US20090221739A1 - Process for the Post-Modification of Homo and Copolymers Prepared by Controlled Free Radical Polymerization Processes - Google Patents

Process for the Post-Modification of Homo and Copolymers Prepared by Controlled Free Radical Polymerization Processes Download PDF

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US20090221739A1
US20090221739A1 US11/794,707 US79470706A US2009221739A1 US 20090221739 A1 US20090221739 A1 US 20090221739A1 US 79470706 A US79470706 A US 79470706A US 2009221739 A1 US2009221739 A1 US 2009221739A1
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alkyl
alcohol
polymer
process according
vinyl
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Ralf Knischka
Ernst Eckstein
Clemens Auschra
Akira Matsumoto
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Assigned to CIBA SPECIALTY CHEMICALS CORP. reassignment CIBA SPECIALTY CHEMICALS CORP. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MATSUMOTO, AKIRA, ECKSTEIN, ERNST, AUSCHRA, CLEMENS, KNISCHKA, RALF
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/45—Anti-settling agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/47—Levelling agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups

Definitions

  • the instant invention pertains to the preparation of polymers or copolymers wherein in a first step a controlled free radical polymerization process is carried out and in a second step the resulting polymer is modified by specific polymer analogous reactions.
  • the final modified polymer or copolymer is useful as a dispersant for pigments, as leveling agent or as rheology modifier for coatings or related applications.
  • Further aspects of the invention are the thus prepared polymers or copolymers, a pigment concentrate containing the polymer or copolymer and a coating material containing the pigment concentrate.
  • Polymeric pigment dispersants are an essential part of new water based or solvent based high solids formulation technology. There is, therefore, an increasing activity in developing new products in these coating areas. So far, only a few classes of polymeric dispersants have been established in the market. In less demanding coating applications, still a lot of low molecular weight surfactants are used. In more demanding applications, e.g. automotive & industrial coatings, polymeric pigment dispersants have to be used to avoid the problems associated with low molecular weight surfactants (water sensitivity, corrosion, foam).
  • the controlled free radical polymerisation is a tool to tailor the microstructure of polymers (e.g. blockcopolymers) in a way that is favorable for dispersing and stabilizing pigments in the mill-base.
  • the combination of CFRP with subsequent post-modification of the stabilizing block allows enlarging the possible groups that can be used as pigment dispersants. With one CFRP-process a large row of different polymer materials for either waterborne or also solvent-borne high solids systems becomes available.
  • polymers or copolymers can be prepared in an easy manner, which otherwise would not be available or can be prepared only with complex reactions.
  • the inventive process comprises a selective polymer-analogous transesterification on polymers, which have been synthesized via nitroxide-mediated polymerization to provide well-defined polymer architectures.
  • This process provides polymers with distinct structural differences compared to polymers with same monomer composition, but synthesized directly from corresponding monomers without post-transesterification.
  • Monomer sequence In direct radical polymerization of two different monomers the monomer sequence statistics along the polymer chain is governed by the copolymerization parameters which in most cases will cause deviation from ideal random distribution of the different monomers. Using the inventive process, the monomer distribution which result from the transesterification step, is only governed by the transesterification reaction and can be expected to provide a more uniform i.e. random distribution along the polymer chain. 2) Residual monomers: Controlled polymerization processes can not be conducted to 100% conversion without significant decrease in livingness of the polymer chains. In well-defined block copolymer synthesis, it is therefore necessary to remove the non-reacted monomers of the first block, before the second block is prolonged with a different monomer.
  • Evaporation at reduced pressure is the easiest way to remove non-reacted monomers, but works only well for monomers with boiling point below 200° C.
  • acrylates of long chain alcohols like C12-C15-alcohols or MPEG-alcohols can not be removed form polyacrylates by distillation. Therefore it is not possible to make block copolymers of such long chain acrylates with pure block structure free of residual monomers.
  • the inventive process via transesterification circumvents the problem of residual non-removable monomers and associated problems of block contamination, is therefore capable to provide polymers with higher level of structural perfection.
  • Acrylate monomers based on unsaturated alcohols like allyl alcohol or oleyl alcohol usually react as crosslinkers.
  • unsaturated alcohols like allyl alcohol or oleyl alcohol
  • conventional radical polymerization as well as in controlled polymerization such acrylates will lead to branching and/or crosslinking, i.e. will prevent the formation of structurally clean linear polymer chains.
  • the inventive process of transesterification allows to introduce unsaturated alcohols to preformed controlled polymers with clean linear chain structure, i.e. provides access to well-defined structures e.g. block copolymers otherwise not accessible by direct radical polymerization.
  • One aspect of the invention is a process for the preparation of a modified polymer or copolymer comprising the steps
  • X represents a group having at least one carbon atom and is such that the free radical X• derived from X is capable of initiating polymerization;
  • At least one monomer used in the steps a1) or a2) is a C 1 -C 6 alkyl or hydroxy C 1 -C 6 alkyl ester of acrylic or methacrylic acid; and a second step
  • the first polymerization step is carried out according to the polymerization reactions a1) (claim 2 ).
  • the second step b) is a transesterification reaction, hydrolysis or an anhydride modification. Particularly preferred is a transesterification reaction (claim 3 ).
  • the transesterification preferably comprises the removal of the C 1 -C 6 alcohol byproduct by distillation.
  • step a1 or a2 of the above described process is carried out twice and a block copolymer is obtained wherein in the first or second radical polymerization step the monomer or monomer mixture contains 50 to 100% by weight, based on total monomers, of a C 1 -C 6 alkyl or hydroxyalkyl ester of acrylic or methacrylic acid and in the second or first radical polymerization step respectively, the ethylenically unsaturated monomer contains no primary or secondary ester bond (claim 4 ).
