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

• US 4,602,065 A
• Filed: 09/18/1984
• Issued: 07/22/1986
• Est. Priority Date: 09/18/1984
• Status: Expired due to Term

• Current Assignee: Chisso Corporation
• Original Assignee: Chisso Corporation
• Inventors: Maehara, Hiroshi, Wada, Masami, Tsuji, Kazuyuki, Konotsune, Shiro, Higashi, Hiromi
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): Lipman, Bernard
• Application Number:
  US06/651,689
• Time in Patent Office: 672 Days
• Field of Search: 525/326.5, 526/279
• US Class Current: 525/326.5
• 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 silicon-containing step ladder polymer

(a) comprising repeating units represented by the general formula ##STR14## a unit represented by the general formula ##STR15## and a unit represented by the general formula ##STR16## where R¹ represents a hydrocarbon group or fluorine-substituted hydrocarbon group, R² represents hydrogen or a trialkylsiloxy group, R³ and R⁴ which may be identical or different with each other, represent individually a hydrocarbon group or fluorine-substituted hydrocarbon group,

(b) in the unit (I) the free CH bond is bonded to the free CH₂ bond in other unit (I), the free CH₂ bond in the unit (II), a hydrocarbon residue of a vinyl polymerization initiator, or hydrogen;

the free Si bond is bonded to the free O bond in other unit (I), the free R² O bond in the unit (II) the free O bond of the unit (III) or independent R² O;

the free CH₂ bond is bonded to the free CH bond in other unit (I), the free CH bond in the unit (II), a hydrocarbon residue of a vinyl polymerization initiator or hydrogen; and

the free O bond is bonded to the free Si bond in other unit (I), the free Si bond in the unit (II), the free Si bond in the unit (III), or R² ;

(c) in the unit (II), the free CH bond is bonded to the free CH₂ bond in the unit (I);

the free Si bond is bonded to the free O bond in the unit (I); and

the free CH₂ bond is bonded to the free CH bond in the unit (I); and

the free R² O bond is bonded to the free Si bond in the unit (I), and

(d) a ring structure is constituted by bondings between a free CH₂ bond in the unit (I) and a free CH bond in a next unit (I) and between a free O bond in the unit (I) and a free Si bond in the next unit (I) or by bondings between a free CH₂ bond in a unit (I) and a free CH bond in a next unit (II) and between a free O bond in the unit (I) and a free Si bond in the next unit (II),

(e) in the unit (III), the free Si bond is bonded to the free O bond in the Unit (I), the free O bond in other unit (III), or independent R² O--;

the free O bond is bonded to the free Si bond in the unit (I), the free Si bond in other unit (III), or independent R²,

(f) the molar ratio of the unit (I) to the unit (II) is between 5;

1 and 100;

1 and the molar ratio of the unit (III) to the total amount of the unit (I)+unit (II) is between 1;

5 and 1-100,

(g) a unit chain of the ladder structure constituted with the units selected from the unit (I) and the unit (II) comprises 5-100 units of said selected units.

2. The polymer as set forth in claim 1 wherein the unit chain having the ladder structure consisting of the units selected from the unit (I) and the unit (II) comprises a polymerized structure coupled by the unit (III) or a chain thereof of less than 5 units.

3. The polymer as set forth in claim 1 having a weight average molecular weight of 3.0×

10³ -6.5×

10⁵ as measured by gel permeation chromatography.

4. The polymer as set forth in claim 1 wherein the infrared absorption spectrum inherent to the siloxane bond in the unit (III) is present within the range wave number between 1020-1090 cm^-1, an infrared absorption spectrum which is inherent to the ring structure formed by the repetition of the repeating unit (I) or from unit (I) and unit (II), that is, 1,5-disilpyran ring formed through the intra-molecular siloxy condensation of 1,3-disilpropylene, is exhibited at 960 cm^-1 and the absorption ratio of the absorption at the wave number of 1080 cm^-1 to the absorption at the wave number of 960 cm^-1 (A1080/A960) is between 0.05-0.37.

5. The polymer as set forth in claim 1, wherein R¹ has 1-10 carbon atoms;

R² represents hydrogen or a trialkylsilyl group comprising an alkyl group having 1-10 carbon atoms, and R³ and R⁴ individually have 1-10 carbon atoms.

6. The polymer as set forth in claim 5 wherein R¹ represents an alkyl or fluorine-substituted alkyl group having 1-4 carbon atoms or a phenyl group;

R² represents hydrogen or a trialkylsilyl group comprising an alkyl group having 1-4 carbon atoms; and

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

7. The polymer set forth in claim 6 wherein R¹ represents a methyl, trifluoropropyl or phenyl group, R² represents hydrogen or a trimethylsilyl group;

and R³ and R⁴ represent individually methyl or phenyl groups.

8. A silicon-containing step ladder polymer having the structure:

space="preserve" listing-type="equation">A--Z--B--Z--.sub.n A'"'"'

where A has the structure;

##STR17## where R⁵ and R⁶ individually represent hydrogen or hydrocarbon residue of the vinyl polymerization initiator provided that if one of them is hydrogen the other is the hydrocarbon residue;

r≧

1, s≧

1, r+s+t=4-99, t is an integer and t/(r+s)=0.01-0.2.

A'"'"' has the following structure;

##STR18## where R⁵, R⁶, r, t and s have the same meanings as above, B has the following structure;

##STR19## where R⁵, R⁶, r, t and s have the same meanings as above, and Z has the following structure;

##STR20## where P is an integer from 1 to 5, and

n is a number of from 0 to 1300.