CN103242491B - The graft copolymer of copolymerization arm with grafting, it is prepared and purposes - Google Patents
The graft copolymer of copolymerization arm with grafting, it is prepared and purposes Download PDFInfo
- Publication number
- CN103242491B CN103242491B CN201210034668.9A CN201210034668A CN103242491B CN 103242491 B CN103242491 B CN 103242491B CN 201210034668 A CN201210034668 A CN 201210034668A CN 103242491 B CN103242491 B CN 103242491B
- Authority
- CN
- China
- Prior art keywords
- acid
- alkyl
- segment
- arm
- graft copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
Graft copolymer composition, it includes：Polymer backbone from multiple polymerizable ethylenically unsaturated monomers；And the multiple polymeric arms being connect with polymer backbone side.The polymeric arms include：(a) at least two different polymeric arms comprising condensation copolymers arm and random copolymer arm；(b) polymeric arms of the segment with (i) condensation copolymers segment and (ii) random copolymer segment, wherein the condensation copolymers segment and random copolymer segment are connected to each other；(c) or combination thereof.
Description
Invention field
It such as uses the present invention provides graft copolymer composition, preparation method and in car repair fast dry-coated
Purposes in the coating of material.
Summary of the invention
The present invention provides graft copolymer and its preparation and uses.In some embodiments, graft copolymer combines
Object includes：Polymer backbone from multiple polymerizable ethylenically unsaturated monomers；And it is respectively connect with polymer backbone side
Multiple polymeric arms.In some embodiments, each polymeric arms are connected to by single endpoint side on polymer backbone.
In a this kind of embodiment, each polymeric arms are connected by the end group side with single terminal ethylenic unsaturated group
On polymer backbone.
In some embodiments, the polymerizable ethylenically unsaturated monomers for being used to prepare polymer backbone include：Methyl
Acrylic acid；Acrylic acid；(methyl) alkyl acrylate, wherein the alkyl is straight chained alkyl, branched alkyl or naphthenic base, it is each
The alkyl has 1 to 18 carbon atom；(methyl) hydroxyalkyl acrylates, wherein the hydroxy alkyl be straight chained alkyl or
Branched alkyl, each alkyl have 2 to 4 carbon atoms；Styrene；Styrene derivative；And their mixture.
In some embodiments, the polymeric arms include at least two different polymeric arms comprising condensation is altogether
Polymers arm and random copolymer arm.In some of such embodiment, condensation copolymers arm includes by polyester macromonomers shape
At polyester copolymer arm, and random copolymer arm includes being total to by the polyacrylate that polyacrylate macromers are formed
Polymers arm.In some of such embodiment, polyester copolymer arm is originated from multiple monomers, and the monomer, which includes (i), to be had at least
The unsaturated polybasic carboxylic acid of two carboxylic moieties；(ii) has the polyalcohol of at least two hydroxylic moieties.In some of such reality
It applies in scheme, polyacrylate arm includes multiple polymerizable ethylenically unsaturated monomers.In some embodiments, polymerizable alkylene
Keyed unsaturated monomer includes：Methacrylic acid；Acrylic acid；(methyl) alkyl acrylate, wherein the alkyl is straight chain alkane
Base, branched alkyl or naphthenic base, each alkyl have 1 to 18 carbon atom；(methyl) hydroxyalkyl acrylates,
Described in hydroxy alkyl be straight chained alkyl or branched alkyl, each alkyl have 2 to 4 carbon atoms；Styrene；Styrene
Derivative；And their mixture.
In other certain embodiments, polymeric arms include having (i) condensation copolymers segment and (ii) random copolymerization
The polyester-polyacrylate copolymer of the segment of object segment, wherein the condensation copolymers segment and random copolymer segment that
This connection.In some embodiments, multiple polymeric arms include to have (i) condensation copolymers segment and (ii) random copolymer
The polyester-polyacrylate copolymer of segment, wherein the condensation copolymers segment and random copolymer segment are connected to each other.
Embodiment is described in detail
The present invention provides graft copolymer and its preparation and uses.This analog copolymer is manufactured for automotive original equipment
It is particularly useful in the fast-curing paint preparation of quotient and repairing and other commercial Applications.Graft copolymer provides the quick of film
Solidification, high crosslink density and levelability and film forming.
In some embodiments, graft copolymer composition includes：From multiple polymerizable ethylenically unsaturated monomers
Polymer backbone；And the multiple polymeric arms respectively being connect with polymer backbone side.In certain embodiments, described poly-
It includes at least two different polymeric arms to close object arm comprising condensation copolymers arm and random copolymer arm.Other certain
In embodiment, polymeric arms include the polyester-of the segment with (i) condensation copolymers segment and (ii) random copolymer segment
Polyacrylate copolymer, wherein the condensation copolymers segment and random copolymer segment are connected to each other.
For purposes of this disclosure, " random copolymer arm " and " random copolymer segment " is interpreted as with random and statistics
The polymer that monomer is incorporated in by mode.For purposes of this disclosure, " segment " refers to the part of polymeric arms.
In some embodiments, each polymeric arms are connected to by single endpoint side on polymer backbone.At one
In this kind of embodiment, each polymeric arms are connected to polymerization by the end group side with single terminal ethylenic unsaturated group
On object skeleton.In another embodiment, condensation copolymers arm passes through the end group with single terminal ethylenic unsaturated group
Side is connected on polymer backbone.In a this kind of embodiment, end group is originated from unsaturated polybasic carboxylic acid.In another embodiment party
In case, random copolymer arm is connected to by the end group side with single terminal ethylenic unsaturated group on polymer backbone.
In a this kind of embodiment, end group is originated from unsaturated methacrylate.In another embodiment, polyester-polypropylene
Acid ester copolymer arm is connected to by the end group side with single terminal ethylenic unsaturated group on polymer backbone.At one
In this kind of embodiment, end group is originated from unsaturated methacrylate.