  • the monomer or monomer mixture contains from 50 to 100% by weight based on total monomers of a C 1 -C 6 alkyl or hydroxyalkyl ester of acrylic or methacrylic acid and in the second polymerization step the ethylenically unsaturated monomer is 4-vinyl-pyridine or pyridinium-ion, 2-vinyl-pyridine or pyridinium-ion, vinyl-imidazole or imidazolinium-ion, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, ⁇ -methyl styrene, ⁇ -methyl styrene or p-tert-butyl-styrene (claim 5 ).
  • the block copolymer is a gradient block copolymer (claim 6 ).
  • the polymer or copolymer is prepared by controlled free radical polymerization (CFRP).
  • CFRP controlled free radical polymerization
  • U.S. Pat. No. 4,581,429 discloses a free radical polymerization process by controlled or “living” growth of polymer chains, which produces defined oligomeric homopolymers and copolymers, including block and graft copolymers.
  • initiators of the partial formula R′R′′N—O—X In the polymerization process the free radical species R′R′′N—O• and •X are generated.
  • •X is a free radical group, e.g. a tert.-butyl or cyanoisopropyl radical, capable of polymerizing monomer units containing ethylene groups.
  • acyclic ring system may be part of a cyclic ring system or substituted to form a acyclic structure.
  • Suitable nitroxylethers and nitroxyl radicals are principally known from U.S. Pat. No. 4,581,429 or EP-A-621 878.
  • nitroxylethers and nitroxyl radicals are described in WO 02/4805 (Ciba) and in WO 02/100831 (Ciba).
  • Nitroxylethers and nitroxyl radicals with more than one nitroxyl group in the molecule are for example described in U.S. Pat. No. 6,573,347 (Ciba), WO 01/02345 (Ciba) and WO 03/004471 (Ciba) These compounds are ideally suitable when branched, star or comb (co)polymers are prepared.
  • alkoxyamine and nitroxylether are used as equivalents.
  • the structural element is part of a 5 or 6-membered heterocyclic ring, which optionally has an additional nitrogen or oxygen atom in the ring system.
  • Substituted piperidine, morpholine and piperazine derivatives are particularly useful.
  • G 1 , G 2 , G 3 , G 4 are independently C 1 -C 6 alkyl or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 together form a C 5 -C 12 cycloalkyl group;
  • G 5 , G 6 independently are H, C 1 -C 18 alkyl, phenyl, naphthyl or a group COOC 1 -C 18 alkyl;
  • X is selected from the group consisting of —CH 2 -phenyl, CH 3 CH-phenyl, (CH 3 ) 2 C-phenyl, (C 5 -C 6 cycloalkyl) 2 CCN, (CH 3 ) 2 CCN,
  • structural element of formula (I) is of formula A, B or O,
  • nitroxylethers are those of formula (Ic), (Id), (Ie), (If), (Ig) or (Ih)
  • R 201 , R 202 , R 203 and R 204 independently of each other are C 1 -C 18 alkyl, C 3 -C 18 alkenyl, C 3 -C 18 alkinyl, C 1 -C 18 alkyl, C 3 -C 18 alkenyl, C 3 -C 18 alkinyl which are substituted by OH, halogen or a group —O—C(O)—R 205 , C 2 -C 18 alkyl which is interrupted by at least one O atom and/or NR 205 group, C 3 -C 12 cycloalkyl or C 6 -C 10 aryl or R 201 and R 202 and/or R 203 and R 204 together with the linking carbon atom form a C 3 -C 12 cycloalkyl radical; R 205 , R 206 and R 207 independently are hydrogen, C 1 -C 18 alkyl or C 6 -C 10 aryl; R 208 is hydrogen, OH, C 1
  • R 201 , R 202 , R 203 and R 201 are ethyl, propyl or butyl and the remaining are methyl; or
  • R 201 and R 202 or R 203 and R 204 together with the linking carbon atom form a C 5 -C 6 cycloalkyl radical and one of the remaining substituents is ethyl, propyl or butyl.
  • X is CH 3 CH-phenyl.
  • G 11 , G 12 , G 13 and G 14 are independently C 1 -C 4 alkyl or G 11 and G 12 together and G 13 and G 14 together, or G 11 and G 12 together or G 13 and G 14 together are pentamethylene;
  • G 15 and G 16 are each independently of the other hydrogen or C 1 -C 4 alkyl;
  • X is as defined above;
  • k is 1, 2, 3, or 4 Y is O or NR 302 or when k is 1 and R 301 represents alkyl or aryl Y is additionally a direct bond;
  • R 302 is H, C 1 -C 18 alkyl or phenyl; if k is 1 R 301 is H, straight or branched C 1 -C 18 alkyl, C 3 -C 18 alkenyl or C 3 -C 18 alkinyl, which may be unsubstituted or substituted, by one or more OH, C 1 -C 8 alkoxy, carboxy, C 1 -C 8 alkoxycarbon
  • G 16 is hydrogen and G 15 is hydrogen or C 1 -C 4 alkyl, in particular methyl, and G 11 and G 13 are methyl and G 12 and G 14 are ethyl or propyl or G 11 and G 12 are methyl and G 13 and G 14 are ethyl or propyl.
  • the 4 imino compounds of formula III can be prepared for example according to E. G. Rozantsev, A. V. Chudinov, V. D. Sholle.:Izv. Akad. Nauk. SSSR, Ser. Khim. (9), 2114 (1980), starting from the corresponding 4-oxonitroxide in a condensation reaction with hydroxylamine and subsequent reaction of the OH group.
  • the compounds are described WO 02/100831 (Ciba)
  • alkyl radicals in the various substituents may be linear or branched.
  • alkyl containing 1 to 18 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
  • Alkenyl with 3 to 18 carbon atoms is a linear or branched radical as for example propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl.
  • alkenyl with 3 to 12, particularly preferred with 3 to 6 carbon atoms.
  • Alkinyl with 3 to 18 is a linear or branched radical as for example propinyl (—CH 2 —C ⁇ CH), 2-butinyl, 3-butinyl, n-2-octinyl, or n-2-octadecinyl. Preferred is alkinyl with 3 to 12, particularly preferred with 3 to 6 carbon atoms.
