US 5,177,151 A · Blends of comb-shaped copolymers of a macromolecular monomer of polyhaloether with terminal olefinic unsaturation

Abstract

This invention relates to a comb-shaped graft copolymer, to a process for making the comb, and to a polymer blend made with the comb. The comb is made by a free radical polymerization of an ethylenically unsaturated monomer with a macromolecular monomer ("macromer" for brevity) of a haloalkylene oxide ("HAO" for brevity) homopolymer, random or block copolymer. The comb copolymer and blends of the comb with a polymer(s) may be cured. A comb with a terminal acrylyl or methacrylyl group or "head" and pendant polyether chains, which always include some HAO repeating units, may be made in an emulsion or suspension polymerization process which provides a comb having adequately high molecular weight so that the comb may be used in blends. The preferred comb of epichlorohydrin has a (meth)acrylyl head at one end, through which it (the macromer) is polymerizable, and a terminal hydroxyl (OH) group, or an end-capping group derived from the OH group at the other end. Each "tine" (pendant chain) of the comb is an uninterrupted one (that is, having no branch) having at least two repeating units derived from a HAO, preferably epichlorohydrin ("ECH"), with the tine terminating with a OH group, or an end-capping group derived from the OH group.

Claims21

Dependent claims

A compatible blend of at least one matrix resin present in a major amount by weight in said blend, and a comb copolymer of a polymerizable olefinically unsaturated monomer and a macromer of poly(haloalkyl oxide) wherein said comb copolymer has a hydrocarbon backbone and said macromer of poly(haloalkyl oxide) is represented by the structure

R--(M).sub.m --Z (LM)
wherein
R represents a monoolefinically unsaturated vinyl group,
M represents at least one ring-opened repeating unit of a poly(haloalkylene oxide),
m represents an integer in the range from 2 to about 500,
Z is a terminal group derived from a ring-opening polymerization or by a coupling reaction;
and, said matrix resin is selected from the group consisting of poly(vinyl chloride) (PVC), poly(styrene-acrylonitrile) (SAN), poly(styrene-acrylonitrile-butadiene) (ABS), poly(styrene-acylonitrile-acrylate) (ASA), poly(vinyl acetate), poly(vinylidene chloride-vinylacetate), poly(vinyl methyl ether) (PVME), chlorinated poly(vinyl chloride) (CPVC), chlorinated polyethylene (CPE), polyepichlorohydrin, chlorobutyl rubber, bromobutyl rubber, chlorosulfonated polyethylene, polychloroprene, Phenoxy (polyhydroxypropylether of bisphenol A), poly(methylmethacrylate) (PMMA), poly(stryenemaleic anhydride) (SMA), poly(ethylene-vinyl acetate) (EVA), polybutyleneterephthalate, (PBT), polyethyleneterephthalate (PET), polyamide (PA), polyurethane (PU), polyolefin (PO) and polycarbonate (PC).

4 more elements

A compatible blend of a matrix resin present in a major amount by weight in said blend, and a comb copolymer of (a) macromer of polyhaloalkylene oxide and (b) a polymerizable olefinically unsaturated monomer, said comb being produced with pendant chains having substantially equal length, said comb copolymer being formed by a free radical polymerization process and, said matrix resin is selected from the group consisting of poly(vinyl chloride) (PVC), poly(styreneacrylonitrile) (SAN), poly(styrene-acrylonitrile-butadiene) (ABS), poly(styrene-acrylonitrile-acrylate) (ASA), poly(vinyl acetate), poly(vinylidene chloride-vinylacetate), poly(vinyl methyl ether) (PVME), chlorinated poly(vinyl chloride) (CPVC), chlorinated polyethylene (CPE), polyepichlorohydrin, chlorobutyl rubber, bromobutyl rubber, chlorosulfonated polyethylene, polychloroprene, Phenoxy (polyhydroxypropylether of bisphenol A), poly(methylmethacrylate) (PMMA), poly(styrene-maleic anhydride) (SMA), poly(ethylene-vinyl acetate) (EVA), polybutyleneterephthalate (PBT), polyethyleneterephthalate (PET), polyamide (PA), polyurethane (PU), polyolefin (PO) and polycarbonate (PC).

