CN103242491A - Graft copolymer with grafted copolymerization arms, and preparation and application thereof - Google Patents
Graft copolymer with grafted copolymerization arms, and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a graft copolymer composition which comprises a polymer framework derived from multiple polymerizable olefinic bond type unsaturated monomers, and multiple polymer arms connected with the lateral sides of the polymer framework, wherein the polymer arms comprise: (a) at least two different polymer arms, including a condensed copolymer arm and a random copolymer arm; (b) polymer arms, each of which has a chain segment composed of (i) a condensed copolymer chain segment and (ii) a random copolymer chain segment; or (c) a combination thereof.
Description
Invention field
The invention provides graft copolymer composition, preparation method and such as the purposes in the coating of the quick drying paint that in car repair, uses.
Summary of the invention
The invention provides graft copolymer and preparation thereof and purposes.In some embodiments, graft copolymer composition comprises: the polymer backbone that is derived from a plurality of polymerizable ethylene linkage formula unsaturated monomers; And a plurality of polymeric arms that are connected with the polymer backbone side separately.In some embodiments, each polymeric arms is connected on the polymer backbone by the single endpoint side.In this class embodiment, each polymeric arms is connected on the polymer backbone by the end group side with single terminal olefinic link formula unsaturated group.
In some embodiments, the polymerizable ethylene linkage formula unsaturated monomer for the preparation of polymer backbone comprises: methacrylic acid; Vinylformic acid; (methyl) alkyl acrylate, wherein said alkyl are straight chained alkyl, branched-chain alkyl or cycloalkyl, and each described alkyl has 1 to 18 carbon atom; (methyl) vinylformic acid hydroxyalkyl acrylate, wherein said hydroxyalkyl is straight chained alkyl or branched-chain alkyl, each described alkyl has 2 to 4 carbon atoms; Vinylbenzene; Styrene derivatives; And their mixture.
In some embodiments, described polymeric arms comprises at least two different polymeric arms, and it comprises condensation copolymers arm and random copolymers arm.In some these class embodiments, the condensation copolymers arm comprises the polyester copolymer arm that is formed by the polyester macromolecule monomer, and the random copolymers arm comprises the acrylate copolymer arm that is formed by the polyacrylic ester macromonomer.In some these class embodiments, the polyester copolymer arm is derived from a plurality of monomers, and described monomer comprises that (i) has the unsaturated polycarboxylic acid of at least two carboxylic moiety; The polyvalent alcohol that (ii) has at least two hydroxylic moieties.In some these class embodiments, the polyacrylic ester arm comprises a plurality of polymerizable ethylene linkage formula unsaturated monomers.In some embodiments, polymerizable ethylene linkage formula unsaturated monomer comprises: methacrylic acid; Vinylformic acid; (methyl) alkyl acrylate, wherein said alkyl are straight chained alkyl, branched-chain alkyl or cycloalkyl, and each described alkyl has 1 to 18 carbon atom; (methyl) vinylformic acid hydroxyalkyl acrylate, wherein said hydroxyalkyl is straight chained alkyl or branched-chain alkyl, each described alkyl has 2 to 4 carbon atoms; Vinylbenzene; Styrene derivatives; And their mixture.
In some other embodiment, polymeric arms comprises having (i) condensation copolymers segment and the (ii) polyester-polyacrylate multipolymer of the segment of random copolymers segment, and wherein said condensation copolymers segment and random copolymers segment are connected to each other.In some embodiments, a plurality of polymeric arms comprise and have (i) condensation copolymers segment and the (ii) polyester-polyacrylate multipolymer of random copolymers segment, and wherein said condensation copolymers segment and random copolymers segment are connected to each other.
Embodiment describes in detail
The invention provides graft copolymer and preparation thereof and purposes.This analog copolymer is particularly useful at the fast-curing paint preparation that is used for automobile original equipment manufacturer and repairing and other industrial application.Graft copolymer provides fast setting, high crosslink density and levelling property and the film-forming properties of filming.
In some embodiments, graft copolymer composition comprises: the polymer backbone that is derived from a plurality of polymerizable ethylene linkage formula unsaturated monomers; And a plurality of polymeric arms that are connected with the polymer backbone side separately.In certain embodiments, described polymeric arms comprises at least two different polymeric arms, and it comprises condensation copolymers arm and random copolymers arm.In some other embodiment, polymeric arms comprises having (i) condensation copolymers segment and the (ii) polyester-polyacrylate multipolymer of the segment of random copolymers segment, and wherein said condensation copolymers segment and random copolymers segment are connected to each other.
For purpose of the present disclosure, " random copolymers arm " and " random copolymers segment " is interpreted as incorporating monomer into wherein polymkeric substance with statistical at random.For purpose of the present disclosure, " segment " refers to the part of polymeric arms.
In some embodiments, each polymeric arms is connected on the polymer backbone by single end points side.In this class embodiment, each polymeric arms is connected on the polymer backbone by the end group side with single terminal olefinic link formula unsaturated group.In another embodiment, the condensation copolymers arm is connected on the polymer backbone by the end group side with single terminal olefinic link formula unsaturated group.In this class embodiment, end group is derived from unsaturated polycarboxylic acid.In another embodiment, the random copolymers arm is connected on the polymer backbone by the end group side with single terminal olefinic link formula unsaturated group.In this class embodiment, end group is derived from unsaturated methacrylic ester.In another embodiment, polyester-polyacrylate multipolymer arm is connected on the polymer backbone by the end group side with single terminal olefinic link formula unsaturated group.In this class embodiment, end group is derived from unsaturated methacrylic ester.