  • hydroxy substituted alkyl examples are hydroxy propyl, hydroxy butyl or hydroxy hexyl.
  • halogen substituted alkyl examples include dichloropropyl, monobromobutyl or trichlorohexyl.
  • C 2 -C 18 alkyl interrupted by at least one O atom is for example —CH 2 CH 2 —O—CH 2 —CH 3 , —CH 2 —CH 2 —O—CH 3 — or —CH 2 CH 2 —O—CH 2 —CH 2 —CH 2 O—CH 2 —CH 3 —. It is preferably derived from polyethlene glycol.
  • a general description is —((CH 2 ) a —O) b —H/CH 3 , wherein a is a number from 1 to 6 and b is a number from 2 to 10.
  • C 2 -C 18 alkyl interrupted by at least one NR 205 group may be generally described as —((CH 2 ) a —NR 205 ) b —H/CH 3 , wherein a, b and R 205 are as defined above.
  • C 3 -C 12 cycloalkyl is typically, cyclopropyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl or trimethylcyclohexyl.
  • C 6 -C 10 aryl is for example phenyl or naphthyl, but also comprised are C 1 -C 4 alkyl substituted phenyl, C 1 -C 4 alkoxy substituted phenyl, hydroxy, halogen or nitro substituted phenyl.
  • alkyl substituted phenyl are ethylbenzene, toluene, xylene and its isomers, mesitylene or isopropylbenzene.
  • Halogen substituted phenyl is for example dichlorobenzene or bromotoluene.
  • Alkoxy substituents are typically methoxy, ethoxy, propoxy or butoxy and their corresponding isomers.
  • C 7 -C 9 -phenylalkyl is benzyl, phenylethyl or phenylpropyl.
  • C 5 -C 10 heteroaryl is for example pyrrol, pyrazol, imidazol, 2,4, dimethylpyrrol, 1-methylpyrrol, thiophene, furane, furfural, indol, cumarone, oxazol, thiazol, isoxazol, isothiazol, triazol, pyridine, ⁇ -picoline, pyridazine, pyrazine or pyrimidine.
  • R is a monovalent radical of a carboxylic acid, it is, for example, an acetyl, propionyl, butyryl, valeroyl, caproyl, stearoyl, lauroyl, acryloyl, methacryloyl, benzoyl, cinnamoyl or ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.
  • C 1 -C 18 alkanoyl is for example, formyl, propionyl, butyryl, octanoyl, dodecanoyl but preferably acetyl and C 3 -C 5 alkenoyl is in particular acryloyl.
  • polymerization process a1) is very suitable.
  • process a1) the nitroxylether according to the structures outlined above splits between the O—X bond.
  • the regulating fragment in formula (I) corresponds to the O—N fragment and the initiating fragment (In) corresponds to the C centered radical of the group X.
  • nitroxylethers and nitroxyl radicals are those of formulae
  • the polymer or copolymer is prepared with a compound of formula (O1)
  • the initiator compound is present in an amount of from 0.01 mol-% to 30 mol-%, more preferably in an amount of from 0.1 mol-% to 20 mol-% and most preferred in an amount of from 0.1 mol-% to 10 mol-% based on the monomer or monomer mixture.
  • the free radical initiator is preferably an azo compound, a peroxide, perester or a hydroperoxide.
  • radical sources are 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methyl-butyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1′-azobis(1-cyclohexanecarbonitrile), 2,2′-azobis(isobutyramide) dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, dimethyl-2,2′-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile, 2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(2-methylpropane), 2,2′-azobis(N,N′-dimethyleneisobutyramidine), free base or hydrochloride, 2,2′-azobis(2-amidinopropane), free base or hydrochloride, 2,
  • the radical source is preferably present in an amount of from 0.01 mol-% to 30 mol-%, more preferred in an amount of from 0.1 mol-% to 20 mol-% and most preferred in an amount of from 0.5 mol-% to 10 mol-% based on the monomer or monomer mixture.
  • the molar ratio of the radical source to the nitroxyl radical may be from 1:10 to 10:1, preferably from 1:5 to 5:1 and more preferably from 1:2 to 2:1.
  • the polymer or copolymer can also be prepared in a controlled way by atom transfer radical polymerization (ATRP). This type of polymerization is, for example, described in WO 96/30421.
  • ATRP atom transfer radical polymerization
  • RAFT Reversible addition fragmentation chain transfer polymerization
  • the polymer or copolymer prepared according to steps a1) or a2) has preferably a polydispersity index of 1.0 to 2.2, more preferably from 1.1 to 1.9 and most preferably from 1.1 to 1.5.
  • the second reaction step i.e. the polymer analogous reaction
  • the polymer analogous reaction is a transesterification reaction, an amidation, hydrolysis or anhydride modification or a combination thereof.
  • Hydrolysis means the cleavage of an ester bond under alkaline or acidic conditions and can be carried out when the polymer or copolymer contains ester functionalities.
  • the degree of hydrolysis may vary in a wide range and depends on reaction time and conditions. For example 5 to 100%, preferably 10% to 70% of the ester functionalities may be hydrolized, to form the free acid group, from which also a salt can be prepared.
  • the metal ion is preferably an alkali metal ion, such as Li + , Na + or Ka + or an ammonium cation, such as NH 4 + or NR 404 , wherein R 404 is hydrogen or C 1 -C 18 alkyl.
  • Anhydride modification can be carried out when the polymer or copolymer contains hydroxyl functionalities.
  • the hydroxyl functionalities come for example from hydroxyl functional monomers, such as hydroxyethyl acrylate or methacrylate.
  • Virtually all aliphatic or aromatic anhydrides can be used in the modification process. Examples for anhydrides are maleic acid anhydride, pyromelitic acid anhydride, cyclohexyldiacid anhydride, succinic acid anhydride, camphoric acid anhydride.
  • Transesterification means to replace the alcohol radical in an ester group of the polymer or copolymer by another alcohol radical.
  • the alcohol radical to be replaced is methanol, ethanol, propanol or butanol.
