Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2001-03-23
2003-08-19
Lipman, Bernard (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S342000
Reexamination Certificate
active
06608144
ABSTRACT:
TECHNICAL FIELD
This invention relates to a hydrolyzable silyl group-containing polyolefin in the form of an ethylene-&agr;-olefin-unconjugated polyene random copolymer rubber having hydrolyzable silyl groups introduced therein, and a method for preparing the same.
BACKGROUND ART
Methods known in the art for obtaining hydrolyzable silicon-containing polyolefins include a method of reacting polyethylene with vinyltrimethoxysilane under polyethylene molding conditions in the presence of a peroxide, and a method of copolymerizing an olefin monomer with an alkenyl group-containing alkoxysilane.
However, the hydrolyzable silicon-containing polyolefins obtained by these methods are solid at room temperature and can be used for resin modification purposes, but cannot be applied as sealants and adhesives.
The applicant proposed (in JP-A 9-59317) a method of obtaining a liquid hydrolyzable silicon-containing polyolefin by reacting a polybutadiene oligomer with a silicon compound. This polymer results in an elastomer, which has an insufficient strength. It is desired to have a practically acceptable hydrolyzable silicon-containing polyolefin having hydrolyzable silyl groups introduced therein.
DISCLOSURE OF THE INVENTION
The present invention has been made under the above-described circumstances, and its object is to provide a hydrolyzable silyl group-containing ethylene-&agr;-olefin-unconjugated polyene random copolymer rubber (EPDM) which can be crosslinked with air-borne moisture at room temperature, and a method for preparing the same.
Making extensive investigations to attain the above objects, the inventor has found that when a specific ethylene-&agr;-olefin-unconjugated polyene random copolymer rubber, that is, an ethylene-&agr;-olefin-unconjugated polyene random copolymer rubber in which the unconjugated polyene is at least one terminal vinyl group-containing norbornene compound of the general formula (I) or (II) shown below is subjected to hydrosilylation reaction with a silicon compound of the general formula (2) shown below, thereby adding the SiH group to a double bond in the copolymer, there is obtained a hydrolyzable silyl group-containing polyolefin (ethylene-&agr;-olefin-unconjugated polyene random copolymer rubber) which can be crosslinked with air-borne moisture at room temperature, and that this hydrolyzable silyl group-containing polyolefin is applicable as one-part RTV without further treatment and useful as elastic sealants and adhesives, and also applicable for resin modification of the crosslinking type by admixing with polyolefins or other resins.
More particularly, ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, etc. are known in the prior art as the diene moiety in ethylene-&agr;-olefin-unconjugated polyene random copolymer rubbers, and the ethylene-&agr;-olefin-unconjugated polyene random copolymer rubbers having these diene moieties do not undergo hydrosilylation reaction with a silicon compound of the general formula (2). Quite unexpectedly, the inventors have found that the hydrosilylation reaction readily takes place when the unconjugated polyene is at least one terminal vinyl group-containing norbornene compound of the general formula (I) or (II), resulting in a hydrolyzable silyl group-containing polyolefin having improved physical properties as mentioned above. The present invention is predicated on these findings.
Accordingly, the invention provides an ethylene-&agr;-olefin-unconjugated polyene random copolymer rubber containing in a molecule hydrolyzable silyl groups represented by the following general formula (1); and a method for preparing the ethylene-&agr;-olefin-unconjugated polyene random copolymer rubber, characterized by subjecting an ethylene-&agr;-olefin-unconjugated polyene random copolymer rubber in which the unconjugated polyene is at least one terminal vinyl group-containing norbornene compound of the following general formula (I) or (II) to hydrosilylation reaction with a silicon compound of the following general formula (2), thereby adding the SiH group of the silicon compound to a double bond in the copolymer.
Herein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms, X is a hydrolyzable group selected from the group consisting of hydride, halogen, alkoxy, acyloxy, ketoxymate, amide, acid amide, and aminoxy groups, and the letter “a” is an integer of 0, 1 or 2.