Polymer backbone
In some embodiments, graft copolymer composition of the invention includes to be originated from multiple polymerizable alkylene keyed insatiable hungers
With the polymer backbone of monomer.In certain embodiments, multiple polymerizable ethylenically unsaturated monomers include：Dihydroxypropyl
It is Arrcostab, haloalkylacrylates, alkyl acrylate alkyl acrylate, alkyl methacrylate, alicyclic
Acrylate, cycloaliphatic methacrylates, benzyl acrylate, aryl methacrylate, acrylonitrile, methacrylonitrile,
Acrylamide, Methacrylamide, N- alkyl acrylamides, N- alkyl methacrylamides, N, N- dialkylacrylamides, N,
N- dialkyl methacrylamides, vinyl aromatic compounds and combination thereof, wherein each alkyl of the monomer
Or aromatic radical can be unsubstituted or substituted.
In other embodiments, multiple polymerizable ethylenically unsaturated monomers include：Methacrylic acid；Acrylic acid；(first
Base) alkyl acrylate, wherein the alkyl is straight chained alkyl, branched alkyl or naphthenic base, each alkyl has 1 to 18
A carbon atom；(methyl) hydroxyalkyl acrylates, wherein the hydroxy alkyl is straight chained alkyl or branched alkyl, it is each described
Alkyl has 2 to 4 carbon atoms；Styrene；Styrene derivative；And their mixture.In some of such embodiment
In, each alkyl of straight chained alkyl, branched alkyl or naphthenic base has 1 to 12 carbon atom.
In certain other embodiments, multiple polymerizable ethylenically unsaturated monomers include methyl methacrylate, first
Base ethyl acrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, methacrylic acid are different
Butyl ester, Tert-butyl Methacrylate, 2-Ethylhexyl Methacrylate, lauryl methacrylate, cyclohexyl methacrylate,
Isobornyl methacrylate, octadecyl methacrylate, methacrylonitrile, methyl acrylate, ethyl acrylate, propylene
Sour n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, acrylic acid 2- ethyl hexyls
Ester, acrylic acid 2- hydroxy methacrylates, hydroxypropyl acrylate, acrylic acid 4- hydroxybutyls, 2-hydroxyethyl methacrylate or first
Base acrylic acid 2- hydroxy propyl esters, styrene, acrylonitrile and combinations thereof.
Polymeric arms
In some embodiments, graft copolymer includes multiple polymeric arms, and the polymeric arms include at least two
Different polymeric arms, wherein each polymeric arms are connect with polymer backbone side.In certain embodiments, two it is different
Polymeric arms include condensation copolymers arm and random copolymer arm.In some embodiments, condensation copolymers arm includes by gathering
The polyester copolymer arm that macromonomer is formed, and random copolymer arm includes being formed by polyacrylate macromers
Polyacrylate copolymer arm.
In some embodiments, graft copolymer of the invention includes the polymer bone of about 40% to 98% weight ratio
The random copolymer arm of frame, 1% to 50% weight ratio；And 1% to 10% weight ratio condensation copolymers arm.In some implementations
In scheme, graft copolymer of the invention includes the polymer backbone of about 40% to 98% weight ratio, 1% to 50% weight ratio
The polyester copolymer arm of polyacrylate copolymer arm and 1% to 10% weight ratio.
In some embodiments, the graft copolymer with polyester arm and polyacrylate arm according to polymethyl
Sour methacrylate standard is 10,000 to 30,000 by the molecular weight of gpc measurement.In some embodiments, there is polyester arm and poly- third
The graft copolymer of olefin(e) acid ester arm according to polymethyl methacrylate standard by gpc measurement molecular weight be 15,000 to 25,
000。
Condensation copolymers arm
In some embodiments, condensation copolymers arm includes polyester arm.In some of such embodiment, polyethylene terephthalate copolymer
Object arm is originated from multiple monomers, and the monomer includes the unsaturated polybasic carboxylic acid that (i) has at least two carboxylic moieties；(ii) has
There is the polyalcohol of at least two hydroxylic moieties.In other this kind of embodiments, polyester arm is originated from the combination of at least three monomers,
The monomer includes：Polyalcohol at least two hydroxylic moieties；The polynary carboxylic of unsaturation at least two carboxylic moieties
Acid；And the saturation polybasic carboxylic acid at least two carboxylic moieties.
In some embodiments, the unsaturated polybasic carboxylic acid at least two carboxylic moieties includes with 4 to 8 carbon
The alkylidene of atom.In other embodiments, the unsaturated polybasic carboxylic acid at least two carboxylic moieties includes maleic acid
Acid anhydride, glutaconate, hexene diacid and combinations thereof.
In some embodiments, polyalcohol has at least two carboxy moieties and straight chained alkyl, branched alkyl or cycloalkanes
Base, wherein each this kind of alkyl has 2 to 14 carbon atoms.In other embodiments, polyalcohol includes ethylene glycol, the third two
Alcohol, neopentyl glycol；2,2,4- trimethyl -1,3- pentanediols；2- methyl-1s, 3-propanediol；2- ethyl -2- methylols -1,3- third
Glycol, hydroxyl pivaloyl hydroxy new pentane acid ester；2- butyl -2- ethyls -1,3-PD, 1,4-CHDM；The tricyclic last of the ten Heavenly stems
Alkane dimethanol；And combination thereof.
In some embodiments, the saturation polybasic carboxylic acid at least two carboxylic moieties includes straight chained alkyl, branch
Alkyl or cycloalkyl, wherein each alkyl has 6 to 36 carbon atoms.In some of the other embodiments, it is saturated polybasic carboxylic acid
Including ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid and cis- -4- cyclohexene -1,2- bis-
Carboxylic acid anhydrides, dimeric dibasic acid, phthalic anhydride, M-phthalic acid, terephthalic acid (TPA) and combinations thereof.
In some embodiments, polyester arm includes to be originated from maleic anhydride, neopentyl glycol, M-phthalic acid and 2- ethyls-
The monomer of 2- methylols -1,3-PD.
In some embodiments, there are one ethylenically unsaturated groups for condensation copolymers arm and/or polyester arm tool.One
In a this kind of embodiment, polyester arm includes the unsaturated dicarboxylic monomer of the connecting pin unit as polyester copolymer.One
In a little embodiments, polyester arm is connect by the connection unit from unsaturated dicarboxylic monomer with polymer backbone.
In some embodiments, the molecular weight of polyester arm measured by GPC according to polymethyl methacrylate standard is
1,500 to 6,500.In some embodiments, polyester arm according to polymethyl methacrylate standard by the molecule of gpc measurement
Amount is 1,500 to 3,000.
