Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2001-03-16
2003-07-22
Lu, Caixia (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S160000, C526S165000, C526S340000
Reexamination Certificate
active
06596828
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a catalyst composition for polymerization of a conjugated diene and a co-catalyst contained in the catalyst composition. The invention also relates to a method for preparing a conjugated diene polymer using the catalyst composition and a novel conjugated diene polymer obtained by the preparation method.
The present invention further relates a catalyst composition for the copolymerization of a conjugated diene and an aromatic vinyl compound and a co-catalyst contained in the catalyst composition. The invention also relates to a method for preparing a copolymer of a conjugated diene and an aromatic vinyl compound using the catalyst composition and a novel copolymer obtained by the preparation method.
BACKGROUND ART
Various proposals have been made so far as to polymerization catalysts for conjugated dienes, and they play a highly important role in industrial fields. In particular, various polymerization catalysts which give a high cis-1,4-linkage content have been studied and developed to obtain conjugated diene polymers with enhanced performance in thermal and mechanical properties. For example, complex catalyst systems containing a compound of a transition metal such as nickel, cobalt and titanium as a main component are known, and some of them have already been widely used in industrial applications as polymerization catalysts for butadiene, isoprene etc. (see, End. Ing. Chem., 48, 784, 1956; Japanese Patent Publication No. 37-8198).
In order to attain a higher cis-1,4-linkage content and superior polymerization activity, complex catalyst systems which consist of a rare earth metal compound and an organometallic compound belonging to Group I to Group III have been studied and developed, and highly stereospecific polymerization has come to be actively studied (Makromol. Chem. Suppl, 4, 61, 1981; J. Polym. Sci., Polym. Chem. Ed., 18, 3345, 1980; German Patent Application No. 2,848,964; Sci. Sinica., 2/3, 734, 1980; Rubber Chem. Technol., 58, 117, 1985 etc.). Among these catalyst systems, complex catalysts containing a neodymium compound and an organoaluminum compound as main components were revealed to give a high cis-1,4-linkage content and have superior polymerization activity. The catalysts have already been used in industrial applications as polymerization catalysts for butadiene etc. (see Macromolecules, 15, 230, 1982; Makromol. Chem., 94, 119, 1981).
With the recent progress of industrial technologies, requirements for polymeric materials as commercial products have become increasingly higher, and development of polymeric materials which have still higher thermal properties (thermal stability etc.) and mechanical properties (tensile modulus, bending modulus etc.) has come to be strongly desired. As one of promising means for achieving the object, there have been attempts to produce a polymer of a high cis-1,4-configuration content in microstructure and a narrow molecular weight distribution by using a catalyst having a high polymerization activity for conjugated dienes. However, no method has so far been found for producing polymers having such characteristics.
Further, various proposals have hitherto been made also as to catalysts for copolymerization of a conjugated diene and an aromatic vinyl compound, and they play an extremely important industrial role. In particular, various copolymerization catalysts which give a high cis-1,4-linkage content have been studied and developed to obtain copolymers of a conjugated diene and an aromatic vinyl compound with enhanced performance in thermal and mechanical properties.
For example, there are known complex catalyst systems containing a compound of transition metal such as nickel, cobalt and titanium (see Kogyo Kagaku Zasshi (Journal of Industrial Chemistry), 72, 2081, 1969; Plast. Kautsch., 40, 356, 1993; Makromol. Chem. Phys., 195, 2623, 199 etc.), complex catalyst systems containing a compound of rare earth metal such as neodymium and gadolinium (Macromol. Rapid Commun. 16, 563, 1992; J. Polym. Sci., ParA; Polym. Chem., 32, 1195, 1994; Polymer, 37, 349, 1996) and the like. Although these catalyst systems exhibit a relatively high cis-1,4-controllability, polymers with a high molecular weight and narrow molecular weight distribution, and copolymers with randomized monomer sequence cannot be obtained by means of these catalysts.
DISCLOSURE OF THE INVENTION
An object of the present invention is to provide a catalyst for the polymerization of a conjugated diene. More specifically, the object is to provide a catalyst for producing polymers with a high cis-1,4-configuration content in the microstructure and a narrow molecular weight distribution. Another object of the present invention is to provide polymers having the aforementioned characteristics, and a method for producing such polymers.
Further object of the present invention is to provide a catalyst for copolymerization of a conjugated diene and an aromatic vinyl compound. More specifically, the object is to provide a catalyst for producing copolymers with high cis-1,4-configuration content in the microstructure, a high molecular weight and a narrow molecular weight distribution. Another object of the present invention is to provide copolymers having the aforementioned characteristics, and a method for producing such copolymers.
The inventors of the present invention conducted various studies to achieve the foregoing objects. As a result, they found that a conjugated diene can be efficiently polymerized by using a catalyst composition comprising a rare earth metal metallocene type polymerization catalyst and a co-catalyst comprising an ionic compound composed of a non-coordinate anion and a cation and/or an aluminoxane in combination, and that a conjugated diene polymer with an extremely high cis-1,4-configuration content in the microstructure and a narrow molecular weight distribution can be produced by using the aforementioned catalyst composition for polymerization.
Moreover, the inventors of the present invention also found that a conjugated diene and an aromatic vinyl compound can be efficiently copolymerized by using a catalyst composition comprising a rare earth metal metallocene-type polymerization catalyst and a co-catalyst containing an ionic compound composed of a non-coordinate anion and a cation and/or an aluminoxane in combination, and that, by using the aforementioned catalyst composition for copolymerization, a copolymer with an extremely high cis-1,4-configuration content in the microstructure as well as a high molecular weight and a narrow molecular weight distribution, preferably a random copolymer with a randomized monomer sequence, can be produced by copolymerizing a conjugated diene and an aromatic vinyl compound. The present invention was achieved on the basis of these findings.
The present invention thus provides a catalyst composition for polymerization of a conjugated diene, which comprises the following components: (A) a metallocene type complex of a rare earth metal compound, and (B) an ionic compound composed of a non-coordinate anion and a cation and/or an aluminoxane. According to preferred embodiments of the present invention, there are provided the aforementioned catalyst composition, wherein the metallocene type complex is a samarium complex; the aforementioned catalyst composition, wherein the ionic compound is triphenylcarbonium tetrakis(pentafluorophenyl)borate, triphenylcarbonium tetrakis-(tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate or 1,1′-dimethylferrocenium tetrakis(pentafluorophenyl)borate; and the aforementioned catalyst composition, which further contains an organometallic compound of an element belonging to Group I to Group III in the periodic table.
According to a further aspect of the present invention, there is provided a co-catalyst for use in combination with a catalyst containing a metallocene type complex of a rare earth metal compound for polymerization of a conjugated diene, which comprises an ionic compound composed of a non-coo
Hou Zhaomin
Kaito Shojiro
Wakatsuki Yasuo
Lu Caixia
Millen White Zelano & Branigan P.C.
Riken
LandOfFree
Catalyst composition does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Catalyst composition, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Catalyst composition will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3010682