Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2001-05-31
2002-05-14
Pezzuto, Helen L. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S172000, C526S266000, C526S268000
Reexamination Certificate
active
06388036
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to the oligomerization, polymerization and copolymerization of substituted and unsubstituted &agr;-methylene-&ggr;-butyrolactones (MBLs) using cobalt chain transfer catalysts to control molecular weight.
TECHNICAL BACKGROUND
The free radical polymerization of &agr;-methylene-&ggr;-butyrolactone, as well as its copolymerization, is described by M. K. Akkapeddi, Polymer, vol. 20, 1979, pp. 1215-1216, and Japanese Patent Application 9012646. However, no catalysts were used and no end-group analyses were disclosed in any of these references.
It is known to use various cobalt complexes (e.g., cobaloximes) as chain transfer catalysts (CTC) to provide macromonomers which provide terminal double bonds for use in polymeric products. See commonly owned U.S. Pat. Nos. 5,310,807, 5,362,813, 5,412,039, 5,502,113, and 5,587,431 and WO 9525765. However, no examples of aromatic group formation during catalysis is shown as in the present invention.
The use of cobalt chain transfer catalysts to control the molecular weight of oligomers and polymers is known. U.S. Pat. Nos. 5,602,220, 5,770,665 and 5,684,101 as well as WO 9613527 disclose this control, but do not teach &agr;-methylene-&ggr;-butyrolactones or aromatic group formation during catalysis. Commonly owned U.S. Pat. No. 5,726,263, and application Ser. Nos. 08/818,860, 09/193,701 and 08/912,593 also disclose this control, but again, do not disclose this particular monomer or aromatic groups formed during catalysis.
SUMMARY OF THE INVENTION
This invention relates to a process for oligomerizing or polymerizing or copolymerizing (&agr;-methylene-&ggr;-butyrolactones to poly(&agr;-methylene-&ggr;-butyrolactones) having controlled molecular weight and aromatic functionality, wherein the process comprises contacting an &agr;-methylene-&ggr;-butyrolactone, optionally in the presence of a comonomer, with a free radical initiator and a cobalt chain transfer catalyst, said &agr;-methylene-&ggr;-butyrolactone having a structure:
wherein R
1
and R
2
are each independently selected from the group (I) consisting of H, —CH(O), —CN and halogen, and from the group (II) consisting of —C(O)OR
5
, —C(O)NR
6
R
7
, —CR
8
(O), —C(O)OC(O)R
9
, —C(O)NR
10
COR
11
, —OC(O)R
12
, —OR
13
, alkyl, substituted alkyl, aryl and substituted aryl; wherein when R
1
or R
2
are selected from group (II), R
1
and R
2
may optionally form a cyclic structure; R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11
, and R
12
are H, alkyl, aryl, substituted alkyl or substituted aryl; R
13
is alkyl, aryl, substituted alkyl or substituted aryl; and wherein the alkyl and substituted alkyl are C
1
-C
12
, and the substituents on the substituted alkyl or substituted aryl contain no functionality which would substantially interfere with free radical polymerization; said process carried out at a temperature from about room temperature to about 240° C., optionally in the presence of a solvent.
