TWI629303B - Graft copolymers with grafted polymeric arms, their preparation and use - Google Patents

Abstract

A graft copolymer composition comprising: a polymer backbone derived from a plurality of polymerizable ethylenically unsaturated monomers; and a plurality of polymeric arms pendant from the polymer backbone. The polymeric arm comprises: (a) at least two different polymeric arms comprising: a condensation copolymer arm and a random copolymer arm, (b) a polymeric arm having (i) a condensation copolymer segment and (ii) a random copolymer And a segment of the random copolymer wherein the condensation copolymer segment and the random copolymer segment are linked to each other; and (c) a combination thereof.

Description

Preparation and application of graft copolymer with graft polymerization arm

The present invention provides graft copolymer compositions, methods of preparation, and applications in coatings such as fast drying coatings for automotive repair.

The condensation copolymer arms and condensation copolymer segments can be prepared by a condensation reaction process known to those skilled in the art including azeotropic esterification. Examples of condensation reaction methods are disclosed in U.S. Patent No. 4,018,815 and U.S. Patent No. 4,066,627, each incorporated by reference in its entirety. Random copolymer arms and random copolymer segments can be prepared by free radical polymerization methods known to those skilled in the art. Examples of free radical polymerization methods are disclosed in U.S. Patent No. 4,818,796 and U.S. Patent No. 5,483,004, each of which are incorporated by reference in their entirety.

Summary of invention

The present invention provides graft copolymers and their preparation and use. In some embodiments, the graft copolymer composition comprises: a polymer backbone derived from a plurality of polymerizable ethylenically unsaturated monomers; and a plurality of polymeric arms each suspended from the polymer backbone. In some embodiments, each polymeric arm is pendant to the polymer backbone via a single end point. In one such embodiment, each polymeric arm is pendant to the polymer backbone via an end group having a single terminal ethylenically unsaturated group.

In some embodiments, the polymerizable ethylenically unsaturated monomer used to prepare the polymer backbone comprises methacrylic acid, acrylic acid, alkyl (meth)acrylate (wherein the alkyl group is a linear alkyl group, a branched alkyl group) Or a cycloalkyl group, each alkyl group having 1 to 18 carbon atoms), a hydroxyalkyl (meth) acrylate (wherein the hydroxyalkyl group is a linear alkyl group or a branched alkyl group, each alkyl group having 2 to 4 Carbon atoms), styrene, styrene derivatives, and combinations thereof.

In some embodiments, the polymeric arm comprises at least two different polymeric arms comprising a condensation copolymer arm and a random copolymer arm. In some such embodiments, the condensation copolymer arm comprises a polyester copolymer arm formed from a polyester macromonomer and the random copolymer arm comprises a polyacrylate copolymer arm formed from a polyacrylate macromonomer. In some such specific examples, the polyester copolymer arm is derived from a plurality of polyols comprising (i) an unsaturated polycarboxylic acid having at least two carboxylic acid moieties; and (ii) a polyol having at least two hydroxyl moieties Monomer. In some such specific examples, the polyacrylate arm comprises a plurality of polymerizable ethylenically unsaturated monomers. In some embodiments, the polymerizable ethylenically unsaturated monomer comprises methacrylic acid, acrylic acid, alkyl (meth)acrylate (wherein the alkyl group is a linear alkyl group, a branched alkyl group or a cycloalkyl group, each An alkyl group having 1 to 18 carbon atoms), a hydroxyalkyl (meth) acrylate (wherein the hydroxyalkyl group is a linear alkyl group or a branched alkyl group, each alkyl group having 2 to 4 carbon atoms), styrene , styrene derivatives and combinations thereof.

In other specific embodiments, the polymeric arm comprises a polyester-polyacrylate copolymer having (i) a condensation copolymer segment and (ii) a segment of a random copolymer segment, wherein the condensation copolymer segment and the random copolymer The segments are connected to each other. In some embodiments, the plurality of polymeric arms comprise (i) a condensation copolymer segment and (ii) a polyester-polyacrylate copolymer of a random copolymer segment in which the condensation copolymer segment and the random copolymer segment are linked to each other.

Detailed description of specific examples

The present invention provides graft copolymers and their preparation and use. These polymers are particularly suitable for automotive OEMs and rapid hardening coating formulations for repairers and other industrial applications. The graft copolymer provides rapid hardening, high crosslink density, and leveling and film construction of the film.

In some embodiments, the graft copolymer composition comprises: a polymer backbone derived from a plurality of polymerizable ethylenically unsaturated monomers; and a plurality of polymeric arms each suspended from the polymer backbone. In certain embodiments, the polymeric arm comprises at least two different polymeric arms comprising a condensed copolymer arm and a random copolymer arm. In other specific embodiments, the polymeric arm comprises a polyester-polyacrylate copolymer having (i) a condensation copolymer segment and (ii) a segment of a random copolymer segment, wherein the condensation copolymer segment and the random copolymer The segments are connected to each other.

For the purposes of this disclosure, "random copolymer arms" and "random copolymer segments" are understood to be polymers in which monomers are incorporated in a random and statistical manner. For the purposes of this disclosure, "segment" refers to a section of a polymer arm.

