Classifications

• • 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
  • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
  • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
• • 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
  • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F16/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
  • C08F16/04—Acyclic compounds
  • C08F16/06—Polyvinyl alcohol ; Vinyl alcohol
• • 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
  • C08F220/00—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
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives 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
  • C08F220/00—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
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts 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
  • C08F220/00—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
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
• • 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
  • C08F220/00—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
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • 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
  • C08F6/00—Post-polymerisation treatments
• • 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
  • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
  • C09D143/04—Homopolymers or copolymers of monomers containing silicon
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
  • C09J143/04—Homopolymers or copolymers of monomers containing silicon

Definitions

• the present invention relates to novel functionalised homopolymers and copolymers of vinyl alcohol comprising one or more aminosilane- and/or aminosilanol containing side chains attached to the polymer backbone via a reactive coupling group; to a process for the preparation of such polymers, and to the use of such polymers in coatings, inks or adhesives.
• Polyvinyl alcohols are commonly used as the basis, or a component, of various forms of coatings. Hydrogen bonding between the alcohol groups present in such polymers leads to a highly ordered structure with a high degree of crystallinity and high melting point. This highly crystalline, highly ordered structure makes it difficult for small molecules to pass through films comprising these polymers.
• protective films comprising polyvinyl alcohol) and vinyl alcohol copolymers can suffer from failures in adhesion, particularly on contact with moisture or as a result of immersion in water.
• JP2003-171600A describes a gas barrier coating composition comprising acetoacetyl modified polyvinyl alcohol; an amino- or imino-functionalised alkoxy silane; and water or a mixture of water and a lower alcohol.
• JP2004-143197A describes a gas barrier coating composition comprising acetoacetyl modified polyvinyl alcohol; an alkoxy silane; an acid catalyst and water, or a mixture of water and a lower alcohol.
• the coatings described in JP2003-171600A and JP2004-143197A are alleged to provide high levels of gas barrier performance and adhesion which are maintained under high humidity levels.
• JP1997-291185A describes an adhesive composition comprising an acetoacetate ester functionalised polyvinyl alcohol) resin that contains specified quantities of acetic acid and an alkali metal salt of acetic acid; and a silane compound.
• aqueous solutions comprising amino functionalised alkoxysilanes to flexible plastic films in the preparation of gas barrier coatings has previously been described (B. Singh et al. in Surface and Coatings Technology, 2007, 201 (16- 17), 7107-7114; and ibid., 2007, 202(2), 208-216).
• R represents an aminosilane- and/or aminosilanol containing side chain attached to the polymer backbone via the reactive coupling group(s);
• n represents the number of side chains, which are present in an amount from about 1 to about 25 mol% of the polymer backbone;
• R is not a side chain derived from 3-aminopropyltriethoxysilane.
• the polymer backbone P is a straight or branched chain homopolymer of vinyl alcohol or a copolymer of vinyl alcohol and at least one other monomer and comprises one or more reactive coupling groups.
• the other monomer(s) preferably contain an alkene group (i.e. carbon-to-carbon double bond) capable of undergoing copolymerisation with vinyl alcohol or a suitable precursor monomer such as a vinyl ester.
• P represents a copolymer of vinyl alcohol and an olefin, such as ethylene or propylene, preferably ethylene.
• the olefin is present in an amount from about 1 to about 50 mol%, more preferably, from about 2 to about 40 mol%, and even more preferably from about 5 to about 20 mol% of the polymer backbone.
• P represents a copolymer of vinyl alcohol and a non-hydrocarbon alkene containing monomer, such as a vinylic (e.g. acrylic) or methacrylic monomer.
• non-hydrocarbon alkene containing monomers examples include, but are not limited to, styrene, acrylonitrile, methacrylonitrile, crotononitrile, vinyl halides, vinylidene halides, (meth)acrylamide, ⁇ , ⁇ -dimethyl acrylamide, vinyl polyethers of ethylene or propylene oxide, vinyl esters such as vinyl formate, vinyl benzoate or vinyl ethers (such as VeoVaTM 10 available from MomentiveTM), vinyl ethers of heterocyclic vinyl compounds, alkyl esters of mono-olefinically unsaturated dicarboxylic acids and in particular esters of acrylic and methacrylic acid; vinyl monomers with hydroxyl functionality 2-hydroxy ethyl (meth)acrylate, 2-hydroxy propyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxy butyl (meth)acrylate, hydroxyl stearyl methacrylate,
• a monomer is indicated with a prefix in brackets (e.g. meth) it shall be understood that it be used in a form with or without the methyl substitution, or alternatively an alternative alkyl group may be present.
• a monomer is indicated with a prefix in brackets (e.g. meth) it shall be understood that it be used in a form with or without the methyl substitution, or alternatively an alternative alkyl group may be present.
