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
1998-10-21
2003-06-24
Mullis, Jeffrey (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...
C525S298000, C525S301000, C525S302000, C526S348300, C526S348800, C526S319000
Reexamination Certificate
active
06583228
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a copolymer of vinyl or vinylidene monomers and a high reactivity polyolefin which is produced by free radical polymerization. The copolymers are useful in many applications, including coatings and adhesives and exhibit improved water resistance, impact strength, flexibility, and processability in many applications.
BACKGROUND OF THE INVENTION
Blends of two or more polymers have often been made, for example in attempts to combine desirable properties of the individual polymers into the blend, to seek unique properties in the blend, or to produce less costly polymer products by including less expensive or scrap polymers in the blend. Compatible polymers tend to form blends that contain small domains of the individual polymers; in the case of “miscible” polymers these occur at the molecular scale, resulting in properties usually considered characteristic of a single polymer. These may include the occurrence of a single glass-transition temperature and optical clarity. Compatible polymers that are not strictly miscible are still likely to form blends with properties that approach those of the miscible blends. Such properties as tensile strength, which rely upon adhesion of the domains to one another, tend not to be degraded when compatible polymers are blended.
Many polymers are poorly compatible with one another, and poor compatibility cannot necessarily be predicted accurately for a given polymer combination, but in general it may be expected when non-polar polymers are blended with more polar polymers. Poor compatibility in a blend can be determined by those skilled in the art, and often evidences itself in poor tensile strength or other physical properties, especially when compared to the component polymers of the blend. Microscopic evidence of poor compatibility may also be present, in the form of large, poorly adhered domains of one or more polymer components in a matrix of another polymer component of the blend. More than one glass-transition temperature may be observed, and a blend of otherwise transparent polymers may be opaque because the domain sizes are large enough to scatter visible light.
Much research has been directed toward finding ways to increase the compatibility of poorly compatible polymers when blended. Approaches that have been used include adding to the blend polymers which show incompatibility with the other, mutually compatible polymers; such added polymers act as a bridge or interface between the incompatible components, and often decrease domain size. Chlorinated polyethylene has been used as such an additive polymer, especially in blends of polyolefins with other, poorly compatible polymers.
Graft polymers, as of incompatible polymers A onto B, are known to aid in blending polymers A and B. Such graft polymers may also serve to aid in blending other incompatible polymers C and D, where A and C are compatible and B and D are compatible. Grafting of monomers capable of vinyl polymerization, such as, methyl methacrylate, styrene and the like, onto polyolefins has been attempted by many means. Grafting onto solid polymer by vapor-phase polymerization, by reaction in an extruder, by peroxidation of the olefinic backbone, and grafting onto pendant double bonds are all routes which have been attempted.
For example, U.S. Pat. Nos. 5,128,410 and 5,229,456 disclose a polymerized olefin having grafted thereto, by covalent bonding, a polymeric methacrylate chain of relatively high molecular weight. The methacrylate chain has a weight average molecular weight (Mw) of at least 20,000 and advantageously between about 30,000 and 150,000. The resulting polyolefin copolymer has a weight average molecular weight between about 50,000 and 1,000,000, preferably a weight average molecular weight of about 200,000-800,000. In the method of manufacturing the grafted copolymer, a non-polar polyolefin, preferably polypropylene or polyethylene, is introduced into an inert hydrocarbon solvent which dissolves (or swells) the polyolefin, by heating to a temperature at which the polyolefin is dissolved. While agitating the solution, methyl methacrylate (MMA) monomer, together with an initiator which generates a constant, low radical flux concentration sufficient to initiate polymerization of the monomer at the temperature of the solution and promote the formation of the covalent bond, is gradually added. The polyolefin with a side-chain grafted thereto is thereafter separated from the solvent by volatilizing the solvent, preferably in a devolatilizing extruder. The graft polymer is then blended with a suitable polyolefin such as polypropylene or polyethylene, and extruded into a desired shape.
U.S. Pat. No. 5,112,507 generically discloses compositions which comprise copolymers of an unsaturated acidic reactant and high molecular weight olefin wherein at least about 20 percent of the total high molecular weight olefin comprises the alkylvinylidene isomer, said copolymers having alternating succinic and polyalkyl groups. The only unsaturated acidic reactant exemplified is maleic acid. The high molecular weight olefin has a sufficient number of carbon atoms such that the resulting copolymer is soluble in lubricating oil. Suitable olefins include those having about 32 carbon atoms or more (preferably having about 52 carbon atoms or more). Preferred high molecular weight olefins include polyisobutenes. Especially preferred are polyisobutenes having number average molecular weights of from about 500 to about 5000 and in which the alkylvinylidene isomer comprises at least 50 percent of the total olefin. The copolymers are disclosed to be useful as dispersants in lubricating oils and fuels.
D.E. 4,030,399 discloses that polymers and copolymers of propylene which, to some extent, have vinylidene terminal groups can be functionalized to give polymers and copolymers of propylene with 0 to 40 wt % of other C
2
and C
8
1 -alkenes, having number average molecular weights (Mn) of 100 to 100,000, a Mw/Mn of 1 to 3, and one functional chain end per macromolecule where “functionality” means a group containing a heteroatom which is bonded to a C atom. Polypropylene homopolymer is the only polymer exemplified. The functionalized polymers can be reacted with polar polymers to give copolymers of propylene.
Published European Patent Application No. 95110985.9 discloses conversion products of polyolefins with predominantly terminal double bonds and a numerical mean number average molecular weight of 250 to 10,000, which have an aliphatic hydrocarbon skeleton which is straight chain or carries C
1
-C
4
alkyl side chains, with 1 to 10 mol per equivalent of double bond of one or more vinyl esters obtainable by reacting the disclosed polyolefins with the vinyl esters in the presence of a free radical initiator at temperatures of 40 to 220° C., whereby these reaction products are then hydrolyzed to the corresponding alcohol or can be converted to the corresponding amines by reductive amination. The conversion products are used in fuel and lubricant compositions as additives.
U.S. Pat. No. 4,062,908 discloses the preparation of vinyl ester copolymers; more particularly, a free-radical induced bulk copolymerization of ethylenically unsaturated compounds is described. The use of the resulting copolymers for coating applications, particularly in non-aqueous dispersions, is also described. The patent discloses a process for the preparation of copolymers of monoethylenically unsaturated compounds in the presence of a free-radical forming initiator by bulk copolymerization as follows: A. 1-50 parts by weight of vinyl esters of saturated aliphatic monocarboxylic acids in which the carboxyl group is attached to a tertiary or quaternary carbon atom, and which carboxylic acids have at least 9 carbon atoms per molecule; B. 1-60 parts by weight of a vinyl aromatic hydrocarbon; C. 0-50 parts by weight of an ester, amide, and/or nitrite of an ethylenically unsaturated monocarboxylic acid having 3 to 4 carbon atoms per molecule; D. 0-30 parts by weight of an ester of
Bagheri Vahid
Moore Lionel
Nkansah Asare
BP Corporation North America Inc.
Henes James R.
Mullis Jeffrey
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