Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1998-07-16
2001-09-18
Zitomer, Fred (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S147000, C526S192000, C526S204000, C526S208000, C526S210000, C526S217000, C526S221000, C526S236000
Reexamination Certificate
active
06291612
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for preparing a vinyl polymer having a controlled molecular weight and a narrow molecular weight distribution.
2. Description of the Prior Art
Molecular weights and molecular weight distributions of polymers have large influences on properties, such as flow properties, of the polymers. Thus, it is very important to prepare polymers having controlled molecular weights and narrow molecular weight distributions for controlling the properties of the prepared polymers and compositions comprising such the polymers.
A method for the easy preparation of a vinyl polymer having a controlled molecular weight and narrow molecular weight distribution, which is disclosed in J. Am. Chem. Soc., 117, 5614-5615 (1995), Macromolecules, 28, 7901-7910 (1995) and the like, comprises living radically polymerizing a vinyl monomer using an organic halide as a polymerization initiator and a monovalent copper complex which is obtained from a cuprous halide and an electron donating compound such as 2,2′-bipyridyl compounds. This process provides the polymer having the controlled molecular weight and narrow molecular weight distribution when the monomer is styrene, methyl acrylate, etc.
However, the molecular weight distributions of the vinyl polymers prepared by the above process are not still satisfactorily narrow. In particular, the molecular weight distributions of the vinyl polymers are slightly broad when this method is used for polymerizing acrylates (e.g. butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, etc.), or methacrylates (e.g. methyl methacrylate, ethyl methacrylate, etc.).
Accordingly, it has been desired to provide a process for preparing vinyl polymers having narrower molecular weight distributions.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a process for preparing a vinyl polymer which has a controlled molecular weight and a narrower molecular weight distribution than the conventional vinyl polymers.
According to the first aspect, the present invention provides a process for preparing a vinyl polymer comprising polymerizing a vinyl monomer using an organic halide as a polymerization initiator in the presence of a cuprous compound as a catalyst in a solvent comprising an organic compound having a dielectric constant of at least 10 at 25° C., preferably a dielectric constant of at least 15 at 25° C.
According to the second aspect, the present invention provides a process for preparing a vinyl polymer comprising polymerizing a vinyl monomer using an organic halide as a polymerization initiator in the presence of a cuprous compound as a catalyst and a 1,10-phenanthroline compound of the formula (I):
wherein R
1
, R
2
, R
3
, R
4
, R5, R
6
, R
7
and R
8
are the same or different and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.
DETAILED DESCRIPTION OF THE INVENTION
The process of the present invention uses an organic halide as a polymerization initiator. The kind of the organic halide is not limited, and any halide which is used as a polymerization initiator for vinyl monomers may be used. Examples of such the organic halide are carbon tetrachloride, carbon tetrabromide, allyl chloride, allyl bromide, allyl iodide, xylene derivatives (e.g. &agr;,&agr;′-dichloro-o-, m- or p-xylene, &agr;,&agr;′-dibromo-o-, m- or p-xylene, etc.), benzene derivatives (e.g. o-, m- or p-bis(&agr;-chloroethyl)benzene, o-, m- or p-bis(&agr;-bromoethyl)benzene, etc.), &agr;-chloroacetates (e.g. methyl &agr;-chloroacetate, ethyl &agr;-chloroacetate, etc.), &agr;,&agr;-dichloroacetates (e.g. methyl &agr;,&agr;-dichloroacetate, ethyl &agr;,&agr;-dichloroacetate, etc.), &agr;,&agr;,&agr;-trichloroacetates (e.g. methyl &agr;,&agr;,&agr;-trichloroacetate, ethyl &agr;,&agr;,&agr;-trichloroacetate, etc.), &agr;-chloropropionates (e.g. methyl &agr;-chloropropionate, ethyl &agr;-chloropropionate, etc.), &agr;-chloroisobutyrates (e.g. methyl &agr;-chloroisobutyrate, ethyl &agr;-isobutyrate, etc.), &agr;-bromoacetates (e.g. methyl &agr;-bromoacetate, ethyl &agr;-bromoacetate, etc.), &agr;,&agr;-dibromoacetates (e.g. methyl &agr;,&agr;-dibromoacetate, ethyl &agr;,&agr;-dibromoacetate, etc.), &agr;,&agr;,&agr;-tribromoacetates (e.g. methyl &agr;,&agr;,&agr;-tribromoacetate, ethyl &agr;,&agr;,&agr;-tribromoacetate, etc.), &agr;-bromopropionates (e.g. methyl &agr;-bromopropionate, ethyl &agr;-bromopropionate, etc.), &agr;-bromoisobutyrates (e.g. methyl &agr;-bromoisobutyrate, ethyl &agr;-bromoisobutyrate, etc.), and the like. These organic halides may be used independently or in admixture of two or more of them.
The amount of the polymerization initiator may be substantially the same as that in the conventional processes.
The process of the present invention uses a cuprous compound as a catalyst. The kind of the cuprous compound is not limited. Examples of the cuprous compound are cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and the like.
The amount of the cuprous compound may be the same as in the conventional processes.
The cuprous compound is preferably used together with an electron donating compound. The kind of the electron donating compound is not limited. Examples of the electron donating compound are nitrogen atom-containing heterocyclic compounds such as bipyridyl (bipyridine) compounds (e.g. 2,2′-bipyridyl, 4,4′-dimethyl-2,2′-bipyridyl, etc.), phenanthroline compounds (e.g. 1,10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, etc.), and the like.
The amount of the electron donating compound is usually between 0.5 and 5 moles, preferably between 2 and 3 moles, per one mole of the cuprous compound.
The kind of the vinyl monomer which is polymerized by the process of the present invention is not limited. Examples of the vinyl monomer are (meth)acrylates (e.g. methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tertbutyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, etc.), styrene and its derivatives (e.g. 2-, 3- or 4-methylstyrene, 2-, 3- or 4-chlorostyrene, 2-, 3- or 4-(chloromethyl)styrene, 2-, 3- or 4-methoxystyrene, 2-, 3- or 4-(methoxycarbonyl)styrene, &agr;-methyl-styrene, etc.), maleic anhydride, and the like. They may be used independently or in admixture of two or more of them.
In one preferred embodiment of the process of the present invention, the vinyl monomer is polymerized in a solvent comprising an organic compound having a dielectric constant of at least 10 measured at 25° C.
The kind of such the organic compound is not limited.
A preferred example of such the organic compound is a carbonyl compound of the formula (II):
R
9
—CO—R
10
(II)
wherein R
9
and R
10
are the same or different and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, or R
9
and R
10
forms a cyclic alkyl group together with the carbonyl group.
Specific examples of the carbonyl compound of the formula (II) are acyclic aliphatic ketones (e.g. acetone, 2-butanone, 2- or 3-pentanone, 2-hexanone, 2-heptanone, 4-methyl-2-pentanone, etc.), cyclic aliphatic ketones (e.g. cyclohexanone, 2-, 3- or 4-methylcyclohexanone, etc.), aromatic ketones (e.g. acetophenone, 2-, 3- or 4-methylacetophenone, etc.), and the like.
Another example of such the organic compound is a nitro compound of the formula (III):
R
11
—NO
2
(III)
wherein R
11
is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 1
Kishimoto Yasuhisa
Kusakabe Masato
Foley & Lardner
Kaneko Corporation
Zitomer Fred
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