Polymer backbone
In some embodiments, graft copolymer composition of the present invention comprises the polymer backbone that is derived from a plurality of polymerizable ethylene linkage formula unsaturated monomers.In certain embodiments, a plurality of polymerizable ethylene linkage formula unsaturated monomers comprise: the vinylformic acid hydroxyalkyl acrylate, methacrylic acid hydroxyl alkyl ester, the alkyl acrylate alkyl acrylate, alkyl methacrylate, alicyclic acrylate, cycloaliphatic methacrylates, the vinylformic acid aryl ester, aryl methacrylate, vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide, the N-alkyl acrylamide, N-alkyl methyl acrylamide, N, N-dialkyl group acrylamide, N, N-dialkyl methyl acrylamide, vinyl aromatic compounds, and their combination, each alkyl of wherein said monomer or aromatic base can be not and to replace or replace.
In other embodiments, a plurality of polymerizable ethylene linkage formula unsaturated monomer comprises: methacrylic acid; Vinylformic acid; (methyl) alkyl acrylate, wherein said alkyl are straight chained alkyl, branched-chain alkyl or cycloalkyl, and each described alkyl has 1 to 18 carbon atom; (methyl) vinylformic acid hydroxyalkyl acrylate, wherein said hydroxyalkyl is straight chained alkyl or branched-chain alkyl, each described alkyl has 2 to 4 carbon atoms; Vinylbenzene; Styrene derivatives; And their mixture.In some these class embodiments, each alkyl of straight chained alkyl, branched-chain alkyl or cycloalkyl has 1 to 12 carbon atom.
In some other embodiment, a plurality of polymerizable ethylene linkage formula unsaturated monomers comprise methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic tert-butyl acrylate, methacrylic acid 2-ethylhexyl, lauryl methacrylate(LMA), cyclohexyl methacrylate, isobornyl methacrylate, the methacrylic acid stearyl, methacrylonitrile, methyl acrylate, ethyl propenoate, the vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-EHA, vinylformic acid 2-hydroxy methacrylate, the vinylformic acid hydroxy propyl ester, vinylformic acid 4-hydroxyl butyl ester, 2-hydroxyethyl methacrylate or methacrylic acid 2-hydroxy propyl ester, vinylbenzene, vinyl cyanide and combination thereof.
Polymeric arms
In some embodiments, graft copolymer comprises a plurality of polymeric arms, and described polymeric arms comprises at least two different polymeric arms, and wherein each polymeric arms is connected with the polymer backbone side.In certain embodiments, two different polymeric arms comprise condensation copolymers arm and random copolymers arm.In some embodiments, the condensation copolymers arm comprises the polyester copolymer arm that is formed by the polyester macromolecule monomer, and the random copolymers arm comprises the acrylate copolymer arm that is formed by the polyacrylic ester macromonomer.
In some embodiments, graft copolymer of the present invention comprises the polymer backbone of about 40% to 98% weight ratio, the random copolymers arm of 1% to 50% weight ratio; And the condensation copolymers arm of 1% to 10% weight ratio.In some embodiments, graft copolymer of the present invention comprises the polymer backbone of about 40% to 98% weight ratio, the acrylate copolymer arm of 1% to 50% weight ratio and the polyester copolymer arm of 1% to 10% weight ratio.
In some embodiments, have polyester arm and polyacrylic ester arm graft copolymer be 10,000 to 30,000 according to the polymethylmethacrylate standard by the molecular weight of gpc measurement.In some embodiments, have polyester arm and polyacrylic ester arm graft copolymer be 15,000 to 25,000 according to the polymethylmethacrylate standard by the molecular weight of gpc measurement.
The condensation copolymers arm
In some embodiments, the condensation copolymers arm comprises the polyester arm.In some these class embodiments, the polyester copolymer arm is derived from a plurality of monomers, and described monomer comprises that (i) has the unsaturated polycarboxylic acid of at least two carboxylic moiety; The polyvalent alcohol that (ii) has at least two hydroxylic moieties.。In other this class embodiment, the polyester arm is derived from the combination of at least three monomers, and described monomer comprises: the polyvalent alcohol with at least two hydroxylic moieties; Unsaturated polycarboxylic acid with at least two carboxylic moiety; And the saturated polycarboxylic acid with at least two carboxylic moiety.
In some embodiments, the unsaturated polycarboxylic acid with at least two carboxylic moiety comprises the alkylidene group with 4 to 8 carbon atoms.In other embodiments, the unsaturated polycarboxylic acid with at least two carboxylic moiety comprises maleic anhydride, propene dicarboxylic acid, hexene diacid and combination thereof.
In some embodiments, polyvalent alcohol has at least two carboxy moieties and straight chained alkyl, branched-chain alkyl or cycloalkyl, and wherein each this class alkyl has 2 to 14 carbon atoms.In other embodiments, polyvalent alcohol comprises ethylene glycol, propylene glycol, neopentyl glycol; 2,2,4-trimethylammonium-1, the 3-pentanediol; The 2-methyl isophthalic acid, ammediol; 2-ethyl-2-methylol-1, ammediol, hydroxyl pivalyl hydroxy new pentane acid ester; 2-butyl-2-ethyl-1, ammediol, 1,4 cyclohexane dimethanol; The tristane dimethanol; And their combination.
In some embodiments, the saturated polycarboxylic acid with at least two carboxylic moiety comprises straight chained alkyl, branched-chain alkyl or cycloalkyl, and wherein each alkyl has 6 to 36 carbon atoms.In some of the other embodiments, saturated polycarboxylic acid comprises oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, 1,4-cyclohexane dicarboxylic acid and cis-4-tetrahydrobenzene-1,2-dicarboxylic anhydride, dimeracid, Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid and combination thereof.
In some embodiments, the polyester arm comprises and is derived from maleic anhydride, neopentyl glycol, m-phthalic acid and 2-ethyl-2-methylol-1, the monomer of ammediol.
