EP1606329A1 - Procede pour la preparation de resine modifiee par des silanes - Google Patents

Procede pour la preparation de resine modifiee par des silanes

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Publication number
EP1606329A1
EP1606329A1 EP04723551A EP04723551A EP1606329A1 EP 1606329 A1 EP1606329 A1 EP 1606329A1 EP 04723551 A EP04723551 A EP 04723551A EP 04723551 A EP04723551 A EP 04723551A EP 1606329 A1 EP1606329 A1 EP 1606329A1
Authority
EP
European Patent Office
Prior art keywords
acid
acetoxy
group
process according
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04723551A
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German (de)
English (en)
Inventor
Michel Gillard
Marcel Vos
Mark Plehiers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PPG BV
Original Assignee
Sigmakalon BV
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Filing date
Publication date
Application filed by Sigmakalon BV filed Critical Sigmakalon BV
Priority to EP04723551A priority Critical patent/EP1606329A1/fr
Publication of EP1606329A1 publication Critical patent/EP1606329A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • 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
    • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
    • 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
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages

Definitions

  • the invention relates to a new method for the preparation of acid group containing polymers, in particular, polymers having acid groups in the side chain thereof.
  • the invention also relates to the modification of the acid groups via a transesterification reaction with an acyloxy silane.
  • the invention described herein extends to the reaction of acid-functional polymers with polyacyloxysilanes to prepare new hydrolysable binders for antifouling paints without the need to start from expensive monomers .
  • the invention also extends to the new hydrolysable binders so prepared.
  • the invention relates to the use of such silylated polymers in applications where the hydrolysable silyl ester groups are advantageous.
  • One such application is as a resin or co- resin for self-polishing antifouling paints.
  • Antifouling paints are used to prevent and delay the fouling of underwater structures (e.g. ships' bottom, docks, fishnets, and buoys) by various marine organisms such as shells, seaweed, and aquatic bacteria.
  • underwater structures e.g. ships' bottom, docks, fishnets, and buoys
  • marine organisms such as shells, seaweed, and aquatic bacteria.
  • the surface roughness of the whole ship may be increased to induce decrease of velocity of the ship or increase of fuel consumption.
  • removal of such aquatic organisms from the ship's bottom needs much labour and a long period of working time.
  • these organisms adhere and propagate on an underwater structure such as a steel structure they deteriorate their anticorrosive coating films leading to a reducing of the lifetime of the underwater structure.
  • Underwater structures are therefore coated with antifouling paint employing polymers containing various hydrolysable groups and more specifically organosilyl groups .
  • silyl polymers used for antifouling paints are produced from silylated monomers.
  • the polymers used in the above-described antifouling paints are based on silylated carboxylate monomers .
  • Polyacyloxysiloxanes are disclosed in US 4 892 907 where they are used as cross-linking agents.
  • Cross-linking of silylated acid polymers is highly undesirable in antifouling paints as this leads to gelation of the composition.
  • JP 5306290 A describes a process to obtain a methacrylic functional group-containing organosilicon compound.
  • the process comprises reacting methacrylic acid with a halogenoalkylsilane (e.g. trialkylsilylchloride) in the presence of a tertiary amine compound having a cyclic structure.
  • a halogenoalkylsilane e.g. trialkylsilylchloride
  • This process has disadvantages such as the reduced availability and storage stability of the silyl chloride.
  • the reaction yields as a by-product a hydrogen halide (which provokes the corrosion of the production equipment) or a halide salt (which has to be removed by filtration) .
  • JP 10195084 A discloses the reaction of unsaturated carboxylic acid such as acrylic acid or methacrylic acid with a trialkylsilylhydride compound in the presence of a copper catalyst.
  • unsaturated carboxylic acid such as acrylic acid or methacrylic acid
  • a trialkylsilylhydride compound in the presence of a copper catalyst.
  • One of the disadvantages of this method is the risk of hydrogenation of the unsaturated carboxylic acid due to a side reaction of the produced H2 on the carbon-carbon double bond.
  • Trialkylsilylcarboxylates of aliphatic carboxylic acids can be obtained by transesterification.
  • H.H. Anderson et al . describe in J.Org.Chem 1716 (1953) the reactions of triethyl silyl acetates with halogenated propionic acids and in J.Org. Che . 1296 (1954) the reactions of trifluoro silyl acetates or propionates with chloroacetic acid; they distil the acetic or propionic acid under reduced pressure.
  • JP 95070152 A discloses reactions of trialkylsilylacetates with C6 to C30 carboxylic acids (e.g. palmitic, myristic, benzoic,...) ; the acetic acid is distilled under reduced pressure or azeotropically with hexane .
  • EP 0204456EP 0342276 disclose the production of metal salts of acid group containing base resins.