• acrylic acid methacrylic acid or another derivative such as ethacrylic acid may be used.
• the non-hydrocarbon alkene containing monomer is selected from the group consisting of acrylic acid, acrylonitrile, acrylamide, 2-acrylamido-2- methylpropane sulphonic acid, methacrylic acid, methyl methacrylate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, ethyl methacrylate and n-butyl methacrylate.
• the resulting copolymer may exist as a reacted adduct in the form a five-membered lactone ring.
• P represents a copolymer of vinyl alcohol and acetoacetoxyethyl methacrylate.
• P represents a copolymer of diacetone acrylamide and vinyl alcohol.
• reactive coupling group means any chemical group attached to the polymer backbone that is capable of forming a bond with an aminosilane- and/or an aminosilanol containing side chain.
• the ketone or ketoester containing functional group is present in an amount from about 1 to about 25 mol%, such as from about 2 to about 15 mol%, preferably from about 3 to about 8 mol% of the polymer backbone.
• the polymer side-chains R are derived from aminosilanes which contain at least one primary amine group capable of reacting with the reactive coupling group(s) present on the polymer backbone and also at least one silanol group (Si-OH) or a precursor group to silanol, such as an alkoxysilane or aryloxysilane.
• the side chains R are derived from a compound of general formula (II):
• R 2 and R 3 independently represent H, C1.9 alkyl, aryl, C-1.9 alkoxy or aryloxy, provided that at least one of R-i , R 2 or R 3 represents a Ci -9 alkoxy or aryloxy group;
• x is in the range from 0 to 9, preferably 0 to 2;
• y is in the range from 1 to 9, preferably 2 to 6.
• x is 0, 1 or 2 and y is 3.
• at least two of R ⁇ R 2 and R 3 independently represent C 1-9 alkoxy, and are preferably selected from the group consisting of methoxy, ethoxy, propoxy and butoxy.
• the side chain R is derived from one or more of the following compounds: aminoethyl triethoxy silane, 2-aminoethyl trimethoxy silane, 2-aminoethyl triethoxy silane, 2-aminoethyl tripropoxy silane, 2- aminoethyl tributoxy silane, 1 -aminoethyl trimethoxy silane, 1 -aminoethyl triethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, 3-aminopropyl tripropoxy silane, 3-aminopropyl tributoxy silane, 3-aminopropyl methyl dimethoxysilane, 3-aminopropyl ethyl dimethoxysilane, 3-aminopropyl-3- aminopropyldiethylethoxysilane ethyl diethoxysilane,
• the side chain R is derived from one or more of the following compounds:
• the side chain R is derived from 3-aminopropyl triethoxy silane, N-(2- aminoethyl)-3-aminopropyl triethoxysilane, or 3-[2-(2-aminoethylamino)ethylamino] propyl-triethoxy silane.
• a suitable hydrazine or hydrazide functionalised aminosilane may also be employed in accordance with the present invention.
• the side chains R are present in an amount from about 2 to about 15 mol%, more preferably in an amount from about 3 to about 8 mol%, of the polymer backbone.
• an excess of aminosilane and/or aminosilanol may be employed during the polymer synthesis relative to the reactive coupling group (e.g. ketone) present. In such instances some of the aminosilane and/or aminosilanol may be present in an unreactive form and therefore not attached to the polymer backbone.
• the side chains R are present in an amount from about 25 to about 200 mol%, such as from about 50 to about 150 mol%, preferably from about 75 to about 125 mol%, relative to the amount of reactive coupling groups present on the polymer backbone.
• the polymers of the present invention are substantially free from acetic acid or an alkali metal salt thereof such as sodium acetate.
• acetic acid or metal salts thereof are added to assist in cross-linking.
• step (b) hydrolysing the homopolymer or copolymer of vinyl acetate of step (a) to obtain a homopolymer or copolymer of vinyl alcohol;
• step (b) reacting the homopolymer or copolymer of vinyl alcohol of step (b) with a suitable reactive coupling agent to obtain a homopolymer or copolymer of vinyl alcohol comprising one or more reactive coupling groups;
• step (c) reacting the resulting homopolymer or copolymer of vinyl alcohol comprising one or more reactive coupling groups of step (c) with a suitable aminosilane and/or an aminosilanol;
• polymer obtained upon completion of each reaction detailed in steps (a) to (d) of the above process may be isolated prior to initiation of the following step or reacted in situ.
• step (a) of the above process vinyl acetate is reacted with at least one other monomer to obtain a straight or branched chain vinyl acetate copolymer. Thereafter, according to step (b), the copolymer of vinyl acetate is hydrolysed to obtain a copolymer of vinyl alcohol.
