WO2018112555A1 - Composition aqueuse de polymère - Google Patents

Composition aqueuse de polymère Download PDF

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Publication number
WO2018112555A1
WO2018112555A1 PCT/AU2017/051457 AU2017051457W WO2018112555A1 WO 2018112555 A1 WO2018112555 A1 WO 2018112555A1 AU 2017051457 W AU2017051457 W AU 2017051457W WO 2018112555 A1 WO2018112555 A1 WO 2018112555A1
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WO
WIPO (PCT)
Prior art keywords
copolymer
ethylenically unsaturated
crosslinking
polymer
unsaturated monomer
Prior art date
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PCT/AU2017/051457
Other languages
English (en)
Inventor
Timothy Warren Davey
Richard Alexander Evans
Kimmo Petteri Kemppinen
Katherine Elizabeth Sarah LOCOCK
Simon John PEAKE
Melissa Skidmore
Christopher Henry Such
Original Assignee
Commonwealth Scientific And Industrial Research Organisation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from AU2016905320A external-priority patent/AU2016905320A0/en
Application filed by Commonwealth Scientific And Industrial Research Organisation filed Critical Commonwealth Scientific And Industrial Research Organisation
Priority to NZ754070A priority Critical patent/NZ754070A/en
Priority to KR1020197021534A priority patent/KR20190090875A/ko
Priority to JP2019534138A priority patent/JP2020514451A/ja
Priority to AU2017383105A priority patent/AU2017383105B2/en
Priority to EP17883595.5A priority patent/EP3559120A4/fr
Publication of WO2018112555A1 publication Critical patent/WO2018112555A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
    • 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
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • 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
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/025—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C08L101/08—Carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • 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
    • C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • C09J133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones

Definitions

  • the present invention relates in general to aqueous polymer compositions.
  • the invention relates to a storage stable crosslinkable aqueous polymer composition, a method of preparing the same, a polymer composition derived therefrom and a substrate coated therewith.
  • Polymer compositions such as adhesives, varnishes and paints, have long been used to adhere, undercoat, protect and/or decorate substrate surfaces.
  • Such polymer compositions typically contain a so called solvent, a binder and optionally pigment.
  • the solvent functions to provide liquidity to the composition and facilitates application of the composition onto a substrate.
  • the binder is typically a polymer that can coat the substrate surface and promote adhesion of the composition to that surface.
  • the polymer typically also promotes adhesion to a second substrate material.
  • the polymer adheres to the substrate surface and can decorate the substrate and/or protect it from wear or the elements.
  • the pigment may be inorganic or organic and provides colour and/or opacity to the composition and can further function to bulk-out the composition or protect the surface of the substrate.
  • Such polymer compositions typically fall into two broad categories, namely so called oil- based compositions and emulsion compositions.
  • the oil-based compositions typically contain a polymer binder, such as an alkyd resin, dissolved in organic solvent. Pigment may also be blended in the composition.
  • the polymer binder used is generally of a type that can undergo crosslinking post application to the substrate to impart superior durability to the cured polymer film.
  • such compositions are commonly referred to in the art as enamel paints and they are renowned for forming hard, water resistant and glossy polymer films.
  • emulsion polymer compositions contain comparatively low levels if no organic solvent and consequently their use has increased considerably.
  • the so called “solvent” in emulsion compositions is predominantly water.
  • the water does not function as a true solvent for the polymer binder but rather as a liquid carrier.
  • the water "solvent” in such compositions presents as a continuous liquid phase in which is dispersed small droplets of typically vinyl and/or acrylic -based polymer particles (i.e. the polymer binder).
  • the dispersed polymer particles are essentially insoluble in the water based liquid carrier. Pigment may also be blended in the emulsion.
  • Emulsion polymer compositions are commonly referred to in the art as water-borne or latex polymer compositions.
  • emulsion polymer composition Upon application of an emulsion polymer composition to a substrate surface, water in the applied composition evaporates or is absorbed by the substrate causing the dispersed polymer droplets to coalesce and form a continuous polymer mass or film.
  • the present invention provides a storage stable crosslinkable aqueous polymer composition comprising:
  • the present invention further provides a method of preparing a storage stable crosslinkable aqueous polymer composition, the method comprising combining or forming in an aqueous liquid:
  • a copolymer made soluble in the aqueous liquid by a fugitive non-gas acid comprising polymerised residues of: (i) ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid, the polymerised residues of that monomer being present in an amount of less than 25 mol%, relative to the total number of mols of polymerised monomer residues of the copolymer;
  • Described herein is a storage stable crosslinkable aqueous polymer composition
  • a storage stable crosslinkable aqueous polymer composition comprising:
  • composition also comprises one or both of:
  • the dispersed particulate material having adsorbed thereon a reversibly blocked crosslinking agent for promoting crosslinking of the copolymer may be combined or present in the aqueous liquid in combination with the fugitive crosslinking inhibitor for inhibiting crosslinking of the copolymer.
  • the present invention also provides a polymer composition derived through loss of aqueous liquid from the storage stable crosslinkable aqueous polymer composition in accordance with the invention.
  • That polymer composition derived through loss of the aqueous liquid will typically be a solid polymer composition.
  • the present invention further provides a substrate having a surface coated with the storage stable crosslinkable aqueous polymer composition in accordance with the invention.
  • the substrate presents on its surface a polymer composition derived through loss of aqueous liquid from the storage stable crosslinkable aqueous polymer composition in accordance with the invention.
  • compositions in accordance with the invention can advantageously be prepared with little if no organic solvent. Solubility of the polymer binder in the aqueous liquid also advantageously avoids problems associated with dispersed polymer particles having to coalesce and form a continuous polymer mass or film.
  • composition being crosslinkable it can advantageously form through loss of aqueous liquid therein a crosslinked continuous polymer mass or film with improved properties, such as improved adhesion, hardness or water resistance.
  • compositions where the polymer binder is soluble in an aqueous liquid, and (b) which provide for crosslinked polymer films are known
  • such compositions are typically provided in a two-pack form.
  • the aqueous soluble polymer binder is provided in one pack and a suitable crosslinking agent is provided in the other pack.
  • the contents of each pack are mixed together and the resulting composition must be applied to a substrate before the crosslinking reaction (initiated by mixing the two packs) produces gels and/or increases the viscosity of the composition beyond a point where it can be practically applied to the substrate.
  • crosslinking reaction initiated by mixing the two packs
  • Such compositions therefore exhibit a limited pot life and no practical storage stability.
  • aqueous polymer compositions in accordance with the invention are not only crosslinkable but they provide that property in a "ready to use" storage stable state (i.e. without the need for introducing additional formulation components to promote crosslinking).
  • aqueous polymer compositions in accordance with the invention being in a crosslinkable ready state, they can advantageously remain in a storage stable state when not in use.
  • Crosslinking of aqueous polymer compositions in accordance with the invention can be promoted simply and only by application onto a surface of a substrate.
  • Aqueous liquid (e.g. water) and other fugitive components present in the composition can then escape from the composition, for example through evaporation and/or being absorbed into the substrate, which in turn initiates the crosslinking process.
  • the present invention may therefore also be described as providing or preparing a self- contained or ready to use storage stable crosslinkable aqueous polymer composition.
  • self-contained or ready to use compositions are commonly referred to as “one- pack” compositions.
  • the present invention may therefore also be described as providing or preparing a one -pack storage stable crosslinkable aqueous polymer composition.
  • compositions containing reactive components that are mixed together and stored in the same container but remain substantially unreacted during storage.
  • compositions are known. However, such compositions are typically formulated such that upon application of the composition to a substrate high temperatures are required to promote crosslinking.
  • the storage stability of such compositions is viable because the crosslinking process is not activated unless the composition is subjected to high temperatures (i.e. temperatures well above typical ambient storage temperatures).
  • compositions according to the invention advantageously do not require application of high temperature to promote crosslinking. Accordingly, compositions according to the invention may also be described as being storage stable ambient temperature crosslinkable aqueous polymer compositions, or alternatively as being storage stable one-pack ambient temperature crosslinkable aqueous polymer compositions.
  • ambient temperature is intended to mean temperatures within the range of typical storage and application of aqueous polymer compositions. Such temperatures would generally fall within the range of about 1°C to about 40°C.
  • compositions according to the invention may be described as being storage stable crosslinkable aqueous polymer compositions that are capable of undergoing crosslinking within a temperature range of about 1°C to about 40°C.
  • aqueous polymer compositions according to the invention because crosslinking of the aqueous polymer compositions according to the invention is promoted through loss of aqueous liquid (e.g. water) and other fugitive components, provided such fugitive components remain in the composition (e.g. when being stored in a sealed container) it can withstand temperatures exceeding 40°C without undergoing premature crosslinking.