  • the salts must be polyorganic salt types and undergo a transesterification of the metal ester groups with a high boiling acid to produce the metal high boiling carboxylate salt of the polymer.
  • the acid groups in the side chains of the polymer may be selected from carboxylic acid, sulphonic acid or phosphoric acid groups.
  • the acid groups are carboxylic acid groups.
  • the organic acid is used as a co-solvent with a further solvent.
  • the said further solvent may be selected to improve the solubility of the non-polar parts of the polymer.
  • the organic acid solvent is an effectively saturated organic acid solvent in the sense that it has no ethylenic unsaturation capable of effecting copolymerisation with the monomer of step (i) under the polymerisation conditions employed, more preferably, the organic acid solvent has no ethylenic unsaturation.
  • the organic acid solvent remains incorporated into the polymer resin solution after step (ii) to assist solubility of the acid polymer and preferably, forms at least a co-solvent for the said acid polymer at the start of a subsequent reaction such as a silylation reaction.
  • the use of the organic acid solvent not only assists the solubility of the acid monomer and acid polymer but is also chosen to be compatible with the products of a subsequent acid polymer reaction, such as a silylation reaction, by not interfering with the reaction process and/or participating in the process.
  • a subsequent acid polymer reaction such as a silylation reaction
  • a low boiling acid solvent can be easily removed by a suitable technique such as distillation during a subsequent acid polymer reaction such as a silylation reaction and the high boiling acid may be removed by reaction with unreacted acyloxy groups and the like on a group which has been reacted with the acid groups of the polymer such as the silicon during polyacyloxysilylation.
  • the low boiling acid solvent is selected to be removeable with, optionally miscible with, more preferably, identical with the acid of a leaving acyloxy group product and the like of a subsequent acid polymer reaction such as the acyloxy group of the silylester in a subsequent monoacyloxysilylation reaction and a high boiling acid is selected to be capable of a transesterification reaction with acyloxy leaving groups and the like on a group which has been reacted with the acid groups of the polymer such as unreacted acyloxy leaving groups during subsequent polyacyloxysilylation reactions of the acid polymer.
  • a subsequent acid polymer reaction such as the acyloxy group of the silylester in a subsequent monoacyloxysilylation reaction
  • a high boiling acid is selected to be capable of a transesterification reaction with acyloxy leaving groups and the like on a group which has been reacted with the acid groups of the polymer such as unreacted acyloxy leaving groups during subsequent polyacyloxysilylation reactions of
  • the said polymer resin acid groups may be silylated in a subsequent step.
  • the silylation is carried out by transesterification of a silyl ester with the acid groups to produce protected silylester side chains on the polymer and the acid of the ester group from the initial silyl ester.
  • the silylation is carried out whilst removing the acid of the initial ester group.
  • the ester of the silylating agent is selected so as to form a low boiling acid as a by product of the silylation reaction which can then be removed from the system by a suitable technique such as thermal decomposition, vacuum distillation, azeotropic distillation with water or an organic solvent.
  • the preferred removal technique is distillation. This may be via a low boiling azeotrope with an organic solvent or by direct distillation of the acid.
  • the said solvent comprises at least one high boiling organic acid.
  • use of a high boiling acid solvent in the subsequent acid polymer silylation reaction with polyacyloxysilanes prevents cross-linking - via the unused acyloxy sites on the reacted silicon and an acid group of a neighbouring polymer chain - by a transesterification reaction of the organic acid solvent with the silyl acyloxy group.
  • the silyl acyloxy group forms its complimentary acid during silylation of the acid group on the polymer or during reaction with the high boiling acid solvent .
  • the presence of high boiling organic, preferably, carboxylic acid solvents will be required in case of reactions with polyacyloxysilanes in order to prevent crosslinking which would lead to gel formation.
  • the preferred resin solvent comprises a low boiling acid which can be removed during the said subsequent silylation reaction together with the acid formed by the silylation reaction.
  • the solubility of the acid polymer is improved.
  • the organic acid so introduced may be chosen to be compatible with the reactants in a subsequent reaction such as with the mono or polyacyloxysilyesters used in a subsequent acid polymer silylation reaction to avoid unwanted side reactions.
  • the organic acid in the solvent is chosen to be the acid complement of the acyloxy group if subsequent monoacyloxysilylation of the polymer resin is required. In this way, the removal of the solvent acid and organic acid from the transesterification can take place simultaneously without the requirement for a pre-removal of acid step.
  • the number of acid groups in the acid polymer is not restricted. However, cross-linking reactions are more likely where the polymer acid content is high during polyacyloxysilylation so the content of high boiling organic acid in such cases may be chosen to restrict cross-linking and subsequent gelation.
  • low boiling is used to contrast with “high boiling” and vice versa and the terms should not be taken as a restriction on the boiling point of the organic acid solvent.