• ethylene may be copolymerised with vinyl acetate to afford an ethylene-vinyl acetate copolymer, which may be subsequently hydrolysed to form an ethylene-vinyl alcohol copolymer (EVOH), as follows:
• step (a) of the above process vinyl acetate is polymerised to obtain a straight or branched chain vinyl acetate homopolymer, i.e. polyvinyl acetate). Thereafter, according to step (b), the homopolymer of vinyl acetate is hydrolysed to polyvinyl alcohol), as follows:
• PVOH may also be prepared by the hydrolysis of other polyvinyl esters) such as polyvinyl formate), polyvinyl benzoate) or polyvinyl ethers).
• a copolymer of vinyl alcohol such as EVOH may also be prepared by copolymerising the relevant monomer with a vinyl ester other than vinyl alcohol and hydrolysing the resulting polymer for instance.
• Such polymers are also within the scope of the present invention.
• step (b) of the process comprises partial hydrolysis of the homopolymer or copolymer of vinyl acetate; for example, between about 25 and about 100 percent hydrolysis, more preferably between about 50 and about 100 percent hydrolysis, yet more preferably between about 70 to about 100 percent hydrolysis, and most preferably between about 80 to about 100 percent hydrolysis.
• Suitable polyvinyl alcohols) for use in the process of the present invention are commercially available (thereby obviating the need for steps (a) and (b) of the process) or may be prepared by conventional synthetic methods.
• the process of the invention comprises the steps of:
• step (c) reacting a homopolymer or copolymer of vinyl alcohol with a suitable reactive coupling agent to obtain a homopolymer or copolymer of vinyl alcohol comprising one or more reactive coupling groups; d. reacting the resulting homopolymer or copolymer of vinyl alcohol comprising one or more reactive coupling groups of step (c) with a suitable aminosilane and/or an aminosilanol; and
• copolymers are commercially available from Nippon Gohsei under the trade name GohsenolTM or from Kuraray under the trade name PovalTM.
• Suitable copolymers of vinyl alcohol (such as EVOH) for use in the process of the present invention are commercially available or may be prepared by conventional synthetic methods.
• copolymers of ethylene and vinyl alcohol are commercially available from Kuraray under the trade name ExcevalTM and from Nippon Gohsei under the trade name SoarnolTM.
• step (c) of the process the homopolymer or copolymer of vinyl alcohol is reacted with a suitable reactive coupling agent to obtain a copolymer of vinyl alcohol comprising one or more reactive coupling groups.
• Step (c) is typically performed in a suitable solvent (i.e. a solvent capable of solvating both the homopolymer or copolymer of vinyl alcohol and the reactive coupling agent, and that is inert to both), such as dimethylformamide (DMF), dimethylsulfoxide (DMSO) or dimethylacetamide (DMAc), at an elevated temperature in the range from about 90 to 190 °C, such as about 135 °C.
• a suitable solvent i.e. a solvent capable of solvating both the homopolymer or copolymer of vinyl alcohol and the reactive coupling agent, and that is inert to both
• DMF dimethylformamide
• DMSO dimethylsulfoxide
• DMAc dimethylacetamide
• this step of the process can be carried out in the concentrated phase or by using an essentially no-solvent process.
• US5719231 describes the reaction of an acetoacetate forming composition with a vinyl alcohol based polymer in the solid phase by spraying the acetoacetate forming composition onto the solid polymer at elevated temperatures.
• An analogous process may be employed in the present invention.
• a paste or dispersion of the polymer in a solvent such as water or a dipolar aprotic solvent or non-solvent such as an organic acid may be made.
• acetic acid may be adsorbed, sprayed or mixed with polymers of vinyl alcohol prior to reaction with diketene (in an analogous method to that described in JP9291185A).
• a paste of the vinyl alcohol polymer in water may be made by mixing the polymer with water, optionally with elevated temperature and stirring of high intensity or by concentrating an existing solution of the polymer under vacuum for instance.
• the functionalisation can be carried out with the polymer dispersed or suspended in a liquid medium which is a good solvent for the acetoacetylation agent.
• the polymer can be dispersed in a hydrocarbon solvent such as hexane or an organic acid such as acetic acid and diketene added to the mixture.
• liquid can be separated by filtration and optionally reused in the process taking advantage of the greater degree of efficiency this offers.
• Unreacted acetoacetylation agent or solvent/dispersal media such as acid may be removed by evaporation, or by washing it from the material with a suitable solvent.
• the particle size and shape of the granulated or powdered polymer is important. A smaller particle size will result in a greater surface area which will advantageously enable more efficient reaction with the acetoacetylation agent. As a result a product with a more homogenous degree of ketoester functionality or a greater degree of functionality if so desired may be obtained. It will be appreciated that the reaction process may be performed using any piece of equipment that is capable of providing sufficient mixing.