Random copolymer arm
In some embodiments, random copolymer arm includes polyacrylate arm.In certain embodiments, polypropylene
Acid esters arm includes multiple polymerizable ethylenically unsaturated monomers.In certain embodiments, multiple polymerizable alkylene keyed are unsaturated
Monomer includes：Hydroxyalkyl acrylates, haloalkylacrylates, alkyl acrylate, alkyl methacrylate,
Cycloaliphatic acrylates, cycloaliphatic methacrylates, benzyl acrylate, aryl methacrylate, acrylonitrile, methyl-prop
Alkene nitrile, vinyl aromatic compounds and combinations thereof, wherein each alkyl or aromatic radical of the monomer can be unsubstituted or take
Generation.
In certain embodiments, multiple polymerizable ethylenically unsaturated monomers include：(methyl) alkyl acrylate,
The wherein described alkyl is straight chained alkyl, branched alkyl or naphthenic base, and each alkyl has 1 to 18 carbon atom；(methyl)
Hydroxyalkyl acrylates, wherein the alkyl is the straight chained alkyl or branched alkyl for respectively having 2 to 4 carbon atoms；Benzene second
Alkene；Styrene derivative；And their mixture.In some of such embodiment, straight chained alkyl, branched alkyl or cycloalkanes
Each alkyl of base has 1 to 12 carbon atom.
In certain other embodiments, multiple polymerizable ethylenically unsaturated monomers include methyl methacrylate, first
Base ethyl acrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, methacrylic acid are different
Butyl ester, Tert-butyl Methacrylate, 2-Ethylhexyl Methacrylate, lauryl methacrylate, cyclohexyl methacrylate,
Isobornyl methacrylate, octadecyl methacrylate, methacrylonitrile, methyl acrylate, ethyl acrylate, propylene
Sour n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, acrylic acid 2- ethyl hexyls
Ester, isobornyl acrylate, acrylic acid 2- hydroxy methacrylates, hydroxypropyl acrylate, acrylic acid 4- hydroxybutyls, methacrylic acid
2- hydroxy methacrylates or methacrylic acid 2- hydroxy propyl esters, acrylonitrile and combinations thereof.
In some embodiments, polyacrylate arm includes from 2-EHA, methacrylic acid 2- hydroxyls
The monomer of base ethyl ester, styrene and methyl methacrylate.
In some embodiments, the dividing by gpc measurement according to polymethyl methacrylate standard of polyacrylate arm
Son amount is 4,000 to 10,000.In some embodiments, polyacrylate arm according to polymethyl methacrylate standard by
The molecular weight of gpc measurement is 5,000 to 8,000.
In some embodiments, it is prepared by radical polymerization process using the chain-transferring agent with acidic group random total
Polymers arm and/or polyacrylate arm.In some embodiments, chain-transferring agent includes 2- thioacetic acid and 3- mercaptopropionic acids.
In some of such embodiment, polyacrylate copolymer tool there are one terminal carboxylate group, then with unsaturated ethylene oxidic ester
Monomer is reacted by acid and glycidyl to form polyacrylate macromers.In some embodiments, no
It includes glycidyl methacrylate and glycidyl acrylate monomer to be saturated glycidyl ester monomer.In some of such reality
It applies in scheme, it will via radical polymerization process by the unsaturated connection unit from glycidyl methacrylate monomer
Polyacrylic acid macromonomer is connected to polymer backbone.
Polymerized segment
In some embodiments, graft copolymer includes multiple polymeric arms, at least two different compositions
Segment, wherein each polymeric arms are vertically connected at polymer backbone.In one embodiment, multiple polymeric arms include tool
There is the polyester-polyacrylate copolymer of (i) condensation copolymers segment and (ii) random copolymer segment, wherein the condensation is altogether
Copolymer segment and random copolymer segment are connected to each other.
In some embodiments, graft copolymer of the invention includes the polymer bone of about 70% to 99% weight ratio
The polymeric arms at least two different segments formed of frame, 1% to 30% weight ratio.In some embodiments, originally
The graft copolymer of invention include the polymer backbone of about 70% to 99% weight ratio, 1% to 30% weight ratio it is poly- by polyester-
The polyester-polyacrylate copolymer arm that acrylate macromer is formed.
In some embodiments, the basis of the graft copolymer with multiple polyester-polyacrylate copolymer arms is poly-
Methyl methacrylate standard is 5,000 to 15,000 by the molecular weight of gpc measurement.In some embodiments, have multiple
The graft copolymer of polyester-polyacrylate copolymer arm according to polymethyl methacrylate standard by the molecule of gpc measurement
Amount is 8,000 to 12,000.
Random copolymer segment
In some embodiments, random copolymer arm includes polyacrylate copolymer arm.In certain embodiments,
Polyacrylate copolymer arm includes multiple polymerizable ethylenically unsaturated monomers.In certain embodiments, multiple polymerizable
Ethylenically unsaturated monomers include：Hydroxyalkyl acrylates, haloalkylacrylates, alkyl acrylate, methyl
Alkyl acrylate, cycloaliphatic acrylates, cycloaliphatic methacrylates, benzyl acrylate, aryl methacrylate,
Acrylonitrile, methacrylonitrile, vinyl aromatic compounds and combinations thereof, wherein each alkyl or aromatic radical of the monomer can
It is unsubstituted or substituted.
In certain embodiments, multiple polymerizable ethylenically unsaturated monomers include：(methyl) alkyl acrylate,
The wherein described alkyl is straight chained alkyl, branched alkyl or naphthenic base, and each alkyl has 1 to 18 carbon atom；(methyl)
Hydroxyalkyl acrylates, wherein the alkyl is the straight chained alkyl or branched alkyl for respectively having 2 to 4 carbon atoms；Benzene second
Alkene；Styrene derivative；And their mixture.In some of such embodiment, straight chained alkyl, branched alkyl or cycloalkanes
Each alkyl of base has 1 to 12 carbon atom.
