Process for producing functional styrene copolymer

Details Process for producing functional styrene copolymer Process for producing functional styrene copolymer

2001-12-19

2002-11-26

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...

C526S151000, C526S153000, C526S160000, C526S240000, C526S274000, C526S279000, C526S299000, C526S310000, C526S347000, C525S333300, C525S383000, C525S384000

Reexamination Certificate

active

06486272

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a process for producing a styrenic copolymer having a functional group and a styrenic copolymer having a functional group. More particularly, the present invention relates to a process for efficiently producing a styrenic copolymer, in particular, a styrenic random copolymer, having a functional group and the syndiotactic configuration and a random styrenic copolymer having a functional group and the syndiotactic configuration and exhibiting improved physical properties such as adhesion with adhesives and compatibility with various rubbers.
BACKGROUND ART
Heretofore, styrenic polymers produced in accordance with the radical polymerization are formed into various shapes in accordance with various molding processes and widely used for home electric appliances, business equipments, utensils, packaging containers, furnitures, toys, synthetic papers and other industrial materials. However, the conventional styrenic polymers have the atactic configuration and have a drawback in that heat resistance and chemical resistance are poor.
To overcome the above drawback of the styrenic polymers having the atactic configuration, the group of investigators in which the present inventors are included succeeded in developing styrenic polymers having a highly syndiotactic configuration. Styrenic copolymers of a styrenic monomer and other monomers having the syndiotactic configuration were also successfully developed. Examples of such polymers and copolymers include syndiotactic copolymers of styrene and substituted styrenes (Japanese Patent Application Laid-Open No. Showa 63(1988)-241009) and syndiotactic copolymers of styrene and polar vinyl monomers (Japanese Patent Application Laid-Open Nos. Heisei 2(1990)-258810, Heisei 2(1990)-258805, Heisei 2(1990)-258812, Heisei 4(1992)-130108, Heisei 4(1992)-185619 and Heisei 4(1992)-298512). Block copolymers of styrene and styrenic compounds having a heteroatom were also developed (Japanese Patent Application Laid-Open No. Heisei 5(1993)-320281).
However, the above processes for producing styrene copolymers having the syndiotactic configuration by copolymerization have the following drawbacks. (1) In the copolymerization with polar vinyl monomers, amorphous byproducts soluble in solvents are occasionally formed in great amounts or the crystalline property and heat resistance which are proper characteristics of the syndiotactic styrene resins are occasionally adversely affected. (2) It is desirable for improving physical properties that a functional group is uniformly distributed within a polymer. However, in a block copolymer of styrene and a styrenic polar comonomer, a monomer having the functional group is incorporated only into growing end portions of a polymer and, therefore, the effect of improving the physical properties is smaller than that of random copolymers in which the monomer units having a functional group are distributed randomly in the molecular chain. (3) When a polar vinyl monomer or a styrenic compound having a functional group is present in the polymerization system without any pretreatments, the activity of a catalyst and productivity markedly decrease due to the monomer or the compound.
DISCLOSURE OF THE INVENTION
Under the above circumstances, the present invention has an object of providing a process for efficiently producing a styrenic copolymer, in particular, a styrenic random copolymer, having a functional group and the syndiotactic configuration and exhibiting improved physical properties such as adhesion with adhesives and compatibility with various rubbers.
As the result of extensive studies by the present inventors to achieve the above object, it was found that, when a vinyl compound having a functional group was treated with a metal compound to mask the functional group and copolymerized with a styrenic compound in the presence of a specific catalyst, the decrease in the activity of the catalyst was suppressed and a styrenic copolymer, in particular, a random styrenic copolymer, having the functional group and the syndiotactic configuration could be efficiently obtained and that the styrenic random copolymer having specific repeating units, the functional group and the syndiotactic configuration was very useful for improving physical properties such as adhesion with adhesives and compatibility with various rubbers. The present invention has been completed based on the knowledge.
The present invention provides a process for producing a styrenic copolymer having a functional group and a syndiotactic configuration, the process comprising bringing a metal compound into interaction with a vinyl compound having a functional group to mask the functional group and copolymerizing the vinyl compound having the masked functional group with a styrenic compound in a presence of a polymerization catalyst comprising (A) a transition metal compound, (B) at least one compound selected from compounds having oxygen and compounds which can form ionic complex compounds by reaction with the transition metal compound and (C) an organometallic compound.
The present invention also provides a random styrenic copolymer having a functional group and a syndiotactic configuration, the copolymer comprising:
(a) styrenic repeating units represented by general formula (II):
wherein R
8
represents hydrogen atom, a halogen atom or a substituent having C, Sn or Si, t represents an integer of 1 to 5 and, when a plurality of R
8
are present, the plurality of R
8
may represent a same group or different groups, and
(b) repeating units which are derived from a vinyl compound having a functional group and represented by general formula (III):
wherein D represents a substituent having —OR
1
, —COR
1
, —CO
2
R
1
, —CN, —NR
1
R
2
, —SR
1
or —PR
1
R
2
, R
1
and R
2
each representing hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkylsilyl group having 3 to 20 carbon atoms; R′ represents a linear or branched hydrocarbon group having 1 to 20 carbon atoms; when a plurality of D are present, the plurality of D may represent a same group or different groups; n represents an integer of 1 to 5; m represents an integer of 0 to 4; and n+m≦5,
wherein the copolymer comprises 0.01 to 50% by mole of repeating unit (b) and a steric regularity of the copolymer comprising repeating unit (a) and repeating unit (b) is syndiotactic.
THE MOST PREFERRED EMBODIMENT TO CARRY OUT THE INVENTION
In accordance with the process of the present invention, a styrenic copolymer, in particular, a random styrenic copolymer, having a functional group and the syndiotactic configuration can be obtained. Block copolymers and graft copolymers can also be produced. Styrenic block copolymers can be produced, for example, by applying the process of the present invention to the two-step process described in Japanese Patent Application Laid-Open No. Heisei 5(1993)-320281. Block, random and alternating styrenic copolymers can be obtained by applying the process of the present invention to the process described in Japanese Patent Application Laid-Open No. Showa 63(1988)-241009.
As the raw material monomers in the process of the present invention, a vinyl compound having a functional group and a styrenic compound can be used.
Examples of the vinyl compound having a functional group include styrenic compounds having a functional group which are represented by general formula (I):
wherein X represents a functional group which can be masked with the metal compound; R
0
represents a hydrocarbon group; when a plurality of X are present, the plurality of X may represent the same group or different groups; when a plurality of R
0
are present, the plurality of R
0
may represent the same group or different groups; n represents an integer of 1 to 5; m represents an integer of 0 to 5; and n+m≦5.
Examples of the preferable styrenic compound having a functional group which is represented by general formula (I) include compounds represented by general formula (I) in which X represent

Affiliated with

Also associated with

Rating

Process for producing functional styrene copolymer does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Process for producing functional styrene copolymer, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for producing functional styrene copolymer will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2992515