryl group having at least three double bonds, and wherein RO(0=)C- and ArWO(0=)C- are attached to vicinal carbons of Y and at least one selected from the group consisting of: a symmetric ester of a cyclohexane dicarboxylate; a dibenzoate plasticizer; a diester of succinic acid; a diester of adipic acid; a trimellitate ester; a diester of maleic acid; a citrate ester; a phosphate ester; an alkyl substituted pyrrolidinone; a polymeric plasticizer; an fatty acid triester of glycerin; and an epoxidized fatty acid triester of glycerin.

[0008] Another embodiment of the invention is a process of making an asymmetric cyclic ester comprising: (a) contacting (i) at least one cyclic dicarboxylic acid anhydride with (ii) at least one C₂ - Cjg aliphatic alcohol, in the presence of (iii) a base to form a reaction mixture and

(b) contacting the reaction mixture with a benzyl halide or phenyl-substituted alkyl halide to form a product. [0009] Another embodiment of the invention is a process of making an epoxidized asymmetric cyclic ester comprising: (a) contacting (i) a cyclic dicarboxylic anhydride including one or two unsaturated bonds with (ii) an aliphatic alcohol, in the presence of (iii) a base to form a reaction mixture, (b) contacting the reaction mixture of (a) with a benzyl halide or phenyl-substituted alkyl halide, to form a second reaction mixture, (c) isolating the resulting unsaturated diester and (d) contacting the unsaturated diester with a peracid.

[0010] Still another embodiment of the invention is a process of making a saturated asymmetric cyclic ester comprising (a) contacting (i) at least one cyclic dicarboxylic anhydride including one or two unsaturated bonds with (ii) an aliphatic alcohol, in the presence of (iii) a base to form a reaction mixture, (b) contacting the reaction mixture of (a) with a benzyl halide or phenyl- substituted alkyl halide, to form a second reaction mixture, (c) isolating the resulting unsaturated diester, and (d) contacting the unsaturated diester with a hydrogenation catalyst and hydrogen gas.

[0011] Yet another embodiment of the invention is a process of making a saturated asymmetric cyclic ester comprising: (a) contacting (i) at least one cyclic dicarboxylic anhydride with (ii) benzyl alcohol or phenyl-substituted alcohol, in the presence of a base to form a reaction mixture, and (b) contacting the reaction mixture of (a) with at least one C₂ - C]₈ alkyl halide to form said mixed diester.

[0012] Still another embodiment of the invention is a process of making an unsaturated asymmetric cyclic ester comprising: (a) contacting (i) a maleic anhydride with (ii) an aliphatic alcohol, in the presence of (iii) a base to form a reaction mixture, (b) contacting the reaction mixture of (a) with a benzyl halide or phenyl-substituted alkyl halide, to form an asymmetric maleate diester, and (c) contacting the ester of (b) with a diene to form an unsaturated

asymmetric cyclic ester.

[0013] Yet another embodiment of the invention is a process of making a saturated asymmetric cyclic ester comprising: (a) contacting (i) a cyclic dicarboxylic anhydride including one, two or three unsaturated bonds with (ii) an aliphatic alcohol, in the presence of (iii) a base to form a reaction mixture including an asymmetric monoester salt, (b) contacting with hydrogen (i) an unsaturated asymmetric monoester acid salt formed in (a) in the presence of (ii) a hydrogenation catalyst, to form a reaction mixture, and (c) contacting the reaction mixture of (b) with a benzyl halide or phenyl-substituted alkyl halide, to form an asymmetric cyclic ester. [0014] Still another embodiment of the invention is a process of making an unsaturated asymmetric cyclic ester comprising: (a) contacting (i) a maleic anhydride with (ii) a benzyl alcohol or phenyl-substituted alcohol, in the presence of (iii) a base to form a reaction mixture, (b) contacting the reaction mixture of (a) with an alkyl halide to form an asymmetric maleate diester, and (c) contacting the ester of (b) with a diene to form an unsaturated asymmetric cyclic ester.

[0015] Another embodiment of the invention is a process of making a 1 ,2- cyclic alkyl/aryl mixed diester comprising (a) contacting at least one (i) cyclic dicarboxylic anhydride with (ii) a C₂ - Ci₈ alkyl alcohol, in the presence of (iii) a trialkyl amine to form a reaction mixture and (b) contacting the reaction mixture with a benzyl halide or phenyl-substituted alkyl halide to form a product.

[0016] Still another embodiment of the invention is a process of making an epoxidized 1 ,2- cyclic alkyl/aryl mixed diester comprising: (a) contacting (i) a cyclic compound selected from the group consisting of (1) a cyclic dicarboxylic acid and (2) a cyclic dicarboxylic anhydride and combinations thereof with (i) an alkyl alcohol, in the presence of (ii) a trialkyl amine to form a reaction mixture and (iii) contacting the reaction mixture of (a) with a benzyl halide or phenyl- substituted alkyl halide, to form a second reaction mixture, (b) isolating the resulting unsaturated diester and (c) contacting the unsaturated diester with a peracid.

|0017[ Yet another embodiment of the invention is a process of making a saturated 1,2- cyclic alkyl/aryl mixed diester comprising: (a) contacting (i) at least one cyclic dicarboxylic anhydride with (ii) an alkyl alcohol, in the presence of (iii) a trialkyl amine to form a reaction mixture (b) contacting the reaction mixture of (a) with a benzyl halide or phenyl-substituted alkyl halide, to form a second reaction mixture, (c) isolating the unsaturated diester, and (d) contacting the unsaturated diester with a hydrogenation catalyst and hydrogen gas.

[0018] An embodiment of the invention is a process of making a saturated 1,2- cyclic alkyl/aryl mixed diester comprising: (a) contacting (i) at least one cyclic dicarboxylic anhydride with (ii) benzyl alcohol or phenyl-substituted alcohol, to form a benzyl half-ester, and (b) contacting the benzyl half ester with (i) a C₂ - Cis alkyl halide in the presence of (ii) a trialkyl amine to form said mixed diester.

[0019] The invention further relates to the use of plasticizers disclosed herein together with other plasticizers not falling into one of the specific embodiments detailed hereinabove. [0020] The invention further relates to processes of making plasticized thermoplastic polymers including the addition of any plasticizer herein to a thermoplastic polymer.

[0021] The foregoing and other features of the invention are hereinafter more fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principles of the invention may be employed.

DETAILED DESCRIPTION OF THE INVENTION

[0022] The compounds of the invention are used to soften thermoplastic polymer resins that would otherwise be brittle and inappropriate for many applications. Plasticizers improve flexibility and tensile strength in such resins.

[0023] The present invention relates to asymmetric cyclic ester plasticizers for thermoplastic polymer resins.

[0024] In particular, an embodiment of the invention is a compound including an asymmetric cyclic ester having the formula (I):

wherein Y is a C₅ to C₈ cyclic alkyl group, wherein R is a straight chain or branched C₂-Ci₈ alkyl group, wherein W is a straight chain or branched C₁ -C5 alkyl group, wherein Ar is a C₆-Ci₅ cyclic aryl group having at least three double bonds, and wherein RO(0=)C- and ArWO(0=)C- are attached to vicinal carbons of Y.

[0025] A general scheme for synthesizing compounds of this invention includes two critical steps. The first (Reaction 1) is ring opening of the anhydride with an alcohol to form an ester and formation of a salt with the concomitantly formed acid.

Reaction 1

The other critical step (Reaction 2) is the formation of the second ester by reacting the salt with an alkyl halide.

Reaction 2

Other intermediate steps may be involved, but the two foregoing reaction steps are common to the general scheme.

[0026] The W-Ar group of formula (I) may be derived from either an alcohol in Reaction 1 or from a phenyl-substituted alkyl halide in Reaction 2. Phenyl-substituted alkyl halides

[X-W-Ar] that are useful in preparing compounds of this invention include: benzyl halide, 1 -halo- 1 -phenyl ethane, 1 -halo-2-phenyl ethane, 4-phenyl butyl halide, and others. The corresponding alcohols are useful for introducing the aryl group in Reaction 1.

benzyl halide 1-halo-l-phenylethane l-halo-2-phenyl ethane 4-phenyl butyl halide

[0027] The central ringed group Y may be selected from a variety of 5, 6, 7, or 8 membered rings or bicyclic systems. The group Y may include one or more substituents including, for example, methyl, ethyl, propyl, bridging methylene, bridging ethylene, hydroxyl, bridging oxygen, carboxylic acid, acetyl and others. Preferably, Y is a six-membered ring, based on cyclohexane, which may be unsaturated or substituted, or both (in blends), singly or multiply. Y may also be an epoxidized cyclohexane, a five membered ring such as cyclopentadiene, cyclopentene, or cyclopentane, a seven membered ring such as cycloheptadiene, cycloheptene, or cycloheptane, or an eight membered ring including cyclooctane and the various polyunsaturated forms of cyclooctane.