  • the term should be taken to be a comparison with the acyloxy leaving group of the silyl ester to be used in the subsequent silylation reaction so that a "high” boiling organic acid may be taken to be one that boils at a higher temperature than the acid of the acyloxy leaving group of a silyl ester in a subsequent acid polymer silylation reaction with a polyacyloxy silane compound whereas "low" boiling organic acid should be taken as a reference to an organic acid having the same or similar boiling point as the acyloxy leaving group or one which forms a low boiling azeotrope therewith ie one that can be convenientely removed during a subsequent silylation reaction.
  • the pre-polymerisation composition comprises other monomers as required to give the final polymer with the required characteristics including the required frequency of acid groups along the polymer backbone .
  • vinyl acids such as alkacrylic acids and acrylic acid can be copolymerised with suitable alkyl alkacrylates such as methyl methacrylate and alkyl acrylates such as ethyl and butyl acrylate .
  • suitable alkyl alkacrylates such as methyl methacrylate and alkyl acrylates such as ethyl and butyl acrylate .
  • the introduction of acid groups into polymers are known to those skilled in the art.
  • the boiling point of the organic acid is between 0°C - 220°C, more preferably, 60°C - 190°C, most preferably, 110°C-160°C.
  • the boiling point of a low boiling acid is in a range which allows it to be removed from the system under conditions which do not cause decomposition of the reactants or products.
  • the low boiling acid should be removable from the system below the decomposition temperature of the silyl ester or the silylated polymer.
  • the low boiling acid has a boiling point in the range 0°C - 200°C, more preferably, 60°C - 170°C, most preferably, 110°C-140°C.
  • the boiling point of a high boiling acid is at least 15°C higher than the corresponding low boiling acid, more preferably, at least 20°C higher, most preferably, at least 25°C higher.
  • the boiling point of the high boiling acid is in the range 20°C - 220°C, more preferably, 80°C - 190°C, most preferably, 130°C-160°C.
  • Suitable organic acid solvents may be selected from acetic acid, enanthic acid, cyclohexane carboxylic acid, propionic acid, glycolic acid, acrylic acid, methacrylic acid, benzoic acid, salicylic acid, 3, 5-dichlorobenzoic acid, lauric acid, stearic acid, nitrobenzoic acid, linoleic acid, ricinoleic acid, oxalic acid, lactic acid, pivalic acid, valeric acid, dimethyl acetic acid, 12- hydroxy stearic acid, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pulvic acid, abietic acid (Rosin®) , dehydroabietic acid, dihydroabietic acid, fully hydrogenated abietic acid (Foral®) , mercaptobenzothiazole, O-cresotinic acid, naphthol-1-carboxylic acid, p-phenyl benzen
  • the effectively saturated (ie. without ethylenic unsaturation capable of effecting copolymerisation with the monomer of step (i) under the polymerisation conditions) acids of the aforementioned acids are selected, more preferably, the acids without any ethylenic unsaturation, most preferably, the carboxylic acids without any ethylenic unsaturation.
  • the low boiling organic acid solvents may be independently selected from one or more of acetic acid, propionic acid, oxalic acid, lactic acid, pivalic acid, valeric acid, dimethyl acetic acid, enanthic acid, cyclohexane carboxylic acid, propionic acid, glycolic acid, acrylic acid, methacrylic acid and the like or their sulfonic acid or phosphoric acid equivalents.
  • the effectively saturated ie.
  • acids of the aforementioned acids are selected, more preferably, the acids without any ethylenic unsaturation, most preferably, the carboxylic acids without any ethylenic unsaturation.
  • the high boiling organic monobasic acid solvent may be selected to have fungicidal or antifouling properties .
  • the organic acids include aliphatic, aromatic, alicyclic and heterocyclic organic acids .
  • Typical examples of the high boiling acid solvents include acetic acid, propionic acid, butyric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isobutyric acid, sec-butyric acid, octanoic acid, isooctanoic acid, nonanoic acid, isononanoic acid, benzoic acid, salicylic acid, 3,5- dichlorobenzoic acid, lauric acid, stearic acid, nitrobenzoic acid, linoleic acid, ricinoleic acid, 12- hydroxy stearic acid, fluoroacetic acid, difluoracetic acid, trifluoroacetic acid, pulvic acid,
  • Rosin dehydroabietic acid, fully hydrogenated abietic acid (Foral®) , abietic dirtier acid, dihydroabietic acid, mercaptobenzothiazole, O-cresotinic acid, naphthol-1- carboxylic acid, p-phenyl benzene sulfonic acid, p-oxy- benzoic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, naphthenic acid, anthracenic acid, beta -naphthalene sulfonic acid, naphthol-1-sulfonic acid, 5-chloro- alpha , alpha -bis (3, 5-dichloro-2-hydroxy phenyl) toluene sulfonic acid, p-phenyl benzoic acid, p- toluene sulfonic acid, p-benzene chlorosulfonic acid, dimethyl dithio carbamic acid, dieth
  • the effectively saturated (ie. without ethylenic unsaturation capable of effecting copolymerisation with the monomer of step (i) under the polymerisation conditions employed) acids of the aforementioned acids are selected, more preferably, the acids without ethylenic unsaturation, most preferably, the carboxylic acids without ethylenic unsaturation, more especially an abietic acid or derivative thereof, most especially fully hydrogenated abietic acid.
