Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-02-17
2003-04-22
Teskin, Fred (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S118000, C526S119000, C526S281000, C526S282000, C526S308000
Reexamination Certificate
active
06552148
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a thermoplastic interpolymer product comprising an &agr;-olefin interpolymerized with at least one vinyl or vinylidene aromatic monomer and/or at least one hindered aliphatic or cycloaliphatic vinyl or vinylidene aromatic monomer and, in at least one aspect, is characterized as having substantially synergistic thermal properties. The invention also relates to a process for manufacturing the interpolymer product wherein the process comprises employing two or more single site catalyst systems in at least one reaction environment (or reactor) and wherein at least two of the catalyst systems have (a) different monomer incorporation capabilities or reactivities and (b) the same or, optionally, different monomer sequencing and/or tacticity characteristics. With unique thermal property attributes, the interpolymer product is useful, for example, for impact, bitumen and asphalt modification, adhesives, dispersions or latexes and fabricated articles such as, but not limited to, foams, films, sheet, moldings, thermoforms, profiles and fibers.
BACKGROUND OF THE INVENTION
The generic class of materials covered by &agr;-olefin/vinyl or vinylidene aromatic and/or hindered aliphatic or cycloaliphatic vinyl or vinylidene interpolymers and including materials such as substantially random &agr;-olefin/vinyl aromatic interpolymers are known in the art and offer a range of material structures and properties which makes them useful in various applications. For example, U.S. Pat. No. 5,460,818, the disclosure of which is incorporated herein by reference, describes substantially random &agr;-olefin/vinyl aromatic monomer interpolymers as compatibilizers for blends of polyethylene and polystyrene. However, known methods and procedures for manufacturing &agr;-olefin/vinyl or vinylidene aromatic and/or hindered aliphatic or cycloaliphatic vinyl or vinylidene interpolymers do not provide independent control of material properties and attributes. That is, crystallinity, melting point and glass transition characteristics are known to inevitably vary with comonomer concentration where increase concentrations result in lower crystallinities, melting point temperatures, glass transition temperatures and service temperatures.
There are several known methods for preparing &agr;-olefin/vinyl or vinylidene aromatic and/or hindered aliphatic or cycloaliphatic vinyl or vinylidene interpolymers such as those described by Francis J. Timmers et al. in U.S. application Ser. No. 08/708,869, filed Sep. 4, 1996 (now abandoned); John G. Bradfute et al. (W. R. Grace & Co.) in WO 95/32095; R. B. Pannell (Exxon Chemical Patents, inc.) in WO 94/00500; and in
Plastics Technology
, p. 25 (September 1992), the disclosures of which are incorporated herein by reference.
Numerous other preparative methods for &agr;-olefin/vinyl or vinylidene aromatic and/or hindered aliphatic or cycloaliphatic vinyl or vinylidene interpolymers have been described in the literature. For example, Longo and Grassi (
Makromol. Chem
., Volume 191, pages 2387 to 2396 [1990]) and D'Anniello et al. (
Journal of Applied Polymer Science
, Volume 58, pages 1701-1706 [1995]), the disclosures of which are incorporated herein by reference, reported the use of a catalytic system based on methylalumoxane (MAO) and cyclopentadienyltitanium trichloride (CpTiCl
3
) to prepare an ethylene-styrene copolymer. Xu and Lin (
Polymer Preprints, Am. Chem. Soc., Div. Polym. Chem
., Volume 35, pages 686,687 [1994]), the disclosure of which is incorporated herein by reference, have reported copolymerization using a MgCl
2
/TiCl
4
/NdCl
3
/Al(iBu)
3
catalyst to give random copolymers of styrene and propylene. Lu et al. (
Journal of Applied Polymer Science
, Volume 53, pages 1453 to 1460 [1994]), the disclosure of which is incorporated herein by reference, have described the copolymerization of ethylene and styrene using a Ticl
4
/NdCl
3
/MgCl
2
/al(Et)
3
catalyst. Sernetz and Mulhaupt, (
Macromol. Chem. Phys
., V. 197, pp. 1071-1083, 1997), the disclosure of which is incorporated herein by reference, have described the influence of polymerization conditions on the copolymerization of styrene with ethylene using Me
2
Si(Me
4
Cp)(n-tert-butyl)TiCl
2
/Methylaluminoxane Ziegler-Natta catalysts. Copolymers of ethylene and styrene produced by bridged metallocene catalysts have been described by Arai, Toshiaki and Suzuki (
Polymer Preprints, Am. Chem. Soc., Div. Polym. Chem
., Volume 38, pages 349, 350 [1997]), the disclosure of which is incorporated herein by reference. Also, random copolymers of ethylene and styrene having high isotacticity are disclosed in
Polymer Preprints
, Vol. 39, no. 1, March 1998 by Toru Aria et al., the disclosure of which is incorporated herein by reference.