[0028] In particular, the group Y is preferably selected from the group consisting of

cyclohexene, cyclohexane, and combinations thereof. The group Y may also be epoxidized cyclohexane, i.e, cyclohexene oxide.

[0029] The group Y may be selected from the group consisting of cyclopentadiene;

cyclopentene; cyclopentane; cycloheptadiene; cycloheptene; cycloheptane; 3-methyl-4- cyclohexene; 4-methyl-4-cyclohexene; 3-methylcyclohexane; 4- methylcyclohexane; 3,6-epoxy- 4-cyclohexene; 3,6-epoxycyclohexane; m-S-norbornene; norbornene; methyl-5-norbornene; bicyclo[2.2.2]oct-5-ene; bicyclo[2.2.2]octane; and combinations thereof. [0030] Alternatively, the group Y may be a residue of a carboxylic acid anhydride, in particular 4-cyclohexene-l,2-dicarboxylic acid anhydride; cyclohexane-l ,2-dicarboxylic acid anhydride; 1 , 2-dicarboxy-4-alkyl cyclohex-4-ene anhydride; l,2-dicarboxy-3-alkyl cyclohex-3-ene anhydride; ds-5-norbornene-2,3-dicarboxylic anhydride; norbornane-2,3-dicarboxylic anhydride; methyl-5- norbornene-2,3-dicarboxylic anhydride; 3,6-epoxy-cyclohexene-l,2-dicarboxylic acid anhydride; 3,6-cyclohexane-l ,2-dicarboxylic acid anhydride; bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride; bicyclo[2.2.2]octane-2,3-dicarboxylic anhydride; and combinations thereof.

[0031] The aliphatic alcohols (which donate the R¹ group of the inventive diesters) used in forming the asymmetric cyclic esters of the invention can (but need not) be halogenated. Such alcohols can be linear, branched, or have cyclic moieties. Preferably, the aliphatic alcohols contain 2 to about 18 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 5 to 9 carbon atoms. Alternatively, the alcohols may include 2 to 8 carbons. Suitable aliphatic alcohols include, for example, ethanol, bromoethanol, rc-propanol, isopropanol, 2- chloropropanol, 3-chloropropanol, 2-methylpropanol, 2-ethylpropanol, ft-butanol, isobutanol, tert-butanol, 2-methylbutanol, 3-methylbutanol, 2-ethylbutanol, 2,2-dimethylbutanol, 2,3- dimethylbutanol, 3,3-dimethylbutanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol, 2-ethylpentanol, 3 ethylpentanol, 4-ethylpentanol, cyclopentyl ethanol, cyclopentyl propanol, cyclopentyl hexanol, cyclopentyl butanol, cyclopentyl pentanol, cyclohexanol, cyclohexyl ethanol, 2-ethylhexanol, rc-nonanol, isononanol, tert-nonanol, decanol, undecanol,

propylheptanol, dodecanol, oleyl alcohol and stearyl alcohol. The various forms of nonanol and decanol are preferred, and isononanol and 2-propylheptanol are most preferred. Other aliphatic alcohols not named herein and other forms of alkyl alcohols named herein are also suitable, provided they have no more than 18 carbons.

[0032] Preferably, R¹ includes 2 to about 18 carbon atoms, more preferably 4 to 10 carbon atoms, for example C₄ to do straight chain or branched alkyl groups, and more preferably 5 to 9 carbon atoms. A blend of compounds having different embodiments of general Formula I, having any of the Y, R¹, W, and Ar groups disclosed herein is envisioned, in any combination .

[0033] The W group includes 1 to 5 carbon atoms, preferably 1 or 2 carbon atoms, and more preferably one carbon atom. The W group is provided by alkyl groups attached to the Ar group, in the reactant Ar-W-X, which participates in the esterification reactions disclosed herein. The formula Ar-W-X can stand for a benzyl halide, an alkyl substituted benzyl halide, or a phenyl substituted alkyl halide.

[0034] The aryl reactants (which donate the Ar group of the inventive diesters) used in the esterification reaction mixture have one or more aromatic rings. Various substituents, including alkyl groups, may be present on the rings. Accordingly, the group Ar may be selected from the group consisting of benzene; methylbenzene; dimethyl benzene, ditertiary butyl benzene;

napththalene, anthracene, cumene and combinations thereof.

[0035] The aryl reactants, which include the W and Ar groups of the diesters of the invention, are preferably halogenated with at least one of F, CI, Br, and I, more preferably Br or CI, and most preferably CI. Suitable halogenated aryl reactants include, for example, benzyl halide, 2- methylbenzyl halide, 3-methylbenzyl halide, 4-methylbenzyl halide, 2-ethylbenzyl halide, 3- ethylbenzyl halide, 4-ethylbenzyl halide, 4-isopropylbenzyl halide, 4-tertiary butylbenzyl halide, 4-(l-methylpropyl)benzyl halide, 2-ethoxybenzyl halide, 3, 4-dimethoxy benzyl halide, 4- methoxy-2-methylbenzyl halide, 4-acetylbenzyl halide, acetylmandelyl chloride, 2-chlorobenzyl halide, 3-chlorobenzyl halide, 4-chlorobenzyl halide, 2,3-dibromobenzyl halide, 2,4-di- iodobenzyl halide, 2,6-dibrombenzyl halide, 3,4-dibromobenzyl halide, 3,5-dichlorobenzyl halide, 2,3,5-tribromobenzyl halide, 2,4,6-trichlorobenzyl halide, 2,3,4,5,6-pentabromobenzyl halide, 1 -phenyl ethyl halide, 2-phenyl ethyl halide, 1 -phenyl butyl halide, 4-phenyl butyl halide, 1-naphthyl halide, and 2-naphthyl halide. Preferred are the chloride forms of the above halides. Most preferred is benzyl chloride.

[0036] Other embodiments of the invention relate to a plastic composition comprising a polymer and a plasticizer blend comprising (a) a first plasticizer comprising an asymmetric cyclic ester o o

having the formula 1 " "

(I), (I) ^{R -}O-C-Y-C-O— W— Ar^ _wnerein Y is a C₅ to C₈ cyclic alkyl group, wherein R¹ is a straight chain or branched C2-C₁₈ alkyl group, wherein W is a straight chain or branched C1-C5 alkyl group, wherein Ar is a C₆-C i5 cyclic aryl group having at least three double bonds, and wherein RO(0=)C- and ArWO(0=)C- are attached to vicinal carbons of Y, and (b) a second plasticizer wherein the second plasticizer is other than that described in (a). The polymer and the plasticizer blend may be present in the plastic composition in a weight ratio of 100:5 to 100:300, preferably 100: 10 to 100:200, more preferably 100:20 to 100: 150. The plasticizer blend may include one or more of the various plasticizers disclosed elsewhere herein. [0037] Asymmetric cyclic ester compounds of the invention include benzyl isononyl cyclohex-4- ene-l ,2-dicarboxylate; benzyl isononyl cyclohexane-l,2-dicarboxylate; butyl benzyl 4- cyclohexene-l,2-carboxylate; butyl benzyl cyclohexane-l,2-dicarboxylate; benzyl 2- propylheptyl 4-cyclohexene-l,2-dicarboxylate; benzyl 2-propylheptyl cyclohexane-1,2- dicarboxylate; benzyl butyl 3-methylcyclohexane-l,2-dicarboxylate; benzyl isononyl 3- methylcyclohexane-l,2-dicarboxylate; benzyl 2-propylheptyl 3-methylcyclohexane-l,2- dicarboxylate; benzyl butyl 4-methylcyclohexane-l ,2-dicarboxylate; benzyl isononyl 4- methylcyclohexane-l,2-dicarboxylate; benzyl 2-propylheptyl 4-methylcyclohexane-l ,2- dicarboxylate; benzyl butyl 3-methylcyclohex-4-ene-l ,2-dicarboxylate; benzyl isononyl 3- methylcyclohex-4-ene-l,2-dicarboxylate; benzyl 2-propylheptyl 3-methylcyclohex-4-ene-l ,2- dicarboxylate; benzyl butyl 4-methylcyclohex-4-ene-l ,2-dicarboxylate; benzyl isononyl 4- methylcyclohex-4-ene-l ,2-dicarboxylate; benzyl 2-propylheptyl 4-methylcyclohex-4-ene-l ,2- dicarboxylate; benzyl butyl norbornane-2,3-dicarboxylate; benzyl isononyl norbornane-2,3- dicarboxylate; benzyl 2-propylheptyl norbornane-2,3-dicarboxylate; benzyl butyl 5-norbornene- 2,3-dicarboxylate; benzyl isononyl 5-norbornene-2,3-dicarboxylate; benzyl 2-propylheptyl 5- norbornene-2,3-dicarboxylate; benzyl butyl methylnorbornane-2,3-dicarboxylate; benzyl isononyl methylnorbornane-2, 3 -dicarboxylate; benzyl 2-propylheptyl methylnorbornane-2,3- dicarboxylate; benzyl butyl l-methyl-5-norbornene-2, 3 -dicarboxylate; benzyl isononyl 1-methyl- 5-norbornene-2,3-dicarboxylate; benzyl 2-propylheptyl l-methyl-5-norbornene-2,3- dicarboxylate; benzyl butyl 3,6-epoxy-cyclohexane-l ,2-dicarboxylate; benzyl isononyl 3,6- epoxy-cyclohexane-l,2-dicarboxylate; benzyl 2-propylheptyl 3,6-epoxy-cyclohexane-l,2- dicarboxylate; benzyl butyl 3,6-epoxy-cyclohexene-l ,2-dicarboxylate; benzyl isononyl 3,6- epoxy-cyclohexene-l,2-dicarboxylate; benzyl 2-propylheptyl 3,6-epoxy-cyclohexene-l,2- dicarboxylate; benzyl butyl bicyclo[2.2.2]octane-2,3-dicarboxylate; benzyl isononyl