• reactors or other vessels where agitation is provided by an overhead stirrer, a magnetic stirrer, most preferably mixing is achieved using an appropriate extruder, z-blade mixer, batch mixer, U trough mixer, RT mixer, compounder, internal mixer, Banbury type mixer, two roll mill, Brabender type mixer, a wide blade mixer (or hydrofoil blade mixer), horizontal (delta or helical) blade mixer, kneader-reactor, or a related variation of one of these mixers such as such as a double z-blade mixer or twin screw extruder.
• Heat introduced to the system may be supplied by conventional means or from microwave radiation.
• the reactive coupling group comprises a ketone- or ketoester containing functional group, more preferably a ketoester containing functional group.
• Suitable reagents capable of the generation of a ketoester (or acetoacetate) group are commercially available and are collectively referred to as acetoacetylation agents.
• the reactive coupling group comprises a ketoester containing functional group derived from an acetoacetylation agent.
• Preferred commercially available acetoacetylation agents include diketene (DK), diketene acetone adduct (DKAA) and an alkyl acetoacetate such as tert-butyl acetoacetate (t-BAA):
• DK and DKAA are important acetoacetylation agents that find wide utility and are suitable for use in the invention.
• DK and DKAA have some issues with their long term stability which can make transport more challenging, particularly in the case of DK.
• the decomposition of the active ketoester functionalisation means that many acetoacetylation agents are supplied in grades that are somewhat below 100%, for instance 95%, 90% or lower and possibly an off colour.
• a particularly preferred acetoacetylation agent is t-BAA.
• Other alkyl acetoacetates may also be used in the present invention; for example, methyl, ethyl, n-propyl, iso- propyl, or n-butyl, t-pentyl acetoacetate.
• the reactor is designed to vent the eliminated alcohol from the system.
• the acetoacetylation agent may optionally be purified to promote a more efficient reaction and/or to obtain a purer end product. Suitable purification methods are known in the art.
• DKAA may be purified by dissolution in acetone, followed by the addition of a hydrocarbon solvent such as hexane to precipitate some or all of the impurities as a solid, allowing pure DKAA to be separated and concentrated.
• a hydrocarbon solvent such as hexane
• the acetoacetylation agent may be purified by distillation.
• t-BAA is an example of a particularly preferred alkyl acetoacetate acetoacetylation agent.
• Many alkyl acetoacetates may be used as facile acetoacetylation agents and as such offer potential in the functionalisation of the polymer with ketoester groups. They form ketoester groups by a transacetoacetylation process, with the formation of an alcohol which may establish an equilibrium with the reactants. In the case of t-BAA the process thus results in the elimination of tert-butanol.
• any other alkyl acetoacetate such as methyl, ethyl, n-propyl, iso-propyl, or n-butyl, t-pentyl acetoacetate for instance may be used.
• Sterically hindered esters such as t-butyl or t- pentyl (synonym t-amyl) groups react significantly faster than do less sterically hindered esters such as methyl or ethyl acetoacetate, but dependant on the identity of the alcohol may generate an alcohol by-product with a higher boiling point.
• the reactor is designed to vent the eliminated alcohol from the system.
• a ketoester functionalised polyvinyl alcohol) (PVOH-KE) may be prepared in accordance with the process of the invention, as follows:
• a ketoester functionalised ethylene-vinyl alcohol copolymer (EVOH-) may be prepared in accordance with the process of the invention, as follows:
• Ketoester-functionalised homo- and copolymers of vinyl alcohol of the type prepared in step (c) may also be prepared using alternative known methodologies.
• a suitable alkene containing monomer with an acetoacetate group may be grafted onto a vinyl alcohol copolymer by means of a radical mechanism.
• acetoacetoxyethyl methacrylate (AAEM) which is commercially available from the Eastman Company, may be combined with the vinyl alcohol polymer and a suitable radical initiator such as an azo or peroxide compound in solution or dispersion.
• the suitable alkene containing monomer with an acetoacetate group may be copolymerized with vinyl acetate or another vinyl ester and the resulting polymer selectively hydrolysed.
• Such methodologies constitute alternative embodiments of the process of the present invention.
• step (d) of the process the homo- or copolymer of vinyl alcohol comprising one or more reactive coupling groups obtained in step (c), for example EVOH-KE or PVOH-KE, is reacted with a suitable aminosilane and/or an aminosilanol.
• a suitable aminosilane and/or an aminosilanol reacts with the reactive coupling group on the polymer backbone (such as the ketoester group) in order to form a secondary amine, for example as follows:
• the aminosilane may be used in unhydrolysed form or may be allowed to hydrolyse in water prior to addition to the polymer.