In some embodiments, condensation copolymers arm and/or polyester arm have an ethylenic unsaturated group.In this class embodiment, the polyester arm comprises the unsaturated dicarboxylic acid monomer as the coupling end unit of polyester copolymer.In some embodiments, the polyester arm is connected with polymer backbone by the connection unit that is derived from the unsaturated dicarboxylic acid monomer.
In some embodiments, the polyester arm is 1,500 to 6,500 according to the polymethylmethacrylate standard by the molecular weight of gpc measurement.In some embodiments, the polyester arm is 1,500 to 3,000 according to the polymethylmethacrylate standard by the molecular weight of gpc measurement.
The random copolymers arm
In some embodiments, the random copolymers arm comprises the polyacrylic ester arm.In certain embodiments, the polyacrylic ester arm comprises a plurality of polymerizable ethylene linkage formula unsaturated monomers.In certain embodiments, a plurality of polymerizable ethylene linkage formula unsaturated monomers comprise: vinylformic acid hydroxyalkyl acrylate, methacrylic acid hydroxyl alkyl ester, alkyl acrylate, alkyl methacrylate, alicyclic acrylate, cycloaliphatic methacrylates, vinylformic acid aryl ester, aryl methacrylate, vinyl cyanide, methacrylonitrile, vinyl aromatic compounds and combination thereof, each alkyl of wherein said monomer or aromatic base can be not and to replace or replace.
In certain embodiments, a plurality of polymerizable ethylene linkage formula unsaturated monomers comprise: (methyl) alkyl acrylate, wherein said alkyl are straight chained alkyl, branched-chain alkyl or cycloalkyl, and each described alkyl has 1 to 18 carbon atom; (methyl) vinylformic acid hydroxyalkyl acrylate, wherein said alkyl is for having straight chained alkyl or the branched-chain alkyl of 2 to 4 carbon atoms separately; Vinylbenzene; Styrene derivatives; And their mixture.In some these class embodiments, each alkyl of straight chained alkyl, branched-chain alkyl or cycloalkyl has 1 to 12 carbon atom.
In some other embodiment, a plurality of polymerizable ethylene linkage formula unsaturated monomers comprise methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic tert-butyl acrylate, methacrylic acid 2-ethylhexyl, lauryl methacrylate(LMA), cyclohexyl methacrylate, isobornyl methacrylate, the methacrylic acid stearyl, methacrylonitrile, methyl acrylate, ethyl propenoate, the vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-EHA, isobornyl acrylate, vinylformic acid 2-hydroxy methacrylate, the vinylformic acid hydroxy propyl ester, vinylformic acid 4-hydroxyl butyl ester, 2-hydroxyethyl methacrylate or methacrylic acid 2-hydroxy propyl ester, vinyl cyanide and combination thereof.
In some embodiments, the polyacrylic ester arm comprises the monomer that is derived from 2-EHA, 2-hydroxyethyl methacrylate, vinylbenzene and methyl methacrylate.
In some embodiments, the polyacrylic ester arm is 4,000 to 10,000 according to the polymethylmethacrylate standard by the molecular weight of gpc measurement.In some embodiments, the polyacrylic ester arm is 5,000 to 8,000 according to the polymethylmethacrylate standard by the molecular weight of gpc measurement.
In some embodiments, use the chain-transfer agent with acidic group to prepare random copolymers arm and/or polyacrylic ester arm by radical polymerization process.In some embodiments, chain-transfer agent comprises 2-Thiovanic acid and 3-thiohydracrylic acid.In some these class embodiments, acrylate copolymer has a terminal acidic group, reacts to form the polyacrylic ester macromonomer with unsaturated glycidyl ester monomer by acid and glycidyl then.In some embodiments, unsaturated glycidyl ester monomer comprises glycidyl methacrylate and glycidyl acrylate monomer.In some these class embodiments, via radical polymerization process the polyacrylic acid macromonomer is connected to polymer backbone by the unsaturated connection unit that is derived from the glycidyl methacrylate monomer.
Polymerized segment
In some embodiments, graft copolymer comprises a plurality of polymeric arms, and it has at least two different segments of forming, and wherein each polymeric arms is vertically connected at polymer backbone.In one embodiment, a plurality of polymeric arms comprise and have (i) condensation copolymers segment and the (ii) polyester-polyacrylate multipolymer of random copolymers segment, and wherein said condensation copolymers segment and random copolymers segment are connected to each other.
In some embodiments, graft copolymer of the present invention comprises the polymer backbone of about 70% to 99% weight ratio, the polymeric arms with at least two different segments of forming of 1% to 30% weight ratio.In some embodiments, graft copolymer of the present invention comprises the polyester-polyacrylate multipolymer arm that is formed by the polyester-polyacrylate macromonomer of polymer backbone, 1% to 30% weight ratio of about 70% to 99% weight ratio.
In some embodiments, have a plurality of polyester-polyacrylate multipolymer arms graft copolymer be 5,000 to 15,000 according to the polymethylmethacrylate standard by the molecular weight of gpc measurement.In some embodiments, have a plurality of polyester-polyacrylate multipolymer arms graft copolymer be 8,000 to 12,000 according to the polymethylmethacrylate standard by the molecular weight of gpc measurement.
The random copolymers segment
In some embodiments, the random copolymers arm comprises the acrylate copolymer arm.In certain embodiments, the acrylate copolymer arm comprises a plurality of polymerizable ethylene linkage formula unsaturated monomers.In certain embodiments, a plurality of polymerizable ethylene linkage formula unsaturated monomers comprise: vinylformic acid hydroxyalkyl acrylate, methacrylic acid hydroxyl alkyl ester, alkyl acrylate, alkyl methacrylate, alicyclic acrylate, cycloaliphatic methacrylates, vinylformic acid aryl ester, aryl methacrylate, vinyl cyanide, methacrylonitrile, vinyl aromatic compounds and combination thereof, each alkyl of wherein said monomer or aromatic base can be not and to replace or replace.