  • aqueous liquid e.g. water
  • other fugitive components e.g. water
  • aqueous polymer compositions (a) where the polymer binder is soluble in an aqueous liquid, and (b) which provide for crosslinked polymer films have also recently been disclosed.
  • WO 2016/191890 discloses so called "switchable" water-based paint or coating compositions. Such compositions are predicated on using an acid gas to promote aqueous solvation of a protonatable polymer. On application of the composition to a substrate the dissolved acid gas is released into the atmosphere which causes the protonated polymer to switch into its non-protonated form and reduce the polymer' s solubility in the aqueous liquid. The non-protonated form of the polymer then forms a film that is said to be substantially water- insoluble.
  • the compositions may comprise a crosslinking agent to promote crosslinking of the resulting polymer film.
  • compositions disclosed in WO 2016/191890 require the use of polymer having a high mol % of polymerised monomer residues that are protonatable to enable that polymer to be solvated in the aqueous liquid.
  • polymer films derived from compositions according to that invention are susceptible to damage upon being exposed to common aqueous acidic substances (e.g. juice, acid rain, sweat, cleaning liquids) through re- protonation of the protonatable polymer and solvation of the polymer film.
  • the storage stable crosslinkable aqueous polymer composition according to the present invention uses copolymer which comprises polymerised residues of ethylenically unsaturated monomer comprising a basic functional group in an amount of less than 25 mol%, relative to the total number of mols of polymerised monomer residues of the copolymer.
  • copolymer can still be sufficiently solubilised in the aqueous liquid when it contains a relatively low mol % of protonatable polymerised monomer residues. That in turn has been found to impart improved properties, such as water (including acidic water) resistance, to polymer film derived from the storage stable crosslinkable aqueous polymer composition.
  • Polymer film derived from the storage stable crosslinkable aqueous polymer composition according to the invention advantageously exhibits improved stain resistance properties relative to polymer derived from, for example, compositions disclosed in WO 2016/191890.
  • the "switchable" water-based paint or coating compositions according to WO 2016/191890 are predicated on using an acid gas.
  • the use of an acid gas in such compositions has also been found to be problematic.
  • the acid gas can promote the formation of bubble imperfections in polymer film formed using the WO 2016/191890 compositions.
  • Certain acid gases can also promote degradation of the protonatable polymer and can also be very toxic.
  • Storage stable crosslinkable aqueous polymer compositions according to the present invention do not use or comprise an acid gas. The problems associated with using an acid gas are therefore advantageously avoided. Unlike most conventional aqueous polymer compositions, those according to the present invention provide for a storage stable crosslinkable composition that can, upon application to a substrate, form crosslinked polymer having a number of properties that approach if not exceed polymer derived from oil-based compositions.
  • aqueous polymer composition in accordance with the invention to not undergo an undesirable degree of crosslinking during storage is believed to stem at least in part from the unique combination of composition components including the aqueous liquid, the polymer binder (i.e. the copolymer), the fugitive non-acid gas, and the combination of reversibly blocked crosslinking agent and the fugitive crosslinking inhibitor.
  • This unique combination of composition components not only provides storage stability to the composition but also enables crosslinking to be initiated when the composition is used in practice, for example upon being applied to a substrate.
  • aqueous polymer compositions described herein may also stem from the use of dispersed particulate material having adsorbed thereon a reversibly blocked crosslinking agent for promoting crosslinking of the copolymer.
  • the copolymer comprises polymerised residues of ethylenically unsaturated monomer comprising a basic functional group that is protonated by a fugitive non-gas acid.
  • Suitable basic functional groups include those selected from amine, amidine, N-heterocycle and combinations thereof.
  • the basic functional group comprises a tertiary amine basic functional group.
  • the basic functional group consists essentially of a tertiary amine functional group.
  • ethylenically unsaturated monomers comprising such a basic functional group include those selected from amino acrylates, amino methacrylates, acrylamides, methacrylamides, vinyl pyridines, vinyl imidazoles, l-(4-vinylphenyl)methanamines, amino maleimides and combinations thereof.
  • the copolymer comprises polymerised residues of ethylenically unsaturated monomer comprising a functional group for promoting crosslinking of the copolymer.
  • Suitable crosslinking functional groups include those selected from hydroxy, carboxylic acid, epoxy, ketone, aldehyde, alkene, alkyne, amine, azide, halide (e.g. alkylhalide, benzylhalide), hydrazide and combinations thereof.
  • the copolymer used in accordance with the invention comprises polymerised residues of hydrophobic ethylenically unsaturated monomer.
  • hydrophobic ethylenically unsaturated monomers include those selected from styrene, alpha-methyl styrene, butyl (meth)acrylate, iso-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, ethyl hexyl (meth)acrylate, crotyl (meth)acrylate, cinnamyl (meth)acrylate, oleyl (meth)acrylate, ricinoleyl (meth)acrylate, cholesteryl (meth)acrylate, cholesteryl (meth)acrylate, vinyl butyrate, vinyl tert-butyrate, vinyl stearate, vinyl laurate, 2-(2-oxo-l-imidazolidinyl)ethyl methacrylate (ethoxy ethyleneurea methacrylate
  • hydrophilic ethylenically unsaturated monomer examples include those selected from (meth)acrylic acid, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, oligo(alkylene glycol)methyl ether (meth)acrylate (OAG(M)A), itaconic acid, p-styrene carboxylic acid(s), p- styrene sulfonic acid(s), vinyl sulfonic acid, vinyl phosphonic acid, ethacrylic acid, alpha- chloroacrylic acid, crotonic acid, fumaric acid, citraconic acid, mesaconic acid, maleic acid, sulfoethyl (meth)acrylates, phosphoethyl (meth)acrylate, phosphorylcholine (meth)acrylate and combinations thereof.
  • the copolymer does not comprise polymerised residues of hydrophilic ethylenically unsaturated monomer in an amount over 10 mol%, relative to the total number of mols of polymerised monomer residue of the copolymer.
  • the copolymer does not comprise polymerised residues of acid functionalised ethylenically unsaturated monomer in an amount over 10 mol%, relative to the total number of mols of polymerised monomer residue of the copolymer.
  • the copolymer used in accordance with the invention is solubilised in the aqueous liquid by a fugitive non-gas acid.
  • Suitable fugitive non-gas acids include those selected from, acetic acid, glycolic acid, lactic acid and combinations thereof.
  • the fugitive non-gas acid comprises acetic acid.
  • the aqueous polymer composition in accordance with the invention comprises a reversibly blocked crosslinking agent.
  • reversibly blocked crosslinking agents include, but are not limited to, reversibly blocked multifunctional hydrazide compounds.
  • crosslinking agent is a reversibly blocked multifunctional hydrazide it may, for example, be reversibly blocked by being converted into a hydrazone compound.
  • Aqueous polymer composition described herein may also comprises one or both of (I) (i) a reversibly blocked crosslinking agent for promoting crosslinking of the copolymer, and (ii) a fugitive crosslinking inhibitor for inhibiting crosslinking of the copolymer by the reversibly blocked crosslinking agent, and (II) dispersed particulate material having adsorbed thereon a reversibly blocked crosslinking agent for promoting crosslinking of the copolymer.
  • fugitive crosslinking inhibitors include those selected from ketones such as acetone, methyl ethyl ketone, diethyl ketone and combinations thereof.
  • the particulate material should be dispersed or dispersible in the aqueous polymer composition. Accordingly, the particulate material will be dispersed or of a type that is dispersible in the aqueous liquid comprising the copolymer solubilised therein. The dispersed or dispersible particulate material will typically be solid particulate material.
  • the dispersed or dispersible particulate material may be non-polymeric.
  • dispersed or dispersible particulate material examples include, but are not limited to, inorganic pigments, organic pigments, extenders, solid fillers and combinations thereof.
  • the present invention provides a storage stable crosslinkable aqueous polymer composition.
  • the compositions in accordance with the invention contain reactive components intimately mixed together.
  • the compositions comprise copolymer presenting functional groups for promoting crosslinking of the copolymer and a reversibly blocked crosslinking agent for promoting crosslinking of the copolymer.
  • the composition in accordance with the invention is advantageously storage stable.
  • compositions being “storage stable” is intended to mean the composition, upon being stored appropriately (e.g. in a sealed container at ambient temperatures), will remain in a practical usable form over a commercially acceptable timeframe.
  • compositions in accordance with the invention remaining in a "practical usable form" during storage is meant that upon use after storage the compositions can be applied and function as originally intended. In practice, that will at least mean the compositions undergo little if no crosslinking during storage and consequently little if no increase in viscosity.