In some embodiments, each polymeric arm is pendant to the polymer backbone via a single end point. In one such embodiment, each polymeric arm is pendant to the polymer backbone via an end group having a single terminal ethylenically unsaturated group. In another embodiment, the condensed copolymer arm is via The end groups of the single terminal ethylenically unsaturated group are pendant attached to the polymer backbone. In a specific embodiment, the end group is derived from an unsaturated polycarboxylic acid. In yet another embodiment, the random copolymer arm is attached to the polymer backbone via pendant groups having a single terminal ethylenically unsaturated group. In a specific embodiment, the end group is derived from an unsaturated methacrylate. In yet another embodiment, the polyester-polyacrylate copolymer arm is attached to the polymer backbone via pendant groups having a single terminal ethylenically unsaturated group. In a specific embodiment, the end group is derived from an unsaturated methacrylate.

Polymer skeleton

In some embodiments, the graft copolymer composition of the present invention comprises a polymer backbone derived from a plurality of polymerizable ethylenically unsaturated monomers. In some embodiments, the plurality of polymerizable ethylenically unsaturated monomers include hydroxyalkyl acrylate, hydroxyalkyl methacrylate, alkyl acrylate, alkyl methacrylate, cycloaliphatic acrylate, cycloaliphatic Methacrylate, aryl acrylate, aryl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-alkyl acrylamide, N-alkyl methacrylamide , N,N-dialkyl acrylamide, N,N-dialkyl methacrylamide, vinyl aromatic hydrocarbons, and combinations thereof, wherein each alkyl or aromatic group of the monomer may be Substituted or substituted.

In other specific examples, the plurality of polymerizable ethylenically unsaturated monomers include methacrylic acid, acrylic acid, alkyl (meth)acrylate (wherein the alkyl group is a linear alkyl group, a branched alkyl group or a cycloalkyl group) Each alkyl group has 1-18 carbons Atom), alkyl hydroxy (meth) acrylate (wherein the hydroxyalkyl group is a linear or branched alkyl group, each alkyl group having 2 to 4 carbon atoms), styrene, styrene derivatives, and combinations thereof . In some such specific examples, the linear alkyl, branched alkyl or cycloalkyl alkyl group has from 1 to 12 carbon atoms in each alkyl group.

In certain other specific examples, the plurality of polymerizable ethylenically unsaturated monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and methacrylic acid. Butyl ester, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, methyl Stearic acid acrylate, methacrylonitrile, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethyl acrylate Ester, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate, styrene, acrylonitrile, and combinations thereof.

Aggregate arm

In some embodiments, the graft copolymer comprises a plurality of polymeric arms comprising at least two different polymeric arms, wherein each polymeric arm is pendantly attached to the polymeric backbone. In some embodiments, the two different polymeric arms comprise a condensed copolymer arm and a random copolymer arm. In some embodiments, the condensation copolymer arm comprises a polyester copolymer arm formed from a polyester macromonomer and the random copolymer arm comprises a polyacrylate copolymer arm formed from a polyacrylate macromonomer.

In some embodiments, the graft copolymer of the present invention comprises from about 40 to 98% by weight of the polymer backbone, from 1 to 50% by weight of the random copolymer arms; and from 1 to 10% by weight of the condensed copolymer arms. In some embodiments, the graft copolymer of the present invention comprises from about 40 to 98% by weight of a polymer backbone, from 1 to 50% by weight of a polyacrylate copolymer arm; and from 1 to 10% by weight of a polyester copolymer arm. .

In some embodiments, the graft copolymer having a polyester arm and a polyacrylate arm has a molecular weight ranging from 10,000 to 30,000 as measured by GPC using a polymethyl methacrylate standard. In some embodiments, the graft copolymer having a polyester arm and a polyacrylate arm has a molecular weight ranging from 15,000 to 25,000 as measured by GPC using a polymethyl methacrylate standard.

Condensed copolymer arm

In some embodiments, the condensation copolymer arm comprises a polyester arm. In some such specific examples, the polyester copolymer arm is derived from a plurality of monomers comprising: (i) an unsaturated polycarboxylic acid having at least two carboxylic acid moieties; and (ii) having at least two a polyol of a hydroxyl moiety. In other such specific embodiments, the polyester arm is derived from a combination of at least three monomers comprising: a polyol having at least two hydroxyl moieties; an unsaturated polycarboxylic acid having at least two carboxylic acid moieties; A saturated polycarboxylic acid having at least two carboxylic acid moieties.

In some embodiments, the unsaturated polycarboxylic acid having at least two carboxylic acid moieties includes an alkylene group having 4 to 8 carbon atoms. In other specific In the examples, the unsaturated polycarboxylic acid having at least two carboxylic acid moieties includes maleic anhydride, glutaconic acid, hexenedioic acid, and combinations thereof.