In certain embodiments, a plurality of polymerizable ethylene linkage formula unsaturated monomers comprise: (methyl) alkyl acrylate, wherein said alkyl are straight chained alkyl, branched-chain alkyl or cycloalkyl, and each described alkyl has 1 to 18 carbon atom; (methyl) vinylformic acid hydroxyalkyl acrylate, wherein said alkyl is for having straight chained alkyl or the branched-chain alkyl of 2 to 4 carbon atoms separately; Vinylbenzene; Styrene derivatives; And their mixture.In some these class embodiments, each alkyl of straight chained alkyl, branched-chain alkyl or cycloalkyl has 1 to 12 carbon atom.
In some other embodiment, a plurality of polymerizable ethylene linkage formula unsaturated monomers comprise methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic tert-butyl acrylate, methacrylic acid 2-ethylhexyl, lauryl methacrylate(LMA), cyclohexyl methacrylate, isobornyl methacrylate, the methacrylic acid stearyl, methacrylonitrile, methyl acrylate, ethyl propenoate, the vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-EHA, isobornyl acrylate, vinylformic acid 2-hydroxy methacrylate, the vinylformic acid hydroxy propyl ester, vinylformic acid 4-hydroxyl butyl ester, 2-hydroxyethyl methacrylate or methacrylic acid 2-hydroxy propyl ester, vinylbenzene, vinyl cyanide and combination thereof.
In some embodiments, the acrylate copolymer segment comprises the monomer that is derived from butyl acrylate, 2-hydroxyethyl methacrylate, vinylbenzene and methyl methacrylate.
In some embodiments, the acrylate copolymer segment is 4,000 to 10,000 according to the polymethylmethacrylate standard by the molecular weight of gpc measurement.In some of the other embodiments, the acrylate copolymer segment be 5,000 to 8,000 according to the polymethylmethacrylate standard by the molecular weight of gpc measurement.
The condensation copolymers segment
In some embodiments, the condensation copolymers segment comprises the polyester copolymer segment.In some these class embodiments, the polyester copolymer segment is derived from a plurality of monomers, and described monomer comprises that (i) has the unsaturated polycarboxylic acid of at least two carboxylic moiety; The polyvalent alcohol that (ii) has at least two hydroxylic moieties.In other this class embodiment, the polyester copolymer segment is derived from the combination of at least three monomers, and described monomer comprises: the polyvalent alcohol with at least two hydroxylic moieties; Unsaturated polycarboxylic acid with at least two carboxylic moiety; And the saturated polycarboxylic acid with at least two carboxylic moiety.
In some embodiments, the unsaturated polycarboxylic acid with at least two carboxylic moiety comprises the alkylidene group with 4 to 8 carbon atoms.In other embodiments, the unsaturated polycarboxylic acid with at least two carboxylic moiety comprises maleic anhydride, propene dicarboxylic acid, hexene diacid and combination thereof.
In some embodiments, polyvalent alcohol has at least two carboxy moieties and straight chained alkyl, branched-chain alkyl or cycloalkyl, and wherein each this class alkyl has 2 to 14 carbon atoms.In other embodiments, polyvalent alcohol comprises ethylene glycol, propylene glycol, neopentyl glycol; 2,2,4-trimethylammonium-1, the 3-pentanediol; The 2-methyl isophthalic acid, ammediol; 2-ethyl-2-methylol-1, ammediol, hydroxyl pivalyl hydroxy new pentane acid ester; 2-butyl-2-ethyl-1, ammediol, 1,4 cyclohexane dimethanol; The tristane dimethanol; And their combination.
In some embodiments, the saturated polycarboxylic acid with at least two carboxylic moiety comprises straight chained alkyl, branched-chain alkyl or cycloalkyl, and wherein each alkyl has 6 to 36 carbon atoms.In some of the other embodiments, saturated polycarboxylic acid comprises oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, 1,4-cyclohexane dicarboxylic acid and cis-4-tetrahydrobenzene-1,2-dicarboxylic anhydride, dimeracid, Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid and combination thereof.
In some embodiments, the polyester copolymer segment comprises and is derived from maleic anhydride, neopentyl glycol, m-phthalic acid and 2-ethyl-2-methylol-1, the monomer of ammediol.
In some embodiments, condensation copolymers arm segment and/or polyester copolymer segment have an ethylenic unsaturated group.In this class embodiment, the polyester copolymer segment comprises the terminal unsaturation dicarboxylic acid monomer, itself and the one or more polymerizable ethylene linkage formula unsaturated monomer reactions that form random copolymers segment and/or acrylate copolymer segment.
In some embodiments, the polyester copolymer segment is 1,500 to 6,500 according to the polymethylmethacrylate standard by the molecular weight of gpc measurement.In some embodiments, the polyester copolymer segment is 1,500 to 3,000 according to the polymethylmethacrylate standard by the molecular weight of gpc measurement.
In some embodiments, use polyester copolymer segment, polymerizable ethylene linkage formula unsaturated monomer and have the chain-transfer agent of acidic group, prepare the polyester-polyacrylate multipolymer by radical polymerization process.In one embodiment, chain-transfer agent comprises the 2-Thiovanic acid.In some these class embodiments, the polyester-polyacrylate multipolymer has a terminal acidic group, itself and unsaturated glycidyl ester monomer by acid and Racemic glycidol radical reaction with formation polyester-polyacrylate macromonomer.In some embodiments, unsaturated glycidyl ester monomer comprises glycidyl methacrylate and glycidyl acrylate monomer.In some these class embodiments, via radical polymerization process the polyester-polyacrylate macromonomer is connected to polymer backbone by the unsaturated connection unit that is derived from the glycidyl methacrylate monomer.