In certain other embodiments, multiple polymerizable ethylenically unsaturated monomers include methyl methacrylate, first
Base ethyl acrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, methacrylic acid are different
Butyl ester, Tert-butyl Methacrylate, 2-Ethylhexyl Methacrylate, lauryl methacrylate, cyclohexyl methacrylate,
Isobornyl methacrylate, octadecyl methacrylate, methacrylonitrile, methyl acrylate, ethyl acrylate, propylene
Sour n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, acrylic acid 2- ethyl hexyls
Ester, isobornyl acrylate, acrylic acid 2- hydroxy methacrylates, hydroxypropyl acrylate, acrylic acid 4- hydroxybutyls, methacrylic acid
2- hydroxy methacrylates or methacrylic acid 2- hydroxy propyl esters, styrene, acrylonitrile and combinations thereof.
In some embodiments, polyacrylate copolymer segment includes from butyl acrylate, methacrylic acid 2-
The monomer of hydroxy methacrylate, styrene and methyl methacrylate.
In some embodiments, polyacrylate copolymer segment according to polymethyl methacrylate standard by GPC
The molecular weight of measurement is 4,000 to 10,000.In some of the other embodiments, the basis of polyacrylate copolymer segment is poly-
Methyl methacrylate standard is 5,000 to 8,000 by the molecular weight of gpc measurement.
Condensation copolymers segment
In some embodiments, condensation copolymers segment includes polyester copolymer segment.In some of such embodiment
In, polyester copolymer segment is originated from multiple monomers, and the monomer, which includes (i), has the unsaturation of at least two carboxylic moieties more
First carboxylic acid；(ii) has the polyalcohol of at least two hydroxylic moieties.In other this kind of embodiments, polyester copolymer segment
Combination from least three monomers, the monomer include：Polyalcohol at least two hydroxylic moieties；With at least two
The unsaturated polybasic carboxylic acid of carboxylic moiety；And the saturation polybasic carboxylic acid at least two carboxylic moieties.
In some embodiments, the unsaturated polybasic carboxylic acid at least two carboxylic moieties includes with 4 to 8 carbon
The alkylidene of atom.In other embodiments, the unsaturated polybasic carboxylic acid at least two carboxylic moieties includes maleic acid
Acid anhydride, glutaconate, hexene diacid and combinations thereof.
In some embodiments, polyalcohol has at least two carboxy moieties and straight chained alkyl, branched alkyl or cycloalkanes
Base, wherein each this kind of alkyl has 2 to 14 carbon atoms.In other embodiments, polyalcohol includes ethylene glycol, the third two
Alcohol, neopentyl glycol；2,2,4- trimethyl -1,3- pentanediols；2- methyl-1s, 3-propanediol；2- ethyl -2- methylols -1,3- third
Glycol, hydroxyl pivaloyl hydroxy new pentane acid ester；2- butyl -2- ethyls -1,3-PD, 1,4-CHDM；The tricyclic last of the ten Heavenly stems
Alkane dimethanol；And combination thereof.
In some embodiments, the saturation polybasic carboxylic acid at least two carboxylic moieties includes straight chained alkyl, branch
Alkyl or cycloalkyl, wherein each alkyl has 6 to 36 carbon atoms.In some of the other embodiments, it is saturated polybasic carboxylic acid
Including ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid and cis- -4- cyclohexene -1,2- bis-
Carboxylic acid anhydrides, dimeric dibasic acid, phthalic anhydride, M-phthalic acid, terephthalic acid (TPA) and combinations thereof.
In some embodiments, polyester copolymer segment include from maleic anhydride, neopentyl glycol, M-phthalic acid and
The monomer of 2- ethyls -2- methylols -1,3-PD.
In some embodiments, condensation copolymers arm segment and/or polyester copolymer segment tool there are one ethylenic bond not
Saturated group.In a this kind of embodiment, polyester copolymer segment includes terminal unsaturation dicarboxylic acid monomer, with formation
The polymerizable ethylenically unsaturated monomers of one or more of random copolymer segment and/or polyacrylate copolymer segment are anti-
It answers.
In some embodiments, polyester copolymer segment according to polymethyl methacrylate standard by gpc measurement
Molecular weight is 1,500 to 6,500.In some embodiments, polyester copolymer segment according to polymethyl methacrylate mark
Standard is 1,500 to 3,000 by the molecular weight of gpc measurement.
In some embodiments, using polyester copolymer segment, polymerizable ethylenically unsaturated monomers and with acidic group
Chain-transferring agent, polyester-polyacrylate copolymer is prepared by radical polymerization process.In one embodiment, chain
Transfer agent includes 2- thioacetic acid.In some of such embodiment, there are one end acid for polyester-polyacrylate copolymer tool
Base is reacted by acid and glycidyl to form polyester-polyacrylate macromolecular with unsaturated glycidyl ester monomer
Monomer.In some embodiments, unsaturated glycidyl ester monomer includes glycidyl methacrylate and acrylic acid contracting
Water glyceride monomers.In some of such embodiment, even by the unsaturation from glycidyl methacrylate monomer
Polyester-polyacrylate macromonomer is connected to polymer backbone by order position via radical polymerization process.
In some embodiments, polyester-polyacrylate macromonomer includes the methyl-prop as connecting pin unit
Olefin(e) acid glycidyl ester monomer.In some embodiments, pass through the unsaturation from glycidyl methacrylate monomer
Polyester-polyacrylate macromonomer is connected to polymer backbone by connection unit via radical polymerization process.