  • compositions according to the invention being storage stable over "a commercially acceptable timeframe" is intended to mean the timeframe over which the composition is manufactured and sold to a consumer, including the timeframe over which a consumer would be expected to use the product. This of course assumes the composition has been stored appropriately over that time period.
  • stored appropriately is meant the composition is stored in a sealed contained of comparable volume to the volume of the composition being stored and at ambient temperature.
  • compositions in accordance with the invention will generally be storage stable for at least one month, or two months, or four months, or six months, or eight months, or ten months, or twelve months, or 14 months.
  • compositions being storage stable and crosslinkable is intended to mean it is self-contained or ready to use in the sense no further formulation components need to be added to enable the composition to form crosslinked polymer.
  • the compositions may therefore also be described as a one-pack storage stable crosslinkable aqueous polymer composition.
  • the storage stable crosslinkable aqueous polymer compositions according to the invention advantageously do not require application of high temperature to promote crosslinking. Accordingly, compositions according to the invention may also be described as being storage stable ambient temperature crosslinkable aqueous polymer compositions, or alternatively as being storage stable one-pack ambient temperature crosslinkable aqueous polymer compositions.
  • compositions according to the invention are outlined in more detail below.
  • the aqueous liquid used in accordance with the invention represents the solvent for the polymer binder (i.e. the copolymer). Unlike emulsion or water-borne polymer compositions, the aqueous liquid component of compositions in accordance with the invention functions as a true solvent for the polymer binder in the sense that polymer binder is soluble in the aqueous liquid.
  • the aqueous liquid will contain a majority (i.e. greater than 50 wt%) of water. Generally, the aqueous liquid will comprise greater than 60 wt %, or 70 wt%, or 80 wt%, or 90 wt%, or 95% water, relative to the total amount of water/water soluble liquid present in the composition.
  • the aqueous liquid may comprise water soluble organic solvent.
  • suitable water soluble organic solvents include those selected from monovalent- alcohols (such as methanol and ethanol), polyvalent-alcohols (such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, hexanediol, pentanediol, glycerine, hexanetriol and thiodiglycol), acetonitrile, ketones (such as acetone and methyl ethyl ketone) and combinations thereof.
  • monovalent- alcohols such as methanol and ethanol
  • polyvalent-alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, hexanediol, pentanediol, glycerine, hexanetriol and thiodiglycol
  • acetonitrile such as acetone and methyl
  • a water soluble organic solvent will generally be present in an amount of less than 50 wt%, or less than 40 wt%, or less than 30 wt%, or less than 20 wt%, or less than 15 wt%, or less than 10 wt%, or less than 8 wt%, or less than 5 wt%, or less than 3 wt%, relative to the total amount of water/water soluble liquid present in the composition.
  • the aqueous liquid consists essentially of water.
  • the copolymer and fugitive non-gas acid are essentially of water.
  • the copolymer used in accordance with the invention is solubilised in the aqueous liquid by a fugitive non-gas acid.
  • a fugitive non-gas acid By the copolymer being “solubilised” in the aqueous liquid "by a fugitive non-gas acid” is meant that the presence of the fugitive non-gas acid associated with the copolymer (as will be discussed in more detail below) promotes solubility of the copolymer in the aqueous liquid.
  • the copolymer per se is substantially insoluble in the aqueous liquid.
  • the copolymer being “soluble” in the aqueous liquid, or the copolymer being “solubilised” in the aqueous liquid by a fugitive non-gas acid is meant the copolymer is or becomes dissolved in the aqueous liquid (through interaction with the fugitive non-gas acid) in the sense the copolymer is not present as a dispersed organic phase within the aqueous liquid.
  • the copolymer used is soluble or solubilised in the aqueous liquid, depending on its concentration in the aqueous liquid there may be some of the copolymer that is not be completely soluble in the aqueous liquid. In that case, some of the copolymer used may present as a dispersed organic phase within the aqueous liquid. Generally, greater than 50 wt.%, or 60 wt.% .%, or 70 wt.% .%, or 80 wt.% .%, or 90 wt.% , or 95 wt.% of the copolymer is soluble or solubilised in the aqueous liquid, relative to the total amount of the copolymer used in the composition.
  • the copolymer may be described as being substantially soluble or solubilised in the aqueous liquid. In any event, it is to be appreciated the majority of the copolymer used will be soluble or solubilised in the aqueous liquid.
  • the copolymer used in accordance with the invention comprises polymerised residues of specified ethylenically unsaturated monomer that impart specific function.
  • the collective function of the specified polymerised residues of ethylenically unsaturated monomer in the copolymer provides the copolymer with a unique set of properties for use in accordance with the invention.
  • copolymer comprising "polymerised residues" of ethylenically unsaturated monomer is intended to mean that the "mer” units within the copolymer chain that are formed as a result of polymerisation of the monomer.
  • the polymerised monomer residues therefore collectively form at least the molecular backbone structure of the polymer chain.
  • the polymerised residues are formed by polymerising ethylenically unsaturated monomer. Such polymerisation is promoted through reaction of the ethylenically unsaturated functional group of the monomer. Those skilled in the art will appreciate that polymerisation of ethylenically unsaturated monomer in this way gives rise to a polymer chain having a backbone with a carbon atom based (-C-C-) molecular structure.
  • the copolymer comprises polymerised residues of ethylenically unsaturated monomer comprising a basic functional group.
  • basic functional group is intended to mean a Bronsted Lowry base functional group in the sense that it can accept a proton.
  • suitable basic functional groups include those selected from amine, amidine, N- heterocycle and combinations thereof.
  • the base functional group may be a primary, secondary or tertiary-base functional group.
  • suitable basic functional groups are selected from tertiary-base functional groups.
  • suitable basic functional groups are selected from tertiary- amine functional groups.
  • a given polymerised ethylenically unsaturated monomer residue will generally comprise one basic functional group, it may contain two or more basic functional groups depending upon the specific ethylenically unsaturated monomer from which it is derived.
  • ethylenically unsaturated monomers that can provide for the polymerised monomer residues comprising a basic functional group include amino acrylates, amino methacrylates, acrylamides, methacrylamides, vinyl pyridines, vinyl imidazoles, l-(4- vinylphenyl)methanamines, amino maleimides and combinations thereof.
  • Examples of specific ethylenically unsaturated monomers that may be used to provide for the polymerised monomer residues comprising a basic functional group include those selected from 2-aminoethyl (meth)acrylate, N-[3-(N,N-dimethylamino)propyl] (meth)acrylamide, N- (3-aminopropyl)(meth)acrylamide, N-[2-(N,N-dimethylamino)ethyl](meth)acrylamide, 2-N- morpholinoethyl (meth)acrylate, 2-(N,N-dimethylamino)ethyl (meth)acrylate, 2-(N,N- diethylamino)ethyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, 2- (diethylamino)ethylstyrene, N,N-dimethyl-l-(4-vinylphen
  • the copolymer used in accordance with the invention comprises polymerised residues of 2-(N, N-dimethylamino)ethyl (meth)acrylate.
  • (meth)acrylate type ethylenically unsaturated monomers is intended to embrace both methacrylate and acrylate ethylenically unsaturated monomers.
  • the copolymer used in accordance with the invention is solubilised in the aqueous liquid by a fugitive non-gas acid.
  • the copolymer comprises polymerised residues of ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid.
  • fugitive non-gas acid is intended to mean a compound that can (i) dissolve and dissociate in the aqueous liquid to provide for an anionic species and a proton, (ii) escape (e.g. through evaporation or by being absorbed into a substrate on which the composition is applied) from aqueous polymer compositions in accordance with the invention under conditions in which the compositions are conventionally used, and (iii) is not a gas at standard temperature and pressure (STP).
  • STP standard temperature and pressure
  • Suitable fugitive non-gas acids include those selected from, acetic acid, glycolic acid, formic acid, lactic acid and combinations thereof.
  • the fugitive non-gas acid comprises or is acetic acid.
  • ugitive non-gas acid is intended to exclude gas acids such as C0 2 , COS, CS 2 and HC1.
  • gas acids such as C0 2 , COS, CS 2 and HC1.
  • Conventional use of aqueous polymer compositions typically takes place at ambient temperature and pressure, for example, at atmospheric pressure and a temperature ranging from about 1°C to about 40°C.
  • the protonated form of the basic functional group of the polymerised monomer residues promotes solubility of the copolymer in the aqueous liquid.
  • copolymer used in accordance with the invention will of course have sufficient polymerised residues of the basic functionalised monomer to ensure that once protonated by the fugitive non-gas acid the resulting salt form of the basic functional group promotes the required solubility of the copolymer in the aqueous liquid.
  • the copolymer comprises polymerised residues of ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid in an amount ranging from about 1-25, or 1-20, or 1-18, or 1-16 or 1-14, or 1-12, or 1-10 mol%, relative to the total number of mols of polymerised monomer residue of the copolymer.
