Process for producing poly (cyclic conjugated diene)

Details Process for producing poly (cyclic conjugated diene) Process for producing poly (cyclic conjugated diene)

1999-05-06

2002-07-30

Teskin, Fred (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S131000, C526S134000, C526S159000, C526S161000, C526S170000, C526S172000, C526S204000, C526S240000, C526S279000, C526S308000, C526S309000, C525S326500, C525S328800, C525S329500, C528S357000, C528S392000

Reexamination Certificate

active

06426396

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
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.
2. Description of the Related Art
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.
Japanese Laid-Open Patent Publication No. 7-247321 discloses a polymerizing process of cyclic conjugated diene using a complex compound of an organic compound containing an IA-group metal such as lithium or sodium as an anionic polymerization catalyst. According to this polymerizing process, the cyclic conjugated diene monomer can be polymerized in a high degree by the organic metal compound which forms the complex.
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.
Japanese Laid-Open Patent Publication No. 6-211916 discloses a polymerizing process of a conjugated diene group using a composite catalyst including a rare-earth metal compound. 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.
There is a process of producing polyparaphenylene using a poly(cyclic conjugated diene) as a precursor. The polyparaphenylene has been expected as a conductive polymer material, but is not dissolved in any solvent, and it is not melted even when heated. Thus, polyparaphenylene is difficult to mold. As an effective method for solving the problem, there is a conventional method of polymerizing a cyclohexadiene derivative to obtain a polymer, using the polymer as an soluble precursor to make a film or the like, and then removing substituents from the cyclohexadiene derivative to convert it into polyparaphenylene.
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. Accordingly, the ratio of the conversion into polyparaphenylene is low so that only a polymer material having a low conductivity can be obtained. 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.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a poly(cyclic conjugated diene) and a polymerizing process for the same; and a phenylene polymer and a process for producing the same, each of which is improved to solve the above-mentioned problems in the related art.
In order to solve the above-mentioned problems, the inventors have eagerly made investigations to succeed in providing a new poly(cyclic conjugated diene) by using a specific catalyst to polymerize a cyclic conjugated diene monomer, and simultaneously succeeded in providing an improved process for polymerizing a cyclic conjugated diene monomer. Thus, the inventors have completed the present invention.
That is, the present invention is a poly(cyclic conjugated diene) comprising: a molecular structure unit having the formula (I) (the molecular structure unit is referred to as a molecular structure unit (A) in this specification) derived from at least one cyclic conjugated monomer, and the unit being bonded to each other at 1,4-position and/or 1,2-position
wherein n is an integer of 1-6; each X individually represents a carbon, silicon or germanium atom; each R
1
individually represents a hydrogen atom or halogen atom, an alkyl, unsaturated hydrocarbon, aryl, cycloalkyl or cyclodienyl group, or a 5-10-membered heterocyclic group having at least one of nitrogen, oxygen and sulfur atoms as a heteroatom; at least one of each individual R
2
represents an aryl substituted with a hydroxyl group and an alkyl group having 1-4 carbon atoms, iminocarboxyl, alkoxyl, aryloxyl, or alkoxysilyl group, —(CH
2
)
p
—OH, —(CH
2
)
p
—C(O)—OH, —(CH
2
)
p
—C(O)—OR
3
, —(CH
2
)
p
—OR
3
, —(CH
2
)
p
—OC(O)—R
3
, —(CH
2
)
p
—OC(O)—OR
3
, —(CH
2
)
p
—C(O)—R
3
, —(CH
2
)
p
—O—(CH
2
)
p
OH wherein each p is respectively an integer of 0-24, R
3
is a linear chain or branched alkyl or aryl group, or a group represented by the following formulae (a)-(h) (in the formulae (a)-(h), Y is a hydrogen atom, an alkyl, alkoxyl, alkoxycarbonyl or cyano group) (these groups of R
2
are referred to as the polar groups in this specification), or an alkylsilyl, halogenated alkyl, halogenated cycloalkyl, halogenated aryl or halogenated aralkyl group (these groups of R
2
are referred to as the non-polar groups); the other R
2
represents a hydrogen or halogen atom, a linear chain or branched alkyl, cycloalkyl, alkylidenyl, aryl, aralkyl, alkynyl, vinyl, alkenyl group wherein a supplied alkenyl radical does not contain any terminal double bond, cyclodienyl group, or a 5-10-membered heterocyclic group having at least one of nitrogen, oxygen and sulfur atoms as a heteroatom (these groups of R
2
are referred to as the substituents); and optionally any two R
2
s are bonded to each other to form a cyclic structure.
Further, the present invention is a poly(cyclic conjugated diene) comprising: a molecular structure unit having the formula (II) (the molecular structure unit is referred to as molecular structure unit (B) in this specification) derived from at least one cyclic conjugated diene monomer, and the unit being bonded to each other at 1,4-position and/or 1,2-position:
wherein n is an integer of 1-6; each X is individual and at least one of them is a silicon or germanium atom; the other X is/are carbon atom(s); each R
11
individually represents a hydrogen or halogen atom, an alkyl, unsaturated hydrocarbon, aryl, cycloalkyl or cyclodienyl group, or a 5-10-membered heterocyclic group having at least one of nitrogen, oxygen and sulfur atoms as a heteroatom; each R
12
individually represents a hydrogen or halogen atom, a linear chain or branched alkyl, cycloalkyl, alkylidenyl, aryl, aralkyl, alkynyl, vinyl, alkenyl group wherein a supplied alkenyl radical does not contain any terminal double bond, cyclodienyl group, or a 5-10-membered heterocyclic group having at least one of nitrogen, oxygen and sulfur atoms as a heteroatom (i.e., the substituents); and optionally any two R
12
s are bonded to each other to form a cyclic structure.
In addition, the present invention is a copolymer comprising two or more kinds of molecular structure units selected from the following 4 kinds of molecular structure units, wherein the molecular structure units (A), (B) and (C) are bonded to a polymer chain at 1,4-position and/or 1,2-position:
one or more kinds of molecular structure unit (molecular structure unit (A)) represented by the formula (I):
wherein n is an integer of 1-6; each X individually represents a carbon, silicon

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