Asymmetric Cyclic Diester Compounds
Compounds useful as plasticizers and the synthesis thereof are disclosed. In general, the invention includes mixed alkyl/aryl 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.
1 . A compound including an asymmetric cyclic ester having the formula (I):
wherein Y is a C 5 to C 8 cyclic alkyl group,
wherein R 1 is a straight chain or branched C 2 -C 18 alkyl group,
wherein W is a straight chain or branched C 1 -C 5 alkyl group,
wherein Ar is a C 6 -C 15 cyclic aryl group having at least three double bonds, and
wherein R 1 O(O═)C‥ and ArWO(O═)C— are attached to vicinal carbons of Y.
2 . A blend of the compounds of claim 1 including at least two different types of at least one of the Y, R 1 , W, and Ar groups.
3 . The compound of claim 1 , wherein Y is selected from the group consisting of cyclohexene, cyclohexane, and combinations thereof.
4 . The compound of claim 1 , wherein Y is cyclohexene oxide.
5 . The compound of claim 1 , wherein Y is selected from the group consisting of cyclopentadiene; cyclopentene; cyclopentane; cycloheptadiene; cycloheptene; cycloheptane; 3-methylcyclohex-4-ene; 4-methylcyclohex-4-ene; 3-methylcyclohexane; 4-methylcyclohexane; 3,6-epoxycyclohexene; 3,6-epoxycyclohexane; cis-5-norbornene; norbornene; methyl-5-norbornene; bicyclo[2.2.2]oct-5-ene; bicyclo[2.2.2]octane; and combinations thereof.
6 . The compound of claim 1 , wherein Y is a residue of a carboxylic acid anhydride
7 . The compound of claim 6 , wherein the carboxylic acid anhydride is selected from the group consisting of 4-cyclohexene-1,2-dicarboxylic acid anhydride; cyclohexane-1,2-dicarboxylic acid anhydride; 1,2-dicarboxy-4-alkyl cyclohex-4-ene anhydride; 1,2-dicarboxy-3-alkyl cyclohex-3-ene anhydride; cis-5-norbornene-2,3-dicarboxylic anhydride; norbornane-2,3-dicarboxylic anhydride; methyl-5-norbornene-2,3-dicarboxylic anhydride; 3,6-epoxy-cyclohexene-1,2-dicarboxylic acid anhydride; 3,6-epoxycyclohexane-1,2-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.
8 . The compound of claim 1 , wherein R 1 is selected from the group consisting of C 4 to C 10 straight chain or branched alkyl groups.
9 . The compound of claim 1 , wherein Ar is selected from the group consisting of benzene; methylbenzene; dimethyl benzene, ditertiary butyl benzene; napththalene, anthracene, cumene and combinations thereof.
10 . A process of making an asymmetric cyclic ester comprising:
a. contacting
i. at least one cyclic dicarboxylic acid anhydride with
ii. at least one C 2 -C 18 aliphatic alcohol, in the presence of
iii. a base to form a reaction mixture and
b. contacting the reaction mixture with a benzyl halide to form a product.
11 . The process of claim 10 , further comprising, after (a)(iii), step (a)(iv), wherein step (a)(iv) includes maintaining the reaction mixture temperature at about 60 to about 130° C.
12 . The process of claim 10 , further comprising, after (b), step (b)(i), wherein (b)(i) includes maintaining the reaction mixture temperature at about 100 to about 180° C.
13 . The process of claim 10 , further comprising, 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.
14 . The process of claim 13 , further comprising, after (e), step (f), wherein step (f) comprises steam stripping the product at a pressure of less than 500 torr.
15 . The process of claim 14 , further comprising after (f), step (g), wherein step (g) comprises stripping the product of moisture at a pressure of less than 200 torr.
16 . The process of claim 10 , wherein the at least one cyclic carboxylic acid anhydride is selected from the group consisting of 4-cyclohexene-1,2-dicarboxylic acid anhydride; cyclohexane-1,2-dicarboxylic acid anhydride; 1,2-dicarboxy-3-alkyl cyclohex-3-ene anhydride; cis-5-norbornene-2,3-dicarboxylic anhydride; norbornane-2,3-dicarboxylic anhydride; methyl-5-norbornene-2,3-dicarboxylic anhydride; 3,6-epoxy-cyclohexene-1,2-dicarboxylic acid anhydride; 3,6-epoxycyclohexane-1,2-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.
17 . The process of claim 10 , wherein the at least one cyclic carboxylic acid anhydride of (a)(i) is selected from the group consisting of 4-cyclohexene-1,2-dicarboxylic acid anhydride and cyclohexane-1,2-dicarboxylic acid anhydride and combinations thereof, and wherein the aliphatic alcohol of (a)(ii) is selected from the group consisting of isononyl alcohol and 2-propylheptyl alcohol, and combinations thereof.
18 . The process of claim 10 , wherein the base is selected from the group consisting of pyridines, tertiary amines, room temperature ionic liquids, and combinations thereof.
19 . 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 a 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.
20 . 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 a 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.
21 . 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 C 2 -C 18 alkyl halide to form said mixed diester.
22 . 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 a 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.
23 . The process of claim 22 , wherein 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-1,3-pentadiene; 4-methyl-1,3-pentadiene; 1,3-cyclohexadiene; sorbic acid esters; ethyl sorbate; 1,2,3,4,5-pentamethylcyclopentadiene; 7-methyl-3-methylene-1,6-octadiene; and combinations thereof.
24 . The process of claim 22 , further comprising contacting the product with a hydrogenation catalyst and hydrogen gas.
25 . The process of claim 22 , further comprising contacting the product with a peracid.
26 . 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. hydrogenating
i. an 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 a phenyl-substituted alkyl halide, to form an asymmetric cyclic ester.
27 . The process of claim 26 , wherein the cyclic dicarboxylic anhydride is phthalic anhydride.
28 . 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.
29 . The process of claim 28 , wherein 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-1,3-pentadiene; 4-methyl-1,3-pentadiene; 1,3-cyclohexadiene; sorbic acid esters; ethyl sorbate; 1,2,3,4,5-pentamethylcyclopentadiene; 7-methyl-3-methylene-1,6-octadiene; and combinations thereof.
30 . A process of plasticizing a polymer comprising contacting the plasticizer of claim 1 with a polymer.
31 . A process of plasticizing a polymer comprising contacting the plasticizer of claim 2 with a polymer.