  • the copolymer used in accordance with the invention comprises polymerised residues of ethylenically unsaturated monomer comprising a basic functional group (that is protonated by the fugitive non-gas acid) in an amount of less than 25 mol%, or less than 20 mol%, or less than 15 mol%, or less than 10 mol%, relative to the total number of mols of polymerised monomer residues of the copolymer.
  • mol % of polymerised residues of ethylenically unsaturated monomer of the copolymer is intended to mean the mol % of polymerised residues of ethylenically unsaturated monomer in the copolymer as determined by nuclear magnetic residence (NMR) spectroscopy.
  • NMR nuclear magnetic residence
  • hydrolytically sensitive ethylenically unsaturated monomer may hydrolyse such that it is the hydrolysed form of the monomer being polymerised that actually presents in the so formed copolymer.
  • the copolymer will be prepared with monomer conversion approaching 100% and with minimal hydrolysis of hydrolytically sensitive ethylenically unsaturated monomer.
  • N-[2-(N,N-dimethylamino)ethyl](meth)acrylamide DMAEMA
  • the amount of that monomer used may undergo some hydrolysis, for example less than 5% or less than 3% hydrolysis during polymerisation. With such hydrolysis the resulting copolymer may comprise a small portion of polymerised residues of methacrylic acid (derived from DMAEMA).
  • the resulting copolymer may contain 0.45 mol % of polymerised residues of methacrylic acid derived from DMAEMA.
  • Such minor hydrolysis of monomers during polymerisation has not been found to adversely affect performance of the resulting copolymer. It is nevertheless desirable to minimise any such hydrolysis of hydrolytically sensitive ethylenically unsaturated monomer during polymerisation.
  • mol % of ethylenically unsaturated monomer being used in the polymerisation process is intended to mean the mol % of a given ethylenically unsaturated monomer introduced during polymerisation, relative to the total number of mols of ethylenically unsaturated monomers introduced during polymerisation to prepare the copolymer.
  • the total mol % of polymerised residues of ethylenically unsaturated monomer in the copolymer used in accordance with the invention is to total 100 mol%. Also the total mol % of ethylenically unsaturated monomer introduced during polymerisation to prepare the copolymer is to total 100 mol%.
  • reaction schemes (i)-(iii) below in which the fugitive non-gas acid presented is acetic acid and the polymerised monomer residue in the copolymer comprising the basic functional group presented is derived from 2-(N, N- dimethylamino) ethyl methacrylate.
  • acetic acid combines with water and dissociates form an acetate anion and H + .
  • a copolymer comprising polymerised residue of 2-(N, N- dimethylamino)ethyl methacrylate (A) interacts with the fugitive non-gas acid such that the basic functional group thereof is protonated to form a salt (B).
  • the protonated form of the polymerised monomer residue (B) promotes solubility of the copolymer in the aqueous liquid.
  • the symbol * represents the remainder of the copolymer.
  • the copolymer used in accordance with the invention comprising polymerised residues of ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid (e.g. (B) in scheme (ii) above) may herein be referred to as the protonated form of the copolymer.
  • the protonated form of the copolymer is soluble in the aqueous liquid.
  • water in the composition can evaporate or be absorbed by the substrate, which in turn can drive the protonated form of the basic functional group of the copolymer into its free base form (e.g. (A) in scheme (ii) above). Due to the fugitive nature of the non-gas acid employed, loss of water from the composition also promotes volatilisation of the fugitive non-gas acid from the composition.
  • Loss of the fugitive non-gas acid from the composition in turn leaves the copolymer in a non-protonated state and substantially water insoluble.
  • the substantially water insoluble form of the copolymer advantageously promotes water resistance of polymer derived from the composition in accordance with the invention.
  • the copolymer used in accordance with the invention comprises polymerised residues of ethylenically unsaturated monomer comprising a functional group for promoting crosslinking of the copolymer.
  • a functional group for promoting crosslinking of the copolymer is intended to mean a functional group that will react with the un-blocked form of the reversibly blocked crosslinking agent used in accordance with the invention and does not react to any significant extent with the blocked form of the reversibly blocked crosslinking agent used in accordance with the invention.
  • the copolymer comprises polymerised residues of ethylenically unsaturated monomer comprising a functional group for promoting crosslinking of the copolymer selected from hydroxy, carboxylic acid, epoxy, ketone, aldehyde, alkene, alkyne, amine, azide, halide (e.g. alkylhalide, benzylhalide), hydrazide and combinations thereof.
  • a functional group for promoting crosslinking of the copolymer selected from hydroxy, carboxylic acid, epoxy, ketone, aldehyde, alkene, alkyne, amine, azide, halide (e.g. alkylhalide, benzylhalide), hydrazide and combinations thereof.
  • ethylenically unsaturated monomer comprising a functional group for promoting crosslinking of the copolymer examples include those selected from glycidyl methacrylate, N-methylolacrylamide, (isobutoxymethyl)acrylamide, hydroxyethyl acrylate, i-butyl- carbodiimidoethyl (meth)acrylate, (meth)acrylic acid, ⁇ - methacryloxypropyltriisopropoxysilane, 2-isocyanoethyl (meth)acrylate, diacetone (meth)acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, diacetone (meth)acrylate, melaic anhydride, (meth)acrolein, crotonaldehyde, aceto acetoxy ethylmethacrylate, vinylaceto acetate and combinations thereof.
  • the copolymer comprises polymerised residues
  • the amount in the copolymer of polymerised residues of ethylenically unsaturated monomer comprising a functional group for promoting crosslinking of the copolymer will of course dictate the crosslink density of polymer derived from the aqueous composition according to the invention.
  • polymerised residues of ethylenically unsaturated monomer comprising a functional group for promoting crosslinking of the copolymer will be present in the copolymer in an amount ranging from about 0.5-20, 0.5-15, 0.5-10, or 0.5-8, or 1-5 mol%, relative to the total number of mols of polymerised monomer residue of a copolymer.
  • the non-pro tonated form of the copolymer used in accordance with the invention will promote water resistance of a polymer mass or film derived from the aqueous polymer composition as herein described
  • the non-protonated basic functional groups of the copolymer in the so formed polymer can be re-protonated, for example upon the polymer being exposed to an acidic aqueous composition. In that case, water resistance of the so formed polymer can be impaired.
  • the copolymer used in the composition undergoes crosslinking as herein described.
  • crosslinking of the copolymer will impart improved properties, such as improved water resistance, to the resulting polymer and reduce impairment of water resistance properties that may arise from the basic functional groups of the copolymer in the polymer again becoming protonated.
  • Crosslinking of the copolymer used in accordance with the invention in polymer derived from the aqueous polymer composition can also impart to the polymer other improved properties such as improved durability, hardness and chemical resistance.
  • the storage stable crosslinkable aqueous polymer composition according to the present invention uses copolymer which comprises polymerised residues of ethylenically unsaturated monomer comprising a basic functional group in an amount of less than 25 mol%, relative to the total number of mols of polymerised monomer residues of the copolymer. Surprisingly, it has been found the copolymer can still be sufficiently solubilised in the aqueous liquid when it contains a relatively low mol % of protonatable polymerised monomer residues.
  • the relatively low mol % of protonatable polymerised monomer residues in the copolymer has in turn has been found to impart improved properties, such as water (including acidic water) resistance and stain resistance properties, to polymer film derived from the storage stable crosslinkable aqueous polymer composition.
  • improved properties such as water (including acidic water) resistance and stain resistance properties
  • the ability to employ copolymer containing a relatively low mol % of protonatable polymerised monomer residues is believed to at least in part stem from the use of a fugitive non-gas acid in the composition.
  • Improved properties of polymer derived from the aqueous polymer composition in accordance with the invention can therefore advantageously be seen to be derived collectively from the relatively low mol % of protonatable polymerised monomer residues of the copolymer, the crosslinked form of the copolymer and the use of a fugitive non-gas acid in the composition.
  • the copolymer used in accordance with the invention comprises polymerised residues of hydrophobic ethylenically unsaturated monomer.
  • hydrophobic and hydrophilic are used in the art as an indicator of favourable or unfavourable interactions of one substance relative to another (e.g. attractive or repulsive interactions such as solubility and insolubility) and are not intended to define absolute qualities of a substance per se.
  • hydrophobic and hydrophilic are intended to be used as an indicator of an ethylenically unsaturated monomers tendency to be soluble or insoluble within water.
  • hydrophobic ethylenically unsaturated monomer to have solubility in water of no more than 20g/L at 25°C
  • hydrophilic ethylenically unsaturated monomer to have solubility in water of greater 20g/L at 25°C.