In some embodiments, the polyester-polyacrylate macromonomer comprises the glycidyl methacrylate monomer as coupling end unit.In some embodiments, via radical polymerization process the polyester-polyacrylate macromonomer is connected to polymer backbone by the unsaturated connection unit that is derived from the glycidyl methacrylate monomer.
Can prepare arm and segment by several different methods.In one embodiment, with the series of steps synthesising graft copolymer.In one embodiment, at first synthetic a plurality of polymeric arms.Can prepare condensation copolymers arm and condensation copolymers segment by the condensation reaction method well known by persons skilled in the art that comprises the azeotropic esterification method.The example of condensation reaction method is the 4th, 018, and is open in No. 815 United States Patent (USP)s and the 4th, 066, No. 627 United States Patent (USP)s, its each incorporate this paper by reference into integral form.Can prepare random copolymers arm and random copolymers segment by radical polymerization well known by persons skilled in the art.The example of radical polymerization is the 4th, 818, and is open in No. 796 United States Patent (USP)s and the 5th, 483, No. 004 United States Patent (USP), its each incorporate this paper by reference into integral form.Can use multiple initiator, it comprises peroxide acetic acid butyl ester, peroxidized t-butyl perbenzoate, the peroxidation acid tert-butyl ester, new peroxide tert-butyl caprate, peroxidation tert-butyl isobutyrate, peroxidation PIVALIC ACID CRUDE (25) tert-pentyl ester, the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, dicumyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, 1,1-two (tert-butyl hydroperoxide)-3,3,5-trimethyl-cyclohexane and such as 2, the azo-compound of 2 '-azo two (isopropyl cyanide).Synthetic each random copolymers arm and condensation copolymers arm only have an ethylenic unsaturated group with the polymeric arms of guaranteeing to generate, its will with polymerizable ethylene linkage formula polymerization of unsaturated monomers to form the skeleton of graft copolymer.Synthetic condensation agent multipolymer segment is so that it has the unsaturated monomer as end group, thereby reacts with the polymerizable ethylene linkage formula unsaturated monomer of the random copolymers segment that forms polymeric arms.
In one embodiment, in second step, with preformed polymeric arms and the polymerizable ethylene linkage formula unsaturated monomer reaction that forms the graft copolymer skeleton.This class reaction can be undertaken by radical polymerization.Use initiator and organic solvent, the single terminal unsaturation group by polymeric arms is with skeleton monomer and polymeric arms copolymerization.Can use multiple initiator, it comprises peroxide acetic acid butyl ester, peroxidized t-butyl perbenzoate, the peroxidation acid tert-butyl ester, new peroxide tert-butyl caprate, peroxidation tert-butyl isobutyrate, peroxidation PIVALIC ACID CRUDE (25) tert-pentyl ester, the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, dicumyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, 1,1-two (tert-butyl hydroperoxide)-3,3,5-trimethyl-cyclohexane and such as 2, the azo-compound of 2 '-azo two (isopropyl cyanide).Can use multiple organic solvent, it comprises butylacetate, ethyl acetate, propylene glycol monomethyl ether acetate, toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK), methyl ethyl ketone, ethyl pentyl group ketone, hexane, heptane, mineral spirits, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbons, ester, ether, ketone etc.
In some embodiments, in multiple solvent based coating or paint composition, can use graft copolymer of the present invention, described solvent based coating or paint composition for example automobile priming paint, surfacer, can be single coating or finish paint or the Clear coating of the primary coat of covering with paint, lacquer, colour wash, etc. for Clear coating/primary coat.These compositions can comprise pigment dispersion, additive, for example antioxidant, Flow Control agent, tensio-active agent, UV stablizer and such as the rheology control agent of fumed silica and microgel.They can be to use them to regulate film properties with the form of other film-forming polymer combination, and described film-forming composition is acrylic resin, polyester, polyurethane, propenoic methyl carbamate, polyester urethane, alkyd, polyethers etc. for example.These coating compositions also can comprise linking agent, for example polymeric polyisocyanate, block polyisocyanate, alkylated melamine etc.These coating also are suitable for using and the printing ink that comprises the ink jet printing transparent or painted coating in using as building (house paint), industry and maintenance coatings.Preparation has the coating of multipolymer of the present invention to be particularly suitable for providing coating at the multiple material such as metal, plastics, matrix material, paper, timber and concrete substrate.Have functional group is placed on desired location controlled and flexible with in the process that adapts to application demand of the present invention with optimum concn, can form firmer coating.Thereby the tackiness agent that graft copolymer of the present invention is particularly useful as in the fast dry coating increases aesthetic feeling, double pack (2K) clear coating composition that described fast dry coating for example uses to be modified by Clear coating to cover in car repair.
Embodiment
Following embodiment further describe and demonstrate within the scope of the present invention exemplary.Provide embodiment only in order to illustrate and be not interpreted as restriction of the present invention, because many variations are possible, and do not deviate from its purport and scope.
Embodiment 1: polyester copolymer (PEM)
1 liter flask is equipped with heating unit, reflux exchanger, thermometer, agitator, water trap, fractional column and N
2Injector.
Flask is remained under the positive pressure of nitrogen, and add the composition of part 1 successively.With mixture heating up to 150 ℃, be heated to 220 ℃ from 150 ℃ then, in 3 hours, improve temperature with constant rate of speed.The water of condensation continuous still battery that forms is gone out system.When temperature reaches 220 ℃, mixture remained under the uniform temp be lower than 5mg KOH/g until acid number.Add the solvent of part 2 then.Final polyester copolymer solution is that OH%=10.0% and solids content are about 75% yellowish transparent polymer solution.
Embodiment 2: the preparation of acrylate copolymer (PAM)
1 liter flask is equipped with condenser, thermometer, agitator, feed hopper, well heater and N
2Injector.Flask is remained under the positive pressure of nitrogen, and add following compositions successively.