• the solvent used in step (d) is one that the polymer backbone and resulting aminosilane functionalized polymer has good solubility in such as water or dipolar aprotic solvents including DMF or DMSO.
• the reaction is performed in a mixture of one or more such solvents and another miscible solvent such as an alcohol (for example, methanol, ethanol, n-propanol or iso-propanol, preferably n-propanol).
• compositions comprising a functionalised polyvinyl alcohol) or vinyl alcohol copolymer of the invention and water or a mixture of water and a Ci -4 alcohol.
• Such compositions are preferably free from acid catalysts and may be used to prepare coatings containing the functionalised homo- and copolymers of vinyl alcohol of the present invention.
• aminosilanes and aminosilanols employed in the present invention are commercially available and/or may be prepared by conventional synthetic methods.
• 3-aminopropyltrimethoxy silane is commercially available from the Sigma-Aldrich corporation, from Power Chemical Corporation under the trade name PC1110TM, and from Onichem under the trade name A301TM.
• 3-aminopropyl triethoxysilane is commercially available from the Sigma-Aldrich corporation, from Wacker Chemie under the trade name Geniosil GF 93TM, and from Gelest under the trade name SIA0610.0TM.
• N-(2-aminoethyl)-3-aminopropyl trimethoxysilane is commercially available from Evonik under the trade name Dynasylan DAMOTM and from Dow Corning under the name Z- 6094 SilaneTM.
• 3-[2-(2-aminoethylamino)ethylamino]propyl trimethoxysilane is commercially available from UCT under the trade name T2910TM and from Evonik under the trade name Dynasylan TRIAMOTM.
• 3-[2-(2-Aminoethylamino)ethylamino]propyl triethoxysilane is commercially available from from Tianjin Zhongxin.
• 3-Aminopropylmethyl dimethoxysilane is commercially available from the Power Chemical Corporation under the trade name SiSiB PC1130TM.
• step (d) of the process is performed by adding either a solution of homo- or copolymer of vinyl alcohol comprising one or more reactive coupling groups, or more preferably the polymer in solid form, to a solution of a suitable aminosilane and/or an aminosilanol.
• the reaction mixture obtained following step (d) of the process is heated to a temperature in the range from about 0 to about 100 °C, preferably in the range from about 40 to about 95 °C, and more preferably in the range from about 60 to about 90 °C.
• reaction mixture obtained following step (d) is treated with an acid, for example a mineral acid such as HCI or an organic acid such as acetic acid.
• the reaction mixture obtained following step (d) is treated with carbon dioxide.
• step (d) may be performed under an inert gas such as nitrogen.
• the functionalised vinyl alcohol polymers of the present invention may be optionally isolated from solution by conventional means, for example by evaporation or spray drying.
• the aminosilane and/or aminosilanol may be combined with the functionalised polymer backbone in the absence of a solvent such as water.
• a solvent such as water.
• the ketoester functionalised homo or copolymer of vinyl alcohol may be mixed with the aminosilane in the absence of a solvent at an elevated temperature at which the polymer may be a melt. It will be appreciated by those skilled in the art that this process may be performed using any piece of equipment that is capable of providing sufficient mixing.
• reactors or other vessels where agitation is provided by an overhead stirrer, a magnetic stirrer, most preferably mixing is achieved using an appropriate an extruder, z-blade mixer, batch mixer, U trough mixer, RT mixer, compounder, internal mixer, Banbury type mixer, two roll mill, Brabender type mixer, a wide blade mixer (or hydrofoil blade mixer), horizontal (delta or helical) blade mixer, kneader-reactor, or a related variation of one of these mixers such as such as a double z-blade mixer or twin screw extruder.
• Any heat introduced to the system may be supplied by conventional means or from microwave radiation.
• the functionalised homo- and copolymers of vinyl alcohol of the present invention contain one of more silanol (Si-OH) groups. It is known the silanol groups of aminosilanes may crosslink to form a Si-O-Si network, according to the following general equation:
• T is any appropriate functional group such as alkyl, H, OH or alkoxy
• Cross-linking of this type can be useful in the preparation of protective (barrier) coatings since the resulting polymers typically offer increased resistance to abrasion, particularly in the presence of solvents in which the polymer is soluble.
• an acid catalyst under heating is required to effect substantial cross-linking.
• the use of such catalysts can negatively affect the resulting coating in terms of their performance (any free acid may lead to a reduction in barrier performance) or aesthetic appearance from a visual or odorous perspective.
• x is in the range from 2 to 9, preferably x is 2;
• y is in the range from 3 to 9, preferably y is 3.
• a process for preparing a cross-linked polymer coating comprises heating a polymer containing more than one aminosilane and/or aminosilanol side-chain of formula (III) in the absence of an acid catalyst.
