Comb polymers from ATRP macromonomers
First Claim
Patent Images
1. A comb copolymer of the formula
{In-[(Ax-By)}p-Z]q
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(I) whereinIn represents the fragment of a polymerization initiator capable of initiating polymerization of ethylenically unsaturated monomers in the presence of a catalyst which activates controlled radical polymerization;
A represents an oligopolymer or polymer fragment which consists of ethylenically unsaturated repeating units of polymerizable monomers or oligopolymers;
x represents a numeral greater than one and defines the number of repeating units in A;
B represents a monomer, oligopolymer or polymer fragment copolymerized with A;
y represents zero or a numeral greater than zero and defines the number of monomer, oligopolymer or polymer repeating units in B;
Z represents a polymer backbone which consists of repeating units from polymerizable, ethylenically unsaturated monomers;
p is one or a numeral greater than one which defines the number of groups of the partial formula
In-(Ax-By)-
(A) per polymer backbone Z; and
q is one or a numeral greater than one which defines the number of groups of the partial formula
-(Ax-By)-
(B) per initiator fragment In;
provided that one of p and q represents one and the other represents one or a numeral greater than one.
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Abstract
The invention relates to comb polymers and macromonomers based on acrylates prepared by the ATRP (Atom Transfer Radical Polymerization) method. These polymers have an improved capability of dispersing pigments in the given solvent. The invention also relates to compositions comprising the comb polymers and macromonomers dispersible inorganic or organic pigment particles. The compositions are used by applying them to any suitable substrate, for example to metal, wood plastic or ceramic materials.
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Citations
18 Claims
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1. A comb copolymer of the formula
{In-[(Ax-By)}p-Z]q-
(I)wherein In represents the fragment of a polymerization initiator capable of initiating polymerization of ethylenically unsaturated monomers in the presence of a catalyst which activates controlled radical polymerization;
A represents an oligopolymer or polymer fragment which consists of ethylenically unsaturated repeating units of polymerizable monomers or oligopolymers;
x represents a numeral greater than one and defines the number of repeating units in A;
B represents a monomer, oligopolymer or polymer fragment copolymerized with A;
y represents zero or a numeral greater than zero and defines the number of monomer, oligopolymer or polymer repeating units in B;
Z represents a polymer backbone which consists of repeating units from polymerizable, ethylenically unsaturated monomers;
p is one or a numeral greater than one which defines the number of groups of the partial formula
In-(Ax-By)-
(A)per polymer backbone Z; and q is one or a numeral greater than one which defines the number of groups of the partial formula
-(Ax-By)-
(B)per initiator fragment In; provided that one of p and q represents one and the other represents one or a numeral greater than one. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 18)
wherein p is a numeral from one to hundred; and
In, A, x, B, y and Z are as defined in claim 1.
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3. A comb polymer according to claim 1 of the formula
In-[(Ax-By)-Z]q-
(IB),wherein q is a numeral from one to six; and
In, A, x, B, y and Z are as defined in claim 1.
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4. A comb copolymer (I) according to claim 1, wherein
In represents the fragment of a polymerization initiator selected from the group consisting of C1-C8-alkylhalides, C6-C15-aralkylhalides, C2-C8-haloalkyl esters, arene sulphonyl chlorides, haloalkanenitriles, α - -haloacrylates and halolactones;
A and B represent polymer blocks which differ in polarity and contain repeating units of polymerizable, ethylenically unsaturated monomers selected from the group consisting of styrenes, acrylic acid, C1-C4-alkylacrylic acid, amides, anhydrides and salts of acrylic acid or C1-C4-alkylacrylic acid, acrylic acid-C1-C24-alkyl esters and C1-C4-alkylacrylic acid-C1-C24-alkyl esters x and y are as defined in claim 1;
Z represents a polymer backbone which consists of repeating units of polymerizable, ethylenically unsaturated monomers selected from the group consisting of styrenes, acrylic acid, C1-C4-alkylacrylic acid, amides, anhydrides and salts of acrylic acid or C1-C4-alkylacrylic acid, acrylic acid-C1-C24-alkyl esters and C1-C4-alkylacrylic acid-C1-C24-alkyl esters, aminofunctional esters of acrylic acid or C1-C4-alkylacrylic acid acrylonitrile, methacrylonitrile, vinyl substituted heterocycles, styrene sulfonic acid and salts, vinylbenzoeic acid and salts, vinylformamide and amidosulphonic acid derivatives;
p represents a numeral from one to hundred; and
q represents one.