Arm and segment can be prepared by a variety of methods.In one embodiment, graft copolymerization is synthesized with series of steps
Object.In one embodiment, multiple polymeric arms are synthesized first.It can be by including the people in the art of azeotropic esterification method
Condensation reaction method prepares condensation copolymers arm and condensation copolymers segment known to member.The example of condensation reaction method is
Disclosed in 4,018, No. 815 United States Patent (USP)s and the 4th, 066, No. 627 United States Patent (USP), it is each with integral form by quote simultaneously
Enter herein.Random copolymer arm and random copolymer chain can be prepared by radical polymerization well known by persons skilled in the art
Section.The example of radical polymerization discloses in the 4th, 818, No. 796 United States Patent (USP) and the 5th, 483, No. 004 United States Patent (USP),
It is each to be incorporated herein by reference with integral form.A variety of initiators can be used comprising peroxide acetic acid butyl ester, peroxide
Change t-butyl perbenzoate, the peroxidation acid tert-butyl ester, new peroxide tert-butyl caprate, peroxidating tert-butyl isobutyrate, peroxidating
Neopentanoic acid tert-pentyl ester, tert-Butyl peroxypivalate, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, mistake
Aoxidize diisopropylbenzene (DIPB), dibenzoyl peroxide, dilauroyl peroxide, 1,1- bis- (tert-butyl hydroperoxide) -3,3,5- trimethyls
Hexamethylene and such as 2, the azo-compound of 2 '-azos two (isobutyronitrile).Synthesize each random copolymer arm and condensation copolymerization
Object arm, will be unsaturated single with polymerizable alkylene keyed to ensure that the polymeric arms generated only have there are one ethylenically unsaturated groups
Body polymerize to form the skeleton of graft copolymer.Synthetic condensation agent copolymer segment is so that it has the unsaturation as end group single
Body, to be reacted with the polymerizable ethylenically unsaturated monomers for the random copolymer segment for forming polymeric arms.
In one embodiment, in second step, by pre-formed polymeric arms and formation graft copolymer backbone
Polymerizable ethylenically unsaturated monomers reaction.This kind of reaction can be carried out by radical polymerization.Use initiator and organic molten
Agent, by the single terminal unsaturation groups of polymeric arms by backbone monomer and polymeric arms combined polymerization.A variety of draw can be used
Send out agent comprising peroxide acetic acid butyl ester, peroxidized t-butyl perbenzoate, the peroxidation acid tert-butyl ester, peroxidating neodecanoic acid
The tert-butyl ester, peroxidating tert-butyl isobutyrate, peroxidating neopentanoic acid tert-pentyl ester, tert-Butyl peroxypivalate, dicetyl peroxydicarbonate
Diisopropyl ester, di-cyclohexylperoxy di-carbonate, cumyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, 1,
1- bis- (tert-butyl hydroperoxide) -3,3,5- trimethyl-cyclohexanes and such as 2, the azo-compound of 2 '-azos two (isobutyronitrile).
A variety of organic solvents can be used comprising butyl acetate, ethyl acetate, propylene glycol monomethyl ether acetate, toluene, dimethylbenzene, first
Base isobutyl ketone, methyl ethyl ketone, ethylpentyl ketone, hexane, heptane, mineral spirits, aliphatic hydrocarbon, alicyclic, aromatic hydrocarbons, ester, ether,
Ketone etc..
In some embodiments, the grafting of the present invention can be used total in multi-solvents type coating or paint composition
The priming paint of polymers, the solvent based coating or paint composition such as automobile, base coat can be single coating or be transparent painting
The finishing coat or clear coat for the primary coat that layer/primary coat is covered with paint, lacquer, colour wash, etc..These compositions may include pigment dispersion, additive, such as antioxygen
Agent, flow control agent, surfactant, UV stabilizer and such as fumed silica and microgel rheology control agent.They can be with
Using them to adjust film properties, the film-forming composition such as acrylic acid tree in the form of being combined with other film forming polymers
Fat, polyester, polyurethane, propenoic methyl carbamate, polyester urethane, alkyd, polyethers etc..These coating compositions are also
It may include crosslinking agent, such as polyisocyanate, block polyisocyanate, alkylated melamine etc..These coating are further adapted for making
It is transparent or coloring for building (house paint), industry and maintenance coatings application and in the ink application including ink jet printing
Coating.The coating of present copolymer is formulated with particularly suitable in such as metal, plastics, composite material, paper, timber and concrete
Coating is provided on many kinds of substance of base material.With being answered with adapting to the present invention functional group is placed on desired locations with optium concentration
With the controlling and flexibility during demand, firmer coating can be formed.The graft copolymer of the present invention is particularly useful as soon
Adhesive in dry coating is with by clear coat modification covering, to increase aesthetic feeling, the fast dry coating is for example in car repair
Double pack (2K) clear coating composition used.
Embodiment
The exemplary implementation scheme that following embodiments further describe and demonstrate within the scope of the present invention.Provide embodiment only
In order to illustrate and be not interpreted as the present invention limitation because it is many variation be possible, without departing from its spirit and scope.
Embodiment 1：Polyester copolymer (PEM)
1 liter of flask is equipped with heating device, reflux condenser, thermometer, blender, dehydrator, still and N2
Injector.
Flask is maintained under positive pressure of nitrogen, and adds the ingredient of part 1 successively.150 DEG C are heated the mixture to,
Then 220 DEG C are heated to from 150 DEG C, temperature is improved with constant rate of speed in 3 hours.The condensed water continuous steaming of formation is distillated into body
System.When temperature reaches 220 DEG C, hold the mixture at identical temperature until acid value is less than 5mg KOH/g.Then addition portion
Divide 2 solvent.The yellowish transparent polymeric that final polyester copolymer solution is OH%=10.0% and solid content is about 75%
Object solution.
Embodiment 2：The preparation of polyacrylate copolymer (PAM)
1 liter of flask is equipped with condenser, thermometer, blender, charging hopper, heater and N2Injector.It will grow
Neck bottle is maintained under positive pressure of nitrogen, and adds following compositions successively.
To flask loading station 1 mixture and heat the mixture to 115 DEG C of temperature.Pass through in 4 hours
Charging hopper adds the solution of part 2, and reaction mixture is maintained at 115 DEG C, continues other 3 hours.Addition portion
Divide 3, reaction mixture is then maintained at 120 DEG C until acid value is less than 5mg KOH/g.Final polyacrylate solution is
The pale yellow transparent polymer solution that OH%=3.5%, Tg=40 DEG C (calculating) and solid content are about 50%.
Embodiment 3：The preparation of polyester-polyacrylate copolymer (PEPAM)
1 liter of flask is equipped with condenser, thermometer, blender, charging hopper, heater and N2Injector.It will grow
Neck bottle is maintained under positive pressure of nitrogen, and adds following compositions successively.
To flask loading station 1 mixture and heat the mixture to 115 DEG C of temperature.Pass through in 4 hours
Charging hopper adds the solution of part 2, and reaction mixture is maintained at 115 DEG C, continues other 3 hours.Addition portion
Divide 3, reaction mixture is then maintained at 120 DEG C until acid value is less than 5mg KOH/g.Final copolymer solution is OH%
=4.2% and solid content be about 55% pale yellow transparent polymer solution.