• the polymer is of formula P-(R) n , where P is as defined above, and R is derived from an aminosilane or aminosilanol of formula (III) as described above.
• the polymer is heated to a temperature of from about 80 to about 120 °C, more preferably to about 100 °C.
• the polymer containing more than one amino side-chain of formula (III) has a backbone P that is a straight or branched chain homopolymer or copolymer of vinyl alcohol of the type defined in formula (I) herein.
• the present invention also provides a cross-linked polymer coating obtainable from such a process.
• the functionalised homo- and copolymers of vinyl alcohol of the present invention may be used in a wide variety of commercial applications in which they may form, or are a component of, a film or layer.
• These will include various coatings applications including inks and adhesives, including for instance in architectural, decorative, industrial, automotive, aeronautical, maritime, protective and functional coatings; inks for news and magazine print, printing solutions for home and commercial use; adhesives or sealants for consumer and industrial use.
• inks and adhesives including for instance in architectural, decorative, industrial, automotive, aeronautical, maritime, protective and functional coatings; inks for news and magazine print, printing solutions for home and commercial use; adhesives or sealants for consumer and industrial use.
• adhesives or sealants for consumer and industrial use.
• there are many forms and methods for the delivery of such coatings for instance architectural coatings for home and industrial use may be applied in the form of a paint or alternatively may be distributed from a multifunctional formulation designed to clean a surface and apply a coating.
• the coating may be applied to the body of a human or other animal, for instance a cosmetic or medicament.
• the adhesive may also take the form of a coating between two surfaces acting as a sealant in a mechanical assembly for instance.
• the polymer may act as a binder in formulations of the type described herein.
• a functionalised homo- or copolymer of vinyl alcohol of the invention as a coating in a composite film structure.
• a coating comprising a functionalised homo or copolymer of vinyl alcohol according to the invention.
• coating compositions comprising functionalised homo- and copolymers of vinyl alcohol of the present invention may optionally include a number of other components appropriate to the application of the composition including by way of non-limiting example pigments, preservatives, wetting agents, surfactants, dispersants open time extenders and the like.
• MowiolTM 4-98 (M4-98TM) and ExcevalTM AQ-4104 (ACM 104TM) was obtained from Kuraray and used as supplied.
• GohsenolTM GH-17R (GH-17RTM) was supplied by Nippon Gohsei and used as supplied.
• the viscosity of PVOH grades is typically expressed in MPas, measured by recording the relevant value of a 4% solution maintained at 20 °C using a Brookfield viscometer.
• M4-98TM is a polyvinyl alcohol) with a viscosity of 4.0 - 5.0 MPas and a 98.0 - 98.8 % degree of hydrolysis.
• AQ- 4104TM is a copolymer of vinyl alcohol (85 - 90 mol%) and ethylene (10 - 15 mol%) with a viscosity of 3.8 - 4.5 MPas and a 98.0 - 99.0 % degree of hydrolysis.
• GH- 17RTM is a polyvinyl alcohol) with a viscosity of 27 - 33 MPas and a 86.5 - 89.0 % degree of hydrolysis.
• APMES 3-Aminopropyltrimethoxysilane
• APTES 3-Aminopropyltriethoxysilane
• DETAPMS 3-Aminopropyltrimethoxysilane
• DETAPES 3-[2-(2-Aminoethylamino)ethylamino]propyl-triethoxysilane
• DKAA 2,2,6-trimethyl-4H-1 ,3-dioxin-4-one
• DKAA 2,2,6-trimethyl-4H-1 ,3-dioxin-4-one
• DKAA Diketene
• t-BAA tert-butyl acetoacetate
• DKAA Is supplied by Sigma Aldrich as a dark brown liquid. Before use in the ketoester grafting process, impurities were removed from DKAA by selective precipitation to prevent contamination of the polymers with the brown coloured impurities.
• Acetone was added dropwise until the solution turned yellow and a small amount brown tar settled at the bottom of the beaker.
• the solution was decanted into a clean beaker, leaving the oil behind which was then discarded.
• the solution was then passed through a Buchner filter and transferred to a pear-shaped Buchi flask. Hexane and acetone were removed from the solution by rotary evaporation at 40 °C, giving a yellow/orange liquid.
• This liquid was added to a fresh portion of hexane (2 L) and the above process was repeated. After removing the hexane and acetone, the temperature of the rotary evaporator's water bath was raised to 50 °C and maintained for one hour (pressure ⁇ 50 mbar) to ensure all solvent had evaporated.
• M4-98TM (60.0 g) and DMSO (540.0 g) were charged to a 1 L flange flask.
• the flask was fitted with an overhead stirrer equipped with a PTFE anchor stirrer shaft and placed under a blanket of nitrogen.
• the flask was heated with an oil bath to an external temperature of 135 - 145 °C, allowing the M4-98TM to fully dissolve.