  • a more typical list of said high boiling acid solvents include benzoic acid, salicylic acid, 3, 5-dichlorobenzoic acid, lauric acid, stearic acid, nitrobenzoic acid, linoleic acid, ricinoleic acid, 12-hydroxy stearic acid, fluoroacetic acid, difluoracetic acid, trifluoroacetic acid, pulvic acid, abietic acid (Rosin) , dehydroabietic acid, fully hydrogenated abietic acid (Foral®) , abietic dimer acid, dihydroabietic acid, mercaptobenzothiazole, 0- cresotinic acid, naphthol-1-carboxylic acid, p-phenyl benzene sulfonic acid, p-oxy-benzoic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, naphthenic acid, anthracenic acid, beta -naphthalene sulf
  • the effectively saturated (ie. without ethylenic unsaturation capable of effecting copolymerisation with the monomer of step (i) under the polymerisation conditions employed) acids of the aforementioned acids are selected, more preferably, the acids without ethylenic unsaturation, most preferably, the carboxylic acids without ethylenic unsaturation, more especially an abietic acid or derivative thereof, most especially fully hydrogenated abietic acid.
  • the reaction may be easily proceeded by merely mixing the materials and heating the mixture. At that time, it is however, necessary to continuously remove the formed low boiling organic basic acid out of the system by, for example, thermal decomposition, vacuum distillation, azeotropic distillation with water or an organic solvent and the like.
  • the acid group containing polymer may be any suitable coating polymer having acid groups on the side chains thereof.
  • the acid group containing polymers obtained by the process of the invention can be homo or co-polymers
  • terpolymers having acid groups in the side chains such as those derived from one or more monomers such as: vinyl monomers including acrylic acid, alkacrylic acids such as methacrylic acid, polyester monomers; alkyd monomers; and epoxy resin monomers.
  • vinyl monomers including acrylic acid, alkacrylic acids such as methacrylic acid, polyester monomers; alkyd monomers; and epoxy resin monomers.
  • silylated polymers and copolymers of said monomers are useful in coating or paint compositions. More preferably they are used as binders in antifouling coating compositions. When used in an antifouling coating composition, they give a film which undergoes neither cracking nor peeling and shows moderate hydrolysability to dissolve into seawater constantly at an adequate rate and which therefore exhibits excellent antifouling properties in the long term.
  • the antifouling coating compositions prepared using the polymers obtained by the process of the invention are tin- free coatings and provide an alternative to the present self-polishing coating technology based on hydrolysable tributyl tin polymers (the use of which is due to be banned in antifouling paints by 2003) .
  • the organosilylated polymers provided by the process of the invention compared to organotin compounds are less toxic, less polar, more hydrophobic and more stable.
  • the molecular weight (Mw) of the acid polymer product is preferably, in the range 2 to 1000 kD, more preferably, 3 to 500 kD, most preferably, 4 to 300 kD.
  • the polymerisation reaction is carried out using a suitable initiator.
  • Suitable initiators are known to those skilled in the art.
  • a suitable free radical initiator for polyacrylates is Vazo 67.
  • Suitable additives known to the skilled person may be added to the base resin including suitable antifouling agents, plasticizer and hydrolysis regulators, hydrolysis regulators, pigments and other additives.
  • the polymerisation reaction is carried out in the range 0°C - 200°C, more preferably, 60-170°C, most preferably, 70-140°C.
  • the weight of acid bearing side chain and/or acid terminated monomer at the start of the polymerisation reaction as compared with total monomer is in the range 0.01 - 80% w/w, more preferably, 0.1 - 30%w/w, most preferably, 0.5-25% w/w.
  • the weight of organic acid solvent expressed as a % of total solvent (ie. including co-solvent) at the start of the polymerisation reaction is in the range 1- 100% w/w, more preferably, 2- 50% w/w, most preferably, 5- 30% w/w.
  • a suitable level is selected in accordance with the level of acid monomer in the pre- polymer mix.
  • the solvent is at least 10 wt% of the total reaction mix at the start of the polymerisation reaction, more preferably, at least 20 wt%, most preferably, at least 30 wt%.
  • the solvent and hence the polymerisation reaction is substantially water free.
  • the polymerisation reaction may be carried out at atmospheric pressure although both higher and lower pressures are also possible .
  • Suitable ranges of solvent are l-99wt% of the total reaction mix, more preferably, 20-80 wt%, most preferably 30-70wt%.