  • the transesterification reaction is carried out at elevated temperatures, typically 70-200° C., by reacting the CFRP polymer with the corresponding alcohol using well-known catalysts, such as tetra-isopropyltitanate, tetra-butyltitanate, alkali- or earth alkali alcoholates like NaOMe or LiOMe.
  • the low boiling product alcohol is removed from the transterification reaction mixture by distillation. If needed, catalyst residues may be removed by adsorption or extraction or otherwise processed or inactivated by known methods, like hydrolysis with water or acids.
  • the choice of the replacing alcohol is important.
  • the replacing alcohol controls the properties of the resulting copolymer.
  • a polar replacing alcohol such as alcohols having e.g. the following formula R—[O—CH 2 —CH 2 —] n —OH, e.g. MPEG-OH
  • R—[O—CH 2 —CH 2 —] n —OH e.g. MPEG-OH
  • solubility depends on the amount of transesterified monomer units. At least 40% of the units should be transesterified to obtain the desired effect.
  • non polar alcohols like higher molecular weight branched aliphatic alcohols can be beneficial.
  • alcohols containing siloxane groups are preferred, e.g. with the following formula
  • solid copolymer If a solid copolymer is required, solid alcohols or polar alcohols which are able to raise the glass transition temperature (Tg) or impart side chain crystallinity should be used.
  • Tg glass transition temperature
  • polar alcohols which are able to raise the glass transition temperature (Tg) or impart side chain crystallinity should be used.
  • An example is behenyl alcohol.
  • the replacing alcohol radical is typically an aliphatic C 6 -C 36 alcohol or a precursor of an alcohol, having at least one —OH group.
  • the alcohol may also be interrupted by 1 to 20 O or N atoms or substituted by halogen, perfluoralkyl, NH 2 , NH(C 1 -C 18 alkyl), N(C 1 -C 18 alkyl) 2 , COO(C 1 -C 18 alkyl), CON(C 1 -C 18 alkyl) 2 , CONH(C 1 -C 18 alkyl), CONH 2 , COOH, COO ⁇ , O(C 1 -C 18 alkyl) or with a Si, P or S containing group, for example alkylhydroxysilicones.
  • the alcohol may also contain heterocylic ring structures, such as 1-(2-hydroxyethyl)-2-pyrrolidinone, 1-(2-hydroxyethyl)-2-imidazolidinone, 2-(2-hydroxyethyl)pyridine, N-2-hydroxyethyl)phtalimide, 4-(2-hydroxyethyl)morpholine, 1-(2-hydroxyethyl)piperazine, N-hydroxymethylphthalimide, 3-hydroxymethylpyridine or (4-pyridyl)-1-propanol.
  • heterocylic ring structures such as 1-(2-hydroxyethyl)-2-pyrrolidinone, 1-(2-hydroxyethyl)-2-imidazolidinone, 2-(2-hydroxyethyl)pyridine, N-2-hydroxyethyl)phtalimide, 4-(2-hydroxyethyl)morpholine, 1-(2-hydroxyethyl)piperazine, N-hydroxymethylphthalimide, 3-hydroxymethylpyridine or (4-pyridyl)-1
  • the alcohols which are interrupted by O or N atoms are not limited to 36 C atoms. These can be oligomeric or polymeric alcohols also. Examples of alcohols interrupted by O atoms are methoxypolyethyleneglycols or all kinds of adducts of ethyleneoxide and/or propyleneoxide (EO/PO). Such EO/PO-adducts can be random or block type structures.
  • the alcohol is an unsubstituted linear or branched C 8 -C 36 alkyl mono alcohol or a mono alcohol derived from ethylenoxide, propylenoxide or mixtures thereof with up to 100 C atoms. (Claim 11 ).
  • fatty acid alcohol ethoxylates alkylphenolethoxylates, alkoxylates of all kinds of monofunctional alcohols or phenols or secondary amines.
  • the alkoxylate is an ethoxylate of a primary alcohol or alkylphenol of structure (A):
  • R is saturated or unsaturated, linear or branched chain alkyl with 1-22 carbon atoms, or alkylaryl or dialkylaryl with up to 24 carbon atoms and n is 1 to 50.
  • the alcohol is an unsubstituted linear or branched C 8 -C 36 alkyl mono alcohol. (Claim 13 ).
  • An example is iso C12-C15 alcohol.
  • Non-polar polymers or copolymers are obtained.
  • the macroalcohol is a primary OH-functional silicone oligomer.
  • R is C 1 -C 18 alkyl, phenyl or C 7 -C 15 aralkyl; n is 1 to 50 and R′ is a linking group with 1 to 20 carbon atoms. (Claim 14 ).
  • Typical linking groups are C 1 -C 18 alkylene, phenylene or C 1 -C 18 alkylene interrupted by 1 to 6 oxygen atoms.
  • the alcohol is a partly or fully fluorinated primary alcohols.
  • examples of commercial fluorinated alcohol mixtures are: Zonyl BA®, Zonyl BA-L®, Zonyl BA-LD®, Zonyl BA-N® from Du Pont (claim 15 ).
  • Aryl is phenyl or naphthyl, preferably phenyl.
  • Precursors of alcohols are for example macroalcohols, such as poly- ⁇ -caprolactone oligomers or ⁇ -caprolactone adducts and similar lactone adducts (e.g. based on valerolactone) or mixed adducts of ⁇ -caprolactone and valerolactone.
  • Typical lactone adducts are adducts of ⁇ -caprolactone to long chain fatty alcohols of structure:
  • R is saturated or unsaturated, linear or branched chain alkyl with 8-22 carbon atoms or alkylaryl or dialkylaryl with up to 24 carbon atoms and n is 1 to 50.
  • macroalcohols based on polyolefins which have typically molecular weights up to 5000, preferably up to 2000.
  • Yet another embodiment are unsaturated alcohols containing carbon-carbon double bonds or carbon triple bonds.
  • An example is oleyl alcohol.
  • Regarding triple bond preferred are primary alkinols like propargyl alcohol and higher homologues like alkylsubstituted propargylalcohol.
