Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1999-03-02
2001-02-20
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...
C526S348200, C526S308000, C526S160000, C526S161000, C526S943000, C502S152000
Reexamination Certificate
active
06191245
ABSTRACT:
The present invention concerns &agr;-olefin/vinyl aromatic monomer and/or hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer interpolymers and a process for their preparation.
&agr;-Olefin/vinyl aromatic monomer interpolymers have been prepared as disclosed by James C. Stevens et al., in EP 0 416 815 A2 published Mar. 13, 1991. In addition, M. Takeuchi et al., in EP 0 707 014 Al published Apr. 17, 1996, disclose a process for producing an aromatic vinyl compound copolymer having a high degree of syndiotactic configuration in its aromatic vinyl chain. Also D. D. Devore et al., in WO 95/00526 published on Jan. 5, 1995, disclose titanium or zirconium complexes containing one and only one cyclic delocalized anionic &pgr;-bonded group wherein the titanium or zirconium is in the +2 formal oxidation state. F. J. Timmers et al., in WO 96/04290 published on Feb. 15, 1996 describes biscyclopentadienyl diene complexes of Group 4 transition metals. Finally K. W. McKay et al., in WO 96/07681, published on Mar. 14, 1996, describes a thermoset elastomer comprising a crosslinked pseudorandom or substantially random interpolymer of at least one &agr;-olefin, at least one vinyl aromatic compound, and at least one diene. The subject invention also provides a thermoplastic vulcanizate comprising the thermoset elastomer as provided in a themoplastic polyolefin matrix.
While these interpolymers have good properties, it is always desirable to have available polymers having an improvement in one or more properties.
The present invention relates to &agr;-olefin/vinyl aromatic monomer and/or hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer interpolymers with characteristic signals in their carbon 13 NMR spectra. In particular, ethylene/styrene copolymers of the present invention have peaks detectable in the carbon 13 NMR spectra which appear in the chemical shift range of 43.70-44.25, generally from 43.75-44.25 ppm and 38.0-38.5 ppm said peaks being at least three times the peak to peak noise.
Another aspect of the present invention pertains to &agr;-olefin/vinyl aromatic monomer and/or hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer interpolymers containing one or more tetrad sequences consisting of &agr;-olefin/vinyl aromatic monomer or hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer/vinyl aromatic monomer or hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer/&agr;-olefin detectable by carbon 13 NMR spectroscopy wherein the monomer insertions of said tetrads occur exclusively in a 1,2 (head to tail) manner.
The present invention also pertains to a process for preparing &agr;-olefin /vinyl aromatic monomer and/or hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer interpolymers, said process comprising subjecting to polymerizing conditions a combination of (1) &agr;-olefin, (2) one or more vinyl aromatic monomers, and (3) optionally, one or more polymerizable ethylenically unsaturated monomers other than (1) or (2) such as an &agr;-olefin or diene; in the presence of a catalyst represented by the general formula:
wherein: each Cp is independently, each occurrence, a substituted cyclopentadienyl group &pgr;-bound to M; E is C or Si; M is a group IV metal, preferably Zr or Hf, most preferably Zr; each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl; each R′ is independently, each occurrence, H, halo, hydrocarbyl, hydrocarbyloxy, silahydrocarbyl, hydrocarbylsilyl, or two R′ groups together can be a hydrocarbyl substituted 1,3-butadiene; m is 1 or 2; and optionally, but preferably, in the presence of an activating cocatalyst.
The polymers of the present invention possess increased modulus, as determined from both tensile stress/strain and dynamic mechanical data, at comparable vinyl aromatic monomer levels.
The present invention can comprise, consist of, or consist essentially of, all or only a portion of the aforementioned components, compounds, substituent groups or reaction steps. Components, compounds, substituent groups or reaction steps can be eliminated singly or in multiples of any two or more.
REFERENCES:
patent: 4076698 (1978-02-01), Anderson et al.
patent: 5362824 (1994-11-01), Furtek et al.
patent: 5362825 (1994-11-01), Hawley et al.
patent: 5703187 (1997-12-01), Timmers
patent: 0 416 815 A2 (1991-03-01), None
patent: 0 572 990 A2 (1993-12-01), None
patent: 0 638 593 A1 (1995-02-01), None
patent: 7/278230 (1995-10-01), None
patent: 95/32095 (1995-11-01), None
patent: WO 96/07681 (1996-03-01), None
Gerald Lancaster et al., “Applications of Insite * Technology in the Rubber/Elastomer Market”, Proceedings of Fifth International Business Forum on Specialty Polyolefins SPO '95 Sep. 20-22, 1995, pp. 109-123.
Derwent Abstract 95-309200/40 (JP 07/207036) Dec. 1, 1993.
Derwent Abstract 95-281168/37 (JP 07/179847) Dec. 22, 1993.
Derwent Abstract 95-401001/51 (JP 07278230) Oct. 24, 1995.
Patent Application Entitled “Constrained Geometry Addition Polymerization Catalysts, Processes for Their Preparation, Precursors Therefor, Methods of Use, and Novel Polymers Formed Therewith” filed in the United States of America on Jul. 3, 1990; Application No. 545,403; Aplicant: J.C. Stevens, G.F. Schmidt, F.J. Timmers D.R. Wilson, P.N. Nickias, S. Lai, G.W. Knight, R.K. Rosen, C-38099-A (Pending).
“Compatibilization of Polyethyleen-Polystyrene Blends with Ethylene-Styrene Random Copolymers”, Chung P. Park et al.,Soc. Plast. Engrs. Antec'96, pp. 1887-1891, May 5-10, 1996 discloses ethylene-styrene copolymers as a compatabilizer for blends of polyethylene and polysyrene.
“Structure, Thermal Transitions and Mechanical Properties of Ethylene/Styrene Copolymers”, Y. Wilson Cheung et al.,Soc. Plast. Engrs. Antec'96, pp. 1634-1637, May 5-10, 1996 discloses various properties of ethylene.styrene copolymers.
“Material Properties and Applications of Ethylene-Styrene Interpolymer sfrom Metallocene Catalyst”, Steve Hoenig et al.,Proceedings of Sixth International Business Forum on Speciaty Polyolefins SPO'96, pp. 261-268, Spet. 25-27, 1996 discloses various properties for ethylene-styrene interpolymers.
Guangxue Xu and Shangan Lin,American Chemical Society, vol. 35, No. 1, “Polymer Preprints: Copolymerization of Styrene and Propene with Supported Ti Catalyst Comprising Nd Compound”, pp. 686-687, (1994).
Campbell, Jr. Richard E.
McAdon Mark H.
Nickias Peter N.
Patton Jasson T.
Redwine Oscar D.
Harlan R.
The Dow Chemical Company
Wu David W.
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