In some embodiments, the polyol has at least two hydroxyl moieties and a linear alkyl group, a branched alkyl group, or a cycloalkyl group, wherein each of the alkyl groups has 2 to 14 carbon atoms. In other specific examples, the polyol includes ethylene glycol, propylene glycol, neopentyl glycol; 2,2,4-trimethyl-1,3-pentanediol; 2-methyl-1,3-propanediol; 2-ethyl-2-hydroxymethyl-1,3-propanediol, hydroxytrimethyl acetate of hydroxytrimethylacetic acid; 2-butyl-2-ethyl-1,3-propanediol, 1,4 - cyclohexanedimethanol; tricyclodecane dimethanol; and combinations thereof.

In some embodiments, the saturated polycarboxylic acid having at least two carboxylic acid moieties includes a linear alkyl group, a branched alkyl group, or a cycloalkyl group, wherein each alkyl group has 6 to 36 carbon atoms. In some other specific examples, the saturated polycarboxylic acid comprises oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, 1,4-cyclohexanedicarboxylic acid, and cis-4-cyclohexane. Alkene-1,2-dicarboxylic anhydride, dimer acid, phthalic anhydride, isophthalic acid, citric acid, and combinations thereof.

In some embodiments, the polyester arm comprises monomers derived from maleic anhydride, neopentyl glycol, isodecanoic acid, and 2-ethyl-2-hydroxymethyl-1,3-propanediol.

In some embodiments, the condensation copolymer arms and/or polyester arms have a ethylenically unsaturated group. In a specific embodiment, the polyester arm comprises an unsaturated dicarboxylic acid monomer as the final unit of the polyester copolymer. In some embodiments, the polyester arm is attached to the polymer backbone via a linking unit derived from an unsaturated dicarboxylic acid monomer.

In some embodiments, the polyester arm has a polymethyl group for GPC The methyl acrylate standard measures molecular weights ranging from 1,500 to 6,500. In some embodiments, the polyester arm has a molecular weight ranging from 1,500 to 3,000 as measured by GPC with a polymethyl methacrylate standard.

Random copolymer arm

In some embodiments, the random copolymer arm comprises a polyacrylate arm. In certain embodiments, the polyacrylate arm comprises a plurality of polymerizable ethylenically unsaturated monomers. In some embodiments, the plurality of polymerizable ethylenically unsaturated monomers include hydroxyalkyl acrylate, hydroxyalkyl methacrylate, alkyl acrylate, alkyl methacrylate, cycloaliphatic acrylate, cycloaliphatic a methacrylate, an aryl acrylate, an aryl methacrylate, an acrylonitrile, a methacrylonitrile, a vinyl aromatic hydrocarbon, and combinations thereof, wherein each alkyl or aromatic group of the monomer may be unsubstituted or Replaced.

In some embodiments, the plurality of polymerizable ethylenically unsaturated monomers include alkyl (meth)acrylates (wherein the alkyl group is a linear alkyl group, a branched alkyl group or a cycloalkyl group, each alkyl group having 1-18 carbon atoms), hydroxyalkyl (meth) acrylate (wherein the alkyl group is a linear alkyl group or a branched alkyl group, each alkyl group having 2 to 4 carbon atoms), styrene, styrene derived And their mixtures. In some such specific examples, the linear alkyl, branched alkyl or cycloalkyl alkyl group has from 1 to 12 carbon atoms in each alkyl group.

In certain other specific examples, the plurality of polymerizable ethylenically unsaturated monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and methacrylic acid. Butyl ester, isobutyl methacrylate, tert-butyl methacrylate, 2-ethyl methacrylate Ester, lauryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, stearyl methacrylate, methacrylonitrile, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate Ester, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-Hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate, styrene, acrylonitrile, and combinations thereof.

In some embodiments, the polyacrylate arm comprises a monomer derived from 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, styrene, and methyl methacrylate.

In some embodiments, the polyacrylate arms have a molecular weight ranging from 4,000 to 10,000 as measured by GPC with a polymethyl methacrylate standard. In some other specific examples, the polyacrylate arm has a molecular weight ranging from 5,000 to 8,000 as measured by GPC using a polymethyl methacrylate standard.

In some embodiments, the random copolymer arms and/or polyacrylate arms are made using a chain transfer agent having an acid group via a free radical polymerization process. In some embodiments, the chain transfer agent comprises 2-indole acetic acid and 3-propionic acid. In some such examples, the polyacrylate copolymer has a terminal acid group which is then reacted with an unsaturated glyceryl ester monomer to form a polyacrylate macromonomer through the acid and glycidyl groups. In some embodiments, the unsaturated glyceryl ester monomer comprises glycidyl methacrylate and glycidyl acrylate monomer. In some such specific examples, the polyacrylate macropump system is derived from methacrylic acid via a free radical polymerization process. The unsaturated linking unit of the acid glycidyl ester monomer is bonded to the polymer backbone.

Polymer segment

In some embodiments, the graft copolymer comprises a plurality of polymeric arms having a segment of at least two different compositions, wherein each polymeric arm is pendantly attached to the polymeric backbone. In a specific embodiment, the plurality of polymeric arms comprise a polyester-polyacrylate copolymer having (i) a condensation copolymer segment and (ii) a random copolymer segment, wherein the condensation copolymer segment and the random copolymer The segments are connected to each other.