  • the alcohol is a primary or secondary alcohol. Most preferred are primary alcohols or alcohol mixtures.
  • the alcohol or alcohol mixture is non-volatile and has a boiling point or range of at least 100° C., more preferably of at least 200° C.
  • the alcohol is a monoalcohol.
  • amidation there is understood the modification of the ester function of a polyacrylate with an amine under the formation of an amide bond.
  • the amine is a monofunctional primary or secondary amine, most preferably a primary aliphatic or aromatic amine.
  • the reaction of the amine with the ester function of the CFRP polymer is typically conducted at elevated temperatures of 70-200° C., optionally in presence of catalysts. In a preferred process, the resulting alcohol is removed during the amidation reaction by distillation.
  • the amine has a high boiling point or boiling range of above 100° C.
  • Typical amines are primary aliphatic or aromatic amines with up to 36 carbon atoms, linear, branched or cyclic.
  • the amine may contain heteroatoms O or N.
  • oligomers and macroamines with a single primary amine and molecular weights of up to 5000.
  • Typical examples are primary amine end-functional alkoxylates.
  • Especially preferred are also primary amines containing other polar groups like ether, ester and amide groups.
  • An ⁇ is a anion of a monovalent organic or inorganic acid; Me is a monovalent metal atom or the ammonium ion. Z is oxygen or sulfur (claim 10 ).
  • R b as C 2 -C 100 alkoxy interrupted by at least one O atom are of formula
  • R c is C 1 -C 25 alkyl, phenyl or phenyl substituted by C 1 -C 18 alkyl
  • R d is hydrogen or methyl
  • v is a number from 1 to 50.
  • These monomers are for example derived from non ionic surfactants by acrylation of the corresponding alkoxylated alcohols or phenols.
  • the repeating units may be derived from ethylene oxide, propylene oxide or mixtures of both.
  • An ⁇ wherein An ⁇ and R a have the meaning as defined above and R a is methyl, benzyl or benzoylbenzyl.
  • An ⁇ is preferably Cl ⁇ , Br ⁇ or ⁇ O 3 S—O—CH 3 .
  • Me + is an alkali metal cation or the ammonium cation.
  • Useful are also silicone functional (meth)acrylates.
  • R a is hydrogen or methyl
  • R b is NH 2 , gycidyl, unsubstituted or with hydroxy substituted C 1 -C 4 alkoxy, unsubstituted C 1 -C 4 alkylamino, di(C 1 -C 4 alkyl)amino, hydroxy-substituted C 1 -C 4 alkylamino or hydroxy-substituted di(C 1 -C 4 alkyl)amino
  • Z is oxygen.
  • the ethylenically unsaturated monomer is selected from the group consisting of ethylene, propylene, n-butylene, i-butylene, styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride, (alkyl)acrylic acid-anhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters, (alkyl)acrylonitriles, (alkyl)acrylamides, vinyl halides or vinylidene halides.
  • the ethylenically unsaturated monomer is styrene, substituted styrene, methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert. butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate, dimethylaminoethylacrylate, methyl(meth)acrylate, ethyl-(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth) acrylate, dimethylaminoethyl(meth)acrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide or dimethylaminopropyl-methacrylamide.
  • Very suitable monomers are for example styrene, C 1 -C 8 alkylesters of acrylic or methacrylic acid, such as n-butylacrylate or methacrylate, acrylonitrile or methacrylonitrile, in particular styrene, acrylonitrile and n-butylacrylate.
  • R a is hydrogen or C 1 -C 4 alkyl
  • R b is NH 2 , O ⁇ (Me + ), glycidyl, unsubstituted C 1 -C 18 alkoxy, C 2 -C 100 alkoxy interrupted by at least one N and/or O atom, or hydroxy-substituted C 1 -C 18 alkoxy, unsubstituted C 1 -C 18 alkylamino, di(C 1 -C 18 alkyl)amino, hydroxy-substituted C 1 -C 18 alkylamino or hydroxy-substituted di(C 1 -C 18 alkyl)amino, —O—CH 2 —CH 2 —N(CH 3 ) or —O—CH 2 —CH 2 N + H(CH 3 ) 2 An ⁇ ; An ⁇ is a anion of a monovalent organic or inorganic acid; Me is a monovalent metal atom or the ammonium
  • All possible polymer chain structures are comprised: e.g. linear or branched. If the monomers are selected from chemically different monomers, all possible monomer sequence structures are comprised, e.g. random-, blocklike, multiblock-, tapered- or gradient arrangement of the different monomers.
  • block copolymers which are prepared in such a way, that the intersection between the two blocks is not a sharp boundary, but represents a continuous transition from one type of monomer to another type of monomer, i.e. both monomers extending to both blocks.
  • This type of polymers can be obtained when the polymerization process is carried out for example in one step using monomers of different copolymerization parameters or by a multistep procedure, in which the monomer composition is stepwise changed by addition of appropriate amounts of another type of monomer.
  • Another preferred procedure for the synthesis of gradient polymers is by using continuous feed processes, in which for example the controlled polymerization is started with a first monomer and before complete conversion, a second monomer is continuously fed to the reaction mixture, thus realizing a continuous transition along the polymer chains.
  • the monomer or monomer mixture of the first radical polymerization contains from 50 to 100% by weight based on total monomers of a C 1 -C 4 alkyl or hydroxyalkyl ester of acrylic or methacrylic acid and the second radical polymerization contains a monomer or monomer mixture possessing no primary or secondary ester bond.
  • Suitable monomers for the second radical polymerization do not react in the postmodification reaction, such as vinyl aromatic monomers or vinyl-aza-heterocycles.
  • Examples are 4-vinyl-pyridine(pyridinium-ion), 2-vinyl-pyridine(pyridinium-ion), vinyl-imida-zole(imidazolinium-ion), dimethylacrylamide, acrylnitrile, 3-dimethylaminopropylmethacrylamide, styrene or substituted styrenes.