  • the polymer as prepared in accordance with the invention has 20-10,000 monomer units, more preferably, 30-5,000 monomer units, most preferably 40-3,000 monomer units in the average polymer chain.
  • polymer refers to the product of a polymerisation reaction, and is inclusive of homopolymers, copolymers, terpolymers, etc.
  • copolymer refers to polymers formed by the polymerisation reaction of at least two different monomers.
  • the process may be generally described as a process for the protection of acid group containing side chains and/or terminal acid groups on polymers by reaction of at least one polymer acid group of formula (I)
  • each R 4 and R 5 may be hydroxyl or may be independently selected from alkyl, aryl, alkoxyl, aryloxyl, -L' -SiR ⁇ R 3 , -L' - (SiRR 5 L' ) n -SiR ⁇ R 3 , alkenyl, alkynyl, aralkyl or aralkyloxyl radicals optionally substituted by one or more substituents independently selected from the group comprising alkyl, alkoxyl, aralkyl, aralkyloxyl, hydroxyl, aryl, aryloxyl, halogen, amino (preferably, tertiary amino) or amino alkyl radicals, or R or R 5 may independently be an -0-C(0)-R 8 group, wherein R 8 is defined as R 7 below;
  • each R 1 , R 2 and R 3 may independently represent hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, alkoxyl, aryl, aryloxyl, aralkyl or aralkyloxyl radical optionally substituted by one or more substituents independently selected from the group comprising alkyl, alkoxyl, aralkyl, aralkyloxyl, aryl, aryloxyl, halogen, hydroxyl, amino (preferably, tertiary amino) or amino alkyl radicals, or R 1 , R 2 or R may independently be an -O-C(O)- R 8 group,
  • L' represents 0, S, or NR 6 , where R 6 is defined as is R 7 below,
  • each n independently represents a number of -Si (R 4 ) (R 5 )- L'- groups from 0 to 1000,
  • R7 is a hydrogen atom, an aralkyl, aryl, alkenyl, alkynyl, or alkyl group optionally substituted, in the case of the hydrocarbyl radicals with one or more substituents selected from the equivalent substituents as defined for R 1 , R 2 , R 3 , R 4 and R 5 above;
  • R 1 , R 2 , R 3 , R 4 , R 5 , L 1 and n are defined above except where R 1 , R 2 , R 3 , R 4 or R 5 are an -0-C(0)-R 8 group in formula II they may be replaced by an -0-C(0)-R 9 group in formula HI;
  • R 9 represents a hydrocarbyl or substituted hydrocarbyl group, wherein said substituted hydrocarbyl is substituted by one or more substituents independently selected from the group comprising alkyl, alkoxyl, aralkyl, aralkyloxyl, aryl, aryloxyl, hydroxyl, halogen, amino (preferably, tertiary amino) or amino alkyl radicals .
  • the organic acid solvent comprises an acid of formula R 7 C(0)OH when all of the radicals R 1 , R 2 , R 3 , R 4 or R 5 are not an -0-C(0)-R 8 group in formula II.
  • the organic acid solvent comprises an acid of formula HO-C(0)-R 9 when one or more of the radicals R 1 , R 2 , R 3 , R 4 or R 5 are an -0-C(0)-R 8 group in formula II.
  • the said R 9 group is the hydrocarbyl residue of a higher boiling acid relative to the boiling point of the acid of which R 8 forms the hydrocarbyl residue.
  • the residue R 8 may be the same or different than R 7 in formula II.
  • R 8 is the same as R 7 in any compound of formula II.
  • the polymer which may be represented as P 1 is a polymer having the indicated acid containing side chain or terminal group of formula I, preferably a plurality of such side chains branching at intervals along the length thereof and/or terminating the polymer chain.
  • P 1 is a polymer having more than 30 carbons in the polymer chain, more preferably, more than 50 carbons in the polymer chain, most preferably, more than 80 carbons in the polymer chain.
  • the number of carbons in the chain is calculated from the weight and/or number average molecular weight of the polymer chain.
  • the polymerisation reaction is carried out in a suitable co-solvent aswell as the organic acid.
  • the silylation may be carried out in a suitable co-solvent in addition to the organic acid.
  • Suitable co-solvents which can be used in the polymerisation or silylation reaction may be independently selected from non polar inert solvents, cyclic and non- cyclic aliphatic hydrocarbons, aromatic hydrocarbons, cyclic and non cyclic ethers, esters and the like, or the produced volatile acid (IV) in the silylation reaction and mixtures thereof.
  • Suitable co-solvents may be independently selected from pentane, cyclopentane, hexane, heptane, cyclohexane, toluene, xylene, benzene, mesitylene, ethylbenzene, octane, decane, decahydronaphthalene, diethyl ether, diisopropyl ether, diisobutyl ether and the like or mixtures thereof.