  • hydrophobic ethylenically unsaturated monomers include, but are not limited to, those selected from styrene, alpha-methyl styrene, methyl methacrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, ethyl hexyl (meth)acrylate, crotyl (meth)acrylate, cinnamyl (meth)acrylate, oleyl (meth)acrylate, ricinoleyl (meth)acrylate, cholesteryl (meth)acrylate, cholesteryl (meth)acrylate, cholesteryl (meth)acrylate, vinyl butyrate, vinyl tert-butyrate, vinyl stearate, vinyl laurate, 2-(2-o
  • references herein to an alkyl group with more than three carbon atoms that can present in a given compound as a structural isomer is intended to embrace all such isomers.
  • reference to butyl (meth)acrylate is intended to embrace n-butyl (meth)acrylate, i-butyl (meth)acrylate and s-butyl (meth)acrylate.
  • the copolymer comprises polymerised residues of hydrophobic ethylenically unsaturated monomer selected from methyl methacrylate, i-butyl (meth)acrylate and combinations thereof.
  • the copolymer used in accordance with the invention will generally comprise polymerised residues of hydrophobic ethylenically unsaturated monomer in an amount ranging from about 50-90, 60-90, or 60-80 mol%, relative to the total number of mols of polymerised monomer residue of the copolymer.
  • Incorporating polymerised residues of hydrophobic ethylenically unsaturated monomer in the copolymer used in accordance with the invention advantageously promotes improved water resistance properties of polymer derived from the aqueous polymer composition.
  • the glass transition temperature (Tg) of a polymer is a parameter often taken into account when formulating polymer composition for a given application.
  • the "Tg” is a narrow range of temperature over which an amorphous polymer (or the amorphous regions in a partially crystalline polymer) changes from a relatively hard and brittle state to a relatively viscous or rubbery state.
  • the Tg of the co-polymer used in the present invention can conveniently be tailored to suit the intended application of the aqueous polymer composition according to the invention.
  • the copolymer used in accordance with the invention comprises polymerised residues of the hydrophobic ethylenically unsaturated monomer that represents a majority of polymerised monomer residues in the copolymer.
  • the polymerised residues of the hydrophobic ethylenically unsaturated monomer may represent at least 50 mol%, relative to the total number of mols of polymerised monomer residue of the copolymer.
  • the polymerised residues of the at least one other ethylenically unsaturated monomer can strongly influence the overall Tg of the copolymer.
  • the amount and type of polymerised residues of the hydrophobic ethylenically unsaturated monomer are selected to provide for a Tg of the copolymer ranging from about -25 °C to about 100°C.
  • polymerised ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid promotes water solubility of the copolymer.
  • the polymerised ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid can not be the polymerised hydrophobic ethylenically unsaturated monomer.
  • polymerised ethylenically unsaturated monomer comprising a functional group for promoting crosslinking of the copolymer could, depending on the nature of the functional group, also function as (i) polymerised ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid and promotes water solubility of the copolymer, or (ii) polymerised hydrophobic ethylenically unsaturated monomer.
  • the copolymer comprises dedicated polymerised residues from each specified category of ethylenically unsaturated monomer.
  • the copolymer comprises polymerised residues of: (i) ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid, the polymerised residues of that monomer being present in an amount of less than 25 mol%, relative to the total number of mols of polymerised monomer residues of the copolymer;
  • the hydrophobic ethylenically unsaturated monomer does not comprise a functional group for promoting crosslinking of the copolymer
  • the ethylenically unsaturated monomer comprising a functional group for promoting crosslinking of the copolymer does not comprise a basic functional group that is protonated by the fugitive non-gas acid.
  • ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid can not be the hydrophobic ethylenically unsaturated monomer and vice versa.
  • Providing the copolymer in a form that is soluble in the aqueous liquid is an important feature of the present invention. However, also important is for the aqueous polymer composition in accordance with the invention to provide for polymer with at least improved water resistance properties.
  • the water resistance properties of the polymer can be impaired by too many basic functional groups in the copolymer subsequently becoming re-pro tonated.
  • the crosslinked nature of the resulting polymer and incorporation of polymerised residues of hydrophobic ethylenically unsaturated monomer in the copolymer can advantageously offset some impairment of water resistance that may stem from basic functional groups of the copolymer becoming re-protonated, as discussed there is an advantage in minimising in the copolymer the amount of polymerised residues of ethylenically unsaturated monomer comprising a basic functional group.
  • the storage stable crosslinkable aqueous polymer composition in accordance with the invention is advantageously formulated to have a relatively low mol % of protonatable polymerised monomer residues of the copolymer.
  • compositions in accordance with the invention can be further improved by using in the copolymer a proportion of polymerised hydrophilic ethylenically unsaturated monomer.
  • polymerised hydrophilic ethylenically unsaturated monomer in the copolymer can assist with promoting solubility of the copolymer in the aqueous liquid and yet minimise adverse water, including acidic water, solvation of polymer derived from the composition.
  • the copolymer used in accordance with the invention further comprises polymerised residue of hydrophilic ethylenically unsaturated monomer.
  • the copolymer may further comprise polymerised residues of hydrophilic ethylenically unsaturated monomer in an amount ranging from about 0.5-10, or about 0.5-5, or about 0.5-3 mol%, relative to the total number of mols of polymerised monomer residue of the copolymer.
  • the copolymer used in accordance with the invention comprises polymerised residues of ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid in an amount of less than about 15, or less than about 12, or less than about 10 mol%, relative to the total number of mols of polymerised monomer residue of the copolymer.
  • the copolymer used in accordance with the invention further comprises polymerised residue of hydrophilic ethylenically unsaturated monomer and polymerised residues of ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid in an amount of less than about 15, or less than about 12, or less than about 10 mol%, relative to the total number of mols of polymerised monomer residue of the copolymer.
  • hydrophilic ethylenically unsaturated monomer examples include those selected from (meth)acrylic acid, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, oligo(alkylene glycol)methyl ether (meth)acrylate (OAG(M)A), hydroxyl terminated oligoethylene glycol) (meth)acrylate, acrylamide, dimethyl acrylamide, methacrylamide, dimethyl methacrylamide, itaconic acid, p-styrene carboxylic acid(s), p-styrene sulfonic acid(s), vinyl sulfonic acid, vinyl phosphonic acid, ethylcrylic acid, alpha-chloroacrylic acid, crotonic acid, fumaric acid, citraconic acid, mesaconic acid, maleic acid, sulfoethyl (meth)acrylates, phosphoethyl (meth)acrylate, phosphorylcholine
  • the copolymer does not comprise polymerised residues of acid functionalised ethylenically unsaturated monomer in an amount over 10 mol%, or 8 mol%, or 5 mol%, relative to the total number of mols of polymerised monomer residue of the copolymer.
  • the alkylene moiety will generally be a C 2 -C6, for example a C 2 or C 3 , alkylene moiety.
  • oligo nomenclature associated with the "(alkylene glycol)" refers to the presence of a plurality of alkylene glycol units.
  • the oligo component of the OAG(M)A will comprise about 2 to about 50, for example from about 2 to about 40, or from about 2 to about 30 or from about 2 to about 20 alkylene glycol repeat units.
  • the copolymer further comprises polymerised residue of hydrophilic ethylenically unsaturated monomer selected from hydroxyethyl (meth)acrylate.
  • polymerised residues of ethylenically unsaturated monomer comprising (i) a basic functional group that is protonated by the fugitive non-gas acid, or (ii) a functional group for promoting crosslinking of the copolymer, is or may be hydrophilic in character
  • the copolymer "further" comprising polymerised residue of hydrophilic ethylenically unsaturated monomer the intention is for copolymer to comprise different polymerised hydrophilic ethylenically unsaturated monomer residue to that which is already present.
  • such further polymerised hydrophilic ethylenically unsaturated monomer is intended to play a different primary function than (i) the polymerised ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid, and (ii) the polymerised ethylenically unsaturated monomer comprising a functional group for promoting crosslinking of the copolymer.
  • Polymerised hydrophilic ethylenically unsaturated monomer of course can not function as the polymerised hydrophobic ethylenically unsaturated monomer.
  • the copolymer further comprises polymerised residue of hydrophilic ethylenically unsaturated monomer
  • the polymerised residue of such hydrophilic ethylenically unsaturated monomer will generally not comprise (i) a basic functional group that is protonated by the fugitive non-gas acid, or (ii) a functional group that can react with the reversibly blocked crosslinking agent to promote crosslinking of the copolymer.
  • the copolymer used in accordance with the invention may be a random or statistical copolymer.
  • the copolymer used in accordance with the invention is not a block copolymer.
  • the copolymer used in accordance with the invention can be solubilised in the aqueous liquid, there is no particular limitation on the number average molecular weight (Mn) of the copolymer.