Herein n is an integer of 0 to 10, R
1
is hydrogen or an alkyl group of 1 to 10 carbon atoms, and R
2
is hydrogen or an alkyl group of 1 to 5 carbon atoms.
Herein R
3
is hydrogen or an alkyl group of 1 to 10 carbon atoms.
BEST MODE FOR CARRYING OUT THE INVENTION
The invention is described in detail below. The hydrolyzable silyl group-containing ethylene-&agr;-olefin-unconjugated polyene random copolymer rubber according to the first embodiment of the invention is an ethylene-&agr;-olefin-unconjugated polyene random copolymer rubber in which the unconjugated polyene is at least one terminal vinyl group-containing norbornene compound of the following general formula (I) or (II) and which contains hydrolyzable silyl groups represented by the formula (1) on side chains or at ends thereof. The hydrolyzable silyl group has a hydrolyzable group attached to a silicon atom. Examples of the hydrolyzable group include hydride, halogen, alkoxy, acyloxy, ketoxymate, amide, acid amide, and aminoxy groups. Of these, the alkoxy, acyloxy, and ketoxymate groups are preferred, with the alkoxy groups being especially preferred.
The method for preparing the hydrolyzable silyl group-containing ethylene-&agr;-olefin-unconjugated polyene random copolymer rubber according to the invention is not critical, although the preferred method is by subjecting an ethylene-&agr;-olefin-unconjugated polyene random copolymer rubber in which the unconjugated polyene is at least one terminal vinyl group-containing norbornene compound of the following general formula (I) or (II) to hydrosilylation reaction with a silicon compound of the following general formula (2).
Herein n is an integer of 0 to 10, R
1
is hydrogen or an alkyl group of 1 to 10 carbon atoms, and R
2
is hydrogen or an alkyl group of 1 to 5 carbon atoms.
Herein R
3
is hydrogen or an alkyl group of 1 to 10 carbon atoms.
Herein R is a monovalent hydrocarbon group of 1 to 12 carbon atoms, X is a hydrolyzable group selected from the group consisting of hydride, halogen, alkoxy, acyloxy, ketoxymate, amide, acid amide, and aminoxy groups, and the letter “a” is an integer of 0, 1 or 2.
The ethylene-&agr;-olefin-unconjugated polyene random copolymer rubber used herein as a first component is desirably one whose diene moiety is at least one terminal vinyl group-containing norbornene compound of the general formula (I) or (II). Among others, 5-vinyl-2-norbornene and 5-methylene-2-norbornene are preferred. Such a copolymer is prepared, for example, by randomly copolymerizing ethylene and propylene with an appropriate amount of 5-vinyl-2-norbornene in a hydrocarbon solvent in the presence of a catalyst containing a vanadium base catalyst and an organic aluminum base catalyst as main components. The vanadium base catalyst used herein includes VOCl
3
, VO(OC
2
H
5
)
3
, etc. and the organic aluminum base catalyst includes triethylaluminum, diethylaluminum ethoxide, etc. It is desired to use at least one vanadium base catalyst and at least one organic aluminum base catalyst in combination. As the catalyst used in the copolymerization, it is acceptable to use so-called metallocene catalysts, for example, the metallocene catalysts described in JP-A 9-40586. The preferred conditions for this copolymerization reaction include a polymerization temperature of 30 to 60° C., more desirably 30 to 50° C., and a polymerization pressure of 4 to 12 kgf/cm
2
, more preferably 5 to 8 kgf/cm
2
, while the unconjugated polyene and the &agr;-olefin are preferably fed in such amounts as to give a molar ratio (unconjugated polyene/a-olefin) of from 0.01 to 0.2.
In the practice of the invention, the ethylene-&agr;-olefin-unconjugated polyene random copol
Hakuta Takashi
Kawasaki Masaaki
Kikuchi Yoshiharu
Nakamura Tsutomu
Yamamoto Akira
Birch & Stewart Kolasch & Birch, LLP
Lipman Bernard
Shin-Etsu Chemical Co. , Ltd.
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