In some embodiments, the graft copolymers of the present invention comprise from about 70 to 99 weight percent polymer backbone, from 1 to 30 weight percent of polymeric arms having at least two different compositions. In some embodiments, the graft copolymer of the present invention comprises from about 70 to 99% by weight of the polymer backbone, and from 1 to 30% by weight of the polyester-polyacrylate formed from the polyester-polyacrylate macromonomer. Copolymer arm.

In some embodiments, a graft copolymer having a plurality of polyester-polyacrylate copolymer arms has a molecular weight ranging from 5,000 to 15,000 as measured by GPC with a polymethyl methacrylate standard. In some embodiments, a graft copolymer having a plurality of polyester-polyacrylate copolymer arms has a molecular weight ranging from 8,000 to 12,000 as measured by GPC using a polymethyl methacrylate standard.

Random copolymer segment

In some embodiments, the random copolymer arm comprises a polyacrylate Copolymer arm. In certain embodiments, the polyacrylate copolymer arm comprises a plurality of polymerizable ethylenically unsaturated monomers. In some embodiments, the plurality of polymerizable ethylenically unsaturated monomers include hydroxyalkyl acrylate, hydroxyalkyl methacrylate, alkyl acrylate, alkyl methacrylate, cycloaliphatic acrylate, cycloaliphatic a methacrylate, an aryl acrylate, an aryl methacrylate, an acrylonitrile, a methacrylonitrile, a vinyl aromatic hydrocarbon, and combinations thereof, wherein each alkyl or aromatic group of the monomer may be unsubstituted or Replaced.

In some embodiments, the plurality of polymerizable ethylenically unsaturated monomers include alkyl (meth)acrylates (wherein the alkyl group is a linear alkyl group, a branched alkyl group or a cycloalkyl group, each alkyl group having 1-18 carbon atoms), hydroxyalkyl (meth) acrylate (wherein the alkyl group is a linear alkyl group or a branched alkyl group, each alkyl group having 2 to 4 carbon atoms), styrene, styrene derived And their mixtures. In some such specific examples, the linear alkyl, branched alkyl or cycloalkyl alkyl group has from 1 to 12 carbon atoms in each alkyl group.

In certain other specific examples, the plurality of polymerizable ethylenically unsaturated monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and methacrylic acid. Butyl ester, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, methyl Stearic acid acrylate, methacrylonitrile, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethyl acrylate Ester, isodecyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate or 2-hydroxy propyl methacrylate Ester, styrene, acrylonitrile, and combinations thereof.

In some embodiments, the polyacrylate copolymer segment comprises monomers derived from butyl acrylate, 2-hydroxyethyl methacrylate, styrene, and methyl methacrylate.

In some embodiments, the polyacrylate copolymer segment has a molecular weight ranging from 4,000 to 10,000 as measured by GPC using a polymethyl methacrylate standard. In some other specific examples, the polyacrylate copolymer segment has a molecular weight ranging from 5,000 to 8,000 as measured by GPC with a polymethyl methacrylate standard.

Condensed copolymer segment

In some embodiments, the condensation copolymer segment comprises a polyester copolymer segment. In some such specific examples, the polyester copolymer segment is derived from a plurality of monomers comprising: (i) an unsaturated polycarboxylic acid having at least two carboxylic acid moieties and (ii) having at least two hydroxyl groups Part of the polyol. In other such specific embodiments, the polyester copolymer segment is derived from a combination of at least three monomers comprising: a polyol having at least two hydroxyl moieties; an unsaturated polycarboxylic acid having at least two carboxylic acid moieties And a saturated polycarboxylic acid having at least two carboxylic acid moieties.

In some embodiments, the unsaturated polycarboxylic acid having at least two carboxylic acid moieties includes an alkylene group having 4 to 8 carbon atoms. In other embodiments, the unsaturated polycarboxylic acid having at least two carboxylic acid moieties includes maleic anhydride, glutaconic acid, hexenedioic acid, and combinations thereof.

In some embodiments, the polyol has at least two hydroxyl moieties And a linear alkyl group, a branched alkyl group or a cycloalkyl group, wherein each of the alkyl groups has 2 to 14 carbon atoms. In other specific examples, the polyol includes ethylene glycol, propylene glycol, neopentyl glycol; 2,2,4-trimethyl-1,3-pentanediol; 2-methyl-1,3-propanediol; 2-ethyl-2-hydroxymethyl-1,3-propanediol, hydroxytrimethyl acetate of hydroxytrimethylacetic acid; 2-butyl-2-ethyl-1,3-propanediol, 1,4 - cyclohexanedimethanol; tricyclodecane dimethanol; and combinations thereof.

In some embodiments, the saturated polycarboxylic acid having at least two carboxylic acid moieties includes a linear alkyl group, a branched alkyl group, or a cycloalkyl group, wherein each alkyl group has 6 to 36 carbon atoms. In some other specific examples, the saturated polycarboxylic acid comprises oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, 1,4-cyclohexanedicarboxylic acid, and cis-4-cyclohexane. Alkene-1,2-dicarboxylic anhydride, dimer acid, phthalic anhydride, isophthalic acid, citric acid, and combinations thereof.

In some embodiments, the polyester copolymer segment comprises monomers derived from maleic anhydride, neopentyl glycol, isodecanoic acid, and 2-ethyl-2-hydroxymethyl-1,3-propanediol.

In some embodiments, the condensation copolymer segment and/or polyester copolymer segment has a ethylenically unsaturated group. In a specific embodiment, the polyester copolymer segment comprises a terminally unsaturated dicarboxylic acid monol reaction with one or more polymerizable ethylenically unsaturated monomers forming a random copolymer segment and/or a polyacrylate copolymer segment. body.

In some embodiments, the polyester copolymer segments have a molecular weight ranging from 1,500 to 6,500 as measured by GPC with a polymethyl methacrylate standard. In some embodiments, the polyester copolymer segment has a range of from 1,500 to 3,000 as measured by GPC using a polymethyl methacrylate standard. Molecular weight.

In some embodiments, the polyester-polyacrylate copolymer is produced via a free radical polymerization process using a polyester copolymer segment, a polymerizable ethylenically unsaturated monomer, and a chain transfer agent having an acid group. In one embodiment, the chain transfer agent comprises 2-indole acetic acid. In some such specific examples, the polyester-polyacrylate copolymer has a terminal acid group that forms a polyester-polyacrylate macromonomer by reacting an acid and a glycidyl group with an unsaturated glyceryl ester monomer. . In some embodiments, the unsaturated glyceryl ester monomer comprises glycidyl methacrylate and glycidyl acrylate monomer. In some such specific examples, the polyester-polyacrylate macromonomer is attached to the polymer backbone via a free radical polymerization process via an unsaturated linkage unit derived from a glycidyl methacrylate monomer.

In some embodiments, the polyester-polyacrylate macromonomer comprises a glycidyl methacrylate monomer as the final unit of attachment. In some embodiments, the polyester-polyacrylate macro-system is coupled to the polymer backbone via a free radical polymerization process via an unsaturated linkage unit derived from a glycidyl methacrylate monomer.

The arms and segments can be prepared in a variety of ways. In one embodiment, a graft copolymer is synthesized in a series of steps. In one embodiment, the plurality of polymeric arms are initially synthesized. The condensation copolymer arms and condensation copolymer segments can be prepared by a condensation reaction process known to those skilled in the art including azeotropic esterification. Examples of condensation reaction methods are disclosed in U.S. Patent No. 4,018,815 and U.S. Patent No. 4,066,627, each incorporated by reference in its entirety. Random copolymer arms and random copolymer segments can be cooked by It is prepared by a free radical polymerization method known to the skilled person. Examples of free radical polymerization methods are disclosed in U.S. Patent No. 4,818,796 and U.S. Patent No. 5,483,004, each of which are incorporated by reference in their entirety. Various initiators can be used, including tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyoctanoate, tert-butyl peroxy neodecanoate, and third peroxyisobutyric acid. Butyl ester, triamyl peroxytrimethylacetate, tert-butyl peroxytrimethylacetate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dicumyl peroxide , benzoic acid peroxide, dilaurol peroxide, 1,1-di(tertiary-butylperoxy)-3,3,5-trimethylcyclohexane and azo compounds such as 2 , 2'-azobis(isobutyronitrile). Each of the random copolymer arms and the condensation copolymer arms are synthesized to ensure that the resulting polymeric arms have only one ethylenically unsaturated group which will polymerize with the polymerizable ethylenically unsaturated monomer to form a backbone of the graft copolymer. The condensation copolymer segment is synthesized such that it has an unsaturated monomer as a terminal group to react with the polymerizable ethylenically unsaturated monomer forming the random copolymer segment of the polymerization arm.

In one embodiment, in the second step, the preformed polymeric arm is reacted with a polymerizable ethylenically unsaturated monomer forming a backbone of the graft copolymer. The reaction can be preformed via a free radical polymerization process. The backbone single system is copolymerized with the polymeric arms through a single terminal unsaturated group of the polymeric arms using an initiator and an organic solvent. Various initiators can be used, including tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyoctanoate, tert-butyl peroxy neodecanoate, and third peroxyisobutyric acid. Butyl ester, triamyl peroxytrimethylacetate, tert-butyl peroxytrimethylacetate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dicumyl peroxide , benzoic acid peroxide, Dilaurol peroxide, 1,1-di(tris-butylperoxy)-3,3,5-trimethylcyclohexane and azo compounds such as 2,2'-azobis ( Isobutyronitrile). Various organic solvents can be used, including butyl acetate, ethyl acetate, propylene glycol monomethyl ether acetate, toluene, xylene, methyl isobutyl ketone, methyl ethyl ketone, ethyl amyl ketone, hexane. , heptane, mineral spirits, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, ketones, and the like.

In some embodiments, the graft copolymers of the present invention may use various solvent-based coatings or paint compositions such as automotive primers, primer surfacers, topcoats that may be a single coating, or clear coatings. / Undercoat of primer coating, or clear coating. These compositions may contain pigment dispersants, additives such as antioxidants, flow control agents, surfactants, UV stabilizers, and rheology control agents such as fumed cerium oxide and microgels. They may be used in combination with other film forming polymers such as acrylics, polyesters, polyurethanes, urethane acrylates, polyester urethanes, alkyds, polyethers, and the like to adjust film properties. These coating compositions may also contain crosslinking agents such as polyisocyanates, blocked polyisocyanates, alkylated melamines, and the like. These coatings are also suitable for use in architectural (house paint), industrial and maintenance coating applications, as well as in ink applications, including inkjet printing of clear or colored coatings. Coatings formulated with the copolymers of the present invention are particularly suitable for providing coatings on a variety of substrates such as metals, plastics, composites, paper, wood and concrete substrates. A more powerful coating can be formed by placing the functional groups in the desired concentration at the desired location to suit the control and flexibility of the application desired for the present invention. The graft copolymer of the invention is particularly useful as a fast drying coating (such as for automotive repair (to be covered with a clear coating lacquer) Increase the aesthetic appeal of the two-package (2K) clear coating composition).

Instance

The following examples further illustrate and demonstrate the specific examples exemplified within the scope of the invention. The examples are for illustrative purposes only and are not to be construed as limiting the invention, and many variations are possible without departing from the spirit and scope.

Example 1: Polyester Copolymer (PEM)

A 1 liter flask was equipped with a heating device, a reflux condenser, a thermometer, a stirrer, a water separator, a fractionation column, and a nitrogen sparge.

The flask was kept under a positive pressure of nitrogen and Part 1 ingredients were added in order. Heating the mixture to 150 ° C, and then heating from 150 ° C to 220 ° C, the temperature The degree is increased at a constant rate within 3 hours. The formed condensed water is continuously distilled from the distillation system. When the temperature reached 220 ° C, the mixture was kept at the same temperature until the acid value was less than 5 mg KOH / gram. Then add part 2 of the solvent. The final polyester copolymer solution was a light yellow transparent polymer solution having an OH% = 10.0% and a solids content of about 75%.

Example 2: Preparation of Polyacrylate Copolymer (PAM)

A 1 liter flask was equipped with a condenser, thermometer, stirrer, addition funnel, heater, and N ₂ injection. The flask was kept under a positive pressure of nitrogen and the following ingredients were added in order.

The Part 1 mixture was fed to the flask and the mixture was heated to a temperature of 115 °C. Add part of the 2 solution through the addition funnel over 4 hours and reverse The mixture should be kept at 115 ° C for another 3 hours. Part 3 was added and the reaction mixture was then maintained at 120 ° C until the acid number was below 5 mg KOH / gram. The final polyacrylate solution was a light yellow transparent polymer solution having OH % = 3.5%, Tg = 40 ° C (calculated) and a solids content of about 50%.

Example 3: Preparation of Polyester-Polyacrylate Copolymer (PEPAM)

A 1 liter flask was equipped with a condenser, thermometer, stirrer, addition funnel, heater, and N ₂ injection. The flask was kept under a positive pressure of nitrogen and the following ingredients were added in order.

The Part 1 mixture is fed to the flask and the mixture is heated to temperature 115 ° C. A portion of the 2 solution was added through an addition funnel over 4 hours and the reaction mixture was maintained at 115 ° C for an additional 3 hours. Part 3 was added and the reaction mixture was then maintained at 120 ° C until the acid number was below 5 mg KOH / gram. The final copolymer solution was a light yellow transparent polymer solution having an OH% = 4.2% and a solids content of about 55%.

Example 4: Preparation of a graft copolymer with a polyacrylate random copolymer arm

A 1 liter flask was equipped with a condenser, thermometer, stirrer, addition funnel, heater, and N ₂ injection. The flask was kept under a positive pressure of nitrogen and the following ingredients were added in order.

The Part 1 mixture was fed to the flask and the mixture was heated to a temperature of 125 °C. A portion of the 2 solution was added via an addition funnel over 5 hours and the reaction mixture was maintained at 125 ° C for an additional 3 hours. Final graft polymer dissolution The solution was a pale yellow transparent polymer solution having OH% = 3.5%, Tg = 53 ° C (calculated), and a solids content of about 65%.

Example 5: Preparation of a graft copolymer having a polyacrylate copolymer and a polyester copolymer arm.

A 1 liter flask was equipped with a condenser, thermometer, stirrer, addition funnel, heater, and N ₂ injection. The flask was kept under a positive pressure of nitrogen and the following ingredients were added in order.

The Part 1 mixture was fed to the flask and the mixture was heated to a temperature of 125 °C. A portion of the 2 solution was added via an addition funnel over 5 hours and the reaction mixture was maintained at 125 ° C for an additional 3 hours. The final graft polymer solution is a light yellow transparent polymer solution with OH% = 3.9%, solid content About 65%.

Example 6: Preparation of a graft copolymer having a polyester-polyacrylate copolymer arm.

A 1 liter flask was equipped with a condenser, thermometer, stirrer, addition funnel, heater, and N ₂ injection. The flask was kept under a positive pressure of nitrogen and the following ingredients were added in order.

The Part 1 mixture was fed to the flask and the mixture was heated to a temperature of 125 °C. A portion of the 2 solution was added via an addition funnel over 5 hours and the reaction mixture was maintained at 125 ° C for an additional 3 hours. The final graft polymer solution was a light yellow transparent polymer solution having an OH% = 3.5% and a solids content of about 65%.

The graft copolymers of Examples 4, 5 and 6 together with the prior art sample Hypomer FS-3060 (linear % acrylic having % solids = 60%, OH % = 3.0% solids) The physical properties of the polyol resin are shown below.

The evaluation methods for sanding, gloss, drying speed, leveling and fullness tests are described below. (1) A metal base coat and a sheet were prepared in accordance with the following description and the formulation of Table 1.

1) ZX-1755 (aluminum pigment) was immersed in NBAC for 30 minutes and then filtered for use.

2) FS-2451 and CAB-381-2 (20%) were mixed with a solvent, and DeuRheo 201P was added at 1000 rpm, followed by dispersion at 2500 rpm for 10 minutes.

3) Then, aluminum pigment solution 1 and leveling agent were added and mixed at 1000 rpm for 3 minutes.

4) Finally add the hardener, Desmodur N3300, to prepare the metal paint, dilute to the spray viscosity NK2 10s with thinner.

5) Spray on an ABS plate with a film thickness of about 10-15 microns and then air dry.

Hypomer FS-2451: Acrylic polyol resin with %=50% solids and OH%=2.4% by weight

CAB-381-2 (20% in NBAC): Eastman acetate butyrate CAB-381-2 with 20% by weight dissolved in n-butyl acetate

DeuRheo 201P: polyethylene wax dispersion for anti-settling

Levaslip 875: Polyoxane Leveling Agent

ZX-1755: Aluminum pigment

Desmodur N 3300: SC% = 100%, NCO% = 21.8% (supply form)

Thinner: NBAC (n-butyl acetate) / XYL (xylene) / PMAC (propylene glycol

Monomethyl ether acetate) / EAC (ethyl acetate) = 4/3/1/1 (weight ratio)

(2) A clear topcoat and a sheet were prepared according to the following description and Table 2-4 formulations.

1) A basic portion and a hardener are separately prepared; a leveling agent and a hardening catalyst are added to the basic portion.

2) Mix the basic part with the hardener and dilute to the spray viscosity with a thinner NK2 14s.

3) Spray on a polished iron sheet with a film thickness of 20 to 25 microns and then air dry for 10 minutes. The panels were each baked at 50 ° C for 10 minutes or at 25 ° C for 40 minutes and then evaluated immediately using a sanding test.

4) Spray on a metal undercoat sheet as described in the above step (1), and the film has a thickness of 25 to 30 μm and then air-dried for 30 minutes. The sheets were baked at 50 ° C, 60 ° C, 70 ° C for 30 minutes and at 80 ° C for 60 minutes. After cooling, the gloss, drying speed, leveling and fullness of the panels were tested.

5) The paint was kept at 25 ° C to observe the gel time.

The following table describes various paint formulations used to test the various compositions shown below. Polyisocyanates are used as hardeners or curing agents. Sources of polyisocyanates include: Desmodur N-75: SC% = 75%, NCO% = 16.5% (supply form); Desmodur N 3790 BA: SC% = 90%, NCO% = 17.8% (supply form); And Desmodur Z 4470 BA: SC% = 70%, NCO% = 11.9%. The polyurethane diluent composition was XYL (xylene) / NBAC (n-butyl acetate) / PMAC (propylene glycol monomethyl ether acetate) = 4 / 3 / 1 by weight.

Evaluation and testing

Follow the instructions below. The test results of the various films formed from the above paint formulations are shown in Tables 5-10.

1) Gloss: The 20° & 60° gloss of the clear topcoat was tested using a BYK fog shader.

2) Drying speed test: The pencil hardness of the transparent topcoat at different baking temperatures was tested with a standard Mitsubishi pencil.

3) Sanding test: The transparent coating on the iron piece was sanded with 800 grit sandpaper. Regarding the sanding test results, the following grades are applicable: 1 sanding; 2 sanding, but a little sticky; 3 difficult to sand, and sticky; 4 not sanding 4) gelling time (hours): manual mixing, Observe when the paint becomes a gel.

5) Leveling: Visually observe whether the light image is a straight line on the transparent topcoat in the light or no light. The leveling test results range from 1 to 5 and 1 is the best and 5 is the worst.

6) Plump: Visually observe and observe whether the paint film is full. The results of the fullness test ranged from 1 to 5 and 1 was the best and 5 was the worst.

