Bisphenol based polyesters useful in photoreceptor matrices

• US 5,162,485 A
• Filed: 12/13/1990
• Issued: 11/10/1992
• Est. Priority Date: 12/13/1990
• Status: Expired due to Fees

• Current Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Original Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Inventors: Odell, Peter G., Murti, Dasarao K.
• Primary Examiner(s): Kight, III, John
• Assistant Examiner(s): BOYKIN, TERRESSA M
• Application Number:
  US07/626,849
• Time in Patent Office: 698 Days
• Field of Search: 528/176, 528/194, 528/219
• US Class Current: 528/194
• CPC Class Codes: C08G 63/193 containing two or more aromatic rings
• CPC Class Codes: G03G 5/056 Polyesters

Abstract

Bisphenol-based polyesters and a process for their preparation having a first step of diacetylizing the bisphenol then polymerizing the diacetate with an aromatic diacid and an aliphatic diacid are disclosed. The bisphenol-based polyesters can be used as binder components in a charge transport or charge generation layers of an organic photoreceptor.

Claims

1. A copolyester of the formula ##STR3## wherein R₁, R₂, and R₃ are independently selected from the group consisting of alkyl and aryl, m and n are numbers greater than zero, and x is a number from about 0.4 to about 0.6.

2. A copolyester according to claim 1 wherein m is a number of from about 4 to about 1000 and corresponds to the degrees of polymerization of the polymer.

3. A copolyester according to claim 1 where in R₁ and R₂ are selected from the group consisting of methyl, ethyl, phenyl, benzyl, napthyl, cyclohexyl, t-butylcyclohexyl, phenylcyclohexyl, and cycloheptyl.

4. A copolyester according to claim 1 wherein R₃ is methyl or hydrogen.

5. A copolyester according to claim 1 having a weight average molecular weight of from about 15,000 to about 150,000.

6. A copolyester according to claim 5 having a weight average molecular weight of from about 30,000 to about 100,000.

7. A copolyester according to claim 1 having a Mw/Mn ratio of from about 2.1 to about 4.0.

8. A copolyester according to claim 7 having a Mw/Mn ratio of from about to 2.1 about 2.8.

9. A copolyester of claim 1 selected from the group consisting of poly[(4,4'"'"'-cyclohexylidenebisphenol)-alt-(terephthalic acid;

sebacic acid)], poly[(4,4'"'"'-cyclohexylidenebisphenol)-alt-(terephthalic acid;

azelaic acid)], poly[(4,4'"'"'-cyclohexylidenebisphenol)-alt-(terephthalic acid;

suberic acid)], poly[(4,4'"'"'-cyclohexylidenebisphenol)-alt-(isophthalic acid;

sebacic acid], poly[(4,4'"'"'-cyclohexylidenebisphenol)-alt-(isophthalic acid;

azelaic acid)], poly[(4,4'"'"'-(1-phenylethylidene)bisphenol)-alt-(isophthalic acid;

suberic acid)], poly[(4,4'"'"'-(1-phenylethylidene)bisphenol)-alt-(terephthalic acid;

sebacic acid)], poly[(4,4'"'"'-(1-phenylethylidene)bisphenol)-alt-(terephthalic acid;

azelaic acid)], poly[(4,4'"'"'-(1-phenylethylidene)bisphenol)-alt-(terephthalic acid;

suberic acid)], poly[(4,4'"'"'-(1-phenylethylidene)bisphenol)-alt-(isophthalic acid;

sebacic acid)], poly[(4,4'"'"'-(1-phenylethylidene)bisphenol)-alt-(isophthalic acid;

azelaic acid)], poly[(4,4,-(1-phenylethylidene)bisphenol)-alt-(isophthalic acid;

suberic acid)], poly[(4,4'"'"'-cyclohexylidene-2,2'"'"'-dimethylbisphenol)-alt-(terephthalic acid;

sebacic acid)], poly[(4,4'"'"'-cyclohexylidene-2,2'"'"'-dimethylbisphenol)-alt-(terephthalic acid;

azelaic acid)], poly[(4,4'"'"'-cyclohexylidene-2,2'"'"'-dimethylbisphenol)-alt-(terephthalic acid;

suberic acid)], poly[(4,4'"'"'-cyclohexylidene-2,2'"'"'-dimethylbisphenol)-alt-(isophthalic acid;

sebacic acid)], poly[(4,4'"'"'-cyclohexylidene-2,2'"'"'-dimethylbisphenol)-alt-(isophthalic acid;

azelaic acid)], poly[(4,4'"'"'-(4-t-butylcyclohexylidene)bisphenol)-alt-(terephthalic acid;