To the mixture of flask loading station 1 and with the temperature of mixture heating up to 115 ℃.In 4 hours, add the solution of part 2 by feed hopper, and reaction mixture is remained under 115 ℃, continue other 3 hours.Add part 3, then reaction mixture is remained on 120 ℃ and be lower than 5mg KOH/g until acid number.Final polyacrylate solution is that OH%=3.5%, Tg=40 ℃ (calculating) and solids content are about 50% faint yellow transparent polymer solution.
Embodiment 3: the preparation of polyester-polyacrylate multipolymer (PEPAM)
1 liter flask is equipped with condenser, thermometer, agitator, feed hopper, well heater and N
2Injector.Flask is remained under the positive pressure of nitrogen, and add following compositions successively.
To the mixture of flask loading station 1 and with the temperature of mixture heating up to 115 ℃.In 4 hours, add the solution of part 2 by feed hopper, and reaction mixture is remained under 115 ℃, continue other 3 hours.Add part 3, then reaction mixture is remained on 120 ℃ and be lower than 5mg KOH/g until acid number.Final copolymer solution is that OH%=4.2% and solids content are about 55% faint yellow transparent polymer solution.
Embodiment 4: the preparation with graft copolymer of polyacrylic ester random copolymers arm
1 liter flask is equipped with condenser, thermometer, agitator, feed hopper, well heater and N
2Injector.Flask is remained under the positive pressure of nitrogen, and add following compositions successively.
To the mixture of flask filling part 1 and with the temperature of mixture heating up to 125 ℃.In 5 hours, add the solution of part 2 by feed hopper, and reaction mixture is remained under 125 ℃, continue other 3 hours.Final graft copolymer solution is that OH%=3.5%, Tg=53 ℃ (calculating), solids content are about 65% faint yellow transparent polymer solution.
Embodiment 5: the preparation with graft copolymer of acrylate copolymer and polyester copolymer arm
1 liter flask is equipped with condenser, thermometer, agitator, feed hopper, well heater and N
2Injector.Flask is remained under the positive pressure of nitrogen, and add following compositions successively.
To the mixture of flask filling part 1 and with the temperature of mixture heating up to 125 ℃.In 5 hours, add the solution of part 2 by feed hopper, and reaction mixture is remained under 125 ℃, continue other 3 hours.Final graft copolymer solution is that OH%=3.9% and solids content are about 65% faint yellow transparent polymer solution.
Embodiment 6: the preparation with graft copolymer of polyester-polyacrylate multipolymer arm
1 liter flask is equipped with condenser, thermometer, agitator, feed hopper, well heater and N
2Injector.Flask is remained under the positive pressure of nitrogen, and add following compositions successively.
To the mixture of flask filling part 1 and with the temperature of mixture heating up to 125 ℃.In 5 hours, add the solution of part 2 by feed hopper, and reaction mixture is remained under 125 ℃, continue other 3 hours.Final graft copolymer solution is the yellowish transparent polymer solution with OH%=3.5% and about 65% solids content.
Embodiment 4,5 and 6 graft copolymer are shown below together with the physical properties of prior art sample Hypomer FS-3060, described prior art sample Hypomer FS-3060 is the straight chain acrylic polyol resin in solid solid %=60%, OH%=3.0%.
Following description is used for the evaluation procedure of polishing, gloss, drying rate, levelling and plumpness test.(1) prepares metal primary coat and plate according to following explanation and table 1 prescription.
1) ZX-1755 (aluminium pigment) is immersed among the NBAC 30 minutes, then that its filtration is standby.
2) with FS-2451 and CAB-381-2 (20%) and solvent, under 1000rpm, add DeuRheo 201P, under 2500rpm, disperseed 10 minutes then.
3) be added on aluminium pigment solution 1 and the flow agent that mixed under the 1000rpm 3 minutes then.
4) finally add stiffening agent Desmodur N3300 to form metallic paint, be diluted to atomizing viscosity NK210s by using thinner.
5) spray at the ABS plate, be about 10 μ m to 15 μ m until film thickness, air-dry then.
The primary coat of table 1 metal
| Sample | Weight (g) |
| Hypomer FS-2451 | 50.0 |
| CAB-381-2 (being 20% in NBAC) | 25.0 |
| NBAC | 4.7 |
| DeuRheo 201P | 2.0 |
| Levaslip 875 | 0.3 |
| ZX-1755 | 8.0 |
| NBAC | 10.0 |
| Amount to | 100 |
| Stiffening agent | - |
| Desmodur N3300 | 7.47 |
Hypomer FS-2451: in solid, the acrylic polyol resin of solid %=50%, OH%=2.4%
CAB-381-2 (be 20% at NBAC): be dissolved in Eastman cellulose acetate butyrate CAB-381-2 in the n-butyl acetate with 20% weight
DeuRheo 201P: the polyvinyl paraffin wax dispersion that is used for antisolvent precipitation
Levaslip 875: the silicone flow agent
ZX-1755: aluminium pigment
Desmodur N 3300:SC%=100%, NCO%=21.8% (delivery form)
Thinner: NBCA (n-butyl acetate)/XYL (dimethylbenzene)/PMAC (propylene glycol monomethyl ether acetate)/EAC (ethyl acetate)=4/3/1/1 (weight ratio)
(2) prepare clear finish and plate according to following explanation and table 2 to the prescription in 4.
1) prepares basic component and stiffening agent respectively; In basic component, add flow agent and curing catalysts.
2) basic component is mixed with stiffening agent and by using thinner to be diluted to atomizing viscosity NK214s.
3) spraying at the polishing iron plate, is 20 μ m to 25 μ m until film thickness, air-dry 10 minutes then.Plate cured under 50 ℃ 10 minutes respectively or is placed on 25 ℃ following 40 minutes, use the polishing test to estimate immediately then.