Embodiment 4：The preparation of graft copolymer with polyacrylate random copolymer arm
1 liter of flask is equipped with condenser, thermometer, blender, charging hopper, heater and N2Injector.It will grow
Neck bottle is maintained under positive pressure of nitrogen, and adds following compositions successively.
To flask fill part 1 mixture and heat the mixture to 125 DEG C of temperature.Pass through in 5 hours
Charging hopper adds the solution of part 2, and reaction mixture is maintained at 125 DEG C, continues other 3 hours.Final
Graft copolymer solution is OH%=3.5%, Tg=53 DEG C (calculating), pale yellow transparent that solid content is about 65% are poly-
Polymer solution.
Embodiment 5：The preparation of graft copolymer with polyacrylate copolymer and polyester copolymer arm
1 liter of flask is equipped with condenser, thermometer, blender, charging hopper, heater and N2Injector.It will grow
Neck bottle is maintained under positive pressure of nitrogen, and adds following compositions successively.
To flask fill part 1 mixture and heat the mixture to 125 DEG C of temperature.Pass through in 5 hours
Charging hopper adds the solution of part 2, and reaction mixture is maintained at 125 DEG C, continues other 3 hours.Final
The pale yellow transparent polymer solution that graft copolymer solution is OH%=3.9% and solid content is about 65%.
Embodiment 6：The preparation of graft copolymer with polyester-polyacrylate copolymer arm
1 liter of flask is equipped with condenser, thermometer, blender, charging hopper, heater and N2Injector.It will grow
Neck bottle is maintained under positive pressure of nitrogen, and adds following compositions successively.
To flask fill part 1 mixture and heat the mixture to 125 DEG C of temperature.Pass through in 5 hours
Charging hopper adds the solution of part 2, and reaction mixture is maintained at 125 DEG C, continues other 3 hours.Final
Graft copolymer solution is with OH%=3.5% and the yellowish clear polymer solution of about 65% solid content.
Object of the graft copolymer together with prior art sample Hypomer FS-3060 of embodiment 4,5 and 6 is illustrated below
Rationality matter, the prior art sample Hypomer FS-3060 are the straight of solid %=60%, OH%=3.0% in terms of solid
Chain acrylic polyol resin.
The evaluation procedure described below for being used to polish, gloss, rate of drying, levelling and plumpness are tested.(1) according to following
Illustrate and table 1 is formulated to prepare metal primary coat and plate.
1) ZX-1755 (aluminium pigment) is immersed in NBAC 30 minutes, is then filtered spare.
2) FS-2451 and CAB-381-2 (20%) are mixed with solvent, DeuRheo 201P is added at 1000rpm, so
Disperse 10 minutes at 2500rpm afterwards.
3) and then addition mixes 3 minutes aluminium pigment solution 1 and levelling agent at 1000rpm.
4) finally addition curing agent Desmodur N3300 are diluted to spraying to form metallic paint by using diluent
Viscosity NK210s.
5) it is sprayed on ABS plates, until film thickness is about 10 μm to 15 μm, is then air-dried.
1 metal primary coat of table
| 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 |
| It amounts to | 100 |
| Curing agent | - |
| Desmodur N3300 | 7.47 |
Hypomer FS-2451：In terms of solid, the acrylic polyol resin of solid %=50%, OH%=2.4%
CAB-381-2 (being 20% in NBAC)：The Eastman acetate butyrates being dissolved in 20% weight in n-butyl acetate
Cellulose CAB-381-2
DeuRheo 201P：Polyvinyl paraffin wax dispersion for antisolvent precipitation
Levaslip 875：Silicone levelling agent
ZX-1755：Aluminium pigment
Desmodur N 3300：SC%=100%, NCO%=21.8% (delivery form)
Diluent：NBCA (n-butyl acetate)/XYL (dimethylbenzene)/PMAC (propylene glycol monomethyl ether acetate)/EAC (acetic acid
Ethyl ester)=4/3/1/1 (weight ratio)
(2) clear finish and plate are prepared according to the formula in following the description and table 2 to 4.
1) foundation and curing agent are prepared respectively；Levelling agent and curing catalysts are added in foundation.
2) foundation is mixed with curing agent and atomizing viscosity NK214s is diluted to by using diluent.
3) it is sprayed on polishing iron plate, until film thickness is 20 μm to 25 μm, is then air-dried 10 minutes.Plate is distinguished
It bakes 10 minutes or is placed at 25 DEG C 40 minutes at 50 DEG C, then evaluated immediately using polishing test.
4) as described in above-mentioned steps (1), sprayed on metal bottom coated plate, until film thickness is 25 μm to 30 μ
Then m is air-dried 30 minutes.Plate is baked 30 minutes at 50 DEG C, 60 DEG C, 70 DEG C respectively, is baked 60 minutes at 80 DEG C.
After cooling, gloss, rate of drying, levelling and plumpness are carried out to plate and tested.
5) coating of spraying is maintained at 25 DEG C to observe gel time.
Following table describes the multiple coating preparation for testing numerous compositions as follows.Polyisocyanate is used as hard
Agent or curing agent.Polyisocyanate source includes：Desmodur N-75：SC%=75%, NCO%=16.5% (delivering
Form)；Desmodur N 3790BA：SC%=90%, NCO%=17.8% (delivery form)；And Desmodur Z
4470BA：SC%=70%, NCO%=11.9%.Polyurethane diluent composition is XYL (dimethylbenzene)/NBAC (acetic acid
N-butyl)/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
Evaluation and test
According to following the description.The test result that the multiple film formed is formulated by above-mentioned coating is shown in table 5 to 10.
1) gloss：20 ° and 60 ° of gloss of clear finish are tested using BYK mist shadow gloss meters.
2) rate of drying is tested：Under different stoving temperatures, the lead of clear finish is tested by standard MITSUBISHI pencils
Hardness.
3) polishing test：Clear coat is ground on iron plate using 800 sand paper.For test result of polishing, following grades
It is applicable：1 can polish；2 can polish, but slightly viscosity；3 be to be difficult to polish and glue；4 can not polish.