  • the Mn of the copolymer will range from about 10,000 to about 50,000, or from about 10,000 to about 40,000
  • Formulae (I) and (II) are intended to represent copolymer that may be used in accordance with the invention comprising polymerised residues of ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid (BFM), ethylenically unsaturated monomer comprising a functional group for promoting crosslinking of the copolymer (CFM), hydrophobic ethylenically unsaturated monomer (HBM) (Formula I), and optionally hydrophilic ethylenically unsaturated monomer (HLM) (Formula II), where * represents the remainder of the copolymer and a-d represent the mol% of the respective polymerised monomer residues.
  • BFM fugitive non-gas acid
  • HBM hydrophobic ethylenically unsaturated monomer
  • HBM hydrophilic ethylenically unsaturated monomer
  • * represents the remainder of the copoly
  • the features (BFM), (CFM), (HBM) and (HLM) are not intended to be limited to a block copolymer structure. Rather, these features are intended to simply represent the components present and not their relative orientation in the copolymer.
  • the copolymer is not a block copolymer. In another embodiment, the copolymer is a statistical or random copolymer.
  • the copolymer used in accordance with the present invention will generally be present in the composition in an amount ranging from about 5 wt.% to about 60 wt.%.
  • the polymerisation technique that may be employed to form the copolymer used in accordance with the invention. Those skilled in the art will be familiar with suitable polymerisation techniques.
  • the copolymer will be prepared using free radical polymerisation.
  • Ethylenically unsaturated monomers that may be used to prepare the copolymer include those herein described.
  • the polymerisation technique used to prepare the copolymer may be conducted in an aqueous, non-aqueous hydrophilic or non-aqueous hydrophobic reaction medium or solvent.
  • Using an aqueous reaction medium to prepare the copolymer is advantageous in that it delivers the copolymer directly in an aqueous medium for incorporation into a waterborne formulation.
  • the copolymer is prepared using an aqueous reaction medium having a pH in the range 4-7.
  • aqueous or non-aqueous hydrophilic reaction mediums include, but are not limited to, water, water miscible organic solvents such as C1-C3 alcohols, alkyl glycols, acetone, methyl ketone, tetrahydrofuran, dioxane, N-methylpyrrolidone, acetonitrile, dimethylformamide, dimethylsulfoxide and combinations thereof.
  • non-aqueous hydrophobic reaction media include benzene, toluene, xylene, alkylbenzenes, dialkylbenzenes, alkanes and combinations thereof.
  • Polymerisation of ethylenically unsaturated monomers by free radical polymerisation may require initiation from a source of free radicals.
  • a source of initiating radicals can be provided by any suitable means of generating free radicals, such as the thermally induced homolytic scission of suitable compound(s) (thermal initiators such as peroxides, peroxyesters, or azo compounds), the spontaneous generation from monomers (e.g. styrene), redox initiating systems, photochemical initiating systems or high energy radiation such as electron beam, X- or gamma-radiation.
  • Thermal initiators are generally chosen to have an appropriate half life at the temperature of polymerisation. These initiators can include one or more of the following compounds:
  • Redox initiator systems are generally chosen to have an appropriate rate of radical production under the conditions of the polymerisation; these initiating systems can include, but are not limited to, combinations of the following oxidants and reductants: oxidants: potassium, peroxydisulfate, hydrogen peroxide, t-butyl hydroperoxide, t- butyl perbenzoate. reductants: iron (II), titanium (III), potassium thiosulfite, potassium bisulfite, sodium formaldehyde sufoxylate, disodium 2-hydroxy-2-sulfinatoacetate, Bruggolit FF06, ascorbic acid, sodium ascorbate, sodium erythorbate.
  • oxidants potassium, peroxydisulfate, hydrogen peroxide, t-butyl hydroperoxide, t- butyl perbenzoate.
  • reductants iron (II), titanium (III), potassium thiosulfite, potassium bisulfite, sodium formaldehyde sufoxylate
  • Initiators that are more readily solvated in hydrophilic reaction media include, but are not limited to, 4,4-azobis(cyanovaleric acid), 2,2'-azobis ⁇ 2-methyl-N-[l,l-bis(hydroxymethyl)-2- hydroxyethyl]propionamide ⁇ , 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'- azobis(N,N'-dimethyleneisobutyramidine), 2,2'-azobis(N,N'-dimethyleneisobutyramidine) dihydrochloride, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis ⁇ 2-methyl-N- [1,1 -bis(hydroxymethyl)-2-ethyl]propionamide ⁇ ,2,2' -azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (known as VA-044), 2,2'-azobis[2-(2-imid
  • Initiators that are more readily solvated in hydrophobic reaction media include azo compounds exemplified by the well known material 2,2'- azobisisobutyronitrile.
  • Other suitable initiator compounds include the acyl peroxide class such as acetyl and benzoyl peroxide as well as alkyl peroxides such as cumyl and t-butyl peroxides. Hydroperoxides such as t-butyl and cumyl hydroperoxides are also widely used.
  • the polymer used contains low levels of monomer that has not undergone polymerisation during manufacture of the polymer.
  • Means for minimising unreacted monomer residue in polymer products are known to those skilled in the art.
  • multiple stage addition of initiator systems during polymerisation can be used to minimise unreacted monomer residue in the so formed polymer.
  • the free radical polymerisation of the monomers may proceed by conventional free radical polymerisation or by so-called living free radical polymerisation.
  • Living polymerisation is generally considered in the art to be a form of chain polymerisation in which irreversible chain termination is substantially absent.
  • An important feature of living polymerisation is that polymer chains will continue to grow while monomer and the reaction conditions to support polymerisation are provided.
  • living polymerisation agent is meant a compound that can participate in and control or mediate the living polymerisation of the ethylenically unsaturated monomers so as to form a living polymer chain (i.e. a polymer chain that has been formed according to a living polymerisation technique).
  • free radical living polymerisation techniques include iniferter polymerisation, stable free radical mediated polymerisation (SFRP), atom transfer radical polymerisation (ATRP), and reversible addition fragmentation chain transfer (RAFT) polymerisation.
  • Molecular weight control of the copolymer can be achieved by the use of conventional chain transfer agents such as thiols, allylic, allylic sulphides (Macromolecules 1988, 21, 3122-3124) styrene derivatives (Polymer 2008, 49, 1079-1131), alkenes such as 2,4-diphenyl-4-methyl-l- pentene, terpenes and similar compounds such as terpinolene, gamma terpinene, 5-ethylidene- 2-norbornene and perillyl alcohol and combinations thereof.
  • chain transfer agents such as thiols, allylic, allylic sulphides (Macromolecules 1988, 21, 3122-3124) styrene derivatives (
  • terpinolene also known as ⁇ -terpinene, 4-isopropylidene-l-methylcyclohexene, or Nofmer TP
  • terpinolene is used as a chain transfer agent when preparing the copolymer in an aqueous reaction medium.
  • terpinolene is used in an amount of no more than about 1.5 mol %, or no more than 1 mol %, relative to the total moles of monomer polymerised.
  • Synthesis of the copolymer may be performed in organic solvent, water or a combination of both. It can be advantageous to make the polymer in an aqueous liquid as the resulting copolymer solution can then be directly used in preparing compositions in accordance with the invention.
  • synthesis of the copolymer may involve use of a non-aqueous or aqueous liquid, the required ethylenically unsaturated monomers, one or more initiators, one or more fugitive non-gas acids, molecular weight control agent (such as a chain transfer agent) with other additives being added if required such as salts, surfactant, de-foaming agents etc.
  • a non-aqueous or aqueous liquid the required ethylenically unsaturated monomers
  • one or more initiators one or more fugitive non-gas acids
  • molecular weight control agent such as a chain transfer agent
  • Synthesis of the copolymer in an aqueous reaction medium can be advantageous. This allows the formulator latitude in adding water miscible co-solvents or other ingredients as part of the process of preparing compositions in accordance with the invention.
  • Synthesis of the copolymer in an aqueous liquid using hydrophobic ethylenically unsaturated monomer is preferably performed by minimising a tendency to form separate monomer/copolymer droplets within the reaction medium.
  • the objective here is of course to form an aqueous copolymer solution and not latex particles.
  • the copolymer comprises polymerised residues of hydrolysis sensitive ethylenically unsaturated monomer and the copolymer is prepared in an aqueous liquid under acidic conditions to (i) promote solubilisation of the copolymer through protonation of its basic functional groups, and (ii) prevent or minimise hydrolysis of any hydrolysis sensitive ethylenically unsaturated monomer being used.
  • hydrolysis sensitive ethylenically unsaturated monomer examples include DMAEMA and methyl methacrylate (MMA).
