Process for preparing polymer by using copper compound

Details Process for preparing polymer by using copper compound Process for preparing polymer by using copper compound

2001-02-12

2002-08-13

Truong, Duc (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From carboxylic acid or derivative thereof

C528S357000, C528S485000, C528S492000, C526S154000, C526S164000, C502S165000

Reexamination Certificate

active

06433130

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a method of producing a polymer using a copper compound.
PRIOR ART
A poly-&agr;-substituted olefin derived from an &agr;-substituted olefin of the general formula CH
2
═CY
1
E (wherein Y
1
represents a phenyl or substituted phenyl group and E represents a hydrogen atom or an alkyl group) by polymerization has so far been produced by various methods. Industrially, it is produced by adding a radical generator to a monomer and carrying out radical polymerization. However, the polymer produced by this method has a fairly broad molecular weight distribution and, because of inclusion of a low-molecular-weight polymer, it is poor in heat resistance.
On experimental scale, it can be obtained also by anionic polymerization, cationic polymerization or group transfer polymerization, for instance. Recently, a method of producing a highly stereoregular poly-&agr;-substituted olefin has been proposed and has attracted attention which comprises polymerizing an &agr;-substituted olefin of the general formula CH
2
═CY
2
H (wherein Y
2
represents a phenyl or substituted phenyl group) using, as a polymerization catalyst component, a transition metal complex alone or a combination of a transition metal complex and an organoaluminum compound [Nobuhide Ishihara et al.: The Society of Polymer Science, Japan, Preprints, 35, 240 (1986); Japanese Kokai Publication Hei-03-72504].
A poly-&agr;-substituted olefin derived from an &agr;-substituted olefin of the general formula CH
2
═CY
3
Z (wherein Y
3
represents a cyano group and Z represents a hydrogen atom or an alkyl group) by polymerization has so far been produced by various methods. Industrially, it is produced by radical polymerization with a radical generator added to a monomer.
As a method of polymerization by which the molecular weight and molecular weight distribution can be controlled, there have been proposed, on the laboratory level, anionic polymerization, coordination polymerization and group transfer polymerization, for instance. To be concrete, a highly stereoregular poly-&agr;-substituted olefin was produced from a monomer of the general formula CH
2
═CHY
3
(wherein Y
3
represents a cyano group) by a production method using an aluminum metal compound and a transition metal compound as polymerization catalysts (Japanese Kokai Publication Hei-01-79206) and a precision polymer having a narrow molecular weight distribution was produced by a polymerization reaction using an organic rare earth metal complex as a catalyst component [Akira Nakamura et al.: 43rd Meeting of The Society of Polymer Science, Japan (May 26, 1994), II-3-08].
Recently, a lactone polymer has attracted attention as biodegradable plastics.
As regards the polymerization of a lactone, anionic polymerization, coordination polymerization and group transfer polymerization, among others, have been proposed, on the laboratory level, as a polymerization method capable of controlling the molecular weight and molecular weight distribution. More specifically, there may be mentioned the method comprising carrying out polymerization using an aluminum-porphyrin complex as a polymerization initiator [Macromolecules, 14, 166 (1981)] and the method comprising using an aluminum-porphyrin complex and a Lewis acid having a bulky substituent as a polymerization initiator (Japanese Kokai Publication Hei-04-323204), among others.
A vinyl monomer has so far been polymerized by various methods. Most of the methods employed in industry comprise adding a radical generator to a vinyl monomer and carrying out radical polymerization under high temperature and high pressure conditions. Recently, anionic polymerization, coordination polymerization and group transfer polymerization, for instance, have been proposed, on the laboratory level, as polymerization methods by which the molecular weight and molecular weight distribution can be controlled.
However, the compounds used in such catalyst systems are generally unstable against oxygen and/or moisture and readily decomposable and, further, require a number of reaction steps for their synthesis. In addition, their instability makes their synthesis difficult, leading to low yields and, as a result, they constitute expensive catalyst systems.
On the other hand, as for the metal in the transition metal complex used in the catalyst systems, titanium, zirconium, hafnium and the like, which are group IV transition elements, hence early transition metals, are generally used. Recently, nickel, palladium and the like, which are group X transition elements, hence late transition metals, have also been used in spite of their rather decreased reactivity [e g. JACS, 117 (23), 6414 (1995)].
The complex containing copper as the nucleus has an advantage in that it has good stability and can be synthesized with ease. Because of its low activity due to its stability, however, it has never been studied as a polymerization catalyst. Only recently, the present inventors found and reported that a copper complex can be used as a catalyst for polymerization of carbodiimide, which is a highly polar monomer, to give a living polymer [Macromolecules, 30, 3159 (1997)].
However, a copper complex has never been applied as a polymerization catalyst for a monomer of relatively low polarity which requires reactivity.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a method of producing a polymer using, as a polymerization catalyst, a copper compound which can easily be synthesized and is stable.
The present inventors have succeeded in solving the problems discussed above by using, as a polymerization catalyst component, a copper compound which can easily be synthesized and is stable.
The method of producing a polymer using a copper compound in accordance with a first aspect of the present invention (hereinafter referred to as “first invention”) comprises using a copper compound represented by the general formula CuXn, LCuXn or L(L′)CuXn (wherein L and L′ each represents a ligand, X represents a halogen atom or an alkoxy, thioxy, allyloxy, amino, secondary amino, tertiary amino, cyano, nitro, alkyl or allyl group, and n represents an integer of 0 to 2) as a catalyst and/or polymerization initiator in polymerizing a vinyl monomer whose polarity value e, when expressed in terms of absolute value, is not more than 1.5.
Preferably, the method of producing a polymer comprises using a copper compound represented by the general formula LCuXna or L(L′)CuXnb (wherein L and L′ each represents a N-coordination compound selected from the group consisting of bisoxazoline, substituted bisoxazoline, an amidinato compound and a diimine represented by the general formula R
3
N═CR
4
CR
5
═NR
6
(wherein R
3
, R
4
, R
5
and R
6
each represents independently an alkyl, allyl, an aryl, a hydrogen atom, or a halogen atom; or at least one group of R
3
and R
4
, R
4
and R
5
, and R
5
and R
6
is combined and represents a cyclic group with the next carbon and/or nitrogen atom), or a O- and N-coordination compound; X represents a halogen atom or an alkoxy, thioxy, allyloxy, amino, secondary amino, tertiary amino, cyano, nitro, alkyl or allyl group; na represents an integer of 1 to 2; and nb represents an integer of 0 to 2) as a catalyst and/or polymerization initiator in polymerizing a vinyl monomer whose polarity value e, when expressed in terms of absolute value, is not more than 1.5.
The method of producing a polymer using a copper compound in accordance with a second aspect of the present invention (hereinafter referred to as “second invention”) comprises using a copper compound represented by the general formula CuXn, LCuXn or L(L′)CuXn (wherein L and L′ each represents a ligand, X represents a halogen atom or an alkoxy, thioxy, allyloxy, amino, secondary amino, tertiary amino, cyano, nitro, alkyl or allyl group, and n represents an integer of 0 to 2) as a catalyst and/or polymerization initiator in polymerizi

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