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
1999-04-19
2001-10-30
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...
C525S193000, C525S240000
Reexamination Certificate
active
06310140
ABSTRACT:
BACKGROUND OF THE INVENTION
The invention relates to thermoplastic elastomers of good dyeability and high strength and elasticity, as well as to high impact-resistant polymer blends produced therefrom, which are suitable for use in the motor vehicle industry, in the domestic appliances industry and in medical technology. The invention also relates to a method for the production of these thermoplastic elastomers.
Thermoplastic elastomers, such as styrene-butadiene block copolymers, thermoplastic polyurethanes, polyester amides, polyether amides, thermoplastic copolyester elastomers and polyolefin alloys with elastomers, are known (Rader, C., Kunststoffe 83 (1993) 10, 777-781, Kunststoffe 86, (1996) 12, 1845-1851).
The special advantage of polyolefin alloys with thermoplastic elastomers lies in that they can be processed easily and recycled advantageously.
The material properties of thermoplastic elastomers based on polyolefin alloys with elastomers, such as the strength and elasticity, are determined by the composition of the polyolefin components and of the elastomeric components and by the distribution of the elastomeric components in the polyolefin component (Moore, P., Polypropylene Handbook, Carl Hanser-Verlag Munich 1996, 218-225).
Known elastomeric components for thermoplastic elastomers based on polypropylene are ethylene-propylene elastomers (EP 672 712; EP 614940), ethylene-propylene-diene elastomers (EP 547 843; EP 409542), ethylene-vinyl acetate copolymers (BE 899507; Coran, A., Rubber Chem. Technol. 54 (1981),892), chlorosulfonated polyethylene (U.S. Pat. No. 4,141,878), elastomeric copolymers of ethylene and C
4
-C
8
olefins, such as elastomeric ethylene-butene copolymers (Kautschuk-Gummi-Kunststoffe 49 (1996) 12, 812-813), ethylene-hexene copolymers or ethylene-octene copolymers (Yu, T., J. Plastic Film & Sheeting 10 (1994) 1,539-564), as well as elastomeric, atactic polypropylenes (EP 334 829) in amounts of 35 to 70% by weight, based on the polyolefin mixture.
Furthermore, the vulcanization of elastomeric components in polyolefin alloys based on polypropylene/ethylene-propylene-diene elastomers, by additives such as dodecyl mercaptan (DE 26 20 820), sulfur (EP 336780) or tetrabutylthiuram disulfide (EP 376 213) is known. However, these formulations have the disadvantage of a strong discoloration, so that semi-finished products and molded objects of these materials can be used only when dyed black.
Thermoplastic elastomers based on polypropylenes and elastomeric C
4
to C
8
olefins have an outstanding dyeability, but a strength level which is significantly lower than that of thermoplastic elastomers based on polypropylenes and vulcanized ethylene-propylene-diene elastomers.
For the formulation of polypropylenes and elastomeric ethylenehexene copolymers, it is known that blends may be modified by electron irradiation (JP 96 301 927).
It is also known that the impact resistance of polypropylenes can be modified by the addition of 10-35% of amorphous ethylene-propylene-diene elastomers (Michaeli, W., Kunststoffberater (1990) 3, 38-43; Kloos, F., Angewandte Makromolekulare Chemie 185/186 (1991), 97-108), ethylene-propylene elastomers (Kim, B., J. Applied Polymer Sci. 60 (1996), 2207-2218, J. Applied Polymer Sci. 60 (1996), 1391-1403), as can reactor blends of polypropylene and ethylene-propylene rubber (Kresge, E., Macromol. Symp. 53 (1992), 173-189, Schwager, H., Kunststoffe 82 (1992) 6, 499-501), ethylene-butene elastomers (Yu, C., SPE-ANTEC '94,2439-2442; SPEANTEC '96, 1995-2000), ethylene-hexene copolymers (Japanese patent 08301 927, Yamaguchi, M., J. Appl. Polymer Sci. 63 (1997), 467-474) and ethylene-octene elastomers (EP 0 769 525, Japanese patent 97 48 920).
SUMMARY OF THE INVENTION
It is an object of the present invention to develop thermoplastic elastomers, which have good dyeability and, at the same time, a high strength and elasticity, as well as to develop high impact-resistant polymer blends produced therefrom.