4) gel time (hour)：Hand mix is observed when the coating of spraying becomes gel.
5) levelling：Ocular estimate, under light, whether the light image observed on clear finish is straight.Levelling test knot
Fruit be 1 to 5, and 1 to be best and 5 be worst.
6) plumpness：Whether ocular estimate, observation paint film are full.Plumpness test result be 1 to 5, and 1 to be best and 5
It is worst.
Table 5：N-75 curing agent and 0.01%Catacure Tin 22,0.2%Levelol 839, OH/NCO=1/1
Table 6：N3790/Z4470 curing agent and 0.01%Catacure Tin 22,0.2%Levelol 839, OH/NCO
=1/1
Table 7：N-75 curing agent and 0.01%Catacure Tin 22,0.2%Levelol 839, OH/NCO=1/1.1
Table 8：N3790/Z4470 curing agent and 0.01%Catacure Tin 22,0.2%Levelol 839, OH/NCO
=1/1.1
Table 9：N-75 curing agent and 0.01%Catacure Tin 22,0.2%Levelol 839, OH/NCO=1/0.9
Table 10：N3790/Z4470 curing agent and 0.01%Catacure Tin 22,0.2%Levelol 839, OH/
NCO=1/0.9
The disclosure can be embodied in other specific forms, without departing from the purport and essential attribute of the present invention.Therefore, as
The explanation of disclosure range should refer to following claims, rather than the foregoing specification.Although aforementioned specification is related to this
Disclosed preferred embodiment, it should be noted that other changes and modification it will be apparent to those skilled in the art that, and can
To carry out the purport or range that these change and change without departing from the disclosure.
Claims (18)
1. graft copolymer composition, it includes：
(1) it is originated from the polymer backbone of multiple polymerizable ethylenically unsaturated monomers；And
(2) the multiple polymeric arms respectively being connect with the polymer backbone side, the polymeric arms independently selected from：
(a) at least two different polymeric arms comprising：Condensation copolymers arm and random copolymer arm, wherein the condensation
Copolymer arm is connect by the end group with single terminal ethylenic unsaturation linking group with the polymer backbone, and its
Described in random copolymer arm pass through end group with single terminal ethylenic unsaturation linking group and the polymer backbone
Connection；
(b) polymeric arms of the segment with (i) condensation copolymers segment and (ii) random copolymer segment, wherein the condensation
Copolymer segment and random copolymer segment are connected to each other, and the wherein described condensation copolymers segment passes through with single end
The end group of ethylenic bond unsaturation linking group is connect with the polymer backbone, or the wherein described random copolymer segment passes through
End group with single terminal ethylenic unsaturation linking group is connect with the polymer backbone；And
(c) combination thereof；
The wherein described random copolymer arm and the random copolymer segment are originated from the chain-transferring agent with acidic group, the acidic group with
The ethylenic bond unsaturation linking group is obtained by the reaction in unsaturated glycidyl ester monomer；And
Wherein, the condensation copolymers arm includes polyester copolymer arm and the random copolymer arm includes polyacrylate
Arm, in the polymeric arms of the segment with (i) condensation copolymers segment and (ii) random copolymer segment, the condensation
Copolymer segment includes polyester copolymer segment, and the random copolymer segment includes acrylate copolymer segment.
2. graft copolymer composition as described in claim 1, wherein in the multiple polymerizable ethylenically unsaturated monomers
Each be each independently selected from：Methacrylic acid；Acrylic acid；(methyl) alkyl acrylate, wherein the alkyl is straight
Alkyl group, branched alkyl or naphthenic base, each alkyl have 1 to 18 carbon atom；(methyl) hydroxyalkyl acrylates,
The wherein described alkyl is the straight chained alkyl or branched alkyl for respectively having 2 to 4 carbon atoms；Styrene；Styrene derivative；With
And their mixture.
3. graft copolymer composition as described in claim 1, wherein the polyester copolymer arm is originated from multiple monomers, it is described
Monomer includes (i) unsaturated polybasic carboxylic acid；(ii) has the combination of the polyalcohol of at least two hydroxylic moieties.
4. graft copolymer composition as described in claim 1, wherein the polyester copolymer arm is originated from the group of three kinds of monomers
It closes, the combination includes：Polyalcohol at least two hydroxylic moieties；Unsaturated polybasic carboxylic acid；And saturation polybasic carboxylic acid.
5. graft copolymer composition as described in claim 3 or 4, wherein the polyalcohol has at least two hydroxylic moieties
And independently selected from：Ethylene glycol, propylene glycol, neopentyl glycol；2,2,4- trimethyl -1,3- pentanediols；2- methyl-1s, 3- the third two
Alcohol；2- ethyl -2- methylol -1,3- propylene glycol, hydroxyl pivaloyl hydroxy new pentane acid ester；2- butyl -2- ethyls -1,3- the third two
Alcohol, 1,4 cyclohexane dimethanol；Tricyclodecane Dimethanol；And combination thereof.
6. graft copolymer composition as described in claim 3 or 4, wherein the unsaturation polybasic carboxylic acid is independently selected from horse
Come acid anhydrides, glutaconate, hexene diacid and combinations thereof.
7. graft copolymer composition as claimed in claim 4, wherein the saturation polybasic carboxylic acid independently selected from ethanedioic acid,
Malonic acid, succinic acid, glutaric acid, adipic acid, 1,4- cyclohexane dicarboxylic acids, cis- -4- cyclohexene -1,2- dicarboxylic anhydrides, dimerization
Acid, phthalic anhydride, M-phthalic acid, terephthalic acid (TPA) and combinations thereof.
8. graft copolymer composition as described in claim 1, wherein the random copolymer arm is originated from multiple polymerizable alkylenes
Keyed unsaturated monomer and the chain-transferring agent with acidic group, wherein the chain-transferring agent includes 2- thioacetic acid and 3- sulfydryls third
Acid.