sebacic acid)], poly[(4,4'"'"'-(4-t -butylcyclohexylidene)bisphenol)-alt-terephthalic acid;

azelaic acid)], poly[(4,4'"'"'-(4-t-butylcyclohexylidene)bisphenol)-alt-terephthalic acid;

suberic acid)], poly[(4,4'"'"'-(4-t -butylcyclohexylidene)bisphenol)-alt-(isophthalic acid;

sebacic acid)], poly[)4,4'"'"'-(4-t-butylcyclohexylidene)bisphenol)-alt -(isophthalic acid;

azelaic acid)], poly[(4,4'"'"'-isopropylidenebisphenol)-alt-(terephthalic acid;

sebacic acid)], poly[(4,4'"'"'-isopropylidenebisphenol)-alt-(terephthalic acid;

azelaic acid)], poly[(4,4'"'"'-isopropylidenebisphenol)-alt-(terephthalic acid;

suberic acid)], poly[(4,4'"'"'-iospropylidenebisphenol)-alt-(isophthalic acid;

sebacic acid)], poly[(4,4'"'"'-iospropylidenebisphenol)-alt-(isophthalic acid;

azelaic acid)], poly[(4,4'"'"'-cycloheptylidenebisphenol) -alt-(terephthalic acid;

sebacic acid)], poly[(4,4'"'"'-cycloheptylidenebisphenol)-alt-(terephthalic acid;

azelaic acid)], poly[(4,4'"'"'-cycloheptylidenebisphenol)-alt-(terephthalic acid;

suberic acid)], poly[(4,4'"'"'-cycloheptylidenebisphenol)-alt-(isophthalic acid;

sebacic acid)], poly[(4,4'"'"'-cycloheptylidenebisphenol)-alt-(isophthalic acid;

azelaic acid)], poly[(4,4'"'"'-isopropylidene-2,2'"'"'-dimethylbisphenol)-alt-(terephthalic acid;

sebacic acid)], poly[(4,4'"'"'-isopropylidene-2,2'"'"'-dimethylbisphenol)-alt-(terephthalic acid;

azelaic acid)], poly[(4,4'"'"'-isopropylidene-2,2'"'"'-dimethylbisphenol)-alt-(terephthalic acid;

suberic acid)], poly[(4,4'"'"'-isopropylidene-2,2'"'"'-dimethylbisphenol)-alt-(isophthalic acid;

sebacic acid)], poly[(4,4'"'"'-isopropylidene-2,2'"'"'-dimethylbisphenol)-alt-(isophthalic acid;

azelaic acid)], poly[(4,4'"'"'-diphenylmethylidenebisphenol)-alt-(terephthalic acid;

sebacic acid)], poly[(4,4'"'"'-diphenylmethylidenebisphenol)-alt-(terephthalic acid;

azelaic acid)], poly[(4,4'"'"'-diphenylmethylidenebisphenol)-alt-(terephthalic acid;

suberic acid)], poly[(4,4'"'"'-diphenylmethylidenebisphenol)-alt-(isophthalic acid;

sebacic acid)], poly[(4,4'"'"'-diphenylmethylidenebisphenol)-alt-(isophthalic acid;

azelaic acid)], poly[(4,4'"'"'-(1,4-phenylenebisisopropylidene)bisphenol)-alt-(terephthalic acid;

sebacic acid)], poly[(4,4'"'"'-(1,4-phenylenebisisopropylidene)bisphenol)-alt-(terephthalic acid;

azelaic acid)], poly[(4,4'"'"'-(1,4-phenylenebisisopropylidene)bisphenol)-alt-(terephthalic acid;

suberic acid)], poly[(4,4'"'"'-(1,4-phenylenebisisopropylidene)bisphenol)-alt-(isophthalic acid;

sebacic acid)], poly[(4,4'"'"'-(1,4-phenylenebisisopropylidene)bisphenol)-alt-(isophthalic acid;

azelaic acid)], poly[(4,4'"'"'-(1,3-phenylenebisisopropylidene)bisphenol)-alt-(terephthalic acid;

sebacic acid)], poly[(4,4'"'"'-(1,3-phenylenebisisopropylidene)bisphenol)-alt-(terephthalic acid;

azelaic acid)], poly[(4,4'"'"'-(1,3-phenylenebisisopropylidene)bisphenol)-alt-(terephthalic acid;

suberic acid)], poly[(4,4'"'"'-(1,3-phenylenebisisopropylidene)bisphenol)-alt-(isophthalic acid;

sebacic acid)], poly[(4,4'"'"'-(1,3-phenylenebisisopropylidene)bisphenol)-alt-(isophthalic acid;