  • the monomer or monomer mixture contains from 50 to 100% by weight based on total monomers of a C 1 -C 6 alkyl or hydroxyalkyl ester of acrylic or methacrylic acid and in the second polymerization the ethylenically unsaturated monomer is 4-vinyl-pyridine or pyridinium-ion, 2-vinyl-pyridine or pyridinium-ion, vinyl-imidazole or imidazolinium-ion, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, ⁇ -methyl styrene, ⁇ -methyl styrene or p-tert-butyl-styrene.
  • the monomers of the controlled polymer prepared according to a first step a1) or a2) contain aminic or acid groups, is than modified in a second step by a transesterification reaction, an amidation, hydrolysis or anhydride modification and thereafter the aminic or acid groups of the modified controlled polymer are converted to salt structures by reaction with a salt forming component.
  • Typical salt forming components for amino groups are for example organic or inorganic acids or alkylhalogenides, especially such salt forming components, which are based on organic cyclic acids or cyclic alkylhalogenides.
  • Typical examples of such salt forming components are described in EP 1275689 (Ciba) and WO 03/046029 (Ciba)
  • Typical salt forming components for acid groups on the modified controlled polymer are inorganic bases, such as NaOH, KOH, NH4OH or volatile aminoalcohols, such as 2-di-methylaminoethanol or 2-amino-2-methylpropanol (AMP), which are frequently used in coatings.
  • inorganic bases such as NaOH, KOH, NH4OH or volatile aminoalcohols, such as 2-di-methylaminoethanol or 2-amino-2-methylpropanol (AMP), which are frequently used in coatings.
  • the polymer or copolymer shows a good solubility at low temperatures and a decreasing solubility at high temperatures. This effect is for example described by Hammouda, B.; Ho, D.; Kline, S in Macromolecules (2002), 35(22), 8578-8585).
  • the process is carried out such, that the resulting polymer shows a lower critical solution temperature in water or water rich solvent mixtures.
  • modified polymers with an LCST temperature range at 20% polymer by weight based on the water or water mixture between 25° C. and 80° C.
  • Polymeric pigment dispersants are an essential part, particularly of new waterbased formulation technology.
  • the controlled free radical polymerisation (CFRP) is a tool to tailor the microstructure of polymers (e.g. block-copolymers) in a way that is favorable for the dispersion and stabilization of pigments in the millbase.
  • CFRP controlled free radical polymerisation
  • the combination of CFRP with subsequent postmodification of the stabilizing block allows enlarging the possible groups that can be used in pigment dispersants.
  • Another aspect of the invention is a polymer or copolymer obtainable in a process as described above. (Claim 16 ). As outlined on page 2 of the description the process according to claim 1 provides polymers with distinct structural differences compared to polymers with same monomer composition, but synthesized directly from corresponding monomers without post-transesterification.
  • a further aspect of the invention is a pigment concentrate comprising
  • Pigments may be organic or inorganic and are, for example, from the 1-aminoanthraquinone, anthanthrone, anthrapyrimidine, azo, azomethine, quinacridone, quinacridonequinone, quinophthalone, dioxazine, diketopyrrolopyrrole, flavanthrone, indanthrone, isoindoline, isoindolinone, isoviolanthrone, perinone, perylene, phthalocyanine, pyranthrone or thioindigo series, including those, where applicable, in the form of metal complexes or lakes.
  • Azos may be, for example, mono- or dis-azo pigments from any known sub-class, obtainable, for example, by coupling, condensation or lake formation.
  • organic pigments include Colour Index Pigment Yellow 3, 12, 13, 14, 17, 24, 34, 42, 53, 62, 74, 83, 93, 95, 108, 109, 110, 111, 119, 123, 128, 129, 139, 147, 150, 164, 168, 173, 174, 184, 188, 191, 191:1, 193, 199, Pigment Orange 5, 13, 16, 34, 40, 43, 48, 49, 51, 61, 64, 71, 73, Pigment Red 2, 4, 5, 23, 48:1, 48:2, 48:3, 48:4, 52:2, 53:1, 57, 57:1, 88, 89, 101, 104, 112, 122, 144, 146, 149, 166, 168, 177, 178, 179, 181, 184, 190, 192, 194, 202, 204, 206, 207, 209, 214, 216, 220, 221, 222, 224, 226, 254, 255, 262,
  • phthalocyanine pigments Preference is given to phthalocyanine pigments, azobenzimidazolone, disazo and polycyclic pigments and also to isoindolinones, perylenes carbon black and diketopyrrolopyrroles.
  • the pigment being a quinacridone, dioxazine, perylene, diketopyrrolopyrrole or disazo condensation pigment.
  • Quinacridones are preferably prepared by oxidation of dihydroquinacridones using hydrogen peroxide, as described, for example, in U.S. Pat. No. 5,840,901 or WO-02/077104.
  • the pigments may be single chemical compounds or mixtures of a plurality of components, including solid solutions or mixed crystals containing a plurality of chemical compounds. Preference is given to uniformly crystalline pigments as they usually yield greater color saturation than physical mixtures and mixed phases. If duller shades are nevertheless desired in the final application, this may be achieved by toning down with colorants of different color in a manner known per se.
  • the pigment concentrate may contain additional solvents, in particular water.
  • composition comprising
  • thermoplastic a thermoplastic, a chemically or structurally crosslinked polymer and b) a polymer or copolymer prepared according to the process of claim 1 or 4 .
  • component a) is a film forming binder material.
  • component a) is a film forming binder material.
  • laim 20 is a film forming binder material.
  • the above composition contains in addition an organic or inorganic pigment or mixtures thereof. (Claim 21 )
  • Film forming physically drying binder resins are typically derived from ⁇ , ⁇ -unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles. Examples are thermoplastic polyacrylates (TPA).
  • TPA thermoplastic polyacrylates
  • Another class is for example derived from natural polymers such as cellulose acetate or butyrate. Also suitable are physically drying alkyd resins or nitrocellulose lacquers.