- -haloacrylates and halolactones;
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5. A comb copolymer (I) according to claim 1, wherein
In represents fragment of a polymerization initiator which is selected from the group consisting of C1-C8-alkylhalides, C6-C15aralkylhalides, C2-C8-haloalkyl esters, arene sulphonyl chlorides, haloalkanenitriles, α - -haloacrylates and halolactones;
A and B represent polymer blocks which differ in polarity and contain repeating units of polymerizable, ethylenically unsaturated monomers selected from the group consisting of 4-aminostyrene, di-C1-C4-alkylaminostyrene, styrene, acrylic acid C1-C4-alkylacrylic acid, acrylic or C1-C4-alkylacrylamides, acrylic or C1-C4-alkylacrylmono- or -di-C1-C4-alkylamides, acrylic or C1-C4-alkylacryl-di-C1-C4-alkyl-amino-C2-C4-alkylamides, acrylic or C1-C4-alkylacryl-amino-C2-C4alkylamides, anhydrides and salts of acrylic acid or C1-C4-alkylacrylic acid, acrylic or C1-C4-alkylacrylic acid-mono- or -di-C1-C4-alkylamino-C2-C4-alkyl esters, acrylic or C1-C4-alkylacrylic acid-hydroxy-C2-C4-alkyl esters, acrylic or C1-C4-alkylacrylic acid-(C1-C4-alkyl)3silyloxy-C2-C4-alkyl esters, acrylic or C1-C4-alkylacrylic acid-(C1-C4-alkyl)3silyl-C2-C4-alkyl esters, acrylic or C1-C4-alkylacrylic acid-heterocyclyl-C2-C4-alkyl esters, C1-C24-alkoxylated poly-C2-C4-alkylene glycol acrylic or C1-C4-alkylacrylic acid esters, acrylic acid-C1-C24-alkyl esters and C1-C4-alkylacrylic acid-C1-C24-alkyl esters;
x and y are as defined in claim 1;
Z represents a polymer backbone which consists of repeating units from polymerizable ethylenically unsaturated monomers selected from the group consisting of 4-aminostyrene and salts thereof, di-C1-C4-alkylaminostyrene and salts thereof, acrylic or C1-C4-alkylacrylic acid or anhydrides and salts thereof, acrylic or C1-C4-alkylacrylic acid-mono- or -di-C1-C4-alkylamino-C2-C4-alkyl esters and salts thereof, acrylic or C1-C4-alkylacrylic acid-hydroxy-C2-C4-alkyl esters, acrylic or C1-C4-alkylacrylic acid-(C1-C4-alkyl)3silyloxy-C2-C4-alkyl esters, acrylic or C1-C4-alkylacrylic acid-(C1-C4-alkyl)3silyl-C2-C4-alkyl esters, acrylic or C1-C4-alkylacrylic acid-heterocyclyl-C2-C4-alkyl esters and salts thereof, C1-C24-alkoxylated poly-C2-C4-alkylene glycol acrylic or C1-C4-alkylacrylic acid esters, acrylic or C1-C4-alkylacrylamides, acrylic or C1-C4-alkylacrylmono- or -di-C1-C4-alkylamides, acrylic or C1-C4-alkylacryl-di-C1-C4-alkylaminoC2-C4-alkylamides and salts thereof, acrylic or C1-C4-alkylacryl-amino-C2-C4alkylamides, acrylonitrile, methacrylonitrile, 4-aminostyrene and salts thereof, di-C1-C4-alkylaminostyrene and salts thereof, vinyl substituted heterocycles, styrene sulfonic acid and salts, vinylbenzoeic acid and salts, vinylformamide and amidosulphonic acid derivatives;
p represents a numeral from one to hundred; and
q represents one.
