Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reexamination Certificate
2002-06-24
2004-02-17
Seidieck, James J. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Compositions to be polymerized by wave energy wherein said...
C522S006000, C522S066000, C522S067000, C522S113000, C522S114000, C522S116000, C522S118000, C522S120000, C522S124000, C522S125000, C522S132000, C522S150000, C522S157000, C522S158000, C522S159000, C522S161000
Reexamination Certificate
active
06693142
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a production method of functional group-terminated vinyl polymers and functional group-terminated vinyl polymers as obtainable by the above method.
BACKGROUND ART
It is known that functional group-terminated polymers may undergo crosslinking, either by themselves or in the presence of another polymer having a terminal or chain-interrupting functional group and an appropriate curing agent depending on the properties of functional groups, to give functional products having outstanding heat resistance, water resistance, durability, compatibility and other characteristics. Moreover, when a polymer has functional groups at all its molecular termini, a chain extension by terminus-terminus crosslinking occurs with good efficiency to give a linear or network high molecular weight polymer and, hence, a resin with excellent elongation and tensile strength characteristics.
Functional group-terminated polymers are of great use as, for example, reactive raw materials for resins such as polyester resin, polyurethane resin, polycarbonate resin, etc., paints, adhesives, self-adhesives, sealants, urethane foams, gel coatings, thermoplastic elastomers, molding compounds, resin modifiers, dampers, elastic wall and floor panels, textile processing agents, UV.EV-curable resin, high-solid paints and so forth. These are also useful as various resin additives and raw materials.
Referring to rubber type polymers among functional group-terminated polymers, many reports are available on their syntheses until now. Moreover, polymers having a functional group at both termini of a polyether backbone chain have heretofore been used as starting materials for urethane adhesives and sealants or modifiers for epoxy adhesives. In addition, polyester resins such as polyethylene terephthalate and polycaprolactone have also been used in many applications. However, as to other resins, particularly those of vinyl monomers having polar groups, the production method for functional group-terminated vinyl polymers has not been implemented on a commercial scale as yet.
As for a production method of polymers of such functional group-terminated highly polar vinyl monomers, for example, Japanese Kokai Publication Hei-5-255415 discloses a process for synthesizing a (meth)acrylic polymer having an alkenyl group at either terminus by using an alkenyl group-containing disulfide as a chain transfer agent. Japanese Kokai Publication Hei-5-262808 discloses a process comprising synthesizing an acrylic polymer having a hydroxyl group at either terminus by using a hydroxyl group-containing disulfide and utilizing these terminal hydroxyl groups, synthesizing an alkenyl group-terminated (meth)acrylic polymer. However, in the former process, a functional group can hardly be introduced into the terminus with certainty and the latter process requires a chain transfer agent in a large amount for synthesizing a hydroxyl group-containing polymer. Thus, these synthetic technologies have drawbacks in some process parameters or others.
Recently much research has been undertaken on the polymerization by the living polymerization method inclusive of living ionic polymerization and living radical polymerization. In the synthesis of polymers by these polymerization techniques, the molecular weight and molecular weight distribution can be controlled and, moreover, by converting the active group at the living terminus to a desired substituent group, a functional group-terminated polymer can be obtainable with comparative ease.
Referring to the production method of a functional group-terminated polymer by utilizing the above-mentioned living ionic polymerization method, Japanese Kohyo Publication Hei-4-501883, for instance, discloses a process for synthesizing a hydroxyl group-terminated poly(meth)acrylic ester and a process for synthesizing a (meth)acrylic acid macromonomer by way of living anionic polymerization. However, in the case of such anionic polymerization, the termination reaction and chain transfer reaction cannot be controlled unless anhydrous or low-temperature conditions are maintained and the reaction does not proceed in the living fashion so that the terminal transformation is rendered impossible. Therefore, the technology is lacking in commercial utility.
Referring to living radical polymerization, Japanese Kokai Publication Hei-9-272714, for instance, discloses a production method of an alkenyl group-terminated (meth)acrylic polymer which comprises using an organohalogen or brominated sulfonyl compound as an initiator and an equivalent amount thereto of a complex of a Group 8 to 11 transition metal as a catalyst. However, the transition metal complex has such a high affinity for oxygen that unless in a completely inert system its catalytic activity is lost to arrest the progress of polymerization. Therefore, the technology is not practically useful as for a production.
SUMMARY OF THE INVENTION
The present invention, developed in light of the above state of the art, has for its object to provide a production method by which a polymer of a functional group-terminated vinyl monomer can be easily and practically produced.
It is another object of the present invention to provide a functional group-terminated vinyl polymer which is useful as a material for the production of various functional products.
The first aspect of the present invention is concerned with a production method of a functional group-terminated vinyl polymer comprising
a step of synthesizing a halogen atom-terminated vinyl polymer by the radical polymerization reaction of a vinyl monomer in the presence of a halogen compound and
a step of introducing a functional group to a terminus by substituting a functional group-containing-group for the terminal halogen atom of said vinyl polymer,
said halogen compound having a structure such that said halogen atom is bound to a carbon atom linked to an aromatic ring and
said radical polymerization reaction being carried out either by light irradiation or light irradiation in the presence of a Group 14 to 16 metal compound or by heating in the presence of a Group 14 to 16 metal compound.
The second aspect of the present invention is concerned with a production method of a functional group-terminated vinyl polymer comprising
a step of synthesizing an iodine atom-terminated vinyl polymer by the radical polymerization reaction of a vinyl monomer in the presence of an iodine compound and
a step of introducing a functional group to the terminus by substituting a functional group-containing group for the terminal iodine atom of said vinyl polymer,
said iodine compound having a structure such that said iodine atom is bound to a carbon atom linked to an aromatic ring and
said radical polymerization reaction being carried out either by heating or by heating in the presence of a radical polymerization initiator.
The third aspect of the present invention is concerned with a functional group-terminated vinyl polymer as obtainable by the production method according to the first aspect or the second aspect of the invention
which has a number average molecular weight of 500 to 50,000 and a terminal functional group introduction rate of not less than 90%.
DISCLOSURE OF THE INVENTION
In the following, the present invention is now described in detail.
In the production method according to the first aspect of the invention, a vinyl monomer is subjected to radical polymerization reaction in the presence of a halogen compound in the first place to synthesize a halogen atom-terminated vinyl polymer.
The vinyl monomer to be used in this first aspect of the invention is not particularly restricted but includes, for example, (meth)acrylic acid, (meth)acrylic esters, styrene derivatives, (meth)acrylonitrile, (meth)acrylamide, vinyl halides, vinyl esters, (meth)acrolein, maleic acid derivatives, fumaric acid derivatives, and so forth. The preferred, among these vinyl monomers, are (meth)acrylic esters, styrene derivatives, (meth)acrylonitrile and vinyl esters. Particularly preferred are (meth)acrylic esters, s
Kakehi Takamaro
Wakiya Takeshi
McClendon Sanza
Seidieck James J.
Sekisui Chemical Co. Ltd.
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