  • Thermally cross linking film forming binder resins are for example those given below.
  • These resins are typically crosslinked with melamine resins or (poly)isocyanate resins and known as thermosetting acrylics.
  • cross linking alkyd resins which can be used as film forming binder resins in the present invention are the conventional stoving lacquers which are used in particular for coating automobiles (automobile finishing lacquers), for example lacquers based on alkyd/melamine resins and alkyd/acrylic/melamine resins (see H. Wagner and H. F. Sarx, “Lackkunstharze” (1977), pages 99-123).
  • Other crosslinking agents include glycouril resins, blocked isocyanates or epoxy resins.
  • the coating compositions may be applied on wood, metal or plastic substrates.
  • the instant coating compositions are particularly suitable both for metal finish coatings and solid shade finishes of automobiles, especially in the case of retouching finishes, as well as various coil coating applications.
  • the coating compositions in accordance with the invention are preferably applied in the conventional manner by two methods, either by the single-coat method or by the two-coat method. In the latter method, a pigment-containing base coat is applied first and then a covering coat of clear lacquer over it.
  • Powder coating composition can be prepared by reacting glycidyl methacrylate with selected alcohol components.
  • Powder coating is a known technology and is described, for example, in “Ullmann's Encyclopedia of Industrial Chemistry, Fifth, Completely Revised Edition, Volume A 18”, pages 438 to 444 (1991).
  • a powder is generally fluidized with supply of air, electrostatically charged and applied to an earthed, preferably metallic substrate.
  • the substrate is subsequently heated, in the course of which the adhering powder melts, coalesces and forms a coherent film on the metal surface. Since powder coating requires no solvent, this technology is especially friendly to the environment.
  • thermoplastic or stovable, crosslinkable polymers which are applied in powder form to predominantly metallic substrates.
  • the manner in which the powder is brought into contact with the workpiece to be coated characterizes the various application techniques, for example electrostatic powder spraying with corona or triboelectric pistols, electrostatic fluidized-bed sintering or by using magnetic brush technology.
  • organic film-forming binders for powder coatings are stoving systems based on, for example, epoxy resins, polyester-hydroxyalkylamides, polyester-glycolurils, epoxypolyester resins, polyester-triglycidyl isocyanurates, hydroxy-functional polyester-blocked polyisocyanates, hydroxy-functional polyester-uretdiones, acrylate resins with hardener or mixtures of such resins.
  • film-forming binders having thermoplastic properties for example polyethylene, polypropylene, polyamides, polyvinyl chlorides, polyvinylidene dichloride or polyvinylidene difluoride.
  • inventive compositions containing the modified controlled polymers as dispersants or rheology modifiers also comprise coating related applications outside paints, like for example printing inks, ink jet inks, liquid colorants for plastics, casting resins, gel coats, filled unsaturated polyester resins like SMC or BMC (sheet molding compounds, bulk molding compounds) or gel coats and also comprise compositions for electronic applications like pigment dispersions for color filters.
  • coating related applications outside paints like for example printing inks, ink jet inks, liquid colorants for plastics, casting resins, gel coats, filled unsaturated polyester resins like SMC or BMC (sheet molding compounds, bulk molding compounds) or gel coats and also comprise compositions for electronic applications like pigment dispersions for color filters.
  • thermoplastic or structurally crosslinked polymers wherein the instant dispersants or rheology modifiers, for example, together with pigments are useful are given below.
  • Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
  • Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
  • Homopolymers and copolymers from 1.)-4.) may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stepreoblock polymers are also included. 6a.
  • Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/butadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of sty
  • 6b Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6.), especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
  • PCHE polycyclohexylethylene
  • PVCH polyvinylcyclohexane
  • 6c Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6a.).
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Graft copolymers of vinyl aromatic monomers such as styrene or ⁇ -methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; st
  • Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
  • halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated
  • Polymers derived from ⁇ , ⁇ -unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
  • Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
  • acrylonitrile/butadiene copolymers for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl
  • Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
  • Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS. 14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides. 15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof. 16.
  • Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g.
  • polyethylene glycol polypropylene glycol or polytetramethylene glycol
  • polyamides or copolyamides modified with EPDM or ABS polyamides condensed during processing (RIM polyamide systems).
  • Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS. 19. Polycarbonates and polyester carbonates.
  • Monomers butylacrylate (BA), hydroxyethylacrylate (HEA), hydroxypropylacrylate (HPA) 4-vinyl-pyridine (4-VP).
  • Modification agents cyclohexylacid anhydride (CHAA), succinic acid anhydride (SAA), methoxy-poly-ethyleneglycole (MPEG 550-OH), HCl, NaOH.
  • Solvents methoxypropylacetate (MPA), Xylene, methoxypropanol (MP), polystyrene (PS), tetrahydrofurane (THF), polyethyleneoxide (POE/PEG).
  • initiator is 2-bromoethylpropionate (MBP)
  • the catalyst is CuBr/CuBr 2
  • the ligand is N,N,N′,N′′,N′′-pentamethyldiethyltriamine (PMDETA).
  • NOR Initiator/regulator is compound O1
  • n-Butylacrylate (n-BA, 128.17 g/mol), 8.55 g compound O1 (317.48 g/mol) and 122.139 of MPA were added, three times degassed with N 2 /vacuum and polymerized at 135° C. under N 2 until a conversion of around 8 mol % is reached. 338.89 g of n-BA is slowly added to the reaction with the dropping funnel and polymerized at 135° C. under N 2 until a conversion of around 48 mol %. Residual monomers and solvents were distilled of at 80° C. and 12 mbar.
  • the degree of polymerization is 75.
  • LCST lower critical solution temperature
  • a 35 wt % solution of the endproduct polymer in water is a clear solution at room temperature, but becomes turbid at elevated temperatures above 70° C.
  • the resulting polymer also formed clear 10 wt % solutions in following organic solvents: butyl acetate, methoxypropylacetate, methoxypropanol, butylglycol and xylene.
  • the 50 wt % solids solution in water displays an LCST of 67° C.
