Silicon-containing step ladder polymer and a process for producing the same

• US 4,585,834 A
• Filed: 07/24/1985
• Issued: 04/29/1986
• Est. Priority Date: 09/18/1984
• Status: Expired due to Term

• Current Assignee: Chisso Corporation
• Original Assignee: Chisso Corporation
• Inventors: Konotsune, Shiro, Maehara, Hiroshi, Wada, Masami, Tsuji, Kazuyuki, Higashi, Hiromi
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): Lipman, Bernard
• Application Number:
  US06/758,367
• Time in Patent Office: 279 Days
• Field of Search: 525/342, 525/386
• US Class Current: 525/342
• CPC Class Codes: C08F 8/42 Introducing metal atoms or metal-containing groups

Abstract

A silicon-containing step ladder polymer comprising a unit represented by the following general formula (I): ##STR1## a unit represented by the following general formula (II): ##STR2## and a unit represented by the following general formula (III): ##STR3## where R¹ represents a hydrocarbon or fluorine-substituted hydrocarbon group, R² represents hydrogen or a trialkyl siloxy group, and R³ and R⁴ which may be identical or different with each other represent individually hydrocarbon or fluorine-substituted hydrocarbon groups, the molar ratio of the unit (I) to the unit (II) is between 5:1-100:1 and the molar ratio of the unit (III) to the total amount of the unit (I)+unit (II) is between 1:5-1:100, as well as a process for producing such polymer.

Claims

1. A process for producing a silicon-containing step ladder polymer which comprises a step of substituting the group X¹ in a polyvinyl silane prepolymer represented by the general formula:

##STR14## where R¹ represents a hydrocarbon group or fluorine-substituted hydrocarbon group, X¹ represents a dialkylamino group comprising alkyls each having 4 or less carbon atoms, chlorine, fluorine or iodine, R⁵ and R⁶ represent individually hydrogen or hydrocarbon residue of a vinyl polymerization initiator, and m represents an integer between 5-100, with an a acyloxy group represented by;

R⁷ COO-- (where R⁷ represents an alkyl group having 4 or less carbon atoms), and a step of carrying out the intra-molecular hydrolysis of the prepolymer, as well as the hydrolytic condensation between the prepolymer and a stepping agent represented by the general formula;

R³ R⁴ Si(OCOR⁷)₂ (where R³ and R⁴ which may be identical or different with each other represent individually hydrocarbon group or fluorine-substituted hydrocarbon groups, and R⁷ represent an alkyl group having 1-4 carbon atoms.

2. The process as defined in claim 1, wherein R¹ has 1-10 carbon atoms, R³ and R⁴ individually have 1-10 carbon atoms and the residue of the polymerization initiator has 2-18 carbon atoms.

3. The process as defined in claim 2, wherein R¹ represents an alkyl group having 1-4 carbon atoms, a fluorine-substituted alkyl group having 1-4 carbon atoms or a phenyl group;

and R³ and R⁴ individually represent alkyl or fluorine-substituted alkyl groups having 1-4 carbon atoms or phenyl groups.

4. The process as defined in claim 3, wherein R¹ represents a methyl, trifluoropropyl or phenyl group and R³ and R⁴ represent individually methyl or phenyl groups.

5. The process as defined in claim 1, wherein R⁷ represents a methyl group.

6. The process as defined in claim 1, wherein X¹ represents a dialkylamino group, and the acyloxylation is carried out by reacting the prepolymer with the addition of an organic acid represented by the general formula:

R⁷ COOH (R⁷ has the same meanings as above) in an inert aromatic hydrocarbon solvent.

7. The process as defined in claim 6, wherein the reaction is carried out at a temperature between -5°

-70°

C. and, preferably, 10°

-50°

C.

8. The process as defined in claim 6, wherein the amount of the acid added is 3-5 molar times and, preferably, 4-4.5 molar times based on Si of the prepolymer.

9. The process as defined in claim 1, wherein X¹ represents chlorine, bromine or iodine and the acyloxylation is carried out by the addition of an acid anhydride represented by the general formula:

(R⁷ CO)₂ O(Where R⁷ has the same meanings as above) to the prepolymer in an inert hydrocarbon solvent.

10. The process as defined in claim 9, wherein the reaction is carried out at a temperature between 20°

-150°

C. and, preferably, 40°

-120°

C.

11. The process as defined in claim 9, wherein the amount of the acid anhydride added is between 1.5-2.5 molar times and, preferably, 2-2.3 molar times based on Si of the prepolymer.

12. The process as defined in claim 1, wherein the hydrolytic condensation for the acyloxylated prepolymer is carried out in an inert aromatic hydrocarbon solvent with the concentration of said acyloxylated prepolymer being at 1-30% by weight and, preferably, 3-15% by weight.

13. The process as defined in claim 1, wherein the hydrolytic precondensation is carried out by adding water in the range of equimolar-100 molar amount and, preferably, equimolar-10 molar amount and, more preferably, equimolar-3 molar amount based on Si relevant to the hydrolytic condensating reaction.