bicyclo[2.2.2]octane-2,3-dicarboxylate; benzyl 2-propylheptyl bicyclo[2.2.2]octane-2,3- dicarboxylate; benzyl butyl bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylate; benzyl isononyl bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylate; benzyl 2-propylheptyl bicyclo[2.2.2]oct-5-ene-2,3- dicarboxylate; butyl 1 -phenylethyl cyclohex-4-ene-l ,2-dicarboxylate; butyl 1 -phenylethyl cyclohexane-l,2-dicarboxylate; butyl 1 -phenylethyl 3-methylcyclohex-4-ene-l,2-dicarboxylate; butyl 1 -phenylethyl 3-methylcyclohexane-l,2-dicarboxylate; butyl 1 -phenylethyl 4- methylcyclohex-4-ene-l ,2-dicarboxylate; butyl 1 -phenylethyl 4-methylcyclohexane-l ,2- dicarboxylate; isononyl 1 -phenylethyl cyclohex-4-ene-l ,2-dicarboxylate; isononyl 1 -phenylethyl cyclohexane-l,2-dicarboxylate; isononyl 1-phenylethyl 3-methylcyclohex-4-ene-l ,2- dicarboxylate; isononyl 1-phenylethyl 3-methylcyclohexane-l,2-dicarboxylate; isononyl 1- phenylethyl 4-methylcyclohex-4-ene-l ,2-dicarboxylate; isononyl 1-phenylethyl 4- methylcyclohexane-l,2-dicarboxylate; 1-phenylethyl 2-propylheptyl cyclohex-4-ene-l,2- dicarboxylate; 1-phenylethyl 2-propylheptyl cyclohexane-l ,2-dicarboxylate; 1-phenylethyl 2- propylheptyl 3-methylcyclohex-4-ene-l,2-dicarboxylate; 1-phenylethyl 2-propylheptyl 3- methylcyclohexane- 1 ,2-dicarboxylate; benzyl butyl 4,5-epoxycyclohexane- l,2-dicarboxylate; benzyl isononyl 4,5-epoxycyclohexane-l,2-dicarboxylate; benzyl 2-propylheptyl 4,5- epoxycyclohexane-l,2-dicarboxylate; benzyl butyl 4,5-epoxy-3-methylcyclohexane-l,2- dicarboxylate; benzyl isononyl 4,5-epoxy-3-methylcyclohexane-l ,2-dicarboxylate; benzyl 2- propylheptyl 4,5-epoxy-3-methylcyclohexane-l,2-dicarboxylate; benzyl butyl 4,5-epoxy-4- methylcyclohexane-l,2-dicarboxylate; benzyl isononyl 4,5-epoxy-4-mefhylcyclohexane-l ,2- dicarboxylate; benzyl 2-propylheptyl 4,5-epoxy-4-methylcyclohexane-l ,2-dicarboxylate; benzyl butyl 5,6-epoxynorbornane-2,3-dicarboxylate; benzyl isononyl 5,6-epoxynorbornane-2,3- dicarboxylate; benzyl 2-propylheptyl 5,6-epoxynorbornane-2,3-dicarboxylate; benzyl butyl 1- methyl-5,6-epoxynorbornane-2,3-dicarboxylate; benzyl isononyl l -methyl-5,6- epoxynorbornane-2,3-dicarboxylate; benzyl 2-propylheptyl l-methyl-5,6-epoxynorbornane-2,3- dicarboxylate; benzyl butyl 3,6-4,5-diepoxycyclohexane-l ,2-dicarboxylate; benzyl isononyl 3,6- 4,5-diepoxy-cyclohexane-l ,2-dicarboxylate; benzyl 2-propylheptyl 3,6-4,5-diepoxy- cyclohexane-l,2-dicarboxylate; benzyl butyl 5,6-epoxybicyclo[2.2.2]octane-2,3-dicarboxylate; benzyl isononyl 5,6-epoxybicyclo[2.2.2]octane-2,3-dicarboxylate; benzyl 2-propylheptyl 5,6- epoxybicyclo[2.2.2]octane-2,3-dicarboxylate; butyl 1-phenylethyl 4,5-epoxycyclohexane-l,2- dicarboxylate; butyl 1-phenylethyl 4,5-epoxy-3-methylcyclohexane-l,2-dicarboxylate; isononyl 1-phenylethyl 4,5-epoxycyclohexane-l,2-dicarboxylate; isononyl 1-phenylethyl 4,5-epoxy-3- methylcyclohexane-l,2-dicarboxylate; 1-phenylethyl 2-propylheptyl 4,5-epoxycyclohexane-l,2- dicarboxylate; 1-phenylethyl 2-propylheptyl 3-methylcyclohex-4-ene-l ,2-dicarboxylate; and combinations thereof.

[0038] Catalyst. A catalyst is advantageously employed in the esterification reaction(s) of the invention. The catalyst is typically a base, preferably an organic base. Suitable organic bases include pyridines, tertiary amines, room temperature ionic liquids, and combinations thereof. Tertiary amines are preferred. Tertiary amines for use in the process of the invention can be represented by the structure R²R³R⁴N where R² - R⁴ may be the same or different alkyl radicals. Examples of suitable trialkyl amines include trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, as well as the normal-, iso-, and tert- configurations of the foregoing, if appropriate. Various combinations of R² - R⁴ where R² - R⁴ can be individually selected from methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, decyl are also possible. Other amines suitable herein include triisoamylamine, methyldiethylamine, dimethylethylamine, dimethylcyclohexylamine, dimethylhexylamine, diethylhexylamine, dimethyldecylamine and others. The preferred amine is triethylamine.

[0039] Pyridines are six-membered heterocycles having 5 carbon atoms and one nitrogen atom in the ring. Pyridine itself has the formula C5H5N, and can be formed by the following reaction:

By substituting other aldehydes for acetaldehyde. one obtains alkyl and aryl substituted pyridines.

[0040] An ionic liquid is a liquid that contains essentially only ions. Some ionic liquids, such as ethylammonium nitrate are in a dynamic equilibrium where at any time more than 99.99% of the liquid is made up of ionic rather than molecular species. Broadly the term includes molten salts, for instance, sodium chloride at temperatures higher than 800°C. Salts that are liquid at room temperature are called room-temperature ionic liquids, or RTILs.

[0041 ] Another embodiment of the invention is a process of making an asymmetric cyclic ester comprising: (a) contacting (i) at least one cyclic dicarboxylic acid anhydride with (ii) at least one C₂ - Cis aliphatic alcohol, in the presence of (iii) a base to form a reaction mixture and (b) contacting the reaction mixture with a benzyl halide or phenyl-substituted alkyl halide to form a product. An illustrative example of this process is depicted in Reaction 3, where cyclohexane- 1 ,2-dicarboxylic anhydride, triethylamine and benzyl chloride are used specifically.

