Poly (cyclic conjugated diene) and process for producing the same

a conjugated diene and polymer technology, applied in the field of poly (cyclic conjugated diene), can solve the problems of inability to obtain sufficient polymer yield, inability to polymerize a cyclic conjugated diene monomer having a polar functional group, and inability to synthesize copolymers. achieve high yield, high heat resistance and oxidation resistance, and high yield

Inactive Publication Date: 2002-01-17
TOYOTA CENT RES & DEV LAB INC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

0041] (2) It is possible to provide a modifying product or a hydrogenated product of a poly(cyclic conjugated diene) having high heat resistance and oxidation resistance, and a hydrogenating process for them by adding hydrogen to the poly(cyclic conjugated diene).
0042] (3) It is possible to obtain a poly(cyclic conjugated diene) at a high yield by conducting polymerizing reaction of a cyclic conjugated diene monomer in the presence of a base compound.
0043] (4) It is possible to obtain a poly(cyclic conjugated diene) at a high yield by conducting polymerizing reaction of a cyclic conjugated diene monomer in an aromatic halide.
0044] (5) It is possible to obtain a poly(cyclic conjugated diene) having a high crystallizability by conducting polymerizing reaction of a cyclic conjugated diene monomer in the presence of a Ni-based catalyst.
0045] (6) It is possible to obtain a phenylene polymer at a high yield by conducting polymerizing reaction of a cyclohexadiene derivative in the presence of a Ni-based catalyst.

Problems solved by technology

In this process, however, a comonomer for synthesizing a copolymer is restricted to an anionic polymerizable monomer.
This is an substantial problem of an anionic polymerizing process.
However, in this process, a sufficient polymer yield cannot be obtained since the rare-earth catalyst has a very high reactivity with a polar compound.
Moreover, it is impossible to polymerize a cyclic conjugated diene monomer having a polar functional group.
In addition, the usable kind of comonomers may be limited.
As described above, in these processes for producing a cyclic diene polymer, the kind of monomers or comonomers which can be selected is greatly restricted, and polymerization activity is also insufficient.
Thus, polyparaphenylene is difficult to mold.
However, the conventional method has the following problem.
First, in the polymerization of cyclohexadiene derivatives by radical polymerizing process, the position-selectivity and stereo-selectivity of the molecular structure of the polymer are low.
Second, in the polymerizing process of a cyclohexadiene derivative using a neutral Ni catalyst, the kind of the polymerizable cyclohexadiene derivatives is limited although the position-selectivity and stereo-selectivity of the molecular structure of the polymer are high.
Its activity is also low, and further monomers which can be copolymerized are also restricted.

Method used

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  • Poly (cyclic conjugated diene) and process for producing the same
  • Poly (cyclic conjugated diene) and process for producing the same
  • Poly (cyclic conjugated diene) and process for producing the same

Examples

Experimental program
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Effect test

example 1

[0335] The catalyst A (109 mg, 0.1 mmol) previously synthesized was dissolved into 15 ml of toluene at room temperature under an argon atmosphere in a glove box, to adjust a catalyst solution. In the meantime, 1,3-cyclohexadiene (8 g, 0.1 mol) which is a cyclic conjugated diene monomer was dissolved into 15 ml of toluene at room temperature under an argon atmosphere in a glove box. While this solution was kept to room temperature and was stirred, the total amount thereof was added to the total amount of the above-mentioned catalyst solution. Polymerization advanced promptly so that a powdery polymer was precipitated from the toluene solution. The polymerizing reaction finished within 30 minutes. A slurry containing the produced polymer was taken out from the glove box, and then was added to a great deal of methanol acidified with hydrochloric acid to precipitate and isolate the polymer. Methanol was then removed by filtration. The resultant was vacuum-dried at room temperature for 2...

example 2

[0337] The catalyst B (18 mg, 0.1 mmol) previously synthesized was dissolved into 15 ml of toluene at room temperature under an argon atmosphere in a glove box, and then 1.8 ml of a toluene solution (aluminum: 10 atomic %) of methyl aluminoxane which is a co-catalyst to adjust a catalyst solution. Thereafter, the same operation as in Example 1 was conducted to polymerize 1,3-cyclohexadiene. The yield of the resultant 1,3-cyclohexadiene was 75%.

[0338] The polymer was a white powder, and insoluble in organic solvents. According to an element analysis, carbon was 90% and hydrogen was 10%. This was satisfactorily consistent with the calculation values based on the monomers. The temperature at which thermal weight loss started was 330.degree. C.

example 3

[0339] The catalyst B (0.5 g) previously synthesized was dissolved into 100 ml of toluene at room temperature under an argon atmosphere in a glove box, and then 50 ml of a toluene solution (aluminum: 10 atomic %) of methyl aluminoxane which is a co-catalyst was added thereto so as to adjust a catalyst solution.

[0340] 50 g of 1,3-cyclohexadiene was dissolved into 200 ml of toluene at room temperature. While this solution was kept to room temperature, the total amount thereof was added to the total amount of the above-mentioned catalyst solution.

[0341] At the same time of the addition, a polymerizing reaction advanced at room temperature at a stroke to obtain polycyclohexadiene. The time for the polymerization was 15 seconds. The yield was 82%.

[0342] The polymer was a white powder, and insoluble in organic solvents. According to an element analysis, carbon was 90% and hydrogen was 10%. This was satisfactorily consistent with the calculation values based on the monomers. The temperatur...

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Abstract

An object of the present invention is to provide a novel poly(cyclic conjugated diene) and a process for producing the same; and a modifying product, a hydrogenated product, and a poly(cyclic conjugated diene) comprising phenylene thereof. The present invention is a polymer having molecular structure units derived from cyclic conjugated diene monomers having a polar group. The basic skeleton of the molecular structure units of this polymer preferably has a 5-8-membered cycloalkene ring. For polymerizing reaction of the cyclic conjugated diene monomer, it is preferred to use a catalyst such as a Ni-based catalyst, and conduct the reaction in a non-polar solvent containing a basic compound or in an aromatic halide solvent. The Ni-based catalyst is used for the polymerization to obtain a polymer having high crystallizability. Its substituents are removed to obtain a paraphenylene polymer.

Description

BACKGROUND OF THE INVENTION[0001] 1. Field of the Invention[0002] The present invention relates to a poly(cyclic conjugated diene), and specifically to a poly(cyclic conjugated diene) derived from a specified cyclic conjugated diene monomer, and a process for producing the same; and a paraphenylene polymer and a polymerizing process for the same.[0003] 2. Description of the Related Art[0004] Conventionally, various attempts have been made to produce a poly(cyclic conjugated diene) by polymerizing a cyclic conjugated diene monomer, a typical example of which is 1,3-cyclohexadiene. In particular, polymers of cyclic conjugated diene monomers having a high 1,4-position content have been expected as polymers having improved thermal, mechanical and electric properties such as high heat resistance and rigidity, a lowered specific gravity and a lowered dielectric constant, resulting from the linear polymerization thereof.[0005] Japanese Laid-Open Patent Publication No. 7-247321 discloses a ...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C08G61/08C08F4/602C08F4/70C08F4/80C08F32/06C08F36/14C08G61/12
CPCC08F32/06C08F36/14C08F4/602C08F4/70C08F4/80C08G61/08C08G61/12
Inventor NAKANO, MITSURUUSUKI, ARIMITSUYAO, QING
Owner TOYOTA CENT RES & DEV LAB INC
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