  • the polymer A6 gives clear solutions 10 wt % in following organic solvents: butyl acetate, methoxypropylacetate, methoxypropanol, butylglycol and xylene.
  • organic solvents butyl acetate, methoxypropylacetate, methoxypropanol, butylglycol and xylene.
  • pigment dispersant part of the polymer A6 was dissolved in water to give a clear 50 wt % solids solution, other parts of the polymer were dissolved in various other organic solvents.
  • the 50 wt % solids solution in water displays an LCST of 70° C.
  • the MPA was distilled under reduced pressure before adding 0.28 g catalyst solution (Ti(AcAc)2(iOPr)2 Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol).
  • 0.28 g catalyst solution Ti(AcAc)2(iOPr)2 Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol.
  • the transesterification was started by slowly distilling off n-Butanol under reduced pressure and increasing the temperature to 145° C. Two additional portions each of 0.28 g catalyst solution were added after 1 h and 2 h later. After 4 h total reaction time the transesterification was terminated after no further n-butanol formation was observed.
  • the resultant very high viscous block copolymer was diluted with MPA to a clear 60 wt % solution.
  • the transesterification was started by slowly distilling off n-Butanol under reduced pressure and increasing the temperature to 145° C. Two additional portions each of 0.15 g catalyst solution were added after 2 h and 4 h later. After 6 h total reaction time the reaction was terminated after no further n-butanol formation was observed.
  • the resultant high viscous block copolymer was diluted with MPA to a clear 60 wt % solution.
  • the transesterification was started by slowly distilling off n-Butanol under reduced pressure and increasing the temperature to 145° C. Two additional portions each of 0.15 g catalyst solution were added after 2 h and 4 h later. After 6 h total reaction time the reaction was terminated after no further n-butanol formation was observed.
  • the transesterification was started by slowly distilling off n-Butanol under reduced pressure and increasing the temperature to 145° C. Two additional portions each of 0.15 g catalyst solution were added after 2 h and 4 h later. After 6 h total reaction time the reaction was terminated after no further n-butanol formation was observed.
  • the transesterification was started by slowly distilling off n-Butanol under reduced pressure and increasing the temperature to 145° C. Two additional portions each of 0.43 g catalyst solution were added after 2 h and 4 h later. After 6 h total reaction time the reaction was terminated after no-further n-butanol formation was observed.
  • Resin free organic pigment concentrate based on the inventive pigment dispersants and Irgalite Blue PG were prepared according to the following Table 1.
  • the organic pigment concentrates from Table 1 are ground for 3 hours with glass beads (2 mm/mb) in a Scandex shaking equipment.
  • the pigment concentrates based on Irgalite Blue PG are then let down to full tone paints by mixing for 12 h on a roll mill according to the following table.
  • Viscosity of pigment concentrate and full tone transparency of dry full tone and gloss at 20° after letdown is measured.
  • the powder coating composition is based on a carboxy-functional polyester, components 1 to 6 (formulation containing the levelling agent) as indicated in Table 1.
  • the components are mixed using a planetary stirrer.
  • the mixture is then extruded on a prism extruder at 300 revolutions/minute at 110° C. and is rolled out.
  • the powder coating composition is coarsely comminuted using a bench cutter and is ground in a Retsch ZM-1 ultracentrifugal mill with a 0.75 mm annular-perforation screen at 15,000 revolutions/minute.
  • the powder is passed through a 125 ⁇ m sieve on a centrifugal sieving machine having an average particle size of from 30 to 50 ⁇ m.
  • the finished powder coating composition is sprayed electrostatically to a coat thickness of 70 to 80 ⁇ m onto aluminium panels using an ESB-Wagner corona cup gun at 60 kV.
  • the coated panels are cured in an electric oven at 200° C. for 10 minutes.
  • Levelling agent 7.0 f 3.5 g) Total: 1000 1010 a) Almatex ® PD7610 from Anderson, USA b) Dodecanedioic acid from DuPont, Germany c) Tinuvin ® 144 from Ciba Specialty Chemicals, Basel, Switzerland d) Tinuvin ® 405 from Ciba Specialty Chemicals, Basel, Switzerland e) Benzoin f) Additol ® XL 490 from UCB Surface Specialties, USA g) A17
  • inventive block copolymer A17 shows comparable performance at lower dosage compared to a commercial benchmark levelling agent.
  • inventive block copolymer A17 has a solid 100% active product form, which is more convenient in handling and what offers significant advantages in production of powder paints.
  • Usual commercial polyacrylate levelling agents are either liquid or sticky resins or are adsorbed on solid silica carrier.
  • polyacrylate pigment dispersants are not fully soluble in non-polar solvents like pure aliphatic hydrocarbons.
  • the solubility of the inventive copolymers was tested in an aliphatic hydrocarbon solvent Shell Catenex 925, which serves as a model for extreme non-polar formulations.
  • inventive copolymers A11, A13 and A15 showed full solubility. This is in contrast to typical commercial polyacrylate dispersants like Efka-4401, which was tested in comparison and formed turbid inhomogeneous mixture.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerization Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)
US11/794,707 2005-01-11 2006-01-02 Process for the Post-Modification of Homo and Copolymers Prepared by Controlled Free Radical Polymerization Processes Abandoned US20090221739A1 (en)

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KR101322668B1 (ko) 2013-10-30
CN100577692C (zh) 2010-01-06
RU2401281C2 (ru) 2010-10-10
EP1861429A1 (en) 2007-12-05
US20110224375A1 (en) 2011-09-15
JP5225689B2 (ja) 2013-07-03
RU2007130535A (ru) 2009-02-20
JP2008527130A (ja) 2008-07-24
US8658741B2 (en) 2014-02-25
KR20070099646A (ko) 2007-10-09
CN101103049A (zh) 2008-01-09
US20130059964A1 (en) 2013-03-07
WO2006074969A1 (en) 2006-07-20
EP1861429B1 (en) 2013-03-13
BRPI0606305A2 (pt) 2009-06-16

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