Reaction 3

[0042] The process may further comprise, after (a)(iii), step (a)(iv), wherein step (a)(iv) includes maintaining the reaction mixture temperature at about 60 to about 130 °C. The process may further comprise, after (b), step (b)(i), wherein (b)(i) includes maintaining the reaction mixture temperature at about 100 to about 180°C. The process may further comprise, after (b), step (c), wherein step (c) comprises washing the product of (b) with water at a pH of less than 6, followed by (d), washing the product of (c) with water at a pH of greater than 8, followed by (e), wherein step (e) comprises washing the product of (d) with water. The process may further comprise, after (e), step (f), wherein step (f) comprises steam stripping the product at a pressure of less than 500 torr, preferably less than 400 torr. The process may yet further include, after (f), step (g), wherein step (g) comprises stripping the product of moisture at a pressure of less than 200 torr, preferably less than 100 torr.

[0043] In a preferred embodiment of the process, the at least one cyclic carboxylic acid anhydride is selected from the group consisting of 4-cyclohexene-l,2-dicarboxylic acid anhydride; cyclohexane-l,2-dicarboxylic acid anhydride; methylcyclohexane-l ,2-dicarboxylic acid anhydride; l ,2-dicarboxy-3-alkylcyclohex-3-ene anhydride; cw-5-norbornene-2,3- dicarboxylic anhydride; norbornane-2,3-dicarboxylic anhydride; methyl-5-norbornene-2,3- dicarboxylic anhydride; 3,6-epoxy-cyclohexene-l ,2-dicarboxylic acid anhydride; 3,6- epoxycyclohexane-l,2-dicarboxylic acid anhydride; bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride; bicyclo[2.2.2]octane-2,3-dicarboxylic anhydride; and combinations thereof.

[0044] In another preferred embodiment of the process, the at least one cyclic carboxylic acid anhydride is selected from the group consisting of 4-cyclohexene-l ,2-dicarboxylic acid anhydride and cyclohexane-l,2-dicarboxylic acid anhydride and combinations thereof, and the aliphatic alcohol is selected from the group consisting of isononyl alcohol and 2-propylheptyl alcohol, and combinations thereof. The process may utilize any base disclosed elsewhere herein, in any combination.

[0045] Another embodiment of the invention is a process of making an epoxidized asymmetric cyclic ester comprising: (a) contacting (i) a cyclic dicarboxylic anhydride including one or two unsaturated bonds with (ii) an aliphatic alcohol, in the presence of (iii) a base to form a reaction mixture, (b) contacting the reaction mixture of (a) with a benzyl halide or phenyl-substituted alkyl halide, to form a second reaction mixture, (c) isolating the resulting unsaturated diester and (d) contacting the unsaturated diester with a peracid. An illustrative example of this process is depicted in Reaction 4, where 4-cyclohexene-l ,2-dicarboxylic anhydride, triethylamine and benz l chloride are used specifically.

Reaction 4

[00461 Peracids. Peracids, or peroxyacids, are excellent epoxidizing agents. For the organic peracids, there is an extra oxygen atom between the carbonyl group and their acidic hydrogen, making them electrophilic towards oxygen. Inorganic peracids include perchloric acid, HC10₄ or perbromic acid, HBr0₄. Attack at the oxygen position by a nucleophile displaces carboxylate, which is a good leaving group. An example of one such reaction involves ethylene and peroxyformic acid, or more appropriately for the invention, the reaction between benzyl isononyl cyclohex-4-ene and a peracid such as m-chloroperbenzoic acid. Other suitable peracids herein include peracetic acid (CH₃C(=0)OOH), and perbenzoic acid (C6H₅C(=0)OOH). The peracid can be formed in situ from the addition of hydrogen peroxide to an acid, e.g. formic acid and hydrogen peroxide will form performic acid (HC(=0)OOH) within a reaction mixture. The reaction mechanism is essentially an electrophilic attack, with a proton being transferred from the epoxide oxygen to the carboxylic acid by-product. First, the nucleophilic π (pi-) bond donates its electrons to the oxygen, breaking the 0-0 bond to form the new carbonyl bond. The electrons from the old O-H bond make up the second new C-0 bond, and the original carbonyl group uses its electrons to pick up the proton.

[0047] Still another embodiment of the invention is a process of making a saturated asymmetric cyclic ester comprising (a) contacting (i) at least one cyclic dicarboxylic anhydride including one or two unsaturated bonds with (ii) an aliphatic alcohol, in the presence of (iii) a base to form a reaction mixture, (b) contacting the reaction mixture of (a) with a benzyl halide or phenyl- substituted alkyl halide, to form a second reaction mixture, (c) isolating the resulting unsaturated diester, and (d) contacting the unsaturated diester with a hydrogenation catalyst and hydrogen gas. An illustrative example of this process is depicted in Reaction 5, where 4-cyclohexene-l ,2- dicarbox lic anhydride, triethylamine and benzyl chloride are used specifically.

Reaction 5

[0048] Yet another embodiment of the invention is a process of making a saturated asymmetric cyclic ester comprising: (a) contacting (i) at least one cyclic dicarboxylic anhydride with (ii) benzyl alcohol or phenyl-substituted alcohol, in the presence of a base to form a reaction mixture, and (b) contacting the reaction mixture of (a) with at least one C₂ - Ci₈ alkyl halide to form said mixed diester. An illustrative example of this process is depicted in Reaction 6, where cyclohexane-l,2-dicarboxylic anhydride, triethylamine and benzyl alcohol are used specifically.

Reaction 6

[0049] Still another embodiment of the invention is a process of making an asymmetric cyclic ester comprising: (a) contacting (i) a maleic anhydride with (ii) an aliphatic alcohol, in the presence of (iii) a base to form a reaction mixture, (b) contacting the reaction mixture of (a) with a benzyl halide or phenyl-substituted alkyl halide, to form an asymmetric maleate diester, and (c) contacting the ester of (b) with a diene to form an asymmetric cyclic ester. In a preferred embodiment, the diene is selected from the group consisting of butadiene; 3-sulfolene; isoprene; 1,3-pentadiene; cyclopentadiene; furan; 1-methoxybutadiene; 1 ,3-hexadiene; 3-methyl-l ,3- pentadiene; 4-methyl-l ,3-pentadiene; 1,3-cyclohexadiene; sorbic acid esters; ethyl sorbate; 1,2,3,4,5-pentamethylcyclopentadiene; myrcene (7-methyl-3-methylene-l ,6-octadiene); and combinations thereof. An illustrative example of this process is depicted in Reaction 7, where maleic anhydride, triethylamine, benzyl chloride, and 1 ,3-butadiene are used specifically.

Reaction 7

[0050] This process may further comprise contacting the unsaturated asymmetric cyclic ester product with a hydrogenation catalyst and hydrogen gas. This process may yet further include contacting the unsaturated asymmetric cyclic ester product with a peracid.

[0051] An embodiment of the invention is a process of making a saturated asymmetric cyclic ester comprising: (a) contacting (i) a cyclic dicarboxylic anhydride including at least one unsaturated bond with (ii) an aliphatic alcohol, in the presence of (iii) a base to form a reaction mixture including an asymmetric monoester salt, (b) contacting with hydrogen (i) an unsaturated asymmetric monoester acid salt formed in (a) in the presence of (ii) a hydrogenation catalyst, to form a reaction mixture, and (c) contacting the reaction mixture of (b) with a benzyl halide or phenyl -substituted alkyl halide, to form an asymmetric cyclic ester. In a preferred embodiment of this process, the cyclic dicarboxylic anhydride is phthalic anhydride. Illustrative examples of this process are depicted in Reaction 8 and Reaction 9.

Reaction 9

[0052] Another embodiment of the invention is a process of making an asymmetric cyclic ester comprising: (a) contacting (i) a maleic anhydride with (ii) a benzyl alcohol or a phenyl- substituted alcohol, in the presence of (iii) a base to form a reaction mixture, (b) contacting the reaction mixture of (a) with an alkyl halide to form an asymmetric maleate diester, and (c) contacting the ester of (b) with a diene to form an asymmetric cyclic ester. In a preferred embodiment of the process, the diene may be selected from the group consisting of butadiene; 3- sulfolene; isoprene; 1,3-pentadiene; cyclopentadiene; furan; 1 -methoxybutadiene; 1,3-hexadiene; 3-methyl-l,3-pentadiene; 4-methyl- 1,3-pentadiene; 1 ,3-cyclohexadiene; sorbic acid esters; ethyl sorbate; myrcene (7-methyl-3 -methyl ene-l,6-octadiene); 1 ,2,3,4,5-pentamethylcyclopentadiene; and combinations thereof. An illustrative example of this process is depicted in Reaction 10.

