Dicarboxylic acid monomers and methods of making and using the same

Patent metadata

Field	Value
Publication number	US-9238609-B2
Application number	US-201414286024-A
Country	US
Kind code	B2
Filing date	May 23, 2014
Priority date	May 23, 2014
Publication date	Jan 19, 2016
Grant date	Jan 19, 2016

Abstract

Disclosed herein are phenylindane dicarboxylic acid (PIDA) monomers, polymer compositions comprising the PIDA monomers, and methods of preparing PIDA monomers. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.

First claim

What is claimed is:

1. A method for preparing a phenylindane dicarboxylic acid monomer, the method comprising:
a) reacting an alkylstyrene under acid catalyzed conditions effective to provide a first reaction product comprising at least one C20 to C32 phenylindane; and
b) reacting the first reaction product under a metal catalyzed oxidation conditions effective to provide a second reaction product comprising a racemic mixture including a phenylindane dicarboxylic acid monomer.

2. The method of claim 1 , wherein the phenylindane dicarboxylic acid monomer does not exhibit a half maximal inhibitory concentration (IC 50 ) less than 0.00025M for alpha or beta in vitro estradiol receptors.

3. The method of claim 1 , wherein the alkylstyrene has a structure represented by the formula:

wherein each of R1 and R2 is each independently selected from hydrogen and C1-C3 alkyl.

4. The method of claim 1 , wherein the alkylstyrene is alpha-methylstyrene.

5. The method of claim 1 , wherein the alkylstyrene is α-p-dimethylstyrene.

6. The method of claim 1 , wherein the phenylindane is trimethyl phenylindane.

7. The method of claim 1 , wherein the phenylindane is tetramethyl phenylindane.

8. The method of claim 1 , further comprising the step of reacting limonene to provide the the alkylstyrene.

9. The method of claim 1 , further comprising the step of reacting an alkylbenzene to provide the alkylstyrene.

10. The method of claim 9 , wherein the alkylbenzene is p-cymene or p-bromo toluene, or a combination thereof.

11. The method of claim 1 , further comprising the step of reacting an acetophenone to provide the alkylstyrene.

12. The method of claim 11 , wherein the acetophenone is reacted in the presence of a Grignard reagent.

13. The method of claim 12 , wherein the Grignard reagant is methyl magnesium bromide.

14. The method of claim 1 , wherein the phenylindane dicarboxylic acid monomer has a structure represented by the formula:

wherein R 1 , R 2 , R 3 , and R 5 are each independently a C1-C3 alkyl group, a is 0-1, b is 0-4, c is 0-4 and d is 0-3, and each R 4 is independently a hydrogen or a C1-C3 alkyl group.

15. The method of claim 1 , wherein the phenylindane dicarboxylic acid monomer has a structure represented by the formula

wherein each R 4 is independently hydrogen or a C1-C3 alkyl group.

16. The method of claim 1 , wherein the phenylindane dicarboxylic acid monomer has a structure represented by the formula:

wherein wherein each R 4 is independently hydrogen or a C1-C3 alkyl group.

17. The method of claim 1 , wherein the phenylindane dicarboxylic acid monomer is 3-(4-carboxyphenyl)-1,1,3-trimethyl-5-indan carboxylic acid, 3-(4-carboxyphenyl)-1,3-diethyl-1-methyl-5-indan carboxylic acid, or 3-(4-carboxyphenyl)-1,3-dipropyl-1-methyl-5-indan carboxylic acid.

18. The method of claim 1 , wherein the phenylindane dicarboxylic acid monomer is this monomer is as 1,3,3-trimethyl-1-phenylindan-4′,5-dicarboxylic acid.

19. The method of claim 1 , wherein the acid catalyzed conditions comprise reacting the alkylstyrene in the presence of hydrochloric acid, sulfuric acid or nitric acid, or a combination thereof.

20. The method of claim 1 , wherein the acid catalyzed conditions or the metal catalyzed oxidation conditions comprise adjusting the temperature to at least about 40° C.