- -haloacrylates and halolactones;
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6. A comb copolymer (I) according to claim 1, wherein
In represents the fragment of a polymerization Initiator which is selected from the group consisting of C1-C8-alkyl halides, C6-C15-aralkylhalides, C2-C8-haloalkyl esters, arene sulphonyl chlorides, haloalkanenitriles, α - -haloacrylates and halolactones;
A and B represent polymer blocks containing repeating units of polymerizable, ethylenically unsaturated monomers selected from the group consisting of styrenes, acrylic acid, C1-C4-alkylacrylic acid, amides, anhydrides and salts of acrylic acid or C1-C4-alkylacrylic acid, acrylic acid-C1-C24-alkyl esters and C1-C4-alkylacrylic acid-C1-C24-alkyl esters;
x and y are as defined in claim 1;
Z represents a polymer block which consists of repeating units from polymerizable ethylenically unsaturated monomers selected from the group consisting of acrylic or C1-C4-alkylacrylic acid or anhydrides and salts thereof, acrylic or C1-C4-alkylacrylic acid-mono- or -di-C1-C4-alkylamino-C2-C4-alkyl esters and salts thereof, acrylic or C1-C4-alkylacrylic acid-hydroxy-C2-C4-alkyl esters, acrylic or C1-C4-alkylacrylic acid-(C1-C4-alkyl)3silyloxy-C2-C4-alkyl esters, acrylic or C1-C4-alkylacrylic acid-(C1-C4-alkyl)3silyl-C2-C4-alkyl esters, acrylic or C1-C4-alkylacrylic acid-heterocyclyl-C2-C4-alkyl esters and salts thereof, C1-C24-alkoxylated poly-C2-C4-alkylene glycol acrylic or C1-C4-alkylacrylic acid esters, acrylic or C1-C4-alkylacrylamides, acrylic or C1-C4-alkylacrylmono- or -di-C1-C4-alkylamides, acrylic or C1-C4-alkylacryl-di-C1-C4-alkylaminoC2-C4-alkylamides and salts thereof, acrylic or C1-C4-alkylacryl-amino-C2-C4alkylamides, acrylonitrile, methacrylonitrile, 4-aminostyrene and salts thereof, di-C1-C4-alkylaminostyrene and salts thereof, vinyl substituted heterocycles, styrene sulfonic acid and salts, vinylbenzoeic acid and salts, vinylformamide and amidosulphonic acid derivatives; and
p represents a numeral from one to hundred; and
q represents one.
- -haloacrylates and halolactones;
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7. A composition comprising
a) 0.1-99.9% by weight of a comb copolymer (I) according to claim 1; - and
b) 0.1-99.9% by weight of dispersible inorganic or organic pigment particles.
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8. A composition according to claim 7, wherein the dispersible organic pigment particles of the component b) are selected from the azo pigment group consisting of azo, disazo, napthol, benzimidazolone, azocondensation, metal complex, isoindolinone, and isoindoline pigments, the chinophthalon pigment, dioxazine pigment and the polycyclic pigment group consisting of indigo, thioindigo, quinacridones, phthalocyanines, perylenes, perionones, anthraquinones, such as aminoanthraquinones or hydroxyanthraquinones, anthrapyrimidines, indanthrones, flavanthrones, pyranthrones, anthantrones, isoviolanthrones, diketoypyrrolopyrrole, and carbazoles, pigments and pearlescent flakes.
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9. A composition according to claim 7 wherein the dispersible inorganic pigment particles of the component b) are selected from the group consisting of aluminium, aluminium oxide, silicon oxide and silicates, iron(III)oxide, chromium(III)oxide, titanium(IV)oxide, zirconium(IV)oxide, zinc oxide, zinc sulphide, zinc phosphate, mixed metal oxide phosphates, molybdenum sulphide, cadmium sulphide, carbon black or graphite, vanadates, chromates, and molybdates, and mixtures, crystal forms or modifications thereof.
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10. A composition according to claim 7 which additionally contains binding agents and conventional additives selected from the group consisting of surfactants, stabilizers, anti-foaming agents, dyes, plasticizers, thixotropic agents, drying catalysts, anti-skinning agents and leveling agents.
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11. A pigment dispersion comprising a composition according to claim 7 and a liquid carrier selected from the group consisting of water, organic solvents and mixtures thereof.
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12. A composition comprising
a′ - ) a comb copolymer (I) according to claim 1; and
b′
) a polymeric binder selected from aqueous emulsion and aqueous dispersion polymers.
- ) a comb copolymer (I) according to claim 1; and
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13. A composition according to claim 12, wherein the polymeric binder is selected from the group consisting of polyacrylates, styrene/acrylate copolymers, ethylene/vinylacetate copolymers, polyvinylchloride and copolymers thereof, polyesters, alkyd polymers, polyurethanes and epoxypolymers.