Reaction 10

[0053] Another embodiment of the invention is a process of making a 1 ,2- cyclic alkyl/aryl mixed diester comprising (a) contacting (i) at least one cyclic dicarboxylic acid anhydride with (ii) a C₂ - Ci8 alkyl alcohol, in the presence of (iii) a trialkyl amine to form a reaction mixture and (b) contacting the reaction mixture of (a) with a benzyl halide or phenyl-substituted alkyl halide, to form a product. The reaction mixture may optionally be heated after the trialkyl amine is fully added to the cyclic dicarboxylic acid or anhydride and the alcohol. After full reaction, the process may further comprise washing the product with water at a pH of less than 6, followed by washing the product of with water at a pH of greater than 8. The product may also be washed with plain water such as tap water, distilled water or deionized water. After washing, the product may be steam stripped at a pressure of less than 500 torr, and also the moisture may be removed by stripping at a pressure of less than 200 torr.

[0054] In a preferred embodiment of the process, the cyclic compound is 1, 2-dicarboxy cyclohex-4-ene anhydride and the aliphatic alcohol is isononyl alcohol.

[0055] Still another embodiment of the invention is a process of making an epoxidized asymmetric cyclic ester comprising: (a) contacting (i) a cyclic dicarboxylic anhydride including one or two unsaturated bonds with (ii) an aliphatic alcohol, in the presence of (iii) a base to form a reaction mixture, (b) contacting the reaction mixture of (a) with a benzyl halide or phenyl- substituted alkyl halide, to form a second reaction mixture, (c) isolating the resulting unsaturated diester and (d) contacting the unsaturated diester with a peracid. 2010/057334

[0056] A further embodiment of the invention is a process of making a saturated 1 ,2- cyclic alkyl/aryl mixed diester comprising: (a) contacting (i) at least one cyclic dicarboxylic anhydride with (ii) an alkyl alcohol, in the presence of (iii) a trialkyl amine to form a reaction mixture, (b) contacting the reaction mixture of (a) with a benzyl halide or phenyl-substituted alkyl halide, to form a second reaction mixture, (c) isolating the resulting saturated diester, and (d) contacting the saturated diester with a hydrogenation catalyst and hydrogen gas.

[0057] Yet another embodiment of the invention is a process of making a saturated 1 ,2- cyclic alkyl/aryl mixed diester comprising: (a) contacting (i) at least one cyclic dicarboxylic anhydride with (ii) benzyl alcohol or phenyl-substituted alcohol, to form a benzyl half-ester, and (b) contacting the benzyl half ester with (i) a trialkyl amine and then (ii) a C₂ - C₁₈ alkyl halide to form said mixed diester.

[0058] The asymmetric cyclic esters of this invention are predominantly of the m-configuration. Isomerization of the predominant ds-form to a predominant trans-form can be effected using methods such as disclosed in U.S. Patent 5,231,218.

[0059] Another embodiment of the invention is a process of plasticizing a polymer comprising contacting any compound disclosed herein with a polymer. The polymers that may be plasticized include PVC, PVB, CPVC homopolymers or copolymers including monomer units selected from the group consisting of ethylene, propylene, butadiene, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, acrylates, acrylates bonded to the oxygen atom of the ester group, alkyl radicals of branched or unbranched alcohols having 1 to 10 carbon atoms, styrene or acrylonitrile, homopolymers or copolymers of cyclic olefins and combinations of the foregoing.

[0060] The polymer may be selected from the group consisting of: a C₄-Cio polyacrylate having identical or different alkyl radicals bonded to the atom of the ester group, polymethacrylate, polymethyl methacrylate, methyl acrylate-butyl acrylate copolymer, methyl methacrylate-butyl methacrylate copolymer, ethylene-vinyl acetate copolymer, chlorinated polyethylene, nitrile rubber, acrylonitrile-butadiene styrene copolymer, ethylene-propylene copolymer, ethylene- propylene-diene copolymer, acrylonitrile-butadiene rubber, styrene-butadiene elastomer, methyl methacrylate-styrene-butadiene copolymer, nitrocellulose, and combinations of the foregoing.

[0061] The asymmetric cyclic esters of this invention can be combined with other plasticizers to formulate a plasticizer package to be used in making plasticized thermoplastic polymers. 4

Examples of plasticizers that might be used in conjunction with a plasticizer of the invention include, without limitation, the following:

[0062] (a) Phosphate plasticizers such as triaryl phosphates, mixed alkyl aryl phosphates, trialkyl phosphates, or specifically, triphenyl phosphate, tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, trichlorethyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, tri-2- ethylhexyl phosphate and triphenyl phosphate.

[0063] (b) Phthalate ester plasticizers such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethyl hexyl phthalate, diisooctyl phthalate, di-ft-octyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, benzyl isononyl phthalate, butyl lauryl phthalate, methyl octyl phthalate, and octyl decyl phthalate.

[0064] (c) Aromatic carboxylic acid ester plasticizers such as trioctyl trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, dioctyl terephthalate, and octyl oxybenzoate.

[0065] (d) Aliphatic dibasic acid ester plasticizers such as dibutyl adipate, di-n-hexyl adipate, di- 2-ethylhexyl adipate, di-/?-octyl adipate, n-octyl-n-decyl adipate, diisononyl adipate, diisodecyl adipate, dicapryl adipate, di-2-ethylhexyl azelate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate, di-«-octyl sebacate, di-2-ethylhexyl sebacate, di-2-ethoxyethyl sebacate, dioctyl succinate, diisodecyl succinate, dioctyl tetrahydrophthalate, di-ft-octyl tetrahydrophthalate, di-2- ethylhexyl cyclohexane- 1 ,2-dicarboxylate, and diisononyl cyclohexane-l,2-dicarboxylate.

[0066] (e) Fatty acid ester derivatives such as butyl oleate, acetyl methyl ricinoleate,

pentaerythritol ester, dipentaerythritol hexaester, triacetin and tributylene.

[0067] (f) Oxyacid ester plasticizers such as acetyl methyl ricinoleate, acetyl butyl ricinoleate, butyl phthalyl butyl glycolate and acetyl tributyl citrate.

[0068] (g) Epoxy plasticizers such as epoxidized soybean oil, epoxidized flaxseed oil, epoxy butyl stearate, epoxy decyl stearate, epoxy octyl stearate, epoxy benzyl stearate, epoxy dioctyl hexahydrophthalate and epoxy didecyl hexahydrophthalate.

[0069] (h) Dihydric alcohol ester plasticizers such as ethylene glycol dibenzoate; diethylene glycol dibenzoate; dipropylene glycol dibenzoate; triethylene glycol di-2-ethyl butyrate; butane diol dibenzoate; hexane diol dibenzoate; isosorbide dioctoate; 2,2-dimethyl-l,3-propane diol dibenzoate; mixed esters derived from 2,2-dimethyl-l ,3-propane diol, benzoic acid and 2- ethylhexanoic acid; and hydroxypivalyl hydroxypivalate ester plasticizers. [0070] (i) Chlorine-containing plasticizers such as chlorinated paraffin, chlorinated diphenyl, chlorinated methyl fatty acids and methoxy chlorinated methyl fatty acids.

[0071] (j) Polyester plasticizers such as polypropylene adipate, polypropylene sebacate, polyester and acetylated polyester.

[0072] (k) Sulfonic acid derivatives such as / oluenesulfonamide, o-toluenesulfonamide, p- toluene sulfone ethylamide, o-toluene sulfone ethyl amide, toluene sulfone-N-ethylamide and p- toluene sulfone-N-cyclohexylamide.

[0073] (1) Citric acid derivatives such as triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, acetyl tri-2-ethylhexyl citrate and acetyl stearyl citrate.

[0074] (m) Other plasticizers not falling into one of the above categories, such as alkyl pyrrolidones surfactants, alkyl imidazoles, N-alkyl hexahydrophthalimide, dibutyl fumarate, dioctyl fumarate, linear alkyl benzenes, and mineral oil.