  • Especially preferred solvents are those which allow reactive distillation ie . which cause no distillation of any of the reactants but which allow preferential distillation of the produced volatile acid (IV) to drive the equilibrium to the right.
  • More especially preferred co-solvents are those which form a low boiling azeotrope with distilled R 7 -C(O)0H during silylation.
  • the co-solvents are independently selected from pentane, hexane, heptane, cyclohexane, toluene and xylene .
  • the solvent in step (i) and any subsequent reaction is at least 80% w/w comprised of one or more of the said organic acid solvent (s) and, optionally, one or more of the said co-solvent (s) , more preferably, at least 90% w/w, most preferably, the solvent in step (i) and any subsequent reaction is substantially entirely comprised of one or more of the said organic acid solvent (s) and, optionally, one or more of the said co-solvent (s) .
  • the relative proportions of solvent components may fluctuate during the reactions either as a result of additions to the reactions or removal from the reactions during the courses thereof.
  • the temperature of the reaction depends on the boiling point of any azeotrope that has to be distilled, the shape of the reactor and the height of any distillation column.
  • the silylation reaction is carried out in the range 0°C - 200°C, more preferably, 60-170°C, most preferably, 110-140°C.
  • the molar ratio of silylester : acid groups on the polymer at the start of the silylation reaction is between 1:100 and 100:1, more preferably between 10:1 and 1:10, most preferably, between 2:1 and 1:2.
  • the molar ratio of silylester : acid groups is approximately 1:1.
  • the solvent is at least 10 wt% of the total reaction mix at the start of the silylation reaction, more preferably, at least 20 wt%, most preferably, at least 30 wt% .
  • the reaction may be carried out at atmospheric pressure although both higher and lower pressures are also possible .
  • Suitable ranges of solvent are l-99wt% of the total silylation reaction mix, more preferably, 20-50 wt%, most preferably 30-40wt%.
  • R 4 and R 5 in formula (II) are each independently selected from the group comprising an alkyl group, an hydroxyl group, an alkoxyl group or an -L'- (SiR 4 RsL' ) n -SiR ⁇ R 2 R 3 group, wherein L' , Ri, R 2 , R3, R 4 and R 5 are as defined above.
  • R 1 , R 2 , R 3 , R 4 and R 5 each independently represent an alkyl group.
  • the said alkyl groups may be branched or linear.
  • Z represents C.
  • the groups R 1 and R 2 and R 3 are the same.
  • the groups R 4 and R 5 are the same.
  • R 4 or R 5 is selected as -L' - (SiRR 5 L' ) n - SiR ⁇ R 3 , the R 4 and R 5 groups attached to the silicon radical in the selected group are not themselves, -L'-
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8 each independently represent a hydrogen atom, an alkyl or an aryl group.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 7 and R 8 each independently represent an alkyl group.
  • R 9 is selected from an alkyl, an alkenyl or an aryl group.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from the group comprising methyl, ethyl, propyl, isopropyl, isobutyl, n-butyl, sec-butyl, t-butyl .
  • R 1 , R 2 , R 3 , R 4 , R 5 R 7 and R 8 are methyl .
  • R 1 , R 2 and R 3 are alkyl groups they are preferably, independently selected from the group consisting of Cl to C8 alkyl groups, preferably Cl to C4, more preferably methyl, ethyl, isopropyl and n-butyl .
  • the said alkyl groups may be branched or linear.
  • n as used herein each independently represent 0 to 500, more preferably, 1 to 100, most preferably 4 to 50. Especially preferred values for n is selected from 0, 1, 2, 3, 4 or 5.
  • each radical R or other parameter so described can be identical or different.
  • each R 4 in compound of formula (II) may be different for each value of n.
  • alkyl relates to saturated hydrocarbon radicals having straight, branched, polycyclic or cyclic moieties or combinations thereof and contains 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, yet more preferably 1 to 4 carbon atoms.
  • radicals may be independently selected from methyl, ethyl, n-propyl, isopropyl n-butyl, isobutyl, set-butyl, tert-butyl, 2-methylbutyl, pentyl, iso-amyl, hexyl, cyclohexyl, 3-methylpentyl, octyl, fully hydrogenated abietyl and the like.
  • alkenyl relates to hydrocarbon radicals having one or several double bonds, having straight, branched, polycyclic or cyclic moieties or combinations thereof and containing from 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, more preferably from 2 to 8 carbon atoms, still more preferably 2 to 6 carbon atoms, yet more preferably 2 to 4 carbon atoms.
  • alkenyl groups include vinyl, allyl, isopropenyl, pentenyl, hexenyl, heptenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, 1-propenyl, 2- butenyl, 2-methyl-2-butenyl, isoprenyl, farnesyl, geranyl, geranylgeranyl, abietyl, dihydroabietyl, abietyl dimer (Dymerex®) , and the like.