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18. A process for the preparation of a comb copolymer of the formula (I) according to claim 1, which comprises polymerising a macromonomer of the formula
In-[(Ax-By)-X]q-
(II),wherein In represents the fragment of a polymerization initiator capable of initiating polymerization of ethylenically unsaturated monomers in the presence of a catalyst which activates controlled radical polymerization;
A represents an oligopolymer or polymer fragment which consists of ethylenically unsaturated repeating units of polymerizable monomers or oligopolymers;
x represents a numeral greater than one and defines the number of repeating units in A;
B represents a monomer, oligopolymer or polymer fragment copolymerized with A;
y represents zero or a numeral greater than zero and defines the number of monomer, oligopolymer or polymer repeating units in B;
X represents a polymerizable, ethylenically unsaturated monomer unit; and
q represents one or a numeral greater than one and defines the number of groups of the partial formula
-(Ax-By)-X
(B′
)per initiator fragment In, with different amounts of polymerizable ethylenically unsaturated monomers.
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14. A macromonomer of the formula
In-[(Ax-By)-X]q-
(II),wherein In represents the fragment of a polymerization initiator capable of initiating polymerization of ethylenically unsaturated monomers in the presence of a catalyst which activates controlled radical polymerization;
A represents an oligopolymer or polymer fragment which consists of ethylenically unsaturated repeating units of polymerizable monomers or oligopolymers;
x represents a numeral greater than one and defines the number of repeating units in A;
B represents a monomer, oligopolymer or polymer fragment copolymerized with A;
y represents zero or a numeral greater than zero and defines the number of monomer, oligopolymer or polymer repeating units in B;
X represents a polymerizable, ethylenically unsaturated monomer unit; and
q represents one or a numeral greater than one and defines the number of groups of the partial formula
-(Ax-By)-X
(B′
)per initiator fragment In. - View Dependent Claims (15, 16, 17)
A and B represent polymer blocks which differ in polarity and contain repeating units of polymerizable, ethylenically unsaturated monomers selected from the group consisting of styrenes, acrylic acid, C1-C4-alkylacrylic acid, amides, anhydrides and salts of acrylic acid or C1-C4-alkylacrylic acid, acrylic acid-C1C24-alkyl esters and C1-C4-alkylacrylic acid-C1-C24-alkyl esters;
X represents a polymerizable, ethylenically unsaturated monomer unit X selected from the group consisting of styrenes, acrylic acid, C1-C4-alkylacrylic acid, amides, anhydrides and salts of acrylic acid or C1-C4-alkylacrylic acid, acrylic acid-C1-C24-alkyl esters and C1-C4-alkylacrylic acid-C1-C24-alkyl esters, acrylonitrile, methacrylonitrile, vinyl substituted heterocycles, styrene sulfonic acid and salts, vinylbenzoeic acid and salts, vinylformamide and amidosulphonic acid derivatives; and
q represents a numeral from one to four.
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16. A composition comprising
a) the macromonomer (II) according to claim 14; - and
b) at least one curing agent.
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17. A process for the preparation of a macromonomer (II) wherein In, A, B, x, y, X and q are as defined in claim 14, which comprises polymerising by atom transfer radical polymerization (ATRP) in the presence of catalytically effective amount of an oxidisable transition metal complex catalyst, an aliphatic monomer or oligomer containing ethylene groups in the presence of a polymerization initiator
In—- Yq′
(III),wherein In represents the fragment of a polymerization initiator capable of initiating polymerization of monomers or oligopolymers containing ethylene groups, —
Y represents a radically transferable atom or group and q′
represents one or a numeral greater than one, and replacing —
Y in a polymerisate of the formula
In-[(Ax-By)-Y]q
(IV)with the polymerizable, ethylenically unsaturated monomer unit —
X.
- Yq′
Specification
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Current AssigneeCiba Specialty Chemicals Corp (BASF SE)
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Original AssigneeCiba Specialty Chemicals Corp (BASF SE)
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InventorsRime, François, Mühlebach, Andreas, Auschra, Clemens, Eckstein, Ernst
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Primary Examiner(s)Wu, David W.
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Assistant Examiner(s)SASTRI, SATYA B
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Application NumberUS10/169,884Publication NumberTime in Patent Office1,699 DaysField of Search524/560, 524/558, 524/566, 523/334, 523/335US Class Current524/560CPC Class CodesC08F 2438/01 Atom Transfer Radical Polym...C08F 293/00 Macromolecular compounds ob...C08F 293/005 using free radical "living"...C08L 51/003 grafted on to macromolecula...C08L 53/00 Compositions of block copol...
