Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
2000-06-05
2002-07-09
Woodward, Ana (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S271000, C524S504000, C525S071000, C525S073000
Reexamination Certificate
active
06417259
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to blends of polyalkylene grafted poly(alkenyl-co-maleimide) with poly(alkenyl-co-maleimide) and to the use of such blends, when extended, in producing high damping, soft gel materials.
BACKGROUND OF THE INVENTION
Imidization between a maleic anhydride and a primary amine group is a known chemical reaction. The synthesis of monofunctional N-alkyl and N-aryl maleimides is also known. They have been used to improve the heat stability of homo- and copolymers prepared from vinyl monomers. Typically, the bulk resins include poly(acrylonitrile-co-butadiene-co-styrene), ABS; a polyblend of poly(acrylonitrile-co-butadiene) and poly(styrene-co-acrylonitrile), SAN; poly(vinyl chloride), poly(styrene-co-acrylonitrile); poly(methyl methacrylate); or the like. The maleimides can be copolymerized with other monomers such as acrylonitrile, butadiene, styrene, methyl methacrylate, vinyl chloride, vinyl acetate and many other comonomers. An alternative practice is to produce copolymers of maleimides with other monomers such as styrene and optionally acrylonitrile and to blend these with ABS and SAN resins. In any event, the polymer compositions are adjusted so that the copolymers are fully compatible with the bulk resins (e.g., ABS and/or SAN) as shown by the presence of a single glass transition point (T
g
) as determined by DSC.
Two or more polymers can be blended together to form a wide variety of random or structured morphologies to obtain products that potentially offer desirable combinations of characteristics. However, obtaining many potential combinations through simple blending may be difficult or even impossible in practice. Frequently, the two polymers are thermodynamically immiscible, which precludes generating a truly homogeneous product. This immiscibility is not always a problem since it can be desirable to have a two-phase structure. However, the situation at the interface between these two phases often lead to problems. The typical case is one of high interfacial tension and poor adhesion between the two phases. This interfacial tension contributes, along with high viscosities, to the inherent difficulty of imparting the desired degree of dispersion to random mixtures and to their subsequent lack of stability, giving rise to gross separation or stratification during processing or use. Poor adhesion leads, in part, to weak and brittle mechanical behavior often observed in dispersed blends and may render some highly structured morphologies impossible.
Provision of an extended grafted copolymer having the impact strength of polypropylene, the elastomeric properties of a block copolymer, high damping properties, and thermostability remains highly desirable.
SUMMARY OF THE INVENTION
The present invention is generally directed to the use of a poly(alkenyl-co-maleimide) to impregnate a polyalkylene grafted poly(alkenyl-co-maleimide) polymer with an extender to form a soft gel composition having damping properties. Such compositions can be useful in producing molded products having heat resistance, high elasticity, and excellent damping properties.
Accordingly, the present invention provides a process for forming a high damping polymer blend. The process includes reacting from about 50 to about 99% (by wt.) of a poly(alkenyl-co-maleimide), from about 1 to about 50% (by wt.) of a maleated polyalkylene-grafted poly(alkenyl-co-maleimide), and from about 0.1 to about 10% (by wt.) of a polyamine under dry conditions sufficient to form a polymer blend. A gel is formed by mixing the polymer blend with an effective amount of extender.
In another aspect, the present invention provides a centipede polymer that includes, or is formed from a mixture that includes, a polyalkylene-grafted poly(alkenyl-co-maleimide), and a poly(alkenyl-co-maleimide).
DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
The polymer and polymer gel of the present invention contains: 100 parts by weight (pbw) of a grafted polymer of a poly(alkenyl-co-maleimide) having at least one maleated polyolefin segment grafted thereto through at least one functional linkage formed by a crosslinking reaction with a diamine grafting agent, from about 10 to about 1,000 pbw of a poly(alkenyl-co-maleimide), and optionally from about 10 to 1,000 pbw of an extender such as oil or a low molecular weight component.
