Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1999-04-29
2001-09-04
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S234000, C526S347100, C526S348000, C526S317100
Reexamination Certificate
active
06284850
ABSTRACT:
FIELD OF THE INVENTION
A combination of a selected arylsulfonyl halide or alkylsulfonyl halide and a compound containing a lower valent transition metal atom can be used to initiate free radical polymerizations of vinyl monomers such as (meth)acrylates and styrenes and under certain conditions, these polymerizations may be living.
TECHNICAL BACKGROUND
Polymers of so-called vinyl monomers made by free radical polymerization are important items of commerce, for instance poly(methyl methacrylate) is used as a glazing material and molding resin, while polystrene is useful in packaging as a film, in foam form as in drinking cups, and as a molding resin. Therefore, new polymerization systems for these types of monomers are always of interest, especially when such polymerizations may provide improved or easier control over the microstructure and/or molecular weight of the polymer produced.
V. Percec et al., Macromolecules, vol. 28, p. 7970-7972 (1995), V. Percec et al., Macromolecules, vol. 29, p. 3665-3668 (1996), B. Barboiu, et al., Abstract of the 36
th
IUPAC International Symposium on Macromolecules, Aug. 4-9, 1996, Seoul Korea, p. 671, ibid. p. 672, V. Percec, et al., Abstract of the 36
th
IUPAC International Symposium on Macromolecules, p. 68, and V. Percec, et al., Polym. Prepr., vol. 38, No. 1, p. 733-735 (1997), report on the homopolymerization of styrene and other monomers using a combination of an arylsulfonyl chloride and a transition metal compound. Some of these polymerizations are reported to be “living”. All of these articles are hereby included by reference.
M. Asscher, et al., J. Chem. Soc. (1964) p. 4962-4971 report the reaction of various aryl sulfonyl chlorides or alkyl sulfonyl chlorides and copper chloride with various olefins such as styrene. No polymers are reported to be products.
A. Orochov, et al., J. Chem. Soc. (1969) p. 255-259 report on the reaction of cupric chloride with an aryl sulfonyl chloride in the presence of styrene. No polymers are reported.
SUMMARY OF THE INVENTION
This invention concerns a process for the polymerization of vinyl monomers, comprising, contacting a free radically polymerizable vinyl monomer with a first compound of the formula A
1
SO
2
X and a second compound which contains a transition metal atom in a lower valent state, wherein A
1
is an aryl, substituted aryl, alkyl or substituted alkyl group, and X is chlorine, bromine or iodine.
DETAILS OF THE INVENTION
Free radically polymerizable vinyl monomers are well known in the art. By a vinyl monomer herein is meant a compound of the formula
wherein R
1
, R
2
, R
3
and R
4
are hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, and at least one of R
1
, R
2
, R
3
and R
4
is not hydrogen or alkyl. For a discussion of free radically polymerizable vinyl monomers see for instance H. Mark, et al., Ed., Encyclopedia of Polymer Science and Engineering, 2nd Ed., Vol. 13, John Wiley & Sons, New York, 1988, p. 708-713, which is hereby included by reference. Suitable vinyl monomers include various vinyl halides such as vinyl chloride, vinyl fluoride and vinylidene fluoride, selected vinyl ethers such as methyl vinyl ether, chloroprene, isoprene, styrene and substituted styrenes, acrylic esters, methacrylic esters, acrylamides, methacrylamides, and substituted acrylic and methacrylic esters and amides such as 2-chloroethyl methacrylate, 2-methoxyethyl methacrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-aminoethyl (meth)acrylamide and the like.
Preferred vinyl monomers include styrenes and a compound of the formula
wherein R
5
is hydrogen or methyl and R
6
is —NR
7
R
8
or —OR
9
. R
7
and R
8
are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, and R
9
is hydrocarbyl or substituted hydrocarbyl. It is preferred that R
7
and R
8
are each independently hydrogen or alkyl containing 1 to 10 carbon atoms, or R
9
is alkyl containing 1 to 10 carbon atoms, more preferred that R
9
is methyl.
By “a styrene” herein is meant a compound of the formula
wherein R
10
is hydrogen or methyl, and R
11
, R
12
and R
13
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group. It is preferred that all of R
10
, R
11
, R
12
and R
13
are hydrogen.
In these polymerizations, only one olefin may be present to form a homopolymer, or more than one olefin may be present to form a copolymer. If only one monomer is present it is preferred that it is not styrene. If more than one polymerizable monomer is present at one time a random or alternating copolymer may be formed. Random copolymers are preferred products of the process. Some combinations of monomers may not free radically copolymerize while others will copolymerize. Such combinations are also well known in the art. Also, copolymers of olefins which do not readily homopolymerize under free radical conditions may be prepared using a more readily polymerizable monomer. An example of such monomer a combination is tetrafluoroethylene and ethylene.
By hydrocarbyl herein a meant a group containing carbon and hydrogen. By “substitued” (such as substituted hydrocarbyl or substituted aryl) is meant a group containing an inert substituent group, such as halo, ether, ester, etc. By inert is meant the group does not interfere with the polymerization process described herein. Unless otherwise specified it is preferred that any hydrocarbyl or alkyl groups herein contain 1 to 30 carbon atoms, and any aryl groups contain 6 to 30 carbon atoms. By an aryl group herein is meant a monovalent radical whose free valence is to a carbon atom of an aromatic ring. It is preferred that such rings are carbocyclic. An aryl group may contain a single ring, 2 or more fused rings, or 2 or more aromatic rings connected by covalent bonds. By a functional group herein is meant an inert functional group that does not interfere with the polymerization process described herein. Examples of such groups include alkoxy, aryloxy, ester, amido and halo.
One part of the polymerization system in the present process is an arylsulfonyl halide or an alkyl sulfonyl halide of the formula A
1
SO
2
X wherein A
1
is an aryl, substituted aryl group, an alkyl group or a substituted alkyl group, and X is chlorine, bromine or iodine. It is preferred that X is chlorine, and/or that A
1
is phenyl, substituted phenyl or methyl. Suitable substituents include one or more of nitro, fluoro, chloro, alkyl, alkoxy, carboxy, hydroxy and dialkylamino. It is more preferred that A
1
is phenyl or p-methoxyphenyl or methyl. Included within the meaning of arylsulfonyl halide or alkylsulfonyl halide halide is any adduct, such as a 1:1 adduct, which is a reaction product of an aryl or alkyl sulfonyl halide and any polymerizable vinyl monomer. In effect, such an adduct is one of the initial products in the polymerization process itself.
Another component of the polymerization process system is a compound containing a lower valent transition metal atom. By this is meant a compound containing at least one transition metal atom that is capable of existing in a (being oxidized to a) higher valent state. Included within the definition of a compound containing a transition metal atom in a lower valent state is a compound or combination of compounds that under the polymerization process conditions can form in situ the desired compound containing a transition metal atom in a lower valent state. In some cases this can include metal itself (or an alloy or a metal oxide thereof) which can either be dissolved or slightly dissolve in the process medium. In another instance, CuCl
2
is reported to form CuCl in the presence of styrene [M. Asscher, et al., J. Chem. Soc. (1963), p. 1887], so addition of CuCl
2
to a polymerization in which styrene was present would fulfill the requirement for the presence of a lower valent metal.
Suitable lower valent metals include Cu[I], Ru[I], Ni[II], Fe[II], Pd[II], Cu[0], Ni[0], Fe[0
Benjamin Steven C.
Choi Ling-Siu
E. I. Du Pont de Nemours and Company
Fricke Hilmar L.
Wu David W.
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