21. The method of claim 1 , wherein the the acid catalyzed conditions or the metal catalyzed oxidation conditions comprise adjusting the temperature in the range of from about 40° C. to about 250° C.

22. The method of claim 1 , wherein the acid catalyzed conditions or the metal catalyzed oxidation conditions comprise maintaining the reaction for at least about 1 hours.

23. The method of claim 1 , further comprising reacting the first reaction product to provide a reaction product comprising at least one acetylated phenylindane.

24. The method of claim 23 , wherein reacting is acetylating with an acetylating agent in the presence of a Friedel-Crafts catalyst to provide reaction product comprising an isomer mixture.

25. The method of claim 24 , wherein the acetylating agent is acetyl chloride, chloroacetyl chloride or acetic anhydride, or a combination thereof.

26. The method of claim 24 , wherein the Friedel-Crafts catalyst comprises aluminum chloride, zinc chloride, or iron(III) chloride, or a combination thereof.

27. The method of claim 23 , wherein the acetylated phenylindane is diacetyl phenylindane.

28. The method of claim 1 , wherein the metal catalyzed oxidation conditions comprise reacting the first reaction product in the presence of an oxidizing agent.

29. The method of claim 28 , wherein the oxidizing agent comprises: chromic anhydride(CrO3); oxygen containing heavy metals comprising one or more of manganese, cobalt, lead, iron, nickel, copper, and vanadium; or oxides of one or more of manganese, cobalt, lead, iron, nickel, copper, and vanadium; or a combination thereof.

30. The method of claim 1 , wherein the metal catalyzed oxidation conditions comprise reacting the first reaction product in the presence of KMnO 4 and pyridine.

31. The method of claim 1 , wherein the first reaction product comprises at least about 50 wt % of phenylindane.

32. The method of claim 1 , wherein the second reaction product comprises at least about 50 wt % of phenylindane dicarboxylic acid.

33. The method of claim 1 , wherein the method provides a final yield of phenylindane dicarboxylic acid of at least about 60%.

34. The method of claim 1 , further comprising purifying the second reaction product under conditions effective to provide a reaction product comprising at least 90 wt % phenylindane dicarboxylic acid.

35. The method of claim 34 , further comprising the step of filtering, separating, washing, or drying, or a combination thereof.

36. The method of claim 34 , wherein purifying comprises dissolving the reaction product using aqueous NaHCO3 solution or glacial acetic acid, or a combination thereof.

37. The method of claim 34 , wherein purifying comprises adjusting the pH of reaction product to a pH effective to provide a solid reaction product.

38. The method of claim 1 , further comprising separating of the second reaction product.

39. The method of claim 38 , wherein the separating comprises chiral separation of the racemic mixture using high pressure liquid chromatography.

40. A method for preparing a phenylindane dicarboxylic acid monomer, the method comprising:
a) reacting alphamethylstyrene under first reaction conditions effective to provide a first reaction product comprising at least one phenylindane;
b) acetylating the first reaction product in the presence of a Friedel-Crafts catalyst to provide second reaction produc

Assignees

• Sabic Global Technologies Bv

Inventors

• Asthana Navinchandra
• Puthamane Kiran Arunkumar
• Naik Shantaram Narayan
• Kumar Minor Senthil
• Ganapathy Bhotla Venkata Ramanarayanan
• Vasudevan Vinodkumar
• Nesakumar Edward J
• Chandra Girish
• Van Der Heijden Ruud
• Kamps Jan Henk
• Uliyanchenko Elena
• Gallucci Robert R

Classifications

• C08G63/64 Primary

  Polyesters containing both carboxylic ester groups and carbonate groups · CPC title

• C07C2/72

  Addition to a non-aromatic carbon atom of hydrocarbons containing a six-membered aromatic ring · CPC title

• C07C51/265 Primary

  having alkyl side chains which are oxidised to carboxyl groups · CPC title

• C07C5/367

  Formation of an aromatic six-membered ring from an existing six-membered ring, e.g. dehydrogenation of ethylcyclohexane to ethylbenzene · CPC title

• C07C2102/08

  Chemistry & Metallurgy · mapped topic