• the internal temperature of the flask was then adjusted to 120 °C.
• Polymer was prepared by the exact same method as described for PVOH-KE1 , except the loading level of DKAA was 30.0 g, 0.211 mol rather than 14.5 g, 0. 02 mol.
• Polymer was prepared by the exact same method as described for PVOH-KE1 , except the loading level of DKAA was 41.6 g, 0.293 mol rather than 14.5 g, 0.102 mol.
• M4-98 (50.0 g) and DMSO (450.0 g) were charged to a 1 L flange flask.
• the flask was fitted with overhead stirrer equipped with a PTFE anchor stirrer shaft and a steady nitrogen flow.
• the flask was heated with an oil bath to an external temperature of 135 - 145 °C, allowing the M4-98 to fully dissolve. Internal temperature of the flask was then adjusted to 120 °C.
• Purified DKAA (64.5 g, 0.454 mol) was added dropwise over a one hour period. One neck of the flange flask was left open to drive off the acetone produced during the acetoacetylation process. Temperature of the flask was maintained at 120 °C for a further hour, before the flask was allowed to cool to ambient temperature.
• the polymer was precipitated in toluene (600 mL DMSO solution into 2.5 L toluene) and dried under vacuum ( ⁇ 50 mbar) at 50 °C overnight.
• This polymer was re- dissolved in methanol (250 mL) and precipitated in acetonitrile (80 mL methanolic solution per 800 mL acetonitrile) and dried under vacuum ( ⁇ 50 mbar) for 24 hours.
• AQ-4104 (55.0 g) and DMSO (495.0 g) were charged to a 1 L flange flask.
• the flask was fitted with an overhead stirrer equipped with a PTFE anchor stirrer shaft and a steady nitrogen flow.
• the flask was heated with an oil bath to an external temperature of 135 - 145 °C, allowing the AQ-4104 to fully dissolve. Internal temperature of the flask was then adjusted to 120 °C.
• the polymer was precipitated in acetone (2 x 50 mL DMSO solution into 1 L acetone) and was dried under vacuum ( ⁇ 50 mbar) at 50 °C for 24 hours. This polymer was re- dissolved in water to give a 10 w/w% solution. The polymer was again precipitated in acetone (2 x 50 mL aqueous solution into 1 L acetone) and dried under vacuum ( ⁇ 50 mbar) at 50 °C for 48 hours.
• Polymer was prepared by the exact same method as described for PVOH-KE5, except the loading level of AQ-4104 was 60.0 g rather than 55.0 g, the loading level of DMSO was 540.0 g rather than 495.0 g and the loading level of DKAA was 16.5 g, 0.116 mol rather than 3.55 g, 0.025 mol.
• Polymer was prepared by the exact same method as described for PVOH-KE 6, except the loading level of DKAA was 8.30 g, 0.058 mol rather than 16.5 g, 0.1 16 mol.
• Polymer was prepared by the exact same method as described for PVOH-KE 6, except the loading level of DKAA was 26.40 g, 0.186 mol rather than 16.5 g, 0.1 16 mol.
• the red/brown solution was precipitated in acetone (300 ml_), giving a light yellow solid which was recovered by filtration.
• the polymer was cut up into smaller pieces and stirred in acetone (300 mL) to extract impurities, before being subsequently recovered by filtration and dried overnight under vacuum at 50 °C. Finally, the polymer was then re-dissolved in distilled water at 100 °C before being re-precipitated in acetone (300 mL) and dried overnight under vacuum at 50 °C.
• GH-17RTM 50 g was weighed and added in to flanges reactor flask, to which DMSO (105 g) was added, followed by t-BAA (20 g). Finally acetic acid (2.5 g) was added. The flask was equipped with an overhead stirrer and condenser and the contents placed under a blanket of nitrogen. The reaction mixture was then agitated and heated by means of an oil bath maintained at 130 °C for 3 hours. After this time the reaction mixture was allowed to cool to ambient temperature. It was then precipitated into acetone by adding it in two equally sized aliquots to acetone (1 L), the precipitate formed from the first aliquot being filtered off by vacuum filtration prior to addition and subsequent filtration of the second aliquot. The resulting white fibrous product was dried overnight under vacuum at 50 °C.
• a stock solution of APTES was created simply by adding the aminosilane to water with agitation and leaving the mixture for a minimum of 24 hours. This solution was then utilised in the following example formulation:
• stirrer slowly, at first
• break up gel with agitation accomplished on a lab scale using a spatula or suchlike
• the basic formulation method has been modified to include carbon dioxide gas.
• the C0 2 gas was added to generate carbonic acid in situ to prevent or control the gelation process. With the exception of the carbon dioxide added in an attempt to control the viscosity of the process it remains essentially similar to that of the basic method A.