  • alkynyl relates to hydrocarbon radicals having one or several triple bonds, having straight, branched, polycyclic or cyclic moieties or combinations thereof and having from 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, more preferably from 2 to 8 carbon atoms, still more preferably from 2 to 6 carbon atoms, yet more preferably 2 to 4 carbon atoms.
  • alkynyl radicals include ethynyl, propynyl, (propargyl) , butynyl, pentynyl, hexynyl and- the like.
  • aryl as used herein, relates to an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes any monocyclic, bicyclic or polycyclic carbon ring of up to 7 members in each ring, wherein at least one ring is aromatic. Said radical may be optionally substituted with one or more substituents independently selected from alkyl, alkoxy, halogen, hydroxyl or amino radicals.
  • aryl examples include phenyl, p-tolyl, 4-methoxyphenyl, 4- (tert-butoxy) phenyl, 3-methyl-4-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 3-aminophenyl, 3-acetamidophenyl, 4- acetamidophenyl, 2-methyl-3-acetamidophenyl, 2-methyl-3- aminophenyl, 3-methyl-4-aminophenyl, 2-amino-3- methylphenyl, 2, 4-dimethyl-3-aminophenyl, 4-hydroxyphenyl, 3-methyl-4-hydroxyphenyl, 1-naphthyl, 2-naphthyl, 3-amino- 1-naphthyl, 2-methyl-3-amino-l-naphthyl, 6-amino-2- naphthyl, 4, 6-dimethoxy-2-naphthyl, t
  • aralkyl as used herein, relates to a group of the formula alkyl-aryl, in which alkyl and aryl have the same meaning as defined above.
  • aralkyl radicals include benzyl, phenethyl, dibenzylmethyl, methylphenylmethyl, 3- (2-naphthyl) -butyl, and the like.
  • Examples of the carboxyl radical part of formula (IV) may include but are not limited to formyl, acetyl, propionyl and butyryl .
  • Examples of the carboxyl radical part of formula R 9 C(0)OH may independently include but are not limited to acetyl, propionyl, butyryl, pivaloyl, oxaloyl, malonyl, succinyl, glutaryl, adipoyl, phthaloyl, isobutyroyl, sec-butyroyl, octanoyl, isooctanoyl, nonanoyl, isononanoyl, abietyl, dehydroabietyl, dihydroabietyl, naphthenyl, anthracenyl, abietyl dimer (Dymerex®) , fully hydrogenated abietyl (Foral®) , benzoyl, 3, 5-dichlorobenzoyl, lauroyl, stearyl, nitrobenzoyl, linoloyl, ricinolyl, 12-hydroxy stearyl, fluoroacetyl, difluo
  • the effectively saturated (ie. without ethylenic unsaturation capable of effecting copolymerisation with the monomer of step (i) under the polymerisation conditions employed) acids of the aforementioned acids are selected, more preferably, the acids without ethylenic unsaturation, most preferably, the carboxylic acids without ethylenic unsaturation, more especially an abietic acid or derivative thereof, most especially fully hydrogenated abietic acid.
  • organosilylated carboxylate compounds of general formula (II) include but are not limited to trimethylsilylformiate, dimethylsilyldiformiate, methylsilyltriformiate, tri-n-butyl 1-acetoxy-silane, din-butyl 1, 1-diacetoxy-silane, n-butyl 1, 1, 1-triacetoxy- silane, tri-n-propyl-1-acetoxy silane, di-n-propyl 1,1- diacetoxy-silane, n-propyl 1, 1, 1-triacetoxy-silane, tri- t-butyl-1-acetoxy-silane, tri-isopropyl-1-acetoxy-silane, tri-isobutyl-1-acetoxy-silane, tri-methyl-1-acetoxy- silane, di- methyl 1, 1-diacetoxy-silane, methyl 1,1,1- triacetoxy-silane, trie
  • Typical examples of the carboxyl part of formula II are acetyl, propionyl, butyryl.
  • R 7 and R 8 may independently be partially or totally hydrogenated alkyl, aralkyl or aryl radicals.
  • the acyloxysilanes may be partially or totally hydrogenated carboxylate compounds as defined above.
  • the halogenated carboxylates are fluorinated or chlorinated. Examples of such compounds include: trimethylsilyltrifluoroacetate and trimethylsilyltrichloroacetate .
  • the process of the invention enables the production of the organosilylated carboxylate polymers with exactly the desired number of the hydrocarbylsilyl protecting units.
  • the organosilylated carboxylate polymers obtained by the process of the invention have a number of dihydrocarbylsiloxane units (n) equal to 0.
  • the organosilylated carboxylates obtained by the process of the invention have a number of dihydrocarbylsiloxane units (n) from 1 to 200, preferably from 1 to 19, more preferably from 1 to 4.