azelaic acid)], poly[(4,4'"'"'-cyclohexylidene-2,2'"'"'-dichlorobisphenol)-alt-(terephthalic acid;

sebacic acid)], poly[(4,4'"'"'-cyclohexylidene-2,2'"'"'-dichlorobisphenol)-alt-(terephthalic acid;

azelaic acid)], poly[(4,4'"'"'-cyclohexylidene-2,2'"'"'-dichlorobisphenol)-alt-(terephthalic acid;

suberic acid)], poly[(4,4'"'"'-cyclohexylidene-2,2'"'"'-dichlorobisphenol)-alt-(isophthalic acid;

sebacic acid)], poly[(4,4'"'"'-cyclohexylidene-2,2'"'"'-dichlorobisphenol)-alt-(isophthalic acid;

azelaic acid)], poly[(4,4'"'"'-cyclohexylidene-2,2'"'"'-dichlorobisphenol)-alt-(terephthalic acid;

glutaric acid)], poly[(4,4'"'"'-(1,4-phenylenebisisopropylidene)bisphenol)-alt-(terephthalic acid;

azelaic acid)], poly[(4,4'"'"'-isopropylidenebisphenol)-alt-(isophthalic acid;

adipic acid)], poly[(4,4'"'"'-cyclohexylidene-2,2'"'"'-dimethylbisphenol)-alt-(terephthalic acid;

pimelic acid)], poly[(4,4'"'"'-cyclohexylidenebisphenol)-alt-(terephthalic acid;

brassylic acid)], poly[(4,4'"'"'-cyclohexylidene-2,2'"'"'-dichlorobisphenol) -alt-(terephthalic acid;

malonic acid)], poly[(4,4'"'"'-(1,4-phenylenebisisopropylidene)bisphenol)-alt-(terephthalic acid;

1,4-cyclohexanedicarboxylic acid)], poly[(4,4'"'"'-isopropylidenebisphenol)-alt-(isophthalic acid;

3,3-dimethylglutaric acid)], poly[(4,4'"'"'-cyclohexylidene-2,2'"'"'-dimethylbisphenol)-alt-(terephthalic acid;

succinic acid] and poly[(4,4'"'"'-cyclohexylidenebisphenol)-alt-(terephthalic acid;

2,3-dibromosuccinic acid)].

10. A copolyester of claim 1 selected from the group consisting of poly[(4,4'"'"'-cyclohexylidenebisphenol)-alt-(terephthalic acid;

isophthalic acid;

sebacic acid)], poly[(4,4'"'"'-cyclohexylidenebisphenol)-alt-(terephthalic acid;

isophthalic acid;

azelaic acid)] and poly[(4,4'"'"'-cyclohexylidenebisphenol)-alt-(terephthalic acid;

isophthalic acid;

suberic acid)].

11. A copolyester of claim 1 selected from the group consisting of poly[(4,4'"'"'-cyclohexylidenebisphenol)-alt-(terephthalic acid;

azelaic acid;

sebacic acid)], poly[(4,4'"'"'-cyclohexylidenebisphenol)-alt-(terephthalic acid;

succinic acid;

glutaric acid)] and poly[(4,4'"'"'-cyclohexylidenebisphenol)-alt-(terephthalic acid;

1,4-cyclohexanedicarboxylic acid;

suberic acid)].

12. A copolyester of claim 1 selected from the group consisting of poly[(4,4'"'"'-cyclohexylidene-2,2'"'"'-dichlorobisphenol;

4,4'"'"'-isopropylidenebisphenol)-alt-(terephthalic acid;

sebacic acid)], poly[(4,4'"'"'-cyclohexylidenebisphenol;

4,4'"'"'-cyclohexylidene-2,2'"'"'-dimethylbisphenol)-alt-(terephthalic acid;

sebacic acid)], poly[(4,4'"'"'-isopropylidene-2,2'"'"'-dimethylbisphenol;

4,4'"'"'-cyclohexylidene-2,2'"'"'-dimethylbisphenol)-alt-(terephthalic acid;

sebacic acid)], and poly[(4,4'"'"'-cyclohexylidenebisphenol] 4,4'"'"'-(1,4-phenylenebisisopropylidene)bisphenol)-alt-(terephthalic acid;

sebacic acid)].

23. A charge transport layer for an organic photoreceptor comprising a bisphenol-based polyester of claim 1 or 12.

24. An organic photoreceptor comprising at least one layer which comprises a bisphenol-based polyester made according to claim 1 or 12.