• the acetoacetylated polymer (3) is then added to the formulation with sufficient agitation to prevent agglomeration. Stirring is continued to dissolve the polymer but it will become necessary to increase the temperature to completely dissolve the polymer. During the process of heating it seems the loss of carbon dioxide from the solution allows at least some degree of gelation to occur. It is our finding that if the resulting lumps can be kept mobile at elevated temperature then it is possible to stir the mixture until the viscosity decreases. Ethanol (4) would then be added in a similar manner to that described in A.
• ketoester functionalised homo- and copolymers of vinyl alcohol were prepared by reaction of DKAA and various vinyl alcohol homo- and copolymers, as follows:
• MowiolTM 4-98 (M4-98TM) is a PVOH sold by Nippon Gohsei and AQ-4104TM is an EVOH sold by Kuraray.
• compositions were prepared by reaction of certain aminosilanes with commercially sourced ketoester functionalized polymers, or from vinyl alcohol homo- and copolymers that were subsequently functionalized by means of an acetoacetylation agent, as follows:
• Ketoester mol% the percentage of the repeat units that have ketoester (KE) functionality. At a level of 10%, 1 in 10 of the PVOH units in the polymer will be KE functionalised.
• Crosslinker mol% the percentage of the KE functionality that is reacted with aminosilane. At a level of 50% this means that half of the KE groups should react with the crosslinker.
• Z-200TM and OKS-3551TM (03551) poly(vinyl alcohol) (PVA) functionalised with KE groups were obtained from Nippon Gohsei. All other polymer backbones were prepared by reacting diketene acetone adduct with Mowiol 4-98TM (M4-98TM, Kuraray) or ExcevalTM AQ-4104 (AQ-4104TM, Kuraray) in DMSO solution.
• M4-98TM is a PVA with a viscosity of 4.0 - 5.0 MPas and a 98.0 - 98.8 % degree of hydrolysis.
• AQ4104TM is a PVA with approximately 14% ethylene and a viscosity of 3.8 - 4.5 MPas and a 98.0 - 99.0 % degree of hydrolysis.
• Sample AS 1G was manufactured as a control without KE functionalised PVA. An estimate for the actual KE functionality grafted on is obtained using FT-IR. Values quoted for AQ4104TM are equivalent to a 100% vinyl alcohol material.
• the packaging materials included oriented polyamide (OPA), and polyolefins such as polyethylene (PE) and polypropylene (PP) in an appropriate filmic format for use in packaging laminates.
• OPA oriented polyamide
• PE polyethylene
• PP polypropylene
• An adhesive typically used in the construction of such laminates was then applied to the top of the layer of the aminosilane modified polymer and a further layer of film placed on top, and air bubbles rubbed out from the laminate. After allowing the isocyanate adhesive to cure for a week, the resulting film was cut into strips for subsequent test.
• the adhesive potential of the barrier layer was then determined by looking at the bond strength between the two laminates using a conventional T-peel test.
• the test involved measuring the force in newtons (N) required to separate the polymer film from the substrate by pulling the two apart mechanically.
• N newtons
• the force required to break apart the laminates constructed with the functionalised polymers of the present invention was then compared with similar laminates made with unmodified and ketoester functionalised polymer backbone.
• the results obtained are summarised in Figure 1. As is evident from Figure 1 , it was observed that the addition of layers of the unmodified polyvinyl alcohol) polymer backbone M4-98TM and ketoester modified polyvinyl alcohol) polymer backbone Z-200TM undermined the bond strength of the adhesive.
• the polymers modified with aminosilane retained a similar and in some cases greater degree of adhesion between the laminate layers.
• a formulation was prepared in which unmodified polymer backbone was mixed with aminosilane (AS 1 G) and the resulting adhesion of a laminate containing the polymer measured. There being no group for the amino group to attach itself to the backbone, the two exist as a mixture in solution and adhesion between the sheets in the resulting laminates was consequently very poor as expected.
• the superior adhesion of the aminosilane functionalised homo- and copolymers of vinyl alcohol will allow them to be used in examples where otherwise it might not be possible to use a barrier layer.
• Unmodified polyvinyl alcohol starts to dissolve essentially immediately on contact with the damp cloth.
• the APTMS, APTES and ETAP S modified PVOHs were found to survive a little longer due to their more hydrophobic composition and enhanced adhesion. After several rubs under these severe conditions they however also started to peel as they had little or no crosslinking.
• the film of DETAPMS had crosslinked to significant or substantial degree upon curing and as a result it was able to withstand the duration of the test (200 rubs).
• the enhanced adhesion of the invention may also benefit from crosslinking with aminosilanes with multiple repeat ethyleneamine units to give it superior mechanical adhesion.

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