Surprisingly, it was found that, by compounding propylene homopolymers and/or propylene copolymers with elastomeric C
4
to C
12
olefin copolymers and/or terpolymers and C
8
to C
14
diacrylates, C
7
to C
16
diallyl compounds, C
9
to C
15
dimethacrylates, C
7
to C
10
divinyl compounds, C
12
to C
17
acrylate esters of polyalcohols, C
15
to C
21
methacrylate esters of polyalcohols and/or C
9
to C
12
triallyl compounds as unsaturated monomers, optionally in the presence of thermally decomposing free radical-forming agents, thermoplastic elastomers are formed, which have a very finely dispersed distribution of the elastomeric components in the polyolefin components and fulfill the above requirements.
DETAILED DESCRIPTION OF THE INVENTION
The object of the invention was attained by thermoplastic elastomers of good dyeability and high strength and elasticity, the incorporated elastomeric particles of which have an average particle diameter of 0.05 to 5 &mgr;m and preferably of 0.1 to 1 &mgr;m, from propylene homopolymers and/or propylene copolymers, elastomers, unsaturated monomers, optionally thermally decomposing free radical-forming agents and adjuvants. The thermoplastic elastomers are produced by a method, in which mixtures of 20 to 80% by weight and preferably 40 to 60% by weight of propylene homopolymers and/or propylene copolymers, 80 to 20% by weight and preferably 60 to 40% by weight of elastomeric C
4
to C
12
olefin copolymers and/or terpolymers, 0.10 to 4.0% by weight and preferably 0.2 to 1.5% by weight, based on the sum of the polymers used, of C
8
to C
14
diacrylates, C
7
to C
16
diallyl compounds, C
9
to C
15
dimethacrylates, C
7
to C
10
divinyl compounds, C
12
to C
17
acrylate esters of polyalcohols, C
15
to C
21
methacrylate esters of polyalcohols and/or C
9
to to C
12
triallyl compounds, as unsaturated monomers, and 0 to 4.0% by weight and preferably 0.2 to 1.5% by weight, based on the sum of the polymers used, of acyl peroxides, alkyl peroxides, hydroperoxides, peroxycarbonates, peresters, ketone peroxides, peroxyketals and/or azo compounds, as thermally decomposing free radical-forming agents, have been reacted in a melt. Before and/or after the reaction, the addition of 0.01 to 2.5% by weight of stabilizers, 0.1 to 1% by weight of antistatic agents, 0.2 to 3% by weight of pigments, 0.05 to 1% by weight of nucleating agent, 5 to 40% by weight of fillers and/or reinforcing agents, 2 to 20% by weight of flame retardants and/or 0.01 to 1% by weight of processing aids, in each case based on the sum of the polymers used, is also possible.
The finely dispersed distribution of the elastomeric component in the polyolefin component, which is of the &mgr;m order in the case of the thermoplastic elastomers of the present invention, can be determined by photographs taken with a transmission electron microscope.
As thermally decomposing, free radical-forming agents, preferably free radical-forming agents with half life times of 20 seconds at temperatures above 150° C. are used.
Pursuant to the invention, the propylene homopolymers preferably are largely isotactic propylene homopolymers, especially isotactic propylene homopolymers, which have been produced using Ziegler-Natta catalysts or metallocene catalysts. Especially suitable for this purpose are propylene homopolymers having a bimodal molecular weight distribution, weight average molecular weights M
w
of 500,000 to 1,500,000 g/mole, number average molecular weights M
n
of 25,000 to 100,000 g/mole and M
w
/M
n
values of 5 to 60, which were synthesized in a reactor cascade.
Likewise, for the thermoplastic elastomers, copolymers of propylene and &agr;-olefins are preferred, having 2 or
4
to 18 carbon atoms, especially random propylene copolymers, propylene block copolymers and/or random propylene block copolymers.
Likewise, mixtures of 50 to 98% by weight of largely isotactic propylene homopolymers and/or copolymers of propylene and &agr;-olefins having 2 or 4 to 18 carbon atoms and 2 to 50% by weight of non-isotactic propylene homopolymers, lar
Bucka Hartmut
Hesse Achim
Radusch Hans-Joachim
Raetzsch Manfred
Reichelt Norbert
Borealis GmbH
Jordan and Hamburg LLP
Nutter Nathan M.
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