A compatible blend of (A) two or more matrix resins together present in a major amount by weight in said blend, irrespective of whether said materials are incompatible with each other, and (B) a comb copolymer of (a) macromer of polyhaloalkylene oxide and (b) a polymerizable olefinically unsaturated monomer in which a portion of said macromer is soluble, at least one of said matrix resins being compatible with pendant chains of said polyhaloalkylene oxide, said comb being produced with pendant chains having substantially equal length by a free radical polymerization process, and, wherein one of said matrix resins is selected from the group consisting of poly(vinyl chloride) (PVC), poly(styreneacrylonitrile) (SAN), poly(styrene-acrylonitrile-butadiene) (ABS), poly(styrene-acrylonitrile-acrylate) (ASA), poly(vinyl acetate), poly(vinylidene chloride-vinylacetate), poly(vinyl methyl ether) (PVME), chlorinated poly(vinyl chloride) (CPVC), chlorinated polyethylene (CPE), polyepichlorohydrin, chlorobutyl rubber, bromobutyl rubber, chlorosulfonated polyethylene, polychloroprene, Phenoxy (polyhydroxypropylether of bisphenol A), poly(methylmethacrylate) (PMMA), poly(styrene-maleic anhydride) (SMA), poly(ethylene-vinyl acetate) (EVA), polybutyleneterephthalate (PBT), polyethyleneterephthalate (PET), polyamide (PA), polyurethane (PU), polyolefin (PO) and polycarbonate (PC).

A process for preparing a polymer blend comprising,

depositing at least one matrix resin in a mixing zone, adding thereto a comb copolymer of a polymerizable olefinically unsaturated monomer and a macromer of polyhaloalkylene oxide and mixing at a sufficiently high temperature and for enough time, until compatibly blended therewith,
said matrix resin being present in said mixing zone in a major amount of weight, and said comb copolymer being present in a minor amount by weight,
said comb copolymer having a hydrocarbon backbone and said macromer of polyhaloalkylene oxide being represented by the structure
R--(M).sub.m --Z (LM)
wherein
R represents a monoolefinically unsaturated vinyl group,
M represents at least one ring-opened repeating unit of a poly(haloalkylene oxide),
m represents an integer in the range from 2 to about 500, and
Z is a terminal group derived from a ring-opening polymerization or by a coupling reaction, selected from the group consisting of --OR.sup.8, ##STR21## --OSiR.sub.3.sup.8, --Cl, --Br, --I, --OCH.sub.2 CH.sub.2 CN, --13 OSO.sub.3 Na, --OSO.sub.3 K, --OSO.sub.3 Li, --OSO.sub.3 NH.sub.4, and --OH, wherein
R.sup.8 is selected from the group consisting of hydrogen, C.sub.1 -C.sub.20 alkyl and haloalkyl, and C.sub.6 -C.sub.20 aryl and aralkyl;
and,
said matrix resin is selected from the group consisting of poly(vinyl chloride) (PVC), poly(styrene-acrylonitrile) (SAN), poly(styrene-acrylonitrile-butadiene) (ABS), poly(styrene-acrylonitrile-acrylate) (ASA), poly(vinyl acetate), poly(vinylidene chloride-vinylacetate), poly(vinyl methyl ether) (PVME), chlorinated poly(vinyl chloride) (CPVC), chlorinated polyethylene (CPE), polyepichlorohydrin, chlorobutyl rubber, bromobutyl rubber, chlorosulfonated polyethylene, polychloroprene, Phenoxy (polyhydroxypropylether of bisphenol A), poly(methylmethacrylate) (PMMA), poly(styrene-maleic anhydride) (SMA), poly(ethylene-vinyl acetate) (EVA), polybutyleneterephthalate (PBT), polyethyleneterephthalate (PET), polyamide (PA), polyurethane (PA), polyolefin (PO) and polycarbonate (PC).

9 more elements

Dependencies are inferred from the claim text.

Blends of comb-shaped copolymers of a macromolecular monomer of polyhaloether with terminal olefinic unsaturation

Life of this patent

Blends of comb-shaped copolymers of a macromolecular monomer of polyhaloether with terminal olefinic unsaturation

Life of this patent

Abstract

Claims21