[0075] The disclosure of the various plasticizers in paragraphs (a) through (m) immediately preceding this paragraph is intended to provide support for any combination of such plasticizers or each individual plasticizer whether in the same paragraph or in different paragraphs.

[0076] A preferred embodiment of the invention is the plasticizer with Structure I where the alkyl group R¹ is an C₉ alkyl group, the Y group is cyclohexyl, and the W is C¾.

[0077] Properties of the plasticizer of Structure I can be used to extend the properties of other plasticizers by making a blend of the plasticizer of Structure I with a second plasticizer such as symmetric esters of cyclohexane dicarboxylates ,e.g. Hexamoll ® DINCH (commercially available from BASF Corporation of Florham Park, New Jersey); with dibenzoate plasticizers such as the dibenzoic acid esters of diethylene and dipropylene glycols such as Benzoflex® 988; (Genovique Specialties Holdings Corporation, Rosemont, Illinois); with aromatic sulfonates such as Mesamoll®; with polyol esters such as Soft-n-Safe; with succinates; with non-phthalate plasticizers; with trimellitites; with citrates; with adipates; with phosphate esters; with alkyl substituted pyrrolidinones; with polymeric plasticizers; and with epoxidized fatty acid esters of glycerin such as epoxidized soybean oil.

[0078] The following experimental examples serve to illustrate, and not limit, the scope of the invention.

[0079] Example 1. A one-liter four-necked round bottom flask was charged with 152 g of 4- cyclohexene-l,2-dicarboxylic acid anhydride and 152 g of isononyl alcohol. A 250 ml addition funnel was charged with 107 g of triethylamine, and a 125 ml addition funnel was charged with 134 g of benzyl chloride. The reaction was blanketed with nitrogen. The reaction was agitated at 250 RPM, and one third of the triethylamine was added to the reaction. The reaction was heated to 125°C and was stirred at 125°C for 5 minutes. The reaction was then cooled to 100°C, and the rest of the triethylamine was added to the reaction. The reaction was stirred at 100- 105°C for 5 minutes.

[0080] The agitation was increased to 300 RPM and the reaction was heated to 120°C. The addition of the benzyl chloride was started dropwise. The reaction temperature rose upon the addition of the benzyl chloride. The temperature was then controlled at 145°C. The addition of the benzyl chloride was completed over 30 minutes. The reaction was then stirred for an additional 90 minutes after the addition of the benzyl chloride was completed.

[0081] The product was washed first with 100 g of water at a pH of 2 and then with 100 g of water at a pH of 12. The product was then washed with 100 g of water. The material was steam stripped at 125°C at 80 mm Hg pressure. The product was then stripped of water at 125°C at 50 mm Hg to give 328.1 g (85%) of benzyl isononyl 4-cyclohexene-l ,2-dicarboxylate .

[0082] Example 2. Using the procedure of Example 1 , 145 g of 1 ,2-cyclohexanedicarboxylic anhydride were reacted with 144 g of isononyl alcohol and 128 g of benzyl chloride to give 338 g (96.5%) of benzyl isononyl cyclohexane-l,2-dicarboxylate.

[0083] Example 3. Using the procedure of in Example 1, 153 g of 4-cyclohexene-l ,2- dicarboxylic acid anhydride were reacted with 78 g of butanol and 134 g of benzyl chloride to yield 283 g (95.1%) of benzyl butyl 4-cyclohexene-l ,2-carboxylate.

[0084] Example 4. Using the procedure of Example 1, 103 g of 1 ,2-cyclohexanedicarboxylic anhydride were reacted with 52 g of butanol and 90 g of benzyl chloride to yield 191 g (90.1%) of benzyl butyl cyclohexane-l,2-dicarboxylate.

[0085] Example 5. Using the procedure of Example 1, 152 g of 4-cyclohexene-l,2-dicarboxylic acid anhydride were reacted with 158 g of 2-propylheptyl alcohol and 136 g of benzyl chloride to yield 356 g (88.9%) of benzyl 2-propylheptyl 4-cyclohexene-l ,2-dicarboxylate.

[0086] Example 6. Using the procedure of Example 1, 153g of 1 ,2-cyclohexanedicarboxylic anhydride were reacted with 166 g of 2-propylheptyl alcohol and 134 g of benzyl chloride to yield 382 g (89.9%) of benzyl 2-propylheptyl cylcohexane-l ,2-dicarboxylate. [0087] Example 7. A solution of 47.5 g of m-chloroperbenzoic acid in 51 1 g of chloroform was placed in a 1 L round bottom flask. The solution temperature was kept between 25-35°C by means of a water bath while 99.88 g of the product of Example 1 was added dropwise to the chloroform solution over the course of 2 hours. The reaction was stirred at 25°C overnight, i.e., -12 hours. The next day the reaction solution was filtered and was extracted with 100 g of 10% sodium bicarbonate solution. The chloroform was then removed under vacuum to give 100.55g of the epoxidized product, benzyl isononyl 4,5-epoxycyclohexane-l ,2-dicarboxylate.

[0088] Example 8. A Parr stirred pressure reactor was charged with 97.44 g of the product of Example 5 and 0.98 g of 5% Pt on carbon. The reactor was sealed and purged with nitrogen. The reactor was then heated to 42°C and was pressurized to 100 psig with hydrogen. The reactor was stirred for 4.5 hours while maintaining the temperature at 42°C and hydrogen pressure at 100 psig. The reactor was cooled to room temperature and the excess pressure was released. The reaction product was filtered through Celite to give 73.9 g (75%) of product. GC analysis of the product indicated that 89.8% of the product benzyl 2-propylheptyl cyclohexane-1,2- dicarboxylate.

[0089] Example 9. A 1 L four-necked round bottom flask was charged with 152.76 g of 4- cyclohexene- 1 ,2-dicarboxylic anhydride and 153.77 g of isononyl alcohol. A 250 ml addition funnel was charged with 106.77 g of triethylamine. The reaction was blanketed with nitrogen. The reaction was agitated at 250 RPM and one-third of the triethylamine was added to the reaction. The reaction temperature quickly rose to 125°C. The reaction was stirred at 125±2°C for 5 minutes. The reaction was then cooled to 100°C, and the rest of the triethylamine was added to the reaction. The reaction was stirred at 100-105°C for 5 minutes before it was cooled to room temperature to give 407.34 g (98.6%) of monoisononyl ester of 4-cyclohexene-l ,2- dicarboxylic acid triethylamine salt.

[0090] Example 10. A Parr stirred pressure reactor was charged with 98.92 g of the product of Example 9 and 1.00 g of 5% Pt on carbon. The reactor was sealed and purged with nitrogen. The reactor was then heated to 38°C and was pressurized to 100 psig with hydrogen. The reactor was stirred for 4.5 hours while maintaining the temperature at 42°C and hydrogen pressure at 100 psig. The reactor was cooled to room temperature and the excess pressure was released. The reaction product was filtered through Celite to give 96.55 g (96.9%) of product. GC analysis of the product indicated that 91.3% of the product was the monoisononyl ester of cyclohexane-l,2-dicarboxylic acid triethylamine salt.

[0091] Example 1 1. A I L reactor was charged with 270.50 g of material prepared as described in Example 10. The agitation was set at 300 RPM and the reaction was heated to 120°C. The addition of the benzyl chloride was started drop wise. The reaction temperature rose upon the addition of the benzyl chloride, and the temperature was then controlled at 145°C. The addition of the benzyl chloride was completed over 30 minutes. After the addition was complete, the reaction was stirred for an additional 90 minutes. The reaction was cooled to 100°C, and the product was washed first with 100 g of water at a pH of 2 and then with 100 g of water at a pH of 12. The product was then washed with 100 g of water. The material was steam stripped at 125°C at 80 mm Hg pressure. The product was then stripped of water at 125° at 50 mm Hg to give 126.72 g (50.5%) of benzyl isononyl cyclohexane-l,2-dicarboxylate.

