Stock material or miscellaneous articles – Hollow or container type article – Polymer or resin containing
Reexamination Certificate
2000-11-17
2001-11-20
Wilson, Donald R. (Department: 1713)
Stock material or miscellaneous articles
Hollow or container type article
Polymer or resin containing
C428S364000, C521S139000, C521S140000, C524S518000, C524S525000, C524S528000, C525S211000, C525S216000, C525S240000, C525S241000
Reexamination Certificate
active
06319577
ABSTRACT:
FIELD OF THE INVENTION
The present invention pertains to blends of &agr;-olefin/vinyl aromatic monomer and/or aliphatic or cycloaliphatic vinyl or vinylidene monomer interpolymers having different vinyl aromatic monomer and/or aliphatic or cycloaliphatic vinyl or vinylidene monomer content or both different vinyl aromatic monomer and/or aliphatic or cycloaliphatic vinyl or vinylidene monomer content and different molecular weight. The blend components are selected to provide superior performance or processability in the blends.
BACKGROUND OF THE INVENTION
The generic class of materials covered by &agr;-olefin/vinyl or 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.
Although of utility in their own right, Industry is constantly seeking to improve the applicability of these interpolymers. Such enhancements nay be accomplished via additives or the like, but it is desrable to develop technologies to provide improvements in processability and/or performance without the addition of additives or further improvements than can be achieved with the addition of additives. To date, the possible advantages of blending to provide materials with superior properties have not been identified.
There is a need to provide blends of &agr;-olefin/vinyl aromatic monomer interpolymers wath superior performance characteristics which will expand the utility of this interesting class of materials.
SUMMARY OF THE INVENTION
The present invention pertains to a blend of polymeric materials comprising a plurality of substantially random interpolymers each interpolymer comprising:
(1) from about 1 to about 65 mole percent of polymer units derived from either
(a) at least one vinyl aromatic monomer or
(b) at least one aliphatic or cycloaliphatic vinyl or vinylidene monomer, or
(c) a combination of at least one vinyl aromatic monomer and at least one aliphatic or cycloaliphatic vinyl or vinylidene monomer, and
(2) from about 35 to about 99 mole percent of polymer units derived from ethylene and/or at least one aliphatic alpha olefin having from 3 to 20 carbon atoms; and wherein:
the amount of polymer units derived from vinyl aromatic monomer and/or aliphatic or cycloaliphatic vinyl or vinylidene monomer in any interpolymer component differs from that amount in another interpolymer component by at least 0.5 mole percent.
The blends of the present invention can comprise, consist essentially of or consist of any two or more of such interpolymers enumerated herein. Likewise, the interpolymers can comprise, consist essentially of or consist of any two or more of the enumerated polymerizable monomers.
DETAILED DESCRIPTION OF THE INVENTION
The percent difference in Mn between the interpolymers in the blends of the present invention is determined by subtracting the Mn of the interpolymer with the lowest Mn from the interpolymer with the highest Mn and dividing the difference with the Mn of the interpolymer with the lowest Mn and multiplying by 100. In those instances wnere more than 2 interpolymers are employed in the blend, the percent difference is determined for each combination of two polymers e.g. for a blend of interpolymers A, B and C, the determination is made for the combinations: A & B, A & C and B & C.
The term “hydrocarbyl” means any aliphatic, cycloaliphatic, aromatic, aryl substituted aliphatic, aryl substituted cycloaliphatic, aliphatic substituted aromatic, or cycloaliphatic substituted aromatic groups. The aliphatic or cycloaliphatic groups are preferably saturated. Likewise, the term “hydrocarbyloxy” means a hydrocarbyl group having an oxygen linkage between it and the carbon atom to which it is attached.
The term “interpolymer” is used herein to indicate a polymer wherein at least two different monomers are polymerized to make the interpolymer. This includes copolymers, terpolymers, etc.
The term “plurality” as used herein means two or more.
The term “substantially random” in the substantially random interpolymer comprising an &agr;-olefin and a vinyl aromatic monomer or aliphatic vinyl or vinylidene monomer 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 comprising an &agr;-olefin and a vinyl aromatic monomer does not contain more than 15 percent of the total amount of vinyl aromatic monomer in blocks of vinyl 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 13C-NMR spectrum of the substantially random interpolymer the peak areas corresponding to the main chain methylene and methine carbons representing either meso dial secuences 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 on 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, pressures time and the like 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 etc. 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. These are only examples of what is specifically intented and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner.
The interpolymers suitable for blending to make the blends comprising the present invention include substantially random interpolymers prepared by polymerizing one or more &agr;-olefins with one or more vinyl aromatic monomers and/or one or more aliphatic or cycloaliphatic vinyl or vinylidene monomers.
Suitable &agr;-olefins include for example, ethylene and &agr;-olefins containing from 3 to about 20, preferably from 3 to about 12, more preferably from 3 to about 8 carbon atoms. Particularly suitable are ethylene, propylene, butene-1,4-methyl-1-pentene, hexene-1 and octene-1. These &agr;-olefins do not contain an aromatic moiety.
Suitable vinyl aromatic monomers include, for example, those represented by the following formula:
wherein R
1
is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 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 about 4 carbon atoms, preferably hydrogen or methyl; Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C
1-4
-alkyl, and C
1-4
-haloalkyl; and n has a value from zero to about 6, preferably from zero to about 2, more preferably zero. Exemplary vinyl arcmatic monomers include styrene, vinyl toluene, &agr;-methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds, and the like. Particularly suitable such
Cheung Yunwa W.
Chum Pak-Wing S.
Gathers John J.
Guest Martin J.
The Dow Chemical Company
Wilson Donald R.
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