Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2002-06-07
2004-11-09
Harlan, Robert D. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S281000, C526S171000, C526S172000
Reexamination Certificate
active
06815516
ABSTRACT:
TECHNICAL FIELD
This invention relates to a novel copolymer produced by a ring-opening metathesis polymerization of a cycloolefin monomer (which copolymer is hereinafter referred to as “ring-opened metathesis copolymer” or merely “copolymer” when appropriate), and a hydrogenation product of the ring-opened metathesis copolymer. More particularly, this invention relates to a ring-opened metathesis copolymer and a hydrogenation product of the copolymer, which exhibit good and balanced low-dielectric property, low water-absorption and high adhesion to metal, and excellent heat resistance. This invention further relates to a process for producing the copolymer and a process for producing the hydrogenation product of the copolymer.
BACKGROUND ART
Hitherto known ring-opened metathesis copolymers from cycloolefin monomers and hydrogenation products of the copolymers have excellent heat resistance, electrical characteristics and low water-absorption, but have a problem of poor adhesion to metal and other materials.
To solve this problem, a method of polymerizing or copolymerizing a cycloolefin monomer having a polar group was proposed. More specifically, a ring-opened metathesis copolymer produced from a cycloolefin monomer having a polar group such as an ester group or a cyano group, and a hydrogenation product thereof were proposed. The proposed copolymer and the hydrogenation product thereof exhibit an enhanced adhesion as compared with the conventional ring-opened metathesis copolymer having no polar group and the hydrogenation product thereof, but, the adhesion is improved only in some small degree, and the dielectric properties and water-absorption are undesirably enhanced.
A ring-opened metathesis homopolymer from norbornene-5,6-dicarboxylic anhydride which is a most popular cycloolefin monomer having a carboxylic anhydride group was proposed (Japanese Examined Patent Publication No. S60-43365, and Polym. Prepr., 18, 110-115 (1177). Further, a method was proposed wherein tetracyclododecene-3,4-dicarboxylic anhydride is homopolymerized, the resulting homopolymer is hydrogenated, and then, a part of the carboxylic anhydride groups of the hydrogenated homopolymer is hydrolyzed with an acid (Japanese Unexamined Patent Publication No. H11-130843). However, the above-mentioned homopolymers of cycloolefin monomers having a carboxylic anhydride group and hydrogenation products thereof still have a problem such that the dielectric properties and low water-absorption are greatly inferior to the polymers produced from a cycloolefin monomer having no polar group. It is described in the above-cited Japanese examined patent publication that norbornene-5,6-dicarboxylic anhydride can be copolymerized with other cycloolefin monomers, but, norbornene-5,6-dicarboxylic anhydride has a greatly different polymerizability from that of a norbornene monomer having no polar group, and therefore, the copolymerization reaction does not occur to any significant degree and a copolymer having a desired copolymerization ratio and a desired molecular weight cannot be obtained.
DISCLOSURE OF THE INVENTION
A first object of the present invention is to provide a highly heat-resistant ring-opened metathesis copolymer and a hydrogenation product thereof, which have excellent electrical properties, low water-absorption and high adhesion to metal and other materials.
A second object of the present invention is to provide processes for producing with high efficiency the above-mentioned ring-opened metathesis copolymer and a hydrogenation product thereof.
To achieve the above-mentioned objects, the present inventors made extensive research and found that, when an organic ruthenium compound having a specific ligand is used as a polymerization catalyst, a cycloolefin monomer having a carboxylic anhydride group can be copolymerized with a cycloolefin monomer having no substituent or a hydrocarbon substituent at any desired copolymerization ratio, and further that the resulting copolymer and a hydrogenation product thereof satisfy mutually contradictory properties, namely exhibit good and balanced electrical properties, low water-absorption and adhesion to metal. Based on these findings, the present invention has been completed.
In one aspect of the present invention, there is provided a ring-opened metathesis copolymer characterized by comprising repeating units [A] represented by the following general formula (1):
wherein O is an oxygen atom, R
1
and R
2
independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and m is an integer in the range of 0 to 2, and repeating units [B] represented by the following general formula (2):
wherein R
3
, R
4
, R
5
and R
6
independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms wherein R
3
or R
5
may be bonded together with R
4
or R
6
to form a ring, and n is an integer of 0, 1 or 2; the ratio of repeating units [A]/repeating units [B] being in the range of 5/95 to 95/5 by mol; said copolymer having a weight average molecular weight in the range of 10,000 to 1,000,000 as measured by gel permeation chromatography and expressed in terms of polystyrene.
In another aspect of the present invention, there is provided a hydrogenation product of the above-mentioned ring-opened metathesis copolymer, wherein 50 to 100% of the double bonds in the backbone chain of the ring-opened metathesis copolymer have been hydrogenated.
In still another aspect of the present invention, there is provided a process for producing the ring-opened metathesis copolymer, characterized by copolymerizing at least one kind of a cycloolefin monomer represented by the following general formula (3):
wherein O, R
1
, R
2
and m are the same as those defined for formula (1), with at least one kind of a cycloolefin monomer represented by the following general formula (4):
wherein R
3
, R
4
, R
5
, R
6
and n are the same as those defined for formula (2), by a ring-opening metathesis copolymerization procedure using a polymerization catalyst comprising as a principal ingredient an organic ruthenium compound having coordinated thereto a heterocyclic carbene compound as ligand.
In a further aspect of the present invention, there is provided a process for producing a hydrogenation product of the above-mentioned ring-opened metathesis copolymer, characterized by hydrogenating the above-mentioned ring-opened metathesis copolymer in the presence of hydrogen by using a hydrogenation catalyst.
BEST MODE FOR CARRYING OUT THE INVENTION
The cycloolefin monomer represented by formula (3) used in the present invention is a cycloolefin monomer having a carboxylic anhydride group, which includes bicycoheptene derivatives [m=0 in formula (3)], tetracyclododecene derivatives [m=1 in formula (3)] and hexacycloheptadecene derivatives [m=2 in formula (3)].
In formula (3), O represents an oxygen atom, and R
1
and R
2
independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group means a straight chain, a branched chain or a cyclic hydrocarbon group, which may be either saturated or unsaturated. As specific examples of the hydrocarbon group, there can be mentioned alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dedecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and nonadecyl; and corresponding alkenyl groups, such as vinyl and allyl groups; corresponding alkadienyl, alkatrienyl and alkatetraenyl groups; and cycloalkyl groups, cycloalkenyl groups and aryl groups.
As specific examples of the cycloolefin monomer of formula (3), there can be mentioned bicycloheptene derivatives such as bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, 2-methylbicyclo[2.2.1]-hept-5-ene-2,3-dicarboxylic anhydride and 2-phenylbicyclo-[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride; tetracyclododecene derivatives such as tetracyclo-[4.4.
Sakamoto Masato
Tsunogae Yasuo
Birch & Stewart Kolasch & Birch, LLP
Harlan Robert D.
Zeon Corporation
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