This invention further relates to the cooligomerization of &agr;-methylene-&ggr;-butyrolactones with comonomers selected from the group consisting of acrylonitrile, methacrylonitrile, vinyl methyl ketone, 4-chlorostyrene, 4-chloromethylstyrene, 2,3-dimethylstyrene, 3,4-dichlorostyrene, 4-bromostyrene, 4-hydroxystyrene, 4-methoxystyrene, 4-oxymethylstyrene, 4-bromomethylstyrene, 4-styrenesulfonic acid, sodium salt of 4-styrenesulfonic acid, 4-styrenesulfonyl chloride, methyl acrylate, ethyl acrylate, propyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, dodecyl acrylate, glycidyl acrylate, acrylamide, N,N′-dimethylacrylamide, bisacrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, acrylic acid, sodium salt of acrylic acid, zinc salt of acrylic acid, acryloyl chloride, [2-(acryloyloxy)ethyl]trimethyl ammonium chloride, 2-ethyloxyethyl acrylate, 2-(N,N′-dimethylamino)-ethyl acrylate, methacryloyl chloride, methacrylic anhydride, acrylic anhydride, [2-(methacryloyloxy)ethyl]trimethyl ammonium chloride, 2-(methacryloyloxy)ethyl methacrylate, 2-(methacryloyloxy)ethylacetoacetate, [2-(methacryloyloxy)propyl]-trimethyl ammonium chloride, vinylchloride, 4-vinylbenzoic acid, vinyl acrylate, vinyl methacrylate, vinyl chloroformate, vinyl pyridine, benzyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate (all isomers), butyl methacrylate (all isomers), 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, alpha methyl styrene, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, tributoxysilylpropyl methacrylate, dimethoxymethylsilylpropyl methacrylate, diethoxymethyl-silylpropylmethacrylate, dibutoxymethylsilylpropyl methacrylate, diisopropoxymethylsilylpropyl methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilylpropyl methacrylate, diisopropoxysilylpropyl methacrylate, isopropenyl butyrate, isopropenyl acetate, isopropenyl benzoate, isopropenyl chloride, isopropenyl fluoride, isopropenyl bromide, itaconic acid, itaconic anhydride, dimethyl itaconate, methyl itaconate, N-tert-butyl methacrylamide, N-n-butyl methacrylamide, N-methyl-ol methacrylamide, N-ethyl-ol methacrylamide, isopropenylbenzoic acid (all isomers), diethylamino alphamethylstyrene (all isomers), para-methyl-alpha-methylstyrene (all isomers), diisopropenylbenzene (all isomers), isopropenylbenzene sulfonic acid (all isomers), methyl 2-hydroxymethylacrylate, ethyl 2-hydroxymethylacrylate, propyl 2-hydroxymethylacrylate (all isomers), butyl 2-hydroxymethylacrylate (all isomers), 2-ethylhexyl 2-hydroxymethylacrylate, isobornyl 2-hydroxymethylacrylate, methyl 2-chloromethylacrylate, ethyl 2-chloromethylacrylate, propyl 2-chloromethylacrylate (all isomers), butyl 2-chloromethylacrylate (all isomers), 2-ethylhexyl 2-chloromethylacrylate, isobornyl 2-chloromethylacrylate, vinylpyrrolidone, and substituted &agr;-methyl-&ggr;-butyrolactones of the following structure:
where R
1
and R
2
are as defined above, and R
3
and R
4
are also independently selected from group (I) and group (II), as defined above.
This invention further relates to the products of the processes described.
DETAILS OF THE INVENTION
The use of catalytic chain transfer catalysts in the free radical polymerization of vinylic monomers is widely known and well reflected in the art. See, for example, U.S. Pat. Nos. 5,587,431, 5,362,813, 5,324,879, 5,028,677, and 4,526,945, all incorporated by reference herein. Conducted by cobalt complexes of a very specific structure, the catalysis allows molecular weight (MW) to be effectively controlled. It is also important that these reactions lead to formation of polymers and oligomers with a terminal double bond strictly one bond per polymer molecule (more than 95% ) as found in T. P. Davis, D. M. Haddleton, S. N. Richards., J. M. S.—Rev. Macromol. Chem. Phys., C34 (1994) 243.
A new monomer, &agr;-methylene-&ggr;-butyrolactone, represented in an unsubstituted form is shown in I below,
Surprisingly it was found that this monomer behaves differently from acrylates or methacrylates, its structural analogues. In case of methacrylates cobalt-catalyzed chain transfer provides polymer with a double bond. Unexpectedly, polymerization of &agr;-methylene-&ggr;-butyrolactone under the same conditions gave an oligomer which have aromatic functionality, as indicated by 7.1-7.4 ppm resonance in the proton NMR spectrum, but no isolated double bonds. The NMR data suggests that the cobalt catalyst causes isomerization of the oligomer and polymer in addition to regular hydrogen abstraction from the propagating radical. Therefore, the resulting oligomers have aromatic functionality but no isolated double bonds.
Hence, cobalt chain transfer catalyst provides not only molecular weight control in &agr;-methylene-&ggr;-butyrolactone polymerization as shown in the examples herein, but also, unusual funct
Gridnev Alexei Alexeyevich
Ittei Steven Dale
Benjamin Steven C.
E. I. du Pont de Nemours and Company
Pezzuto Helen L.
LandOfFree
Oligomerization, polymerization and copolymerization of... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Oligomerization, polymerization and copolymerization of..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Oligomerization, polymerization and copolymerization of... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2915104