4) as described in the above-mentioned steps (1), spraying at the metal bottom coated plate, is 25 μ m to 30 μ m until film thickness, air-dry 30 minutes then.Plate was cured under 50 ℃, 60 ℃, 70 ℃ 30 minutes respectively, under 80 ℃, cured 60 minutes.After cooling, plate is carried out gloss, drying rate, levelling and plumpness test.
5) coating with spraying remains under 25 ℃ to observe gel time.
Following table is described the multiple coating formulation that is used for test multiple composition as follows.Polymeric polyisocyanate is used as stiffening agent or solidifying agent.The polymeric polyisocyanate source comprises: Desmodur N-75:SC%=75%, NCO%=16.5% (delivery form); Desmodur N 3790BA:SC%=90%, NCO%=17.8% (delivery form); And Desmodur Z 4470BA:SC%=70%, NCO%=11.9%.The polyurethane diluent composition is XYL (dimethylbenzene)/NBAC (n-butyl acetate)/PMAC (propylene glycol monomethyl ether acetate)=4/3/1 weight ratio.
Table 2:OH/NCO=1: 1 mole
Table 3:OH/NCO=1: 1.1 moles
Table 4:OH/NCO=1: 0.9 mole
Estimate and test
According to following explanation.In the test result of table 5 to the multiple film that is formed by the above-mentioned coating prescription shown in 10.
1) gloss: 20 ° and 60 ° of gloss using BYK mist shadow glossmeter test clear finish.
2) drying rate test: under different stoving temperatures, by the pencil hardness of standard MITSUBISHI pencil test clear finish.
3) polishing test: use 800 sand paper to grind Clear coating at iron plate.For the polishing test result, following grade is suitable for: 1 is what can polish; 2 is what can polish, but omits toughness; 3 is to be difficult to polish and glue; 4 is what can not polish.
4) gel time (hour): hand mix, when the coating of spraying is observed when becoming gel.
5) levelling: appearance method, under light, whether the light image of observing on the clear finish is straight.The levelling test result is 1 to 5, and 1 for preferably 5 for the poorest.
6) plumpness: appearance method, whether the observation paint film is full.The plumpness test result is 1 to 5, and 1 for preferably 5 for the poorest.
Table 5:N-75 solidifying agent and 0.01%Catacure Tin 22,0.2%Levelol 839, OH/NCO=1/1
Table 6:N3790/Z4470 solidifying agent and 0.01%Catacure Tin 22,0.2%Levelol 839, OH/NCO=1/1
Table 7:N-75 solidifying agent and 0.01%Catacure Tin 22,0.2%Levelol 839, OH/NCO=1/1.1
Table 8:N3790/Z4470 solidifying agent and 0.01%Catacure Tin 22,0.2%Levelol 839, OH/NCO=1/1.1
Table 9:N-75 solidifying agent and 0.01%Catacure Tin 22,0.2%Levelol 839, OH/NCO=1/0.9
Table 10:N3790/Z4470 solidifying agent and 0.01%Catacure Tin 22,0.2%Levelol 839, OH/NCO=1/0.9
Can embody the disclosure with other specific form, and not deviate from purport of the present invention and essential attribute.Therefore, as the explanation of disclosure scope, should be with reference to claim subsequently, rather than aforesaid specification sheets.Although aforementioned specification relates to preferred embodiment of the present disclosure, it should be noted that other change and modification it will be apparent to those skilled in the art that, and can carry out these changes and modification and do not deviate from purport of the present disclosure or scope.
Claims (20)
1. graft copolymer composition, it comprises:
(1) is derived from the polymer backbone of a plurality of polymerizable ethylene linkage formula unsaturated monomers; And
(2) a plurality of polymeric arms that connect with described polymer backbone side chain separately, described polymeric arms is independently selected from:
(a) at least two different polymeric arms, it comprises: condensation copolymers arm and random copolymers arm;
(b) have (i) condensation copolymers segment and the (ii) polymeric arms of the segment of random copolymers segment, wherein said condensation copolymers segment and random copolymers segment are connected to each other; And
(c) their combination.
2. graft copolymer composition as claimed in claim 1, each in wherein said a plurality of polymerizable ethylene linkage formula unsaturated monomers is selected from independently of one another: methacrylic acid; Vinylformic acid; (methyl) alkyl acrylate, wherein said alkyl are straight chained alkyl, branched-chain alkyl or cycloalkyl, and each described alkyl has 1 to 18 carbon atom; (methyl) vinylformic acid hydroxyalkyl acrylate, wherein said alkyl is for having straight chained alkyl or the branched-chain alkyl of 2 to 4 carbon atoms separately; Vinylbenzene; Styrene derivatives; And their mixture.
3. graft copolymer composition as claimed in claim 1, wherein said condensation copolymers arm comprises the polyester copolymer arm, and described random copolymers arm comprises the polyacrylic ester arm.
4. graft copolymer composition as claimed in claim 3, wherein said polyester copolymer arm is derived from a plurality of monomers, and described monomer comprises that (i) has the unsaturated polycarboxylic acid of at least two carboxylic moiety; The combination that (ii) has the polyvalent alcohol of at least two hydroxylic moieties.
5. graft copolymer composition as claimed in claim 3, wherein said polyester copolymer arm is derived from the combination of three monomers, and described combination comprises: the polyvalent alcohol with at least two hydroxylic moieties; Unsaturated polycarboxylic acid with at least two carboxylic moiety; And the saturated polycarboxylic acid with at least two carboxylic moiety.
6. as claim 4 or 5 described graft copolymer compositions, wherein said polyvalent alcohol has at least two hydroxylic moieties and is independently selected from: ethylene glycol, propylene glycol, neopentyl glycol; 2,2,4-trimethylammonium-1, the 3-pentanediol; The 2-methyl isophthalic acid, ammediol; 2-ethyl-2-methylol-1, ammediol, hydroxyl pivalyl hydroxy new pentane acid ester; 2-butyl-2-ethyl-1, ammediol, 1,4 cyclohexane dimethanol; The tristane dimethanol; And their combination.