Also several patent describe the manufacture of &agr;-olefin/vinyl aromatic monomer interpolymers such as propylene/styrene and butene/styrene in U.S. Pat. No. 5,244,996, issued to Mitsui Petrochemical Industries Ltd.; U.S. Pat. No. 5,652,315, also issued to Mitsui Petrochemical Industries Ltd.; or DE 197 11 339 A1 to Denki Kagaku Kogyo KK, the disclosures of all three of which are incorporated herein by reference. Ethylene/styrene copolymer produced by bridged metallocene catalysts are also described in U.S. Pat. No. 5,652,315, issued to Mitsui Toatsu Chemicals, Inc.
Pseudo-random ethylene/vinyl aromatic interpolymers and the catalyst systems for making the same are disclosed in U.S. Pat. No. 5,703,187 and EP 416 815 A2, the disclosures of which are incorporated herein by reference.
U.S. patent application Ser. No. 08/991,836, filed Dec. 16, 1997 (now abandoned) and WO 98/10018, the disclosures of both of which are incorporated herein, in their entireties, by reference, indicate that a suitable method for manufacturing substantially random ethylene/vinyl aromatic interpolymers involves polymerizing a mixture of polymerizable monomers in the presence of one or more metallocene or constrained geometry catalysts in combination with various cocatalysts. However, the exemplified compositions therein all involve the same single catalyst composition of a titanium-based constrained geometry catalyst together with tris(pentafluorophenyl)boron as the activator and methylaluminoxane as the cocatalyst. That is, all reported examples were monocatalyzed interpolymers. Furthermore, there is no explicit disclosure in these descriptions that interpolymer made using multiple catalyst systems can provide improved thermal properties such as substantially higher meting points at substantially comparable crystallinities or diffused T
g
responses.
Blends comprising &agr;-olefin/vinylidene aromatic monomer and/or hindered aliphatic or cycloaliphatic vinylidene monomer interpolymers are described in WO 95/27755, in the names of Chung P. Park et al. and WO 98/10018, in the names of Martin J. Guest et al., the disclosures of which are incorporated herein by reference. All of the exemplified compositions consisted of physical melt blend preparations using component interpolymers made from a single catalyst composition. That is, the blends were not made using an in-situ or multiple reactor interpolymerization technique, nor were they manufactured using multiple catalyst compositions and, as such, all component polymers were monocatalyzed.
Moreover, melt blending is not known to provide independent or unique control of thermal resistance, melting behavior and glass transition characteristics as no complete data of such attributes are reported in WO 95/27755 nor WO 98/10018. Thus it remains, although known &agr;-olefin/vinyl or vinylidene aromatic interpolymers have several important attributes, they also exhibit several important deficiencies. For example, known &agr;-olefin/vinyl or vinylidene aromatic interpolymer compositions, whether monocatalyzed or the melt blends, are characterized as having relatively low maximum service temperatures and narrow glass transition temperature ranges or widths (i.e. less than 15°
Cheung Yunwa W.
Guest Martin J.
Kolthammer Brian W.
Rosen Robert K.
Teskin Fred
The Dow Chemical Company
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