32. A copolyester according to claim 1 wherein x is about 0.5.

13. A bisphenol-based polyester of the formula:

##STR4## wherein R₁, R₂ and R₃ are independently selected from the group consisting of alkyl and aryl, m and n are numbers greater than zero, and x is a number from about 0.4 to about 0.6 said process comprising the steps of;

a) diacetylizing at least one bisphenol of the formula above; and

b) polymerizing the product obtained from step (a) with at least one aromatic acid of the formula above and at least one aliphatic diacid of the formula above.

14. The polyester according to claim 13 wherein the bisphenol is selected from the group consisting of (4,4'"'"'-cyclohexylidenebisphenol), (4,4'"'"'-(1-phenylethylidene)bisphenol), (4,4'"'"'-cyclohexylidene-2,2'"'"'-dimethylbisphenol), (4,4'"'"'-(4-t-butylcyclohexylidene)bisphenol), (4,4'"'"'-isopropylidenebisphenol), (4,4'"'"'-cycloheptylidenebisphenol), (4,4'"'"'-isopropylidene-2,2'"'"'-dimethylbisphenol), (4,4'"'"'-diphenylmethylidenebisphenol), (4,4'"'"'-(1,4-phenylenebisisopropylidene)bisphenol), (4,4'"'"'-(1,3-phenylenebisisopropylidene)bisphenol), (4,4'"'"'-cyclohexylidene-2,2'"'"'-dichlorobisphenol), and (4,4'"'"'-(1,4-phenylenebisisopropylidene)bisphenol).

15. The polyester according to claim 14 wherein the bisphenol is 4,4'"'"'-cyclohexylidenebisphenol.

16. The polyester according to claim 13 wherein the bisphenol is 4,4'"'"'-(1-phenylethylidene)bisphenol.

17. The polyester according to claim 13 wherein the aromatic diacid is selected from the group consisting of isophthalic acid, phthalic acid and terephthalic acid.

18. The polyester according to claim 17 wherein the aromatic diacid is terephthalic acid.

19. The polyester according to claim 13 wherein the aliphatic diacid is of the formula HO₂ C(CH₂)_n CO₂ H wherein n is from 2-9.

20. The polyester of claim 19 wherein the aliphatic diacid is selected from the group consisting of sebacic acid, azelaic acid and suberic acid.

21. The polyester of claim 20 wherein the aliphatic diacid is sebacic acid.

22. The polyester of claim 19 wherein n is from 4 to 9.

25. A polymer formed from the polycondensation of at least one bisphenol and a mixture of at least one aliphatic diacid of the formula HO₂ C(CH₂)_n CO₂ H wherein n is an integer and at least one aromatic diacid, the ratio of the acid mixture to bisphenol/diacetate being about 1 to 1, and the ratio the aliphatic diacids to the aromatic diacids in said mixture being from about 60:

40 to about 40;

60.

26. A polymer according to claim 25 wherein n is from 2-9.

27. A polymer according to claim 26 wherein n is from 4-9.

28. A photoreceptor matrix formed from the polymer according to claim 25.

34. A polymer according to claim 25 wherein said ratio is about 50:

50.

29. A photoreceptor matrix comprising a polymer formed by the polycondensation of a diacetate of at least one bisphenol selected from the group consisting of (4,4'"'"'-cyclohexylidenebisphenol), (4,4'"'"'-(1-phenylethylidene)bisphenol), (4,4'"'"'-cyclohexylidene-2,2'"'"'-dimethylbisphenol, (4,4'"'"'-(4-t-butylcyclohexylidene)bisphenol), (4,4'"'"'-isopropylidenebisphenol), (4,4'"'"'-cycloheptylidenebisphenol), (4,4'"'"'-isopropylidene-2,2-dimethylbisphenol), (4,4'"'"'-diphenylmethylidenebisphenol), (4,4'"'"'-(1,4-phenylenebisisopropylidene) bisphenol), (4,4'"'"'-(1,3-phenylenebisisopropylidene)bisphenol), (4,4'"'"'-cyclohexylidene-2,2'"'"'-dichlorobisphenol), and (4,4'"'"'-(1,4-phenylenebisisopropylidene)bisphenol), a mixture of at least one aromatic diacid selected from the group consisting of terephthalic isophthalic or phthalic, and at least one aliphatic diacid of the formula HO₂ C(CH₂)_n CO₂ H wherein n is an integer, wherein the ratio the aliphatic diacids tot he aromatic diacids in said mixture being from about 60:

40 to about 40;

60.

30. The photoreceptor matrix according to claim 29 wherein n is from 2-9.

31. The photoreceptor matrix according to claim 30 wherein n is from 4-9.

33. A bisphenol-based polyester according to claim 52 wherein x is about 0.5.