[0092] Example 12. A I L four-necked round bottom flask was charged with 166.3 g of 4- methyl-4,5-cyclohexene-l ,2-dicarboxylic anhydride and 152.18 g of isononyl alcohol. A 250 ml addition funnel was charged with 107 g of triethylamine, and a 125 ml addition funnel was charged with 134 g of benzyl chloride. The reaction was blanketed with nitrogen. The reaction was agitated at 250 RPM, and one third of the triethylamine was added to the reaction. The reaction was heated to 125°C and was stirred at 125°C for 5 minutes. The reaction was then cooled to 100°C, and the rest of the triethylamine was added to the reaction. The reaction was stirred at 100-105°C for 5 minutes. The agitation was increased to 300 RPM and the reaction was heated to 120°C. The addition of the benzyl chloride was started drop wise. The reaction temperature rose upon the addition of the benzyl chloride. The temperature was then controlled at 145°C. The addition of the benzyl chloride was completed over 30 minutes. The reaction was then stirred for an additional 90 minutes after the addition of the benzyl chloride was completed. The product was washed first with 100 g of water at a pH of 2 and then with 100 g of water at a pH of 12. The product was then washed with 100 g of water. The material was steam stripped at 125°C at 80 mm Hg pressure. The product was then stripped of water at 125°C at 50 mm Hg to give 328.1 g (85%) of benzyl isononyl 4-methyl-4,5-cyclohexene-l ,2-dicarboxylate.

[0093] Example 13. A 500 ml four-necked round bottom flask, fitted with a mechanical agitator, was charged with 104.24 g of 1 ,2-cyclohexanedicarboxylic anhydride and 88.95 g of 2- ethylhexanol. To this assembly were added a thermocouple and Friedrichs condenser with nitrogen inlet. A 250 ml addition funnel charged with 69.77 g of triethylamine, and another 250 ml addition funnel charged with 96.05 g of 1 -chloro-l -phenylethane (93.6% purity by GC) were connected via a Claisen adapter to the assembly. The reaction was blanketed with nitrogen. The reaction was stirred and one-third of the triethylamine was added to the reaction. The reaction temperature quickly rose to 120°C. The reaction was then cooled to 99°C over 10 minutes. Then the remainder of the triethylamine was added to the reaction. The reaction was stirred at 90°C for 10 minutes. Addition of 1-chloro-l-phenylethane took 8 minutes after which the reaction temperature was 89°C. With heating the reaction temperature rose to 142°C over 38 minutes whereupon salts were visible in the reaction mixture. Reaction was maintained at 142°C for 2 hours before it was cooled to 1 10°C. Water (100 ml) was added and the mixture acidified to a pH of <4.5. The organic layer was washed with 200 ml water. The organic was then treated with 150 ml water and 50% NaOH (11.6 g) to give a mixture with a pH of >9. The organic layer was again washed with 200 ml water. The organic portion was steam stripped at 123-4°C at 50 mm Hg pressure. Water was distilled from the product at up to 132°C at 50 mm Hg to give 183.1 g (70%) of 2-ethylhexyl 1-phenylethyl cyclohexane-1 ,2-dicarboxylate that was of 93.3% purity by GC.

[0094] Comparative Testing: Benzyl isononyl 4-cyclohexene- 1 ,2-dicarboxylate (Compound A) and benzyl isononyl cyclohexane-l ,2-dicarboxylate (Compound B) are useful in some of the same applications as butyl benzyl phthalate (BBP). The inventive compounds were compared to three known plasticizer products: BBP, a fast fusing phthalate, commercially available from Ferro Corporation, Cleveland, Ohio, as Santicizer^® 160; di-isononyl phthalate (DINP), a widely used phthalate; and diisononyl cyclohexane-1 , 2-dicarboxylate (DINCH).

[0095] The parameters presented in Table 1 are as follows: Volatility - Activated Carbon Method - 1 DAY (Ref: ASTM 1203); Volatility - Activated Carbon Method - 6 DAY (Ref: ASTM 1203) Kerosene Extraction (Ref: ASTM D1239, D543); Brabender Fusion times:

ASTM D2538 - 02 Standard Practice for Fusion of Poly(Vinyl Chloride) (PVC) Compounds Using a Torque Rheometer. Cold Flex Temp: (Ref: ASTM D 1043 - 02 Standard Test Method for Stiffness Properties of Plastics as a Function of Temperature by Means of a Torsion Test (Clash-Berg Cold Flex Temperature Method); Shore A Hardness (Ref: ASTM D2240 - 05 Standard Test Method for Rubber Property-Durometer Hardness (Shore A Hardness) and ASTM D618 - 05 Standard Practice for Conditioning Plastics for Testing ). Water sensitivity testing, ASTM D1239 - 07: Standard Test Method for Resistance of Plastic Films to Extraction by Chemicals, is a rapid test to determine plasticizer loss from plastic film when immersed in liquids commonly used in households.

[0096] The inventive examples are COMPOUND A, in Inventive Example (Exl) and

COMPOUND B, in Inventive Example 2 (Ex2), while the comparative (prior art) examples are CE1. CE2, and CE3.

[0097] The inventive products COMPOUND A and COMPOUND B outperformed DINCH in all tests except cold flex temperature. The products performed between BBP and DINP in all the tests; outperforming DINP with faster fusion time, softer Shore A, and far lower kerosene extraction, and outperforming BBP in cold flex and having lower volatility.

Table 1. Comparative Property Testing Data Summary.

[0098] Example 14. A one-liter three-necked flask equipped with a condenser, thermometer, and addition funnel was charged with 271 g of isodecyl alcohol and 191 g of triethylamine. The reaction was blanketed with nitrogen and was stirred using a magnetic stirring bar. The flask was immersed in an ice-water bath to control the reaction temperature. The addition funnel was charged with 265 g of benzoyl chloride. The benzoyl chloride was added to the reaction over 1.5 hours. The ice-water bath was removed, and the reaction was heated to 50°C for 30 minutes to ensure that the reaction was complete, and the stirring rate was increased to ensure adequate mixing.

[0099] The reaction was then washed with 150 g of deionized water, and the pH was adjusted to 2 (by addition of concentrated hydrochloric acid) to remove excess triethylamine. The organic layer was isolated using a 1 L separatory funnel. In the same manner, the organic layer was then washed with (a) 150 g of deionized water, (b) 150 g of deionized water with the pH adjusted to 9 (with 50% NaOH solution) to remove excess benzoic acid, and finally (c) 150 g of deionized water.

[00100] The excess water was stripped off under vacuum to give 460 g of product, which was analyzed by GC-MS and determined to be 97% pure as isodecyl benzoate. An additional 2% of the product was isomeric alkyl benzoates from the starting alcohol.

[0100] Example 15. Using the formulation of Table 2, plastisols were made with the plasticizer blend using the percentages indicated of Compound B and Isodecyl Benzoate shown in Table 3. The performance data are shown in Table 3.

Table 2

Table 3

[0101] Plasticizer blends of Examples 16 through 19 were incorporated into plastisols using the formulation shown in Table 4. Plas-Chek ® 775 is a plasticizer, and Therm-Check ® 130 is a stabilizer, both commercially available from Ferro Corporation, Cleveland, Ohio. TABLE 4

[0102] Example 16. Using the formulation of Table 4, the following plastisols were made with the plasticizer blend using the percentages indicated of Compound B and DINCH. The performance data are shown in Table 5.

Table 5

[0103] Example 17. Using the formulation of Table 4, the following plastisols were made with the plasticizer blend using the percentages indicated of Compound B and Soft-n-Safe. Soft-n- Safe is a plasticizer available as GRINSTED® Soft-n-Safe from Danisco A/S, Copenhagen, Denmark. The performance data are shown in Table 6.

Table 6

[0104] Example 18. Using the formulation of Table 4, the following plastisols were made with the plasticizer blend using the percentages indicated of Compound B and Mesamoll®. Mesamoll is a plasticizer commercially available from Lanxess Deutschland GmbH, Leverkusen Germany. The performance data are shown in Table 7. Table 7

[0105] Example 19. Using the formulation of Table 4, the following plastisols were made with the plasticizer blend using the percentages indicated of Compound B and Benzoflex 988. The performance data are shown in Table 8.

Table 8

[0106] It will be appreciated that although the examples herein primarily concern a plasticizer for use in PVC resins, the use of the compositions disclosed herein is also envisioned with a variety of thermoplastic polymer resins, elastomers, and thermoplastic elastomer compositions. Examples of other resins are, but not limited to, silicones, polyurethanes, latexes, polysulfides, polyacrylates, and Butyl/PIB sealants.

[0107] Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and illustrative example shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general invention concept as defined by the appended claims and their equivalents.

