Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
1999-03-02
2001-02-06
Nutter, Nathan M. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S216000, C525S222000, C525S227000, C525S228000, C525S232000, C525S236000, C525S237000, C525S240000
Reexamination Certificate
active
06184294
ABSTRACT:
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not applicable.
FIELD OF THE INVENTION
The present invention pertains to blends (A) of interpolymers made from monomer components comprising at least one &agr;-olefin and at least one aromatic vinylidene monomer and/or at least one hindered aliphatic vinylidene monomer and/or at least one cycloaliphatic vinylidene monomer and (B) olefinic polymers.
The generic class of materials covered by &agr;-olefin/hindered vinylidene monomer substantially random interpolymers and including materials such as &agr;-olefin/vinyl aromatic monomer interpolymers are known in the art and offer a range of material structures and properties which makes them useful for varied applications, such as compatibilizers for blends of polyethylene and polystyrene as described in U.S. Pat. No. 5,460,818.
One particular aspect described by D'Anniello et al. (Journal of Applied Polymer Science, Volume 58, pages 1701-1706 (1995)) is that such interpolymers can show good elastic properties and energy dissipation characteristics. In another aspect, selected interpolymers can find utility in adhesive systems, as illustrated in U.S. Pat. No. 5,244,996, issued to Mitsui Petrochemical Industries Ltd.
Although of utility in their own right, Industry is constantly seeking to improve the applicability of these interpolymers, for example to extend the temperature range of application. Such enhancements may be accomplished via additives, but it is desirable to develop technologies to provide improvements in processability or performance without the addition of additives or further improvements than can be achieved with the addition of additives.
Park et al., in WO 95/27755 describes a method of increasing the toughness and solvent resistance of a homopolymer or interpolymer of a monovinylidene aromatic monomer, by blending it with an olefin polymer such as a polyethylene or ethylene/octene copolymer. However because of the incompatability of these two types of resins, there is a requirement for a compatabilizer which Park teaches can be a pseudo random interpolymer of an aliphatic &agr;-olefin and a vinylidene aromatic monomer.
Bradfute et al., in WO 95/32095 discloses multilayer films having at least one layer which is an ethylene/styrene copolymer.
McKay et al., in WO 96/07681 describes a thermoset elastomer comprising a crosslinked pseudorandom or substantially random interpolymer of at least one &agr;-olefin, at least one vinylidene 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.
There is a need to provide materials based on &agr;-olefin/vinylidene aromatic monomer interpolymers with superior performance characteristics to the unmodified polymers, which will further expand the utility of this interesting class of materials. This superior characteristics include, but are not limited to, low temperature toughness, mechanical strength and melt processability.
The present invention pertains to a fabricated article other than a film comprising a blend of polymeric materials consisting of
(A) from 1 to 99 weight percent of one or more &agr;-olefin/vinylidene monomer non-crosslinked substantially random interpolymers, wherein the distribution of the monomers of said interpolymers can be described by the Bernoulli statistical model or by a first or second order Markovian statistical model, and each having been made from monomer components comprising:
(1) from 0.5 to 65 mole percent of either
(a) at least one vinylidene aromatic monomer, or
(b) at least one hindered aliphatic vinylidene monomer, corresponding to the formula:
wherein A
1
is a sterically bulky, aliphatic or cycloaliphatic substituent of up to 20 carbons, R
1
is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R
2
is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R
1
and A
1
together form a ring system or
(c) a combination of at least one vinylidene aromatic monomer and at least one hindered aliphatic vinylidene monomer; and
(2) from 35 to 99.5 mole percent of at least one aliphatic &agr;-olefin having from 2 to 20 carbon atoms; and
(B) from 99 to 1 weight percent of one or more homopolymers or copolymers of monomer components comprising aliphatic &agr;-olefins having from 2 to 20 carbon atoms, or aliphatic &agr;-olefins having from 2 to 20 carbon atoms and containing polar groups.
The present invention also pertains to an expandable composition comprising the aforementioned blend and a foaming or expansion agent.
The blends and or foams of the present invention can “comprise”, “consist essentially of” or “consist of” any two or more of such polymers or interpolymers enumerated herein.
These blends provide an improvement in one or more of the polymer properties such as, but not limited to, mechanical properties, low temperature performance, relaxation/damping behavior and melt flow properties as compared to a like property of either of the individual polymers of said blend.
The term “interpolymer” is used herein to indicate a polymer wherein at least two different monomers are polymerized to make the interpolymer.
The term “copolymer” as employed herein means a polymer wherein at least two different monomers are polymerized to form the copolymer.
The term “mer(s)” means the polymerized unit of the polymer derived from the indicated monomer(s).
The term “monomer residue” or “polymer units derived from” means that portion of the polymerizable monomer molecule which resides in the polymer chain as a result of being polymerized with another polymerizable molecule to make the polymer chain.
The term “substantially random” in the substantially random interpolymer resulting from polymerizing one or more &agr;-olefin monomers and one or more vinylidene aromatic monomers or hindered aliphatic or cycloaliphatic vinylidene monomers, and optionally, with other polymerizable ethylenically unsaturated monomer(s) as used herein means that the distribution of the monomers of said interpolymer can be described by the Bernoulli statistical model or by a first or second order Markovian statistical model, as described by J. C. Randall in
POLYMER SEQUENCE DETERMINATION, Carbon-
13
NMR Method,
Academic Press New York, 1977, pp. 71-78. Preferably, the substantially random interpolymer resulting from polymerizing one or more a-olefin monomers and one or more vinylidene aromatic monomer, and optionally, with other polymerizable ethylenically unsaturated monomer(s) does not contain more than 15 percent of the total amount of vinylidene aromatic monomer in blocks of vinylidene aromatic monomer of more than 3 units. More preferably, the interpolymer was not characterized by a high degree of either isotacticity or syndiotacticity. This means that in the carbon
−13
NMR spectrum of the substantially random interpolymer the peak areas corresponding to the main chain methylene and methine carbons representing either meso diad sequences or racemic diad sequences should not exceed 75 percent of the total peak area of the main chain methylene and methine carbons.
Any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component or a value of a process variable such as, for example, temperature, pressure, time is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 are expressly enumerated in this specification. For values which are less than one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. The
Broos Rene
Chaudhary Bharat I
Cheung Yunwa W.
Gathers John J.
Guest Martin J.
Nutter Nathan M.
The Dow Chemical Company
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