9. graft copolymer composition as claimed in claim 8 can gather wherein the random copolymer arm is originated from least four
Ethylenically unsaturated monomers are closed, the polymerizable ethylenically unsaturated monomers are each independently selected from：(methyl) acrylic acid alkyl
Ester, wherein the alkyl is straight chained alkyl, branched alkyl or naphthenic base, each alkyl has 1 to 18 carbon atom；(first
Base) hydroxyalkyl acrylates, wherein the alkyl is the straight chained alkyl or branched alkyl for respectively having 2 to 4 carbon atoms；Benzene
Ethylene；Styrene derivative；And their mixture.
10. graft copolymer composition as described in claim 1, wherein the random copolymer segment is from multiple polymerizable
Ethylenically unsaturated monomers and the chain-transferring agent with acidic group, wherein the chain-transferring agent includes 2- thioacetic acid and 3- sulfydryls third
Acid.
11. graft copolymer composition as claimed in claim 10, wherein the polyester copolymer segment is originated from multiple monomers,
The monomer includes (i) unsaturated polybasic carboxylic acid；(ii) has the polyalcohol of at least two hydroxylic moieties.
12. graft copolymer composition as claimed in claim 10, wherein the polyester copolymer segment is originated from least three kinds
Monomer, the monomer are each independently selected from：Polyalcohol at least two hydroxylic moieties；Unsaturated polybasic carboxylic acid；And
It is saturated polybasic carboxylic acid.
13. the graft copolymer composition as described in claim 11 or 12, wherein the polyalcohol has at least two hydroxyls
Part and independently selected from：Ethylene glycol, propylene glycol, neopentyl glycol；2,2,4- trimethyl -1,3- pentanediols；2- methyl-1s, 3- third
Glycol；2- ethyl -2- methylol -1,3- propylene glycol, hydroxyl pivaloyl hydroxy new pentane acid ester；2- butyl -2- ethyls -1,3- the third two
Alcohol, 1,4 cyclohexane dimethanol；Tricyclodecane Dimethanol；And combination thereof.
14. graft copolymer composition as claimed in claim 11, wherein the unsaturation polybasic carboxylic acid is independently selected from horse
Come acid anhydrides, glutaconate, hexene diacid and combinations thereof.
15. graft copolymer composition as claimed in claim 12, wherein the saturation polybasic carboxylic acid is independently selected from second two
Acid, malonic acid, succinic acid, glutaric acid, adipic acid, 1,4- cyclohexane dicarboxylic acids, cis- -4- cyclohexene -1,2- dicarboxylic anhydrides, two
Polyacids, phthalic anhydride, M-phthalic acid, terephthalic acid (TPA) and combinations thereof.
16. graft copolymer composition as claimed in claim 10, wherein the random copolymer segment is originated from least four
Polymerizable ethylenically unsaturated monomers, the polymerizable ethylenically unsaturated monomers are each independently selected from：(methyl) acrylic acid
Arrcostab, wherein the alkyl is straight chained alkyl, branched alkyl or naphthenic base, each alkyl has 1 to 18 carbon atom；
(methyl) hydroxyalkyl acrylates, wherein the alkyl is the straight chained alkyl or branched alkane for respectively having 2 to 4 carbon atoms
Base；Styrene；Styrene derivative；And their mixture.
17. coating composition, it includes the graft copolymer compositions described in any one of claim 1 to 16.
18. the substrate of coating, any one of coat on the substrate and have cured claim 1 to 16 described in graft copolymerization
The drying layer of compositions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210034668.9A CN103242491B (en) | 2012-02-14 | 2012-02-14 | The graft copolymer of copolymerization arm with grafting, it is prepared and purposes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210034668.9A CN103242491B (en) | 2012-02-14 | 2012-02-14 | The graft copolymer of copolymerization arm with grafting, it is prepared and purposes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103242491A CN103242491A (en) | 2013-08-14 |
| CN103242491B true CN103242491B (en) | 2018-08-21 |
Family
ID=48922391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210034668.9A Active CN103242491B (en) | 2012-02-14 | 2012-02-14 | The graft copolymer of copolymerization arm with grafting, it is prepared and purposes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103242491B (en) |
Families Citing this family (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 (1)
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5674686B2 (en) * | 2009-03-09 | 2015-02-25 | カウンシル・オヴ・サイエンティフィック・アンド・インダストリアル・リサーチ | pH-sensitive graft copolymer |
-
2012
- 2012-02-14 CN CN201210034668.9A patent/CN103242491B/en active Active
Patent Citations (1)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103242491A (en) | 2013-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101291437B1 (en) | Process for the production of aqueous binder latices | |
| JP5173422B2 (en) | Aqueous coating compositions based on acrylate copolymers | |
| EP3288988B1 (en) | Aqueous dispersions | |
| CN105008472B (en) | Methods for repairing defects in automotive coatings | |
| DE4242518C2 (en) | Aqueous polymer dispersions for clear coats | |
| JPH10508338A (en) | Aqueous two-component polyurethane coatings, their preparation and their use in a process for preparing multilayer coatings | |
| EP2342242B1 (en) | Process for preparing aqueous copolymer dispersions | |
| EP3191232A1 (en) | Methods and compositions for coating substrates | |
| US10233353B2 (en) | Waterborne base coat compositions and processes for preparing waterborne base coat compositions | |
| EP1541647A1 (en) | Aqueous two-component coating compositions | |
| CN103242491B (en) | The graft copolymer of copolymerization arm with grafting, it is prepared and purposes | |
| JP2004275965A (en) | Method for forming coating film | |
| US20070142591A1 (en) | High temperature polymerization process for making caprolactone-modified branched acrylic polymers | |
| JP2002356644A (en) | Coating composition | |
| US20110160379A1 (en) | Coating composition to obtain surface effects | |
| JP7364126B1 (en) | Acrylic resin water dispersion, its manufacturing method and water-based paint | |
| US9982161B2 (en) | Graft copolymers with grafted polymeric arms, their preparation and use | |
| JP2002294066A (en) | Resin composition and coating composition containing the same | |
| TWI629303B (en) | Graft copolymers with grafted polymeric arms, their preparation and use | |
| US8771797B2 (en) | Aqueous coating composition | |
| CN115485333A (en) | Aqueous coating composition | |
| CN117597391A (en) | Crosslinkable acrylic modified epoxy coating compositions | |
| CN112143354A (en) | Low-VOC (volatile organic compound) water-based coating composition with improved application performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |