Polyorganosiloxane resin – poly(METH)acrylate copolymer and method for the preparation thereof

Abstract

A polyorganosiloxane resin – poly(meth)acrylate copolymer and methods for its preparation and use are provided. The copolymer has resinous polyorganosiloxane pendant groups and an organic polymer backbone. The copolymer may be prepared via condensation reaction. The copolymer is useful as an additive for coatings.

Description

POLYORGANOSILOXANE RESIN - POLY(METH)ACRYLATE COPOLYMER ANDMETHOD FOR THE PREPARATION THEREOFCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 672,411 filed on July 17, 2024 under 35 U.S.C. §119 (e). U.S. Provisional Patent Application Serial No. 63 / 672,411 is hereby incorporated by reference.TECHNICAL FIELD

[0002] A polyorganosiloxane resin - poly(meth)acrylate copolymer and methods for its preparation and use are provided. More particularly, the copolymer has resinous polyorganosiloxane pendant groups and a poly(meth)acrylate backbone.INTRODUCTION

[0003] There is a need in the coatings industry for matte and gloss clear coatings and direct to metal coatings with better corrosion protection and scratch resistance than currently available. The industry seeks higher performance at lower cost for protective and general industrial coatings. Silicones have been proposed to improve performance of such coatings, however, adding silicone to an organic coating can cause problems such as phase separation and incompatibility, which are detrimental to coating performance.SUMMARY

[0004] A method for preparing a polyorganosiloxane resin - poly(meth)acrylate copolymer comprises: 1) contacting, under conditions to effect condensation reaction, components comprising A) a polyorganosiloxane resin, B) a random (meth)acrylic polymer, and C) a condensation reaction catalyst. The invention further relates to the polyorganosiloxane resin - poly(meth)acrylate copolymer prepared by the method. The polyorganosiloxane resin - poly(meth)acrylate copolymer is useful as an additive in coatings.DETAILED DESCRIPTION

[0005] In the method for preparing the polyorganosiloxane resin - poly(meth)acrylate copolymer introduced above, component A) is the polyorganosiloxane resin. The polyorganosiloxane resin contains moieties capable of undergoing condensation reaction (z.e. , moieties of formula OZ, wherein each Z is independently selected from the group consisting of H and an alkyl group of 1 to 12 carbon atoms). For example, component A) the polyorganosiloxane resin can be OH-functional, alkoxy-functional, or both OH-functional and alkoxy-functional. The content of silicon bonded moieties of formula OZ in the polyorganosiloxane resin (SiOZ%) may be measured by29Si-NMR according to the procedure described below. However, the polyorganosiloxane resin may contain a total SiOZ% of at least10%, alternatively 10% to to 65%, alternatively 10% to 50%, relative to Si.

[0006] The polyorganosiloxane resin comprises siloxane units that may be any combination of M, D, T, and Q units, with the proviso that at least some of the siloxane units, per molecule are T units, Q units, or both T and Q units. The siloxane units making up the polyorganosiloxane resin may be described using the short notation below in Table 1. The D, T, and Q units as described in Table 1 are made up of one more of the species, e.g., the D unit may comprise DI, D2 or both; the T unit may comprise any one or more of Tl, T2, and T3; and the Q unit may comprise any one or more of QI, Q2, Q3, and Q4.

[0007] In the polyorganosiloxane resin notation in Table 1 , each R is an independently selected monovalent hydrocarbyl group. Suitable monovalent hydrocarbyl groups include alkyl groups, alkenyl groups, and aryl groups. Suitable alkyl groups may have 1 to 12 carbon atoms.Alternatively, the alkyl groups are exemplified by methyl, ethyl, propyl (including n-propyl and isopropyl) and butyl including (n-butyl, isobutyl, tert-butyl, and sec-butyl). Alternatively, the alky l group for R may be methyl or ethyl; alternatively methyl. Suitable alkenyl groups may have 2 to 12 carbon atoms. Alternatively, the alkenyl groups may be exemplified by vinyl, allyl and hexenyl groups. Alternatively the alkenyl group for R may be selected from the group consisting of vinyl and hexenyl, and alternatively the alkenyl group for R may be vinyl. Suitable aryl group may have 6 to 18 carbon atoms. Alternatively, the aryl groups may be exemplified byphenyl, tolyl, xylyl, benzyl, anthracenyl and naphthyl. Alterantively, the aryl group for R may be phenyl.

[0008] In the resin notation in Table 1, each OZ is independently selected from a hydroxyl or alkoxyl group (i.e.. where Z is H or an alkyl group as described and exemplified above).Alternatively, each OZ may be independently selected from hydroxyl, methoxy, and ethoxy. The OZ content of a polyorganosiloxane resin may be determined using29Si nuclear magnetic resonance spectroscopy (29Si NMR). Reference chemical shifts to internal solvent resonance and are reported relative to tetramethylsilane. Each siloxane unit in the resin shows up in a unique position. Integration under the areas of the peaks allows calculation of the concentration of SiOZ groups relative to silicon atoms, wherein M = R3S1O1 2. and OZ=OH or alkoxyl.

[0009] The SiOZ content relative to silicon atoms may be determined as a mol% using the following formula with the label for each peak in the formula corresponding to the integrated area under the peak corresponding to the label:SiOZ content (mol%) relative to Si = 100

[0010] Alternatively, component A), the polyorganosiloxane resin may, comprise unit formula A-I) (using the summary notation shown above in Table 1):A-I) [R3SiO>2]m[R2Si(OZ)aO(2-a),2]n[RSi(OZ)bO(3-b) / 2]o[Si(OZ)cO(4-e) 2]p, wherein each R is the independently selected monovalent hydrocarbyl group, each Z is independently selected from the group consisting of H and an alkyl group of 1 to 12 carbon atoms, subscripts a. b, and c represent average numbers of moieties of formula OZ (e.g., hydroxyl and / or alkoxyl groups) in each D, T, and Q unit, and subscripts m, n, o, and p represent mole fractions of each unit in the unit formula A-I). Subscripts a, b, and c have average values such that 0 < a < l; 0 < b < 2; 0 < c < 3; and a quantity (a + b + c) has a value sufficient to provide the resin with the total SiOZ mol% of 10% to 65% relative to Si, determined as described above. Subscripts m, n, o, and p have values such that 0 < m < 0.5; 0 < n < 0.5; 0 < o < 0.5; 0 < p < 0.6; and a quantity (m + n + o + p) = l.

[0011] Alternatively, the polyorganosiloxane resin may be an MTQ resin, which comprises unit formula AI-1) (when in unit formula A-I) shown above, subscript n = 0, and each of subscripts m, o, and p are greater than 0). Unit formula Al- 1 ) is:I R3SiOi / 2]m| RSi(OZ)bO(3-b) / 2 lol Si(OZ)cO(4-c) / 2 Ip. wherein R and Z are as described above, a quantity (b + c) has the value sufficient to provide the resin with the total SiOZ mol% of 10% to 65% relative to Si; 0 < m < 0.5; 0 < o < 0.5; 0 < p < 0.6; and a quantity7(m + o + p) = 1.

[0012] Alternatively, the polyorganosiloxane resin may be an MQ resin, which comprises unit formula AI-2) (when in unit formula A-I) shown above, subscripts n and o are both 0).Unit formula AI-2) is: [R3SiOi / m[Si(OZ)cO(4-c) / 2]p. wherein R and Z are as described above, subscript c has the value sufficient to provide the resin with the total SiOZ mol% of 10% to 65% relative to Si, and 0.3 < m < 0.7 and 0.3 < p < 0.7, and a quantity (m + p) - 1. Alternatively, subscripts m and p may have values such that 0.4 < m < 0.5 and 0.5 < p < 0.6.

[0013] In unit formulae A-I), AI-1) and Al-2), each R is the monovalent hydrocarbyl group as described and exemplified above. Alternatively, each R may be independently selected from the group consisting of alkyl and aryl. Alternatively, each R may be independently selected from the group consisting of methyl and phenyl. Alternatively, in any M unit of formula | R iSiCUI, each R may be methyl.

[0014] Alternatively, component A), the polyorganosiloxane resin, may be a silsesquioxane resin (which includes T units). The silsesquioxane resin may comprise unit formula A-II): [R2Si(OZ)aO(2-a) / 2]r[RSi(OZ)bO(3-b) / 2]s, wherein R and Z are as described above; subscripts a and b represent average numbers of OZ moieties in each unit, and subscripts a and b have values such that 0 < a < l; 0 < b < 2; and a quantity (a + b) has the value sufficient to provide the resin with the total SiOZ mol% of 10% to 65% relative to Si; subscripts r and s represent mole fractions of each unit in the unit formula, and subscripts r and s have values such that 0.1 < r < 0.5; 0.5 < s < 0.9; and a quantity (r + s) = 1. Alternatively, subscripts r and s may have values such that 0.2 < r < 0.5 and 0.5 < s < 0.8.

[0015] In the unit formulae A-I), AI-1), AI-2, and All) described above, each OZ is independently selected from the group consisting of a hydroxyl moiety and an alkoxyl moiety as described and exemplified above. Alternatively, each OZ may be independently selected from the group consisting of hydroxyl, methoxy, and ethoxy.

[0016] Weight average molecular weight of A) the polyorganosiloxane resin depends on various factors including the selections of M, D, T, and Q units and the selections of R and Z, however, the polyorganosiloxane resin may have a weight average molecular weight of 1 ,000 g / mol to 9,000 g / mol. Alternatively, the polyorganosiloxane resin may have a weight average molecular weight of at least 1,000 g / mol, alternatively at least 1,100 g / mol, alternatively at least 1,500 g / mol, alternatively at least 2,000 g / mol, alternatively at least 2,500 g / mol, alternatively at least 3,000 g / mol, alternatively at least 3,500 g / mol, and alternatively at least 4,000 g / mol; while at the same time, the polyorganosiloxane resin may have a weight average molecular weight ofup to 9,000 g / mol, alternatively up to 8,500 g / mol, alternatively up to 8,200 g / mol, alternatively up to 8,000 g / mol, alternatively up to 7,500 g / mol, alternatively up to 7,000 g / mol, alternatively up to 6,500 g / mol, alternatively up to 6,000 g / mol, alternatively up to 5,500 g / mol, alternatively up to 5,000 g / mol, and alternatively up to 4,500 g / mol. Molecular weight of the polyorganosiloxane resin may be measured by GPC according to the method described below in the EXAMPLES.

[0017] The polyorganosiloxane resin is known in the art and may be prepared by known methods, such as hydrolysis and condensation starting from mixtures of chlorosilanes or alkoxy silanes, as described, for example, in the Siheone Resins Rterynediatey Seieedon Gtadeof Midland, Michigan, US A (2019). Selected polyorganosiloxane resins for use herein may be found from the Silicone Resins Intermediates Selection Guide from The Dow Chemical Company. For example, the following methoxyfunctional polyorganosiloxane resins are commercially available from The Dow Chemical Company: DOWSIL™ 2405 Resin (with methoxy content of 28 weight %), DOWSIL™ 3037 Intermediate (a phenyl, methyl, methoxy functional resin with a methoxy content of 15-18 weight % and a weight average molecular weight up to 1,500 Daltons); and DOWSIL™ 3074 Intermediate (a phenyl, methyl, silicone, methoxy functional resin with a methoxy content of 15- 18 weight % and a weight average molecular weight of 1,200 to 1,700 Daltons).

[0018] In the method for preparing the polyorganosiloxane resin - poly(meth)acrylate copolymer, component B) is the random (meth)acrylic polymer. The random (meth)acrylic polymer has a weight average molecular weight of 3,000 g / mol to 100,000 g / mol measured by GPC according to the method described below in the EXAMPLES. Alternatively, B) the random (meth)acrylic polymer may have a weight average molecular weight of at least 3,000 g / mol, alternatively at least 3,500 g / mol, alternatively at least 4,000 g / mol, alternatively at least 4,500 g / mol, and alternatively at least 4,600 g / mol; while at the same time the random (meth)acrylic polymer may have a weight average molecular weight of up to 100,000 g / mol, alternatively up to 50,000 g / mol, alternatively up to 25,000 g / mol, alternatively up to 12,500 g / mol, alternatively up to 10,000 g / mol, alternatively up to 5,000 g / mol, and alternatively up to 4,700 g / mol, each measured by GPC.

[0019] The random (meth)acrylic polymer comprisesBl) a first structural unit derived from a hydroxyl-group containing (meth)acrylic acid ester, wherein the (meth)acrylic acid ester has formula;whereinR4is H or methyl, andD1is a divalent hydrocarbyl group of at least 2 carbon atoms;B2) a second structural unit derived from an alkenyl-functional aromatic compound, wherein the alkenyl-functional aromatic compound has formula, whereinR5is an alkenyl group of 2 to 6 carbon atoms, each of R6, R7, R8, R9, and R10is independently selected from H, an alkyl group of 1 to 4 carbon atoms, and a substituted alkyl group of 1 to 4 carbon atoms, with the proviso that, per molecule at least 3 of R6, R7, R8, R9, and R10are H;B3) a third structural unit derived from a (meth)acrylic acid alkyl ester, wherein the(meth)acrylic acid alkyl ester has formula, whereinR4is H or methyl, andR11is an alkyl group of 1 to 30 carbon atoms or an oxygen substituted monovalent hydrocarbyl group of 1 to 30 carbon atoms; andB4) a fourth structural unit derived from a (meth)acrylic acid, wherein the (meth)acrylic acid has formula;wherein R4is H or methyl;wherein the structural units Bl), B2), B3), and B4) are present in mole fractions bl, b2, b3, and b4, respectively; and wherein said mole fractions have values such that0.1 < bl < 0.5;0.1 < b2 < 0.5;0.1 < b3 < 0.8;0.01 < b4 < 0.2; and a quantity (bl + b2 + b3 + b4) = 1.

[0020] In the formula for the (meth)acrylic acid ester above, each R4is independently selected from H and methyl. Alternatively, each R4in this formula may be H. D1is a divalent hydrocarbyl group of at least 2 carbon atoms. Alternatively, D1may be an alkylene group of 2 to4 carbon atoms. D1may be linear or branched. D1may be, for example

[0021] The hydroxyl-group containing (meth)acrylic acid ester may be selected from the group consisting of (meth)acrylic acid 2-hydroxyethyl ester; (meth)acrylic acid 2-hydroxypropyl ester; (meth)acrylic acid 3 -hydroxy propyl ester; (meth)acrylic acid 2-hydroxybutyl ester; (meth)acrylic acid 3-hydroxybutyl ester; (meth)acrylic acid 4-hydroxybutyl ester; and a combination of two or more thereof. Such (meth)acrylic acid esters are commercially available, e.g., from Sigma- Aldrich Inc. of St. Louis, Missouri, and other sources.

[0022] In the formula for the alkenyl functional aromatic compound above, Rsis an alkenyl group of 2 to 6 carbon atoms, each of R6, R7, R8, R9, and R10is independently selected from H, an alkyl group of 1 to 4 carbon atoms, and a substituted alkyl group of 1 to 4 carbon atoms, with the proviso that, per molecule at least 3 of R6, R7, R8, R9, and R10are H. The alkenyl group for R5is exemplified by vinyl, allyl, butenyl and hexenyl; alternatively vinyl or allyl. The alkyl groups are exemplified by methyl, ethyl, propyl (including n-propyl and isopropyl), and butyl (including n-butyl, isobutyl, sec -butyl, and tert-butyl). Substituted alkyl groups are exemplified by the alkyl groups wherein at least one heteroatom containing group is substituted for a hydrogen atom. The heteroatom may be, for example, N or O. The heteroatom containing group may be an alkylamino group, such as diethylaminoethyl, or diethylaminopropyl.

[0023] Alternatively, the alkenyl-functional aromatic compound may be selected from the group consisting of sty rene; t-butylstyrene; a-methylstyrene; p-methylstyrene; divinylbenzene;N, N-dielhy I -p- aminoethyl st rene; vinyltoluene; p-tert-butylstyrene; and a combination of two or more thereof. Such alkenyl-functional aromatic compounds are commercially available, e.g., from Sigma-Aldrich Inc. of St. Louis, Missouri, and other sources.

[0024] In the formula for the (meth)acrylic acid alkyl ester above, each R4is H or methyl. Alternatively, R4in the formula for the (meth)acrylic acid alkyl ester may be methyl. In this formula, R11is an alkyl group of 1 to 30 carbon atoms or an oxygen substituted monovalent hydrocarbyl group.

[0025] Alternatively, the (meth)acrylic alkyl ester may be selected from the group consisting of (meth)acrylic acid methyl ester; (meth)acrylic acid ethyl ester; (meth)acrylic acid propyl ester; (meth)acrylic acid buh l ester; (meth)acrylic acid pentyl ester; (meth)acrylic acid hexyl ester; (meth)acrylic acid cyclohexyl ester; (meth)acrylic acid 2-ethylhexyl ester; (meth)acrylic acid isooctyl ester; (meth)acrylic acid decy l ester; (meth)acrylic acid dodecyl ester; (meth)acrylic acid myristyl ester; (meth)acrylic acid palmityl ester; and (meth)acrylic acid stearyl ester; (meth)acrylic acid methoxymethyl ester; (meth)acrylic acid ethoxymethyl ester; (meth)acrylic acid 2-ethoxyethyl ester; (meth)acrylic acid 2-butoxy ethyl ester; (meth)acrylic acid 2- methoxyethyl ester; (meth)acrylic acid 2-propoxyethyl ester; (meth)acrylic acid 3- methoxypropyl ester; (meth)acry lie acid 4-methoxy butyl ester; and a combination of two or more thereof. Such (meth)acrylic acid alkyl esters are commercially available, e.g. , from The Dow Chemical Company of Midland, Michigan, USA, Sigma- Aldrich Inc., and other sources.

[0026] In the formula for the (meth)acrylic alkyl acid described above, each R4is independently selected from H or methyl. Alternatively, the (meth)acrylic alkyl acid may be selected from the group consisting of methacrylic acid, acrylic acid, and a combination of both. Alternatively, the (meth)acrylic alkyl acid may be acrylic acid. Acrylic acid and methacrylic acid are commercially available, e.g., from Sigma- Aldrich, Inc.

[0027] The random (meth)acrylic polymer comprises structural units B l), B2), B3), and B4) derived from the hydroxyl-group containing (meth)acrylic acid, the alkenyl-functional aromatic compound, the (meth)acrylic acid alkyl ester, and the (meth)acrylic acid, as described above. The structural units Bl), B2), B3), and B4) are present in mole fractions bl, b2, b3, and b4, respectively (wherein Bl) the hydroxyl-group containing (meth)acrylic acid, B2) the alkenyl- functional aromatic compound, B3) the (meth)acrylic acid alkyl ester, and B4) the (meth)acrylic acid are used in amounts to provide said mole fractions). Said mole fractions have values such that 0.1 < bl < 0.5; 0.1 < b2 < 0.5; 0. 1 < b3 < 0.8; 0.01 < b4 < 0.2; and a quantity (bl + b2 + b3 + b4) = 1. Alternatively, the mole fractions may have values such that 0.15 < bl < 0.4; 0. 15 < b2 < 0.25; 0.2 < b3 < 0.7; 0.1 < b4 < 0.2; and alternatively 0.15 < bl < 0.3; 0.175 < b2 < 0.225; 0.45 < b3 < 0.65; 0.05 < b4 < 0.15.

[0028] Component B), the random (meth)acrylic polymer, may be prepared from the hydroxylgroup containing (meth)acrylic acid ester, alkenyl-functional aromatic compound, (meth)acrylic acid alkyl ester, and (meth)acrylic acid in amounts sufficient to provide the subscripts bl, b2, b3, and b4 described above by known methods such as those disclosed in European Patent Publication 3 699 246 Al at paragraphs

[0017] to

[0047] . Random (meth)acrylic polymers suitable for use as component B) are commercially available, and are exemplified by PARALOID™ AU-608B Resin, PARALOID™ AU-608S Resin, PARALOID™ AU-608X Resin, PARALOID™ AU-1453, all of which are commercially available from The Dow Chemical Company. Component B), the random (meth)acrylic polymer, may comprise unit formula:wherein R4, D1, R6, R7, R8, R9, R10, Rn, and subscripts bl, b2, b3, and b4 are as described ab ove, and wherein D3is a divalent hydrocarbyl group with 1 to 5 carbon atoms.

[0029] In the method for making the polyorganosiloxane resin - poly(meth)acrylate copolymer herein, components A) and B) are used in a weight ratio of component A) : component B) of 1 : at least 2 (A:B ratio). Alternatively, the A:B ratio may be 1 :2 to 1:10, alternatively 1 :1 to 1:9, alternatively 1 :1 to 1:6, and alternatively 1 :2 to 1:9.

[0030] In the method for making the polyorganosiloxane resin - poly(meth)acrylate copolymer herein, component C) is the condensation reaction catalyst. Without wishing to be bound by theory, it is thought that the OZ moieties in A) the polyorganosiloxane resin and the OH and / or OR11moieties in B) the random (meth)acrylic polymer undergo condensation reaction to form the polyorganosiloxane resin - poly(meth)acrylate copolymer described herein, and component C) may be used to facilitate the condensation reaction.

[0031] Suitable condensation reaction catalysts include organotin compounds and bases. Organotin compounds for condensation reaction catalysis are those where the valence of the tin is either +4 or +2, i.e.. Tin (IV) compounds or Tin (II) compounds. Examples of tin (IV) compounds include dibutyl tin dilaurate, dimethyl tin dilaurate, di-(n-butyl)tin bis-ketonate,dibutyl tin diacetate, dibutyl tin maleate, dibutyl tin diacetylacetonate, dibutyl tin dimethoxide, dibutyl tin dioctanoate, dibutyl tin diformate, dimethyl tin di-neodeconoate, dibutyl tin di- neodeconoate, dibutyl tin dibenzoate, butyl tin tri-2-ethylhexanoate, dioctyl tin diacetate, dimethyl tin dichloride, and a combination of two or more thereof. Examples of tin (II) compounds include tin (II) salts of organic carboxylic acids such as tin (II) diacetate, tin (II) dioctanoate, tin (II) ethylhexanoate, tin (II) dilaurate, and a combination of two or more thereof. Suitable organotin compounds for condensation reaction catalysis are commercially available, such as from Sigma- Aldrich, Inc. or Evonik Industries AG of Essen, Germany under the tradename DABCO™ or KOSMOS™.

[0032] Alternatively, organotin commpounds may be undesirable for certain applications, and a base may be used as the condensation reaction catalyst. A suitable base catalyst may be selected from the group consisting of NaOH, KOH, NaOCHs. LiOH, potassium tertiary butoxide, LiOCHs, KOCH3, a potassium silanolate, and a combination thereof.

[0033] The amount of condensation reaction catalyst used in the method for making the the polyorganosiloxane resin - poly(meth)acrylate copolymer herein is sufficient to catalyze the condensation reaction described above, and the exact amount depends on various factors including the hydroxyl and alkoxyl content of A) the polyorganosiloxane resin, the hydroxyl and alkoxyl content of B) the random (meth)acrylic polymer, and the conditions (<?.g., reaction time and temperature) selected for step 1) of the method described herein. However, the amount of C) the condensation reaction catalyst may be 0.05% to 2%, alternatively 0.08% to 1.5%, based on combined weights of components A), B), and C).

[0034] One or more optional additional components may be used in the method for preparing the polyorganosiloxane resin - poly(meth)acrylate copolymer. Component D) is an optional solvent. One or more of components A), B), and C) may be dissolved in a solvent before combining these components. Alternatively, D) the solvent may be added separately in step 1). The solvent may be added to facilitate delivery and mixing of the components. Solvents that can be used herein are those that help fluidize the components, but essentially do not react with the components. The solvent may be selected based on solubility the components and volatility of the solvent. The solubility refers to the solvent being sufficient to dissolve and / or disperse a component. Volatility refers to vapor pressure of the solvent, which may be sufficient to solubilize the components under the conditions selected for step 1) of the method described herein but still be removed by conventional stripping, distillation, or wiped film evaporation techinques when the condensation reaction is stopped.

[0035] Suitable solvents include polyorganosiloxanes with suitable vapor pressures, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane and other lowmolecular weight polyorganosiloxanes, such as 0.5 to 1.5 cSt DOWSIL™ 200 Fluids and DOWSIL™ OS FLUIDS, which are commercially available from The Dow Chemical Company.

[0036] Alternatively, the solvent may comprise an organic solvent. The organic solvent can be a ketone such as acetone, methylethyl ketone, or methyl isobutyl ketone; an aromatic hydrocarbon such as benzene, toluene, ethylbenzene or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, or ethylene glycol n-butyl ether, a halogenated hydrocarbon such as dichloromethane, 1,1,1 -trichloroethane or methylene chloride; an acetate such as butyl acetate; chloroform; dimethyl sulfoxide; dimethyl formamide, acetonitrile; tetrahydrofuran; white spirits; mineral spirits; naphtha; n- methyl pyrrolidone; or a combination thereof.

[0037] The amount of solvent will depend on various factors including the type of solvent selected, the amounts and types of components A), B), and C) selected for use in the method, and the condensation reaction conditions. However, the amount of solvent may range from 1% to 99%, alternatively 2% to 90%, based on the weight of all components used in step 1) of the method. All or a portion of the solvent may optionally be removed after the step 1), or step 2), when present.

[0038] In addition, E) water may optionally be added during step 1 ) of the method described herein. Component E), water, is not generally limited, and may be utilized neat (z.e., absent any carrier vehicles and / or solvents), and / or pure (i.e., free from, or substantially free from, minerals and / or other impurities). For example, E) the water may be processed or unprocessed prior to use in the method described herein. Examples of processes that may be used for purifying the water include reverse osmosis, distilling, filtering, deionizing, and combinations of two or more thereof, such that the water (B) may be RO, deionized, distilled, and / or filtered. Alternatively, E) the water may be unprocessed (e.g., may be tap water, i.e., provided by a municipal water system or well water, used without further purification). Alternatively, E) the water may be purified before its addition in step 1). Alternatively, E) the water may be utilized as a mixture e.g., solution or suspension) comprising a solvent, such as any of those listed above for component D). Alternatively, the solvent may contain residual water introduced with the solvent in step 1).

[0039] The water may be utilized in any amount, which will be selected by one of skill in the art, depending on various factors, e.g., the particular condensation reaction catalyst selected, the reaction parameters employed, the scale of the reaction e.g. , total amount of components A) and B) to undergo condensation reaction). However, the amount of water may be 0 to 2 weight partsof water, per 100 weight parts of components A), B) and C) combined, alternatively 0.1 to 1.5 weight parts, on the same basis.

[0040] As introduced above, the method for preparing the polyorganosiloxane resin - poly(meth)acrylate copolymer comprises: 1) contacting components A), B), and C), and optionally D) and / or E), as described above, under conditions to effect condensation reaction. The exact conditions may be selected by one skilled in the art depending on various factors including the amount of the polyorganosiloxane resin - poly(meth)acrylate copolymer to be prepared, available equipment, and desired reaction time. For example, the conditions to effect condensation reaction in step 1) may comprise heating the components at a temperature of 50 °C to 150 °C, alternatively 50 °C to 100 °C, for up to 4 days, alternatively 1 hour to 4 days, alternatively 1 hour to 2 days, alternatively 2 hours to 10 hours, and alternatively 6 hours to 8 hours. The equipment to use for step 1) is not specifically restricted. For example, a batch reactor with mixing means such as an agitator and / or baffles; and heating and cooling means, such as a jacket, may be used. Step 1) prepares a condensation reaction product comprising the polyorganosiloxane resin - poly(meth)acrylate copolymer and residual catalyst, and said condensation reaction product may further comprise D) the solvent, when used, a side product such as water and / or alcohol generated by the condensation reaction, and unreacted component A) and / or component B).

[0041] The method may optionally further comprise one or more additional steps. For example, one or more of the components may be dissolved in D) the solvent before step 1). When a base is used as component C), the method may further comprise neutralizing the condensation reaction catalyst after step 1), which may comprise adding an acid to the condensation reaction product. For example, a neutralizing agent such as an acid such as acetic acid, HC1, calcium carbonate, potassium carbonate, and / or sodium bicarbonate may be added to the condensation reaction product to neutralize the base. The method may further comprise recovering the polyorganosiloxane resin - poly(meth)acrylate copolymer from the condensation reaction product. Recovering may be performed by any convenient means such as stripping and / or filtration, using conventional equipment. Stripping may be performed with heating, optionally under reduced pressure, such as 25 mmHg to < 760 mmHg. Alternatively, wiped film evaporation may be used. Filtration may be beneficial when a base catalyst is used and the catalyst is subsequently neutralized, which may result in formation of a solid side product. A solvent exchange may be performed, for example, if an aromatic solvent such as xylene is used in the method, but a different solvent is desired e.g., butyl acetate) for delivery of the polyorganosiloxane resin - poly(meth)acrylate copolymer.

[0042] The polyorganosiloxane resin - poly(meth)acrylate copolymer prepared as described herein may be used in various end use applications, such as an additive for coatings.EXAMPLES

[0043] The following examples are provided to illustrate the invention to one skilled in the art and are not to be construed so as to limit the scope of the invention set forth in the claims.Starting materials used in these examples are summarized below in Table 2.Table 2 - Starting Materials

[0044] In this Synthesis Example 1, an alkoxy-functional polyorganosilicate resin (Resin A2: MTMeQ resin) was prepared as follows: To a 3L three- necked flask equipped with a magnetic stir-bar and a thermometer, were added 500 g of toluene, and 300g of MQ Resin Al (described above in Table 2). The mixture was stirred at RT to dissolve the resin. Next 220.4 g methyltriethoxysilane and 0.3 g of potassium hydroxide were added to the solution and the mixture was heated to reflux for 8 hrs. Afterwards, the mixture was cooled to RT and followedby the addition of 1.0 g of acetic acid. The solution was then filtered via 0.45 um membrane filter; and the volatiles were removed using a rotary evaporator to give the title resin as a clear liquid, (viscosity: ~9,000cP). The product was MTMeQ Resin A2, which was a liquid without solvent, and analysis results by29SiNMR and GPC are shown above in Table 2.

[0045] In this Working Example 1, Synthesis of polyorganosiloxane resin - (meth)acrylate copolymer 1 was performed as follows: To a IL flask equipped with a magnetic stir-bar and a thermometer, were added 35.0 g of MQ Resin Al (as described above in Table 2) and 200g of butyl acetate. Next 200 g of Acrylic Polyol B (69% in buty l acetate; GPC: Mw=4,671, PDI=2.311) and 0.2 g of potassium hydroxide were added into the solution. The mixture was stirred at 120 °C for 48 hrs. Afterwards, the mixture was cooled to RT, followed by the addition of 0.5 g of acetic acid. The resulting solution was then filtered via 0.45 um membrane filter and stripped using a rotary evaporator at 40 °C. The final solution was diluted to 46% solids in butyl acetate as a clear and homogenous solution. The solution remained clear and homogenous upon storage at RT (> 6 months) and gave a semi-clear casting film on PET.

[0046] The properties of polyorganosiloxane resin - (meth)acrylate copolymer 1 were analyzed as follows: GPC (vs. PS) showed Mw-6,550 g / mol, PDI=2.858. Si-resin wt% in the total resin content: 26.6%.29Si-NMR: SiOZ% = 4.45% (mole Si);13C-NMR showed the formation of Si-OCIL- bond linkage as a copolymer.

[0047] In this Working Example 2, Synthesis of polyorganosiloxane resin - (meth)acrylate copolymer 2 was performed as follows: To a IL flask equipped with a magnetic stir-bar and a thermometer, were added 40.0 g of MTMeQ resin A2 prepared in Synthesis Example 1 (SiOZ = 31.5% of Si mole by29Si-NMR), 200g of butyl acetate, 200g of Acrylic Polyol B and 0.2 g of potassium hydroxide were added into the solution. The resulting mixture was stirred at 120 °C for 48 hrs. Afterwards, the mixture was cooled to RT and followed by the addition of 0.5 g of acetic acid. The solution was then filtered via 0.45 um membrane filter and stripped using a rotary evaporator at 40 °C. The final solution was diluted to 46% solids in butyl acetate as a clear and homogenous solution. The solution remained clear and homogenous upon storage at RT (>6 months) and gave a clear casting film on PET.

[0048] The properties of polyorganosiloxane resin - (meth)acrylate copolymer 2 were analyzed as follows: GPC (vs. PS) showed Mw=8,868 g / mol, and PDI=3.520. Si-resin wt% in the total resin content: 26.6% / 29Si-NMR: SiOZ% = 8.45% (mole Si):13C-NMR showed the formation of Si-OCEE- bond linkage as a copolymer.Table 2: Solids and hydroxyl number of polyorganosiloxane resin - (meth)acrylate copolymers 1 and 2Table 3: SEC data on polyorganosiloxane resin - (meth)acrylate copolymers prepared inWorking Examples 1 and 2Description of OH# determination

[0049] The hydroxyl number is the number of mg potassium hydroxide equivalent to the hydroxyl groups in 1 gram of material. The hydroxyl groups are acetylated with a known amount of acetic anhydride. The excess anhydride is decomposed with water and the acetic acid formed titrated with potassium hydroxide solution. Due to the catalyst the determination can be performed at room temperature.Reagents a. Tetrahydrofuran b. Acetic Anhydride c. 4-(dimethylamino)pyridine d. I M KOH solution in methanol e. 1 % Phenolphthalein in methanol f. Di water g. Acetylating solution:Pour + / - 500ml tetrahydrofuran into a 1 liter volumetric flask, add 125 ml acetic anhydride using a graduated cylinder to the flask, and fill up to the mark with tetrahydrofuran. h. Catalyst solution:Dissolve 10g 4-(dimethylamino)pyridine in 1 liter tetrahydrofuran (colorless to yellow. If kept in a brown colored flask, the solution is stable for months). i. Hydrolysis solution:Prepare a solution of 4 volume parts tetrahydrofuran and 1 part Di water.Titration Procedurea. Weigh the correct amount of sample into a 250ml conical flask (see Sample Weight Table below. Note a). b. Dissolve the sample in 40ml tetrahydrofuran. c. Add 25 ml of the catalyst solution into the flask. d. Add 10 ml acetylating solution to the flask. e. Stopper the flask and swirl to obtain a homogenous solution. f. Leave for 5 minutes at room temperature. g. Add 20 ml hydrolysis solution and swirl (sometimes haziness occurs). h. Leave the solution for 30 minutes at room temperature swirling the flask every 5 minutes. i. Add 40 ml tetrahydrofuran and 10 drops Phenolphthalein solution. j. Titrate the solution with 1 Molar KOH solution until the color changes from colorless to pink, and stays pink for at least 30 seconds. k. Run a blank determination in duplicate omitting the sample. m. Determine the acid value of the sample according to ASTM DI 980- 87. n. Calculate the hydroxyl value of the sample. Repeat the determination if the difference between the two values exceeds the tolerances of 0.8 units for hydroxyl values below 20, and1.7 for hydroxyl values between 20 and 200. o. Calculate the average of the two determinations according to the following equation.whereinOH = hydroxyl value of the sample (as such) in mg KOH / g resin;VI = ml of potassium hydroxide solution needed for the sampleV2 = average ml of potassium hydroxide solution needed for the blankN = normality of the potassium hydroxide solution m = weight of the polymer in gAV = acid value of the sample (as such)Notes: a. Select sample weight and weighing accuracy from the following table:b. Potentiometric determination is also possible. In that case the indicator addition is not needed. Especially with hydroxyl values below 5, this is recommended.Reference: This method is based on method C-V 17a developed for DGF in Germany at Huis AG, dated 1.10.9 published in Fat and Science Technology, no. 9, 1990, pag. 371-373.Description of SEC (Size Exclusion Chromatography)

[0050] Sample preparation: The samples were prepared in THF eluent at concentration ~ 5 mg / mL copolymer. The solution was shaken on a flat-bed shaker at ambient temperature for about 2 hours. The solution was filtered through a 0.45 um PTFE syringe filter prior to injection.

[0051] SEC condition: SEC was performed based on a Waters 2695 LC pump and autosampler. The flow rate was set at 1 mL / min, and the injection volume was set at 100 uL. SEC separation was carried out on 2 Agilent PLgel Mixed-C columns held at 35 °C. The detector was Shodex RI-201 differential refractive index detector held at 35 °C.

[0052] Data process: Agilent GPC software Cirrus version 3.3 was used for data collection and data reduction. A total of 16 polystyrene (PS) linear narrow molecular weight standards from Agilent having Mp values from 2,752 to 0.58 kg / mol were used for molecular weight rd calibration. A 3 order polynomial was used for calibration curve fitting. Thus, all molecular weight averages, distributions and references to molecular weight provided in this report are PS equivalent values.Description of NMR

[0053] 2.5 gms to 3 gm of polymer solution and about 5 gm of solvent (CDCh+Cr(acac)3) were loaded into a 5 mm diameter Teflon NMR tube and the spectra obtained as per conditions and instrumentation in Table 4Table 4: NMR procedure and instrumentation

[0054] In this Working Example 3, polyorganosiloxane resin - (meth) acrylate copolymer 3 was prepared as follows: 111 gms of Acrylic Polyol B (described above in Table 2) were mixed with 12.94 gms of DT Resin A3 (described above in Table 2) in a round bottom flask. An additional 55 gms of Butyl acetate were added to reduce the solid loading to ~50%. To the well mixed sample, 1.81 gms of Tin ethyl Hexanoate catalyst were added, followed by the addition of 1 .53 of distilled water. The flask was loaded on to a rotary evaporator and the temperature was raised to 72 °C while the vacuum was held at 400 mm bar Hg. The reaction was run for 5 hrs. The final weight of the reaction product was 180 gms and was a clear low viscosity liquid. The reaction product had an NVC of 50% and an OH# of 52.5 and nominal resin content of 7%.

[0055] In this Working Example 4, polyorganosiloxane resin - (meth)acrylate copolymer 4 was prepared as follows: 110 gms of Acrylic Polyol B were mixed with 19.97 gms of DT Resin A3 in a round bottom flask. An additional 50 gms of Butyl acetate were added to reduce the solid loading to ~50%. To the well mixed sample, 1.82 gms of Tin ethyl Hexanoate catalyst were added, followed by the addition of 0.25 gms of distilled water. The flask was loaded on to a rotary evaporator and the temperature was raised to 82 °C while the vacuum was held at 300 mm bar Hg. The reaction was run for 5 hrs. The final weight of the reaction product was 172 gms and was a clear low viscosity liquid. The reaction product had an NVC of 53% and an OH# of 52.5 and nominal resin content of 11%.

[0056] In this Working Example 5, polyorganosiloxane resin - (meth)acrylate copolymer 5 was prepared as follows: 50 gms of Acrylic Polyol B were mixed with 23.0 gms of DT Resin A3 in a round bottom flask. An additional 40 gms of Butyl acetate were added to reduce the solid loading to ~50%. To the well mixed sample, 0.9 gms of Tin ethyl Hexanoate catalyst were added. The flask was loaded on to a rotary evaporator and the temperature was raised to 80 °C while the vacuum was held at 160 mm bar Hg. The reaction was run for 5 hrs. An additional 15 ml of Butyl acetate was added to the reaction product. The final weight of the product was 92 gms and was a clear high viscosity liquid, close to gel point. The reaction product had an NVC of 50% and an OH# of 52.5 and nominal resin content of 18%.The polyorganosiloxane resin - (meth)acrylate copolymers prepared in Working Examples 3, 4, and 5 were analyzed according to the same procedures described above, and properties are reported below in Tables 5-7.Table 5: Solids and hydroxyl number of polyorganosiloxane resin - (meth)acrylate copolymers prepared in Working Examples 3, 4, and 5Table 6: SEC data on polyorganosiloxane resin - (meth)acrylate copolymers prepared inWorking Examples 3, 4, and 5Table 7 : Si NMR compositions of polyorganosiloxane resin - (meth)acrylate copolymers prepared in Working Examples 3, 4, and 5Notes on NMR:• Values above are reported as mole ratios of the silicon units listed• < = a maximum mole ratio has been estimated from the information available in the spectra acquired.• - = not observed.DEFINITIONS AND USAGE OF TERMS

[0057] All amounts, ratios, and percentages herein are by weight, unless otherwise indicated by the context of the specification. The articles ‘a’, ‘an’, and ‘the’ each refer to one or more, unless otherwise indicated by the context of specification. The singular includes the plural unless otherwise indicated by the context of the specification. The SUMMARY and ABSTRACT are hereby incorporated by reference. The amounts of all starting materials in a composition total 100%. The transitional phrases “comprising”, “consisting essentially of’, and “consisting of’ are used as described in the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018 at section §2111.03 I., II., and III. Any feature or aspect of the invention may be used in combination with any other feature or aspect recited herein. The abbreviations used herein have the definitions in Table A.Table A - Abbreviations

Claims

Claims:

1. A method for preparing a polyorganosiloxane resin - poly(meth)acrylate copolymer, wherein the method comprises:1) contacting, under conditions to effect condensation reaction, components comprisingA) a polyorganosiloxane resin having a weight average molecular weight of 1 ,000 g / mol to 9,000 g / mol and a total SiOZ mol% of 10% to 65% mole of Si, wherein each Z is independently selected from the group consisting of H and an alkyl group of 1 to 12 carbon atoms,B) a random (meth)acrylic polymer with a weight average molecular weight of 3,000 g / mol to 100,000 g / mol, wherein the random (meth)acrylic polymer comprisesBl) a first structural unit derived from a hydroxyl-group containing (meth)acrylic acid ester, wherein the (meth)acrylic acid ester has formula;whereinR4is H or methyl, andD1is a divalent hydrocarbyl group of at least 2 carbon atoms;B2) a second structural unit derived from an alkenyl-functional aromatic compound, wherein the alkenyl-functional aromatic compound has formulaR5is an alkenyl group of 2 to 6 carbon atoms, each of R6, R7, R8, R9, and R10is independently selected from H, an alkyl group of 1 to 4 carbon atoms, and a substituted alkyl group of 1 to 4 carbon atoms, with the proviso that, per molecule at least 3 of R6, R7, R8, R9, and R10are H;B3) a third structural unit derived from a (meth)acrylic acid alkyl ester, wherein the(meth) acrylic acid alkyl ester has formula, whereinR4is H or methyl, andR11is an alkyl group of 1 to 30 carbon atoms or an oxygen substituted monovalent hydrocarbyl group of 1 to 30 carbon atoms; andB4) a fourth structural unit derived from a (meth)acrylic acid, wherein the(meth)acrylic acid has formula, wherein R4is H or methyl; wherein the structural units Bl), B2), B3), and B4) are present in mole fractions bl, b2, b3, and b4, respectively; and wherein said mole fractions have values such that0.1 < bl < 0.5;0.1 < b2 < 0.5;0.1 < b3 < 0.8;0.01 < b4 < 0.2; and a quantity (bl + b2 + b3 + b4) = 1 , andC) a condensation reaction catalyst; thereby preparing a condensation reaction product comprising the polyorganosiloxane resin - poly(meth)acrylate copolymer.