14. The process as defined in claim 13, wherein the hydrolysis is carried out under the presence of an acid or base.

15. The process as defined in claim 1, wherein the hydrolytic condensation is carried out at a temperature between -5°

-80°

C. and, preferably, 20°

-60°

C.

16. The process for producing the silicon-containing step ladder polymer as defined in claim 1, wherein the acyloxylated prepolymer is hydrolized under the coexistence of the stepping agent R³ R⁴ Si(OCOR⁷)₂.

17. The process for producing the silicon-containing step ladder polymer as defined in claim 1, wherein the intra-molecular hydrolytic condensation is carried out for the acyloxylated prepolymer and, thereafter, the stepping agent R³ R⁴ Si(OCOR⁷) is added to perform hydrolytic condensation.

18. The process as defined in claim 1, wherein after the completion of the reaction for the hydrolytic condensation, the reaction solution is heated to a temperature between 50°

-150°

C. and, preferably, 70°

-120°

C. for 0.5-5 hours.

19. The process as defined in claim 1, wherein after the hydrolytic condensation, hexaalkylsilazane of the general formula:

R⁸₃ Si--NH--SiR⁸₃ (where R⁸ represents an alkyl having 1-10 carbon atoms) or a trialkyl acyloxysilane of the general formula R⁸₃ Si--OCOR⁹ (where R⁸ has the same meanings as above and R⁹ represents an alkyl group having 1-4 carbon atoms) is added to the resultant polymer for reaction.

20. A process for producing a silicon-containing step ladder polymer, wherein a polyvinyl silane prepolymer represented by the general formula:

##STR15## (where R¹ represents a hydrocarbon group or a fluorine-substituted hydrocarbon group, X² represents an alkoxy group having 7 or less carbon atoms or a thioalkoxy group having 7 or less carbon atoms, R⁵ and R⁶ represent individually hydrogen or hydrocarbon residue of a vinyl polymerization initiator an m represents an integer between 5-100) is reacted with an acid anhydride represented by the general formula;

(R⁷ CO)₂ (where R⁷ represents an alkyl group having 1-4 carbon atoms under the presence of a compound as the stepping agent represented by the general fromula R³ R⁴ SiY₂ (where R³ and R⁴ represent individually hydrocarbon or fluorine-substituted hydrocarbon groups, which may be identical or different with each other, and Y represents an acyloxy group having 2-5 carbon atoms, an alkoxy group having 1-4 carbon atoms or a thioalkoxy group having 1-4 carbon atoms).

21. The process as defined in claim 20, wherein R¹ has 1-10 carbon atoms;

R³ and R⁴ individually have 1-10 carbon atoms; and

the residue of the vinyl polymerization initiator has 2-18 carbon atoms.

22. The process as defined in claim 21, wherein R¹ represents an alkyl or fluorine-substituted alkyl group having 1-4 carbon atoms or phenyl group, and R³ and R⁴ represent individually alkyl or fluorine substituted alkyl groups having 1-4 carbon atoms or phenyl group.

23. The process as defined in claim 22, wherein R¹ represents a methyl, trifluoropropyl or phenyl group, R³ and R⁴ represent individually methyl or phenyl groups, and Y represents an ethoxy group.

24. The process as defined in claim 20, wherein R⁷ represents a methyl group.

25. The process as defined in claim 20, wherein the reaction is carried out at a temperature between 30°

-170°

C., preferably, 50°

-130°

C. and, more preferably, 50°

-90°

C. at a reduced pressure between 50-200 mmHg.

26. The process as defined in claim 20, wherein Y represents the acyloxy group, and the reaction is carried out with the acid anhydride at 1-3 molar times and, preferably, 1.2-2 molar times of Si in the vinyl polymer.

27. The process as defined in claim 20, wherein Y represents an alkoxy or thioalkoxy group and the reaction is carried out with the amount of acid anhydride being 1-3 molar times and, preferably, 1.2-2 molar times of Si of the vinyl polymer and the stepping agent.

28. The process as defined in claim 20, wherein water is added, after the completion of the reaction, for carrying out the hydrolysis or hydrolytic condensation and hydrolysis.

29. The process as defined in claim 28, wherein the hydrolysis or the hydrolytic condensation and hydrolysis with the addition of water is carried out at a reaction temperature between -5°

-80°

C. and, preferably, 20°

-60°

C.

30. The process as defined in claim 28, wherein the amount of water added is less than the equimolar amount based on Si of the vinyl polymer.

31. The process as defined in claim 28, wherein after the reaction of the hydrolytic condensation, the resultant reaction solution is heated to a temperature between 50°

-150°

C. and, preferably, 70°

-120°

C. for 0.5-5 hours.

32. The process as defined in claim 28, wherein after the hydrolysis or the hydrolytic condensation and the hydrolysis, hexaalkylsilazane represented by the general formula R⁸₃ Si--NH--Si--R⁸₃ (where R⁸ represents an alkyl having 1-10 carbon atoms) or a trialkyl acyloxysilane represented by the general formula R⁸₃ Si--OCOR⁹ (where R⁸ has the same meanings as above and R⁹ represents an alkyl group having 1-4 carbon atoms) is added to the resultant polymer for reaction.