7. graft copolymer composition as claimed in claim 3, wherein said unsaturated polycarboxylic acid with at least two carboxylic moiety is independently selected from maleic anhydride, propene dicarboxylic acid, hexene diacid and combination thereof.
8. graft copolymer composition as claimed in claim 3, wherein said saturated polycarboxylic acid with at least two carboxylic moiety is independently selected from oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, 1,4-cyclohexane dicarboxylic acid, cis-4-tetrahydrobenzene-1,2-dicarboxylic anhydride, dimeracid, Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid and combination thereof.
9. graft copolymer composition as claimed in claim 3, wherein said random copolymers arm is derived from a plurality of polymerizable ethylene linkage formula unsaturated monomers.
10. graft copolymer composition as claimed in claim 9, wherein said random copolymers arm is derived from least four polymerizable ethylene linkage formula unsaturated monomers, described polymerizable ethylene linkage formula unsaturated monomer is selected from independently of one another: (methyl) alkyl acrylate, wherein said alkyl is straight chained alkyl, branched-chain alkyl or cycloalkyl, and each described alkyl has 1 to 18 carbon atom; (methyl) vinylformic acid hydroxyalkyl acrylate, wherein said alkyl is for having straight chained alkyl or the branched-chain alkyl of 2 to 4 carbon atoms separately; Vinylbenzene; Styrene derivatives; And their mixture.
11. graft copolymer composition as claimed in claim 1, wherein said condensation copolymers segment comprises the polyester copolymer segment, and described random copolymers segment comprises the acrylate copolymer segment.
12. graft copolymer composition as claimed in claim 11, wherein said polyester copolymer segment is derived from a plurality of monomers, and described monomer comprises that (i) has the unsaturated polycarboxylic acid of at least two carboxylic moiety; The polyvalent alcohol that (ii) has at least two hydroxylic moieties.
13. graft copolymer composition as claimed in claim 11, wherein said polyester copolymer segment is derived from least three monomers, and described monomer is selected from independently of one another: the polyvalent alcohol with at least two hydroxylic moieties; Unsaturated polycarboxylic acid with at least two carboxy moieties; And the saturated polycarboxylic acid with at least two carboxylic moiety.
14. as claim 12 or 13 described graft copolymer compositions, wherein said polyvalent alcohol has at least two hydroxylic moieties and is independently selected from: ethylene glycol, propylene glycol, neopentyl glycol; 2,2,4-trimethylammonium-1, the 3-pentanediol; The 2-methyl isophthalic acid, ammediol; 2-ethyl-2-methylol-1, ammediol, hydroxyl pivalyl hydroxy new pentane acid ester; 2-butyl-2-ethyl-1, ammediol, 1,4 cyclohexane dimethanol; The tristane dimethanol; And their combination.
15. graft copolymer composition as claimed in claim 12, wherein said unsaturated polycarboxylic acid with at least two carboxylic moiety is independently selected from maleic anhydride, propene dicarboxylic acid, hexene diacid and combination thereof.
16. graft copolymer composition as claimed in claim 12, wherein said saturated polycarboxylic acid with at least two carboxylic moiety is independently selected from oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, 1,4-cyclohexane dicarboxylic acid, cis-4-tetrahydrobenzene-1,2-dicarboxylic anhydride, dimeracid, Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid and combination thereof.
17. graft copolymer composition as claimed in claim 11, wherein said random copolymers segment are derived from a plurality of polymerizable ethylene linkage formula unsaturated monomers.
18. graft copolymer composition as claimed in claim 11, wherein said random copolymers segment is derived from least four polymerizable ethylene linkage formula unsaturated monomers, described polymerizable ethylene linkage formula unsaturated monomer is selected from independently of one another: (methyl) alkyl acrylate, wherein said alkyl is straight chained alkyl, branched-chain alkyl or cycloalkyl, and each described alkyl has 1 to 18 carbon atom; (methyl) vinylformic acid hydroxyalkyl acrylate, wherein said alkyl is for having straight chained alkyl or the branched-chain alkyl of 2 to 4 carbon atoms separately; Vinylbenzene; Styrene derivatives; And their mixture.
19. coating composition, it comprises the described graft copolymer composition of claim 1.
20. the substrate that applies applies and has solidified the drying layer of the described graft copolymer composition of claim 1 at described substrate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108456275A (en) * | 2018-05-04 | 2018-08-28 | 泰兴盛嘉树脂有限公司 | The preparation method of the ultrafast dry car refinishing paint Hydroxylated acrylic resin of low temperature |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6372840B1 (en) * | 1999-06-28 | 2002-04-16 | Ppg Industries Ohio, Inc. | Dual stabilized dispersions of gelled polymeric microparticles and coatings produced therefrom |
| WO2010103366A1 (en) * | 2009-03-09 | 2010-09-16 | Council Of Scientific & Industrial Research | Ph sensitive graft copolymer |
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2012
- 2012-02-14 CN CN201210034668.9A patent/CN103242491B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6372840B1 (en) * | 1999-06-28 | 2002-04-16 | Ppg Industries Ohio, Inc. | Dual stabilized dispersions of gelled polymeric microparticles and coatings produced therefrom |
| WO2010103366A1 (en) * | 2009-03-09 | 2010-09-16 | Council Of Scientific & Industrial Research | Ph sensitive graft copolymer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108456275A (en) * | 2018-05-04 | 2018-08-28 | 泰兴盛嘉树脂有限公司 | The preparation method of the ultrafast dry car refinishing paint Hydroxylated acrylic resin of low temperature |
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