2. The method of claim 1, wherein the conditions to effect condensation reaction in step 1) comprise heating the components at a temperature of 50 °C to 150 °C for up to 4 days.

3. The method of claim 1 or claim 2, further comprising: 2) neutralizing the condensation reaction catalyst after step 1) or recovering the polyorganosiloxane resin - poly(meth)acrylate copolymer from the condensation reaction product, or both.

4. The method of any one of claims 1 to 3, wherein A) the polyorganosiloxane resin comprises unit formula: [R3SiOi / 2]m[R2Si(OZ)aO(2-a) / 2]ii[RSi(OZ)bO(3-b) / 2]o[Si(OZ)cO(4-c) / 2]p, wherein each R is an independently selected monovalent hydrocarbyl group: each Z is independently selected from the group consisting of H and an alkyl group of 1 to 12 carbon atoms; subscripts a, b, and c represent average numbers of moieties of formula OZ per unit, and subscripts a, b, and c have values such that0 < a < 1;0 < b < 2;0 < c < 3; and a quantity (a + b + c) has a value sufficient to provide the resin with the total SiOZ mol% of 10% to 50%; and subscripts m, n, o, and p represent mole fractions of each unit in the unit formula, and subscripts m, n, o, and p have values such that0 < m < 0.5;0 < n < 0.5;0 < o < 0.5;0 < p < 0.6; and a quantity (m + n + o + p) = 1.

5. The method of any one of claims 1 to 3, wherein A) the polyorganosiloxane resin comprises unit formula: [R2Si(OZ)aO(2-a) / 2]r[RSi(OZ)bO(3-b) / 2]s, wherein each R is an independently selected monovalent hydrocarbyl group; each Z is independently selected from the group consisting of H and an alkyl group of 1 to 12 carbon atoms; subscripts a and b represent average numbers of moieties of formula OZ per unit, and subscripts a and b have values such that0 < a < 1;0 < b < 2; and a quantity (a + b) has a value sufficient to provide the resin with the total SiOZ mol% of 10% to 50%; and subscripts r and s represent mole fractions of each unit in the unit formula, and subscripts r and s have values such that0.1 < r < 0.5;0.5 < s < 0.9; and a quantity (r + s) = 1.

6. The method of claim 4 or claim 5, wherein A) the polyorganosiloxane resin has one or more of: each R is independently selected from the group consisting of methyl and phenyl; and each Z is independently selected from the group consisting of H, methyl, and ethyl.

7. The method of any one of claims 1 to 6, wherein B) the random (meth)acrylic polymer has one or more of: the hydroxyl-group containing (meth)acrylic acid ester is selected from the group consisting of (meth)acrylic acid 2-hydroxy ethyl ester; (meth)acrylic acid 2-hydroxypropyl ester; (meth)acrylic acid 3-hydroxypropyl ester; (meth)acrylic acid 2 -hydroxybutyl ester; (meth)acrylic acid 3-hydroxybutyl ester; (meth)acrylic acid 4-hydroxybutyl ester; and a combination of two or more thereof; the vinyl aromatic compound is selected from the group consisting of styrene; t- butylstyrene; a-methylstyrene; p-methylstyrene: divinylbenzene; N,N-diethyl-p- aminoethylstyrene; vinyltoluene; p-tert-butylstyrene; and a combination of two or more thereof; the (meth)acrylic alkyl ester is selected from the group consisting of (meth)acrylic acid methyl ester; (meth)acrylic acid ethyl ester; (meth)acrylic acid propyl ester; (meth)aciy lie acid butyl ester; (meth)acrylic acid penty l ester; (meth)acrylic acid hexyl ester; (meth)acrylic acid cyclohexyl ester; (meth)acrylic acid 2-ethylhexyl ester; (meth)acrylic acid isooctyl ester; (meth)acrylic acid decyl ester; (meth)acrylic acid dodecyl ester; (meth)acrylic acid myristyl ester; (meth)acrylic acid palmityl ester; and (meth)acrylic acid stearyl ester; (meth)acrylic acid methoxymethyl ester; (meth)acrylic acid ethoxymethyl ester; (meth)acrylic acid 2-ethoxyethyl ester; (meth)acrylic acid 2-butoxyethyl ester; (meth)acrylic acid 2-methoxy ethyl ester; (meth)acrylic acid 2-propoxyethyl ester; (meth)acrylic acid 3 -methoxy propyl ester;(meth)acrylic acid 4-methoxybutyl ester; and a combination of two or more thereof; and the (meth)acrylic alkyl acid is selected from the group consisting of methacrylic acid, acrylic acid, and a combination of both.

8. The method of any one of claims 1 to 7, wherein C) the condensation reaction catalyst is selected from the group consisting of an organotin compound and a base.

9. The method of claim 8, wherein the organotin compound comprises dibutyl tin dilaurate, dimethyl tin dilaurate, di-(n- butyl)tin bis-ketonate, dibutyl tin diacetate, dibutyl tin maleate, dibutyl tin diacetylacetonate, dibutyl tin dimethoxide, dibutyl tin dioctanoate, dibutyl tin diformate, dimethyl tin di- neodeconoate, dibutyl tin di-neodeconoate, dibutyl tin dibenzoate, butyl tin tri-2-ethylhexanoate, dioctyl tin diacetate, dimethyl tin dichloride, tin (II) diacetate, tin (II) dioctanoate, tin (II) ethyl hexanoate, tin (II) dilaurate, stannous octoate, stannous oleate, stannous acetate, stannous laurate, stannous stearate, stannous naphthanate, stannous hexanoate, stannous succinate, stannous caprylate, and a combination of any two or more thereof; and wherein the base is selected from the group consisting of NaOH, KOH, NaOCHs, LiOH, potassium tertiary butoxide, LiOCH t, KOCH3, and a potassium silanolate.

10. The method of claim 9, wherein the catalyst is the base, the method further comprises neutralizing the catalyst after step 1), and wherein neutralizing comprises adding an acid to the condensation reaction product.

11. The method of any one of claims 1 to 10, further comprising using a solvent during step 1).

12. The method of claim 11, wherein the solvent comprises butyl acetate.

13. The method of any one of claims 1 to 12, further comprising adding water during step 1).

14. A polyorganosiloxane resin - poly(meth)acrylate copolymer prepared by the method of any one of claims 1 to 13.

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