The poly(alkenyl-co-maleimide) used in the impregnation of and in the formation of the graft copolymer is a centipede polymer formed by imidizing a poly(alkenyl-co-maleic anhydride) with at least one primary amine, preferably at least two different primary amines. The centipede polymer has a high molecular weight spine connected with many relatively short side chains. The length of the main chain usually is longer than the entanglement length, which is herein defined theoretically as an order of magnitude of 100 repeating units. The length of the side chains preferably is smaller than or equal to the entanglement length. The alkenyl units of the poly(alkenyl-co-maleimide) centipede polymer are polymers formed from R
1
(R
2
)ethylene monomers or alkenyl benzene monomers such as styrene, or &agr;-methylstyrene, p-methylstyrene, 4-phenylstyrene, m-methylstyrene, p-tert-butylstyrene, dimethylstyrene, and the like. The terms “alkenyl benzene” and “vinyl aromatic” are understood to be interchangeable as used herein. The R
1
(R
2
)ethylene contributed units of the poly(R
1
(R
2
)ethylene-co-maleimide) centipede polymer contain 4 to about 40 carbon atoms wherein R
1
and R
2
are the same or different substituents on the same or different carbon atom of the ethylene group, selected from unsubstituted and substituted C
1
-C
20
alkyl groups. The substituted groups, such as C
2
-C
20
alkoxyalkyl groups, are non-reactive with the remaining components of the centipede polymers. Examples of unsubstituted and substituted alkyl groups R
1
and R
2
in the R
1
(R
2
)ethylenes are independently substituted or unsubstituted alkyl groups containing 1 to 20 carbons such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclopropyl, 2,2-dimethylcyclopropyl, cyclopentyl, cyclohexyl, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl, methoxyheptyl, methoxyoctyl, methoxynonyl, methoxydecyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl, ethoxyhexyl, ethoxyheptyl, ethoxyoctyl, ethoxynonyl, ethoxydecyl, propoxymethyl, propoxyethyl, propoxypropyl, propoxybutyl, propoxypentyl, propoxyhexyl, propoxyheptyl, propoxyoctyl, propoxynonyl, propoxydecyl, butoxybutoxymethyl, butoxyethyl, butoxypropyl, butoxybutyl, butoxypentyl, butoxyhexyl, butoxyheptyl, butoxyoctyl, butoxynonyl, butoxydecyl, pentyloxymethyl, pentyloxyethyl, pentyloxypropyl, pentyloxybutyl, pentyloxypentyl, pentyloxyhexyl, pentyloxyoctyl, pentyloxynonyl, pentyloxydecyl, hexyloxymethyl, hexyloxyethyl, hexyloxypropyl, hexyloxybutyl, hexyloxypentyl, hexyloxyhexyl, hexyloxyheptyl, hexyloxyoctyl, hexyloxynonyl, hexyloxydecyl, heptyloxymethyl, heptyloxyethyl, heptyloxypropyl, heptyloxybutyl, hexyloxypentyl, heptyloxyhexyl, heptyloxyheptyl, heptyloxyoctyl, heptyloxynonyl, heptyloxydecyl, octyloxymethyl, octyloxyethyl, octyloxypropyl, octyloxybutyl, octyloxypentyl, octyloxyhexyl, octyloxyheptyl, octyloxynonyl, octyloxyoctyl, decyloxymethyl, decyloxyethyl, decyloxypropyl, decyloxybutyl, decyloxypentyl, decyloxyhexyl, decyloxyheptyl, 1-methylethyl, 1-methylpropyl, 1-methylbutyl, 1-methylpentyl, 1-methylhexyl, 1-methylheptyl, 1-methyloctyl, 1-methylnonyl, 1-methyldecyl, 2-methylpropyl, 2-methylbutyl, 2-methylpentyl, 2-methylhexyl, 2-methylheptyl, 2-methyloctyl, 2,3-dimethylbutyl, 2,3,3-trimethylbutyl, 3-methylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 2,3,3,4-tetramethylpentyl, 3-methylhexyl, 2,5-dimethylhexyl, and the like. Preferred alkenyl monomers for forming the poly(alkenyl-co-maleic anhydride) are styrene and isobutylene.
The p
Foltz Victor J.
Wang Xiaorong
Bridgestone Corporation
Burleson David G.
McCollister Scott
Woodward Ana
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