Claims

A plastic composition comprising a polymer and a plasticizer blend comprising

a. a first plasticizer comprising an asymmetric cyclic ester having the formula (I), and p p

(J) R¹-0-C-Y-C-0— W— Ar

wherein Y is a C₅ to C₈ cyclic alkyl group,

wherein R¹ is a straight chain or branched Ci'g alkyl group,

wherein W is a straight chain or branched C₁-C5 alkyl group,

wherein Ar is a C₆-C]₅ cyclic aryl group having at least three double bonds, and wherein RO(0=)C- and ArWO(0=)C- are attached to vicinal carbons of Y, and b. a second plasticizer wherein the second plasticizer is other than that described in (a).

The composition of claim 1 , wherein the polymer is selected from the group consisting of PVC, PVB, CPVC, homopolymers or copolymers including monomer units selected from the group consisting of ethylene, propylene, butadiene, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, acrylates, acrylates bonded to the oxygen atom of the ester group, alkyl radicals of branched or unbranched alcohols having 1 to 10 carbon atoms, styrene or acrylonitrile, homopolymers or copolymers of cyclic olefins and combinations thereof.

The composition of claim 1 , which the polymer is selected from the group consisting of: a C₄-C₁₀ polyacrylate having identical or different alkyl radicals bonded to the atom of the ester group, polymethacrylate, polymethyl methacrylate, methyl acrylate-butyl acrylate copolymer, methyl methacrylate-butyl methacrylate copolymer, ethylene- vinyl acetate copolymer, chlorinated polyethylene, nitrile rubber, acrylonitrile-butadiene styrene copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer,

acrylonitrile-butadiene rubber, styrene-butadiene elastomer, methyl methacrylate-styrene- butadiene copolymer, nitrocellulose, and combinations thereof.

The composition of claim 1 , wherein the polymer is PVC.

5. The composition of claim 1, wherein the second plasticizer is selected from the group consisting of (a) phosphate plasticizers, phthalate ester plasticizers; (c) aromatic carboxylic acid ester plasticizers; (d) aliphatic dibasic acid ester plasticizers; (e) fatty acid ester derivatives; (f) oxyacid ester plasticizers; (g) epoxy plasticizers; (h) dihydric alcohol ester plasticizers; (i) chlorine-containing plasticizers; (j) polyester plasticizers; (k) sulfonic acid derivatives; and (1) citric acid derivatives; and combinations thereof.

6. The composition of claim 5, wherein the second plasticizer is (a) a phosphate plasticizer selected from the group consisting of triaryl phosphates, mixed alkyl aryl phosphates, trialkyl phosphates, and combinations thereof.

7. The composition of claim 5, wherein the second plasticizer is (b) a phthalate ester plasticizer selected from the group consisting of dialkyl phthalates and benzyl alkyl phthalates including: dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethyl hexyl phthalate, diisooctyl phthalate, di-«-octyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, di-2-propylheptyl phthalate, diundecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, benzyl isononyl phthalate, 2,2,4-trimethyl-l ,3-pentandiol 1 -isobutyrate benzyl phthalate, butyl lauryl phthalate, methyl octyl phthalate, and octyl decyl phthalate, and combinations thereof.

8. The composition of claim 5, wherein the second plasticizer is (c) an aromatic carboxylic acid ester plasticizers selected from the group consisting of trioctyl trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, dioctyl terephthalate, and octyl oxybenzoate, and combinations thereof.

9. The composition of claim 5, wherein the second plasticizer is (d) an aliphatic dibasic acid ester plasticizer selected from the group consisting of dibutyl adipate, di-n-hexyl adipate, di- 2-ethylhexyl adipate, di-^-octyl adipate, n-octyl-n-decyl adipate, diisononyl adipate, diisodecyl adipate, dicapryl adipate, di-2-ethylhexyl azelate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate, di-w-octyl sebacate, di-2-ethylhexyl sebacate, di-2-ethoxyethyl sebacate, dioctyl succinate, diisodecyl succinate, dioctyl tetrahydrophthalate, di-rc-octyl tetrahydrophthalate, di-2-ethylhexyl cyclohexane-l,2-dicarboxylate, and diisononyl cyclohexane-l ,2-dicarboxylate, and combinations thereof.

10. The composition of claim 5, wherein the second plasticizer is (e) a fatty acid ester derivative selected from the group consisting of butyl oleate, acetyl methyl ricinoleate, pentaerythritol ester, dipentaerythritol hexaester, triacetin and tributylene, and combinations thereof.

1 1. The composition of claim 5, wherein the second plasticizer is (f) an oxyacid ester plasticizer selected from the group consisting of acetyl methyl ricinoleate, acetyl butyl ricinoleate, butyl phthalyl butyl glycolate and acetyl tributyl citrate, and combinations thereof.

12. The composition of claim 5, wherein the second plasticizer is (g) an epoxy plasticizer

selected from the group consisting of epoxidized soybean oil, epoxidized flaxseed oil, epoxy butyl stearate, epoxy decyl stearate, epoxy octyl stearate, epoxy benzyl stearate, epoxy dioctyl hexahydrophthalate and epoxy didecyl hexahydrophthalate.

13. The composition of claim 5, wherein the second plasticizer is (h) a dihydric alcohol ester plasticizer selected from the group consisting of: ethylene glycol dibenzoate; diethylene glycol dibenzoate; dipropylene glycol dibenzoate; triethylene glycol di-2-ethyl butyrate; butane diol dibenzoate; hexane diol dibenzoate; isosorbide dioctoate; 2,2-dimethyl-l,3- propane diol dibenzoate; mixed esters derived from 2,2-dimethyl- 1,3 -propane diol, benzoic acid; 2-ethylhexanoic acid; and hydroxypivalyl hydroxypivalate ester plasticizers, and combinations thereof.

14. The composition of claim 5, wherein the second plasticizer is (i) a chlorine-containing

plasticizer such as chlorinated paraffin, chlorinated diphenyl, chlorinated methyl fatty acids and methoxychlorinated methyl fatty acids, and combinations thereof.

15. The composition of claim 5, wherein the second plasticizer is (j) a polyester plasticizer selected from the group consisting of polypropylene adipate, polypropylene sebacate, polyester and acetylated polyester, and combinations thereof.

16. The composition of claim 5, wherein the second plasticizer is (k) a sulfonic acid derivative selected from the group consisting of /7-toluenesulfonamide, o-toluenesulfonamide, /^-toluene sulfone ethylamide, o-toluene sulfone ethyl amide, toluene sulfone-N-ethylamide and p- toluene sulfone-JV-cyclohexylamide, and combinations thereof.

17. The composition of claim 5, wherein the second plasticizer is (1) a citric acid derivatives selected from the group consisting of triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, acetyl tri-2-ethylhexyl citrate and acetyl stearyl citrate, and

combinations thereof.

18. The composition of claim 5, wherein the second plasticizer is selected from the group

consisting of alkyl pyrrolidines, surfactants, alkyl imidazoles, N-alkyl hexahydrophthalimide, dibutyl fumarate, dioctyl fumarate, linear alkyl benzenes, mineral oil, and combinations thereof.

19. A plastic composition comprising a polymer and of a plasticizer blend comprising a. a plasticizer comprising an asymmetric cyclic ester having the formula (I):

p p

(J) R¹-0-C-Y-C-0— W— Ar

wherein Y is a C₅ to C₈ cyclic alkyl group,

wherein R¹ is a straight chain or branched C₂-Ci₈ alkyl group,

wherein W is a straight chain or branched C 1-C5 alkyl group,

wherein Ar is a C₆-Ci5 cyclic aryl group having at least three double bonds, and

wherein RO(0=)C- and ArWO(0=)C- are attached to vicinal carbons of Y

and at least one selected from the group consisting of:

b. a symmetric ester of a cyclohexane dicarboxylate; a dibenzoate plasticizer; a diester of succinic acid; a diester of adipic acid; a trimellitate ester; a diester of maleic acid; a citrate ester; a phosphate ester; an alkyl substituted pyrrolidinone; a polymeric plasticizer; an fatty acid triester of glycerin; and an epoxidized fatty acid triester of glycerin.

20. The composition of claim 19, wherein the polymer is selected from the group consisting of: a C4-C 10 polyacrylate having identical or different alkyl radicals bonded to the atom of the ester group, polymethacrylate, polymethyl methacrylate, methyl acrylate-butyl acrylate copolymer, methyl methacrylate-butyl methacrylate copolymer, ethylene-vinyl acetate copolymer, chlorinated polyethylene, nitrile rubber, acrylonitrile-butadiene styrene copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, acrylonitrile-butadiene rubber, styrene-butadiene elastomer, methyl methacrylate-styrene- butadiene copolymer, nitrocellulose, and combinations thereof.