  • the acid content of the aqueous liquid reaction medium may vary depending on the amount of basic functional groups of the copolymer and the hydrolysis sensitivity of the ethylenically unsaturated monomer being used.
  • the acid concentration [H + ] in the aqueous liquid reaction medium will fall within the range of 0.5 to 2, or 0.75-1.5, or 0.8-1.2 molar equivalents to the mols of ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid being used.
  • the copolymer may be prepared in batch or by feed-addition of reactants over time.
  • the polymerisation may be performed under a suitable non-oxygen containing atmosphere as is commonly done for free radical polymerizations. Without limiting the invention, it can be advantageous to deoxygenate the reaction media, all reactants and their solutions as is typically done in conventional free radical polymerizations.
  • the copolymer is prepared by feed addition of the ethylenically unsaturated monomers to an aqueous liquid.
  • the copolymer is prepared by feed addition of the ethylenically unsaturated monomers comprising fugitive non-gas acid to an aqueous liquid.
  • aqueous copolymer synthesis procedure is as follows.
  • the polymerisation is carried out by deoxygenating water in a reaction vessel and kept under nitrogen and a portion of initiator may be added. The solution is stirred and heated to 60 C.
  • seed polymer previously prepared, for example from a previous synthesis batch
  • This seed polymer can be the same composition as the polymer being made or it can be different but it should still contain polymerised ethylenically unsaturated monomers as described herein. It will be appreciated by those skilled in the art that such seed polymer should be compatible with the bulk copolymer being produced but it doesn't necessarily need to be the same overall composition. Seed polymer can be used in an amount up to about 5%, or 4% or 3 (v/v).
  • seed polymer is believed to assist with solubilising the in-coming ethylenically unsaturated monomer and provide for a homogeneous reaction zone.
  • copolymers can be made without the use of the seed polymer.
  • a feed of the ethylenically unsaturated monomer, fugitive non-gas acid and chain transfer agent (if required) is then added to the reaction vessel via a pump over 4 hours. Simultaneously to this feed, a separate feed of initiator (if required) in water is added via a pump over a six hour period. At the end of the addition of initiator, an additional batch initiator may be added if required. Under these conditions, conversion of ethylenically unsaturated monomers is generally essentially complete with only trace amounts (ca. ⁇ 0.5% mole) of unreacted ethylenically unsaturated monomer remaining. This may be further reduced if required by conventional methods such as the addition of redox couples such as t-butyl hydroperoxide and sodium formaldehyde sulfoxylate.
  • redox couples such as t-butyl hydroperoxide and sodium formaldehyde sulfoxylate.
  • hydrolysis of hydrolysis sensitive ethylenically unsaturated monomer may occur during polymerisation. However, this will generally be less than about 5 mol % of that monomer and has no apparent adverse effect on the performance of the compositions according to the invention.
  • the resulting aqueous solution is advantageously suitable for direct use in preparing the aqueous polymer composition according to the invention.
  • the other components used in the composition are introduced as required. Variations and adjustments to the above procedure may be applied by those skilled in the art depending on the scale, reaction time required etc.
  • An additional variation is that salts maybe added to the solution before during or after the polymerization to adjust the viscosity of the solution.
  • a preferred salt for this purpose is ammonium acetate with other salts such ammonium bicarbonate also suitable.
  • Feeding the ethylenically unsaturated monomer into the reaction vessel provides an ability to skew feed the monomers or add different monomers throughout the polymerization. This allows a high degree of customization of the copolymer formed.
  • All ethylenically unsaturated monomers can also be added simultaneously in a constant ratio to each other.
  • the copolymer may also be synthesized in organic solvent.
  • One advantage of synthesizing the polymer in such solvent is that issues with monomer hydrolysis can be minimised or avoided. However, in that case the solvent will of course need to be removed and the resulting copolymer isolated then dissolved in acidic water for use in accordance with the invention.
  • synthesis in non-aqueous solvent may be done in batch or continuous feed.
  • the present invention also provides a method of preparing an aqueous copolymer composition, the method comprising polymerising in an aqueous liquid comprising a fugitive non-gas acid ethylenically unsaturated monomer selected from:
  • ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid, that monomer being used in an amount of less than 25 mol%, relative to the total number of mols of ethylenically unsaturated monomers introduced during polymerisation to prepare the copolymer;
  • That method comprises polymerising in an aqueous liquid which comprises a fugitive non-gas acid, ethylenically unsaturated monomer selected from each of groups (i), (ii) and (iii).
  • aqueous liquid, fugitive non-gas acid and ethylenically unsaturated monomers used are as described herein.
  • ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid may be used in an amount ranging from about 1-20 or 1-15, or 1- 10 mol%, relative to the total number of mols of ethylenically unsaturated monomers introduced during polymerisation to prepare the copolymer.
  • the ethylenically unsaturated monomer comprising a basic functional group (that is protonated by the fugitive non-gas acid) is used in an amount of less than 20 mol%, or less than 15 mol%, or less than 10 mol%, relative to the total number of mols of ethylenically unsaturated monomers introduced during polymerisation to prepare the copolymer.
  • ethylenically unsaturated monomer comprising a functional group for promoting crosslinking of the copolymer will be used in an amount ranging from about 0.5-20, 0.5-15, 0.5-10, or 0.5-8, or 1-5 mol%, relative to the total number of mols of ethylenically unsaturated monomers introduced during polymerisation to prepare the copolymer.
  • generally hydrophobic ethylenically unsaturated monomer will be used in an amount ranging from about 50-90, 60-90, or 60-80 mol%, relative to the total number of mols of ethylenically unsaturated monomers introduced during polymerisation to prepare the copolymer.
  • the method of preparing or forming an aqueous copolymer solution further comprises polymerising hydrophilic ethylenically unsaturated monomer.
  • hydrophilic ethylenically unsaturated monomer will be used in an amount ranging from about 0.5-10, or about 0.5-5, or about 0.5-3 mol%, relative to the total number of mols of ethylenically unsaturated monomers introduced during polymerisation to prepare the copolymer.
  • the ethylenically unsaturated monomers are polymerised such that the so formed copolymer does not comprise polymerised residues of acid functionalised ethylenically unsaturated monomer in an amount over 10 mol%, or 8 mol%, or 5 mol %, relative to the total number of mols of polymerised monomer residue of the copolymer.
  • the copolymer is prepared or formed using an aqueous reaction medium having a pH in the range 4-7.
  • the acid concentration [H + ] in the aqueous liquid reaction medium will fall within the range of 0.5 to 2, or 0.75-1.5, or 0.8-1.2 molar equivalents to the mols of ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid being used.
  • the aqueous polymer composition in accordance with the invention comprises a reversibly blocked crosslinking agent for promoting crosslinking of the copolymer.
  • the reversibly blocked crosslinking agent is provided in the composition in combination with a fugitive crosslinking inhibitor for inhibiting crosslinking of the copolymer by the reversibly blocked crosslinking agent.
  • a fugitive crosslinking inhibitor for inhibiting crosslinking of the copolymer by the reversibly blocked crosslinking agent.
  • the reversibly blocked crosslinking agent may be provided in the composition by being adsorbed on dispersed particulate material.
  • the crosslinking agent being "reversibly blocked” is intended to mean the crosslinking agent is capable of presenting in the composition according to the invention in a blocked form and an unblocked form.
  • the crosslinking agent does not react to any significant extent, if at all, with polymerised monomer residues of the copolymer that provide a functional group for promoting crosslinking of the copolymer.
  • the un-blocked form the crosslinking agent can readily react with polymerised monomer residues of the copolymer that provide a functional group for promoting crosslinking of the copolymer to thereby crosslink the copolymer.
  • crosslinking agent being "reversibly" blocked is therefore intended to mean the crosslinking agent in effect can present in equilibrium within the aqueous polymer composition between a blocked and an un-blocked form.
  • the reversibly blocked crosslinking agent per se may be introduced to the aqueous liquid or it can be formed in situ.
  • BG represents the blocking group(s) and CA represents the crosslinking agent and P represents the copolymer having functional groups that can reversibly react with CA.
  • CA is multifunctional as it will be required to crosslink the copolymer.
  • ADH has two hydrazide groups. Blocking groups such as acetone can react with at least one hydrazide group to make a hydrazone and so prevent crosslinking with reactive groups of the copolymer.
  • the presence of water e.g. from the aqueous liquid
  • the reverse reaction can also occur and an equilibrium is set up between the blocked and unblocked forms of the crosslinking agent.
  • BG from the composition can evaporate or be absorbed by the substrate thereby promoting crosslinking of the copolymer P and in turn drive the equilibrium to formation of further unblocked crosslinking agent and its reaction with the copolymer P.
  • that loss of BG e.g. acetone
  • the centre (II) and far left (I) positions represent uncrosslinked polymer that exists in the composition during storage and is favoured by the presence of excess BG.