  • reaction progress may be monitored by any suitable analytical method as well as with the determination of the amount of acid distilled.
  • the advantage of this invention is that the process uses reactants, which can be easily handled. Another advantage lies in the simplicity and safety of the procedure (no filtration of salt or trapping of corrosive gaseous matter) . Furthermore, another advantage is that the reaction may take place without any added catalyst and can be performed under reduced pressure. A further advantage is that the formed carboxylic acid may be removed, preferably, under distillation, preferably, azeotropic distillation. Due to its shortness, its easy work-up procedure and its high yield the process of the present invention can be considered as a substantial improvement over the existing methods described above.
  • the claimed synthesis route can be carried out at high temperatures and is therefore quick and efficient.
  • the claimed route can be used for the synthesis of hydrolysable trialkylsilyl ester bearing polymers which can be used as resins for tin-free self polishing antifouling paints without having recourse to use of the expensive and difficult to prepare trialkylsilyl (meth) acrylate monomers .
  • a premix was prepared in a separate vessel; it contained 180 g of butyl acrylate (BA) [10.0 w% of monomers] 810 g of methyl acrylate (MeA) [45.0 w% of monomers] 27 g of methacrylic acid (MA) [1.5 w% of monomers]
  • BA butyl acrylate
  • MeA methyl acrylate
  • MA methacrylic acid
  • MMA methylethacrylate
  • total time about 5 hours
  • the premix was added drop by drop to the reaction vessel (total time : about 5 hours) whilst maintaining the temperature at 100 °C.
  • a premix was prepared in a separate vessel; it contained: 167 g of butyl acrylate (BA) [13.9 w% of monomers] - 832 g of methyl methacrylate (MMA) [69.3 w% of monomers]
  • BA butyl acrylate
  • MMA methyl methacrylate
  • the premix was added drop by drop to the reaction vessel (total time: about 4 hours) whilst maintaining the temperature at 100°C. Forty-five minutes after the end of the addition of the premix, the first of three post- additions of 2.4 g (0.2 w% VAZ067 with further 45 minutes intervals between additions was made. Hereafter the temperature was increased up to 110°C for 1 hour to complete the reaction.
  • the solution had been thinned down with 300 g xylene.
  • the resin solution had a solid content of 43 % and a viscosity of 89 dPa.s. This polymer solution contained 76.9 mequiv.methacryric acid/lOOg.
  • the yield was 56 % on acetic acid after distilling 220 ml. Three re-additions of 200 ml xylene and continuation of the distillation raised the yield to 94.5 % (converted TBSiAc).
  • the final resin had a viscosity of 6 dPa.s, a Mw of
  • Example 10 Postderivatization of example 8 with MTDMS- acetate (Methyltri-dimethylsiloxy-acetate)
  • the molecular weight distribution was determined by gel permeation chromatograpy (GPC) with tetrahydrofurane (THF) as solvent and polystyrene as reference.
  • Adhesion was studied by evaluating the adhesion of a drawdown (gap 150um) either on glass or on an epoxy primer before and after immersion in water (during 24 hours when on glass, for the stated period of time when on epoxy primer) . The changes caused by water immersion are reported.
  • the hydrolysability has been evaluated by making drawdowns on glass.
  • the films had been dried for several days at ambient temperature. Then the films had been immersed in an alkaline solution (NaOH, pH 12.0-13.4).
  • the number of minutes (induction time) before hydrolysis could be observed is called the induction time. Normally reported is the number of minutes to get full hydrolysis of the film.

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Abstract

La présente invention a trait à un procédé pour la production d'un groupe acide contenant une résine polymérique comprenant les étapes suivantes : (i) la formation d'une composition de prépolymérisation comportant un monomère comprenant au moins un groupe acide dans une chaîne latérale et un solvant comportant au moins un acide organique ; et (ii) la réaction de ladite composition pour former un groupe acide contenant une résine polymérique.
EP04723551A 2003-03-26 2004-03-26 Procede pour la preparation de resine modifiee par des silanes Withdrawn EP1606329A1 (fr)

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EP03251911 2003-03-26
EP03251911A EP1462467A1 (fr) 2003-03-26 2003-03-26 Procédé pour la préparation de résine modifiée par des silanes
PCT/EP2004/003256 WO2004085502A1 (fr) 2003-03-26 2004-03-26 Procede pour la production de groupe acide contenant une resine polymerique
EP04723551A EP1606329A1 (fr) 2003-03-26 2004-03-26 Procede pour la preparation de resine modifiee par des silanes

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US6172149B1 (en) * 1998-10-14 2001-01-09 Westvaco Corporation Rosin-fatty acid vinylic polymers as sizing compositions
FR2826964B1 (fr) * 2001-07-06 2003-09-05 Atofina Procede de fabrication de (meth) acrylates silanes

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