The present disclosure may be embodied in other specific forms without departing from the spirit or essential attributes of the invention. Therefore, when indicating the scope of disclosure, reference should be made to the appended claims, rather than the foregoing description. </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt;

Claims (14)

A graft copolymer composition comprising: (1) a polymer backbone derived from a plurality of polymerizable ethylenically unsaturated monomers; and (2) a plurality of polymeric arms each suspended from a polymer backbone, the polymerization The arm series are independently selected from the group consisting of: (a) at least two different polymeric arms comprising: a condensation copolymer arm and a random copolymer arm, wherein the condensation copolymer arm comprises a polyester copolymer arm and the random The copolymer arm comprises a polyacrylate arm, and wherein the random copolymer arm is derived from at least four polymerizable ethylenically unsaturated monomers, each independently selected from the group consisting of alkyl (meth)acrylates, Wherein the alkyl group is a linear alkyl group, a branched alkyl group or a cycloalkyl group, each alkyl group having 1 to 18 carbon atoms and a hydroxyalkyl (meth) acrylate, wherein the alkyl group has 2-4 each a linear or branched alkyl group of a carbon atom, a styrene, a styrene derivative, and a mixture thereof, (b) a polymeric arm having a segment of (i) a condensation copolymer segment and (ii) a random copolymer segment, Wherein the condensation copolymer segment and the random copolymer segment are linked to each other, wherein the condensation is common The segment comprises a polyester copolymer segment and the random copolymer segment comprises an acrylate copolymer segment, and wherein the random copolymer segment is derived from at least four polymerizable ethylenically unsaturated monomers, each independently selected from the group consisting of Group: alkyl (meth)acrylate wherein the alkyl group is a linear alkyl group, a branched alkyl group or a cycloalkyl group, each alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl (meth) acrylate Wherein the alkyl group is a linear or branched alkyl group having from 2 to 4 carbon atoms, styrene, a styrene derivative, and mixtures thereof; (c) its combination. The graft copolymer composition of claim 1, wherein the plurality of polymerizable ethylenically unsaturated monomers are each independently selected from the group consisting of methacrylic acid, acrylic acid, and (meth)acrylic acid. An ester wherein the alkyl group is a linear alkyl group, a branched alkyl group or a cycloalkyl group, each alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl (meth) acrylate, wherein the alkyl group each has 2 A linear or branched alkyl group of 4 carbon atoms, a styrene, a styrene derivative, and a mixture thereof. The graft copolymer composition of claim 1, wherein the polyester copolymer arm is derived from a plurality of unsaturated polycarboxylic acids comprising (i) at least two carboxylic acid moieties; and (ii) at least A monomer of a combination of two hydroxyl moiety polyols. The graft copolymer composition of claim 1, wherein the polyester copolymer arm is derived from a combination of three monomers comprising: a polyol having at least two hydroxyl moieties; having at least two carboxylic acids a partially unsaturated polycarboxylic acid; and a saturated polycarboxylic acid having at least two carboxylic acid moieties. The graft copolymer composition of claim 3 or 4, wherein the polyol has at least two hydroxyl moieties and is independently selected from the group consisting of ethylene glycol, propylene glycol, neopentyl glycol; 2,2,4-trimethyl-1,3-pentanediol; 2-methyl-1,3-propanediol; 2-ethyl-2-hydroxymethyl-1,3-propanediol, hydroxytrimethyl Hydroxytrimethyl acetate of acetic acid; 2-butyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanedimethanol; tricyclodecane dimethanol; and combinations thereof. A graft copolymer composition as claimed in claim 1 wherein The unsaturated polycarboxylic acid having at least two carboxylic acid moieties is independently selected from the group consisting of maleic anhydride, glutaconic acid, hexenedioic acid, and combinations thereof. The graft copolymer composition of claim 1, wherein the saturated polycarboxylic acid having at least two carboxylic acid moieties is independently selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, Adipic acid, 1,4-cyclohexanedicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic anhydride, dimer acid, phthalic anhydride, isophthalic acid, citric acid, and combinations thereof. The graft copolymer composition of claim 1, wherein the polyester copolymer segment is derived from a plurality of unsaturated polycarboxylic acids comprising (i) having at least two carboxylic acid moieties and (ii) having at least A monomer of a polyol of two hydroxyl moieties. The graft copolymer composition of claim 1, wherein the polyester copolymer segment is derived from at least three monomers each independently selected from the group consisting of: a polyol having at least two hydroxyl moieties; having at least two a carboxylic acid moiety of an unsaturated polycarboxylic acid; and a saturated polycarboxylic acid having at least two carboxylic acid moieties. The graft copolymer composition of claim 8 or 9, wherein the polyol having at least two hydroxyl moieties is independently selected from the group consisting of ethylene glycol, propylene glycol, and neopentyl glycol; 2,2,4-trimethyl-1,3-pentanediol; 2-methyl-1,3-propanediol; 2-ethyl-2-hydroxymethyl-1,3-propanediol, hydroxytrimethyl Hydroxytrimethyl acetate of acetic acid; 2-butyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanedimethanol; tricyclodecane dimethanol; and combinations thereof. a graft copolymer composition as in claim 8 of the patent application, The unsaturated polycarboxylic acid having at least two carboxylic acid moieties is independently selected from the group consisting of maleic anhydride, glutaconic acid, hexenedioic acid, and combinations thereof. The graft copolymer composition of claim 8, wherein the saturated polycarboxylic acid having at least two carboxylic acid moieties is independently selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, Adipic acid, 1,4-cyclohexanedicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic anhydride, dimer acid, phthalic anhydride, isophthalic acid, citric acid, and combinations thereof. A coating composition comprising the graft copolymer composition of claim 1 of the patent application. A coated substrate having a dried layer coated with a final hardened graft copolymer composition as in claim 1 of the patent application.