  • the blocking group is a fugitive blocking group in the sense that it can readily escape from the applied composition along with water and the fugitive non-gas acid.
  • the loss of BG drives the equilibrium to provide for unblocked crosslinking agent, which in turn of course facilitates crosslinking of the copolymer.
  • the reversibly blocked crosslinking agent for promoting crosslinking of the copolymer is blocked with a fugitive blocking group(s).
  • a fugitive blocking group(s) is intended to mean a compound that (i) functions to block reactivity of the crosslinking agent with the crosslinking functional groups of the copolymer, and (ii) can escape (e.g. through evaporation or by being absorbed into the substrate) from aqueous polymer compositions in accordance with the invention under conditions in which the compositions are conventionally used.
  • the crosslinking agent will require at least two functional groups capable of reacting with functional groups for promoting crosslinking that form part of the copolymer.
  • functional groups of the crosslinking agent that can react with functional groups of the copolymer to form a crosslink may herein be described as the reactive functional groups of the crosslinking agent.
  • at least two of the reactive functional groups of the crosslinking agent will each react with a functional group on two separate copolymer chains in order to form the crosslink.
  • the crosslinking agent While all reactive functional groups of the crosslinking agent can be reversibly blocked as herein described, it is possible to perform the present invention with one of such reactive groups remaining unblocked. In that case the unblocked reactive functional group of the crosslinking agent may react with a functional group of the copolymer for promoting crosslinking. However, because all remaining reactive functional groups of the crosslinking agent are reversibly blocked the crosslinking agent will not crosslink the copolymer until at least one of the reversibly blocked reactive functional groups becomes unblocked (and reacts with the copolymer).
  • crosslinking agent being "reversibly blocked” covers situations where all, or all but one, of the reactive functional groups are blocked (reversibly) from undergoing reaction with the copolymer to form a crosslink as herein described.
  • the amount of reversibly blocked crosslinking agent used in accordance with the invention will generally be tailored to react with substantially all of the functional groups provided by the copolymer for promoting crosslinking.
  • the amount of reversibly blocked crosslinking agent will of course vary depending upon the number of reactive functional groups provided by the crosslinking agent. For example, where the reversibly blocked crosslinking agent comprises two reactive functional groups the number of mols of the reversibly blocked crosslinking agent will be approximately half the number of mols of functional groups provided by the copolymer for promoting crosslinking. Similarly, where the reversibly blocked crosslinking agent comprises three reactive functional groups, the number of mols of reversibly blocked crosslinking agent may be approximately 1/3 of the number of mols of functional groups provided by the copolymer for promoting crosslinking, and so on. In one embodiment, the mole ratio of the reversibly blocked crosslinking agent and the number of functional groups for promoting crosslinking of the copolymer ranges from about 0.5 mole equivalents to about 1.5 mole equivalents.
  • An example of a suitable reversibly blocked crosslinking agent includes, but is not limited to, reversibly blocked multifunctional hydrazide compounds.
  • multifunctional hydrazide compound in intended to mean a compound having two or more hydrazide functional groups.
  • the multifunctional hydrazide compound comprises two, three, or four hydrazide functional groups.
  • the reactive (crosslinking) functional groups of such a multifunctional hydrazide compound are the hydrazide functional groups.
  • a hydrazide functional group can react with functional groups containing a carbonyl moiety such as a ketone or aldehyde. Accordingly, where a reversibly blocked multifunctional hydrazide compound is used as a crosslinking agent in accordance with the invention the copolymer will of course comprise polymerised residues of ethylenically unsaturated monomer comprising a functional group for promoting crosslinking of the copolymer selected from a carbonyl containing functional group such as a ketone, aldehyde and combinations thereof.
  • the multifunctional hydrazide compound is reversibly blocked in the form of a hydrazone compound.
  • the reversibly blocked crosslinking agent is selected from a multi functional hydrazone compound or a compound comprising at least one hydrazone functional group and one hydrazide functional group.
  • multifunctional hydrazone compound is intended to mean a compound having two or more hydrazone functional groups.
  • a multi functional hydrazone compound used in accordance with the invention will generally contain no more than one hydrazide functional group. In one embodiment, a multifunctional hydrazone compound used in accordance with the invention contains no hydrazide functional groups.
  • the reversibly blocked crosslinking agent used in accordance with the invention comprises two hydrazone functional groups and no hydrazide functional groups.
  • the reversibly blocked crosslinking agent used in accordance with the invention comprises one hydrazone functional group and one hydrazide functional group.
  • reversibly blocked crosslinking agents that may be used in accordance with the invention comprising two hydrazone functional groups and no hydrazide functional groups, or one hydrazone functional group and one hydrazide functional group include, but are not limited to, those defined by general formulae (I)-(IV) below.
  • R represents a divalent organic group or a covalent bond
  • Ri-R 4 are each independently selected from hydrogen and an organic group.
  • R and Ri-R j are each independently selected from optionally substituted alkyl, optionally substituted alkenyl, and optionally substituted alkynyl. In a further embodiment, R and Ri-R j each independently contain from 1 to 24 carbon atoms, or from 1 to 12 carbon atoms.
  • Ri and R 2 or R 3 and R 4 are independently joined together to form a cyclic group.
  • R -R are each independently hydrogen or independently selected from Ci-C 6 alkyl, Ci-C 6 alkenyl, and Ci-C 6 alkynyl, and R is selected from C 1 -C 12 optionally substituted alkyl.
  • each of Ri-R 4 is a methyl group and R is selected from C 1 -C 12 optionally substituted alkyl.
  • R is a divalent organic group as illustrated that is substituted with a further hydrazone functional group.
  • R may be a divalent alkyl, alkenyl, or alkynyl group substituted with a hydrazone functional group.
  • reaction scheme (II) To further explain the reversibly blocked nature of the reversibly blocked crosslinking agent used in accordance with the invention reference is made to reaction scheme (II) below.
  • a dihydrazide compound i.e. the unblocked form of the crosslinking agent
  • acetone in the presence of water to form a dihydrazone compound.
  • This equilibrium is predominantly in favour of formation of the hydrazone compound (also see below the discussion on the function of the fugitive crosslinking inhibitor).
  • loss of acetone can promote reaction of any dihydrazide compound present with the copolymer (that also contains acetone or aldehyde group) to promote crosslinking.
  • loss of acetone from the composition can promote crosslinking of the copolymer and in turn drive the equilibrium to formation of further dihydrazide compound. Furthermore, formation of the dihydrazide compound of course also releases the blocking group in the form of acetone.
  • the acetone is fugitive and can also escape from the applied composition along with water, fugitive non-gas acid and any other volatile components in the composition. Loss of the acetone from the composition is a driving force in the equilibrium to provide for the dihydrazide compound, which in turn of course facilitates crosslinking of the copolymer.
  • the reversibly blocked crosslinking agent is selected from succinic acid di(propylidene hydrazide), oxalic acid di(2-propylidene hydrazide), adipic acid di(2- propylidene hydrazide), adipic acid di(2-butylidene hydrazide), adipic acid di(4-hydroxy-4- methyl-2pentylidene hydrazide, ethylenediaminetetracetic acid tetrahydrazide (EDTA- tetrahydrazide) and combinations thereof.
  • succinic acid di(propylidene hydrazide) oxalic acid di(2-propylidene hydrazide)
  • adipic acid di(2-butylidene hydrazide) adipic acid di(4-hydroxy-4- methyl-2pentylidene hydra
  • Hydrazone compounds suitable for use as a reversibly blocked crosslinking agent in accordance with the invention can be prepared by techniques well known to those skilled in the art. For example, multifunctional hydrazide compounds can be reacted with an aldehyde or ketone. When preparing the aqueous polymer composition (discussed in more detail below), such hydrazone reversibly blocked crosslinking agent may be prepared and introduced to the aqueous liquid or they can advantageously be formed in situ when preparing the composition.
  • hydrazides such as those derived from N-methyliminodiacetic acid, and EDTA.
  • a two-step reaction is generally required to covert the acids into methyl esters and then reaction with hydrazine to give the hydrazide. This illustrated below with EDTA:
  • the reaction can also be applied in the preparation of hydrazide functional polymers.
  • Polymers that contain methyl esters derived either from methyl acrylate, methyl methacrylate or other polymerisable methyl esters can be converted to polyhydrazides by the reaction of hydrazine with the polymer.
  • the polymers may contain other repeat units derived from other monomers or alternatively only a proportion of methyl esters maybe chosen to be reacted such that the polymer may correspondingly contain a proportion of hydrazide groups between 1 and 100% of the methyl esters available, e.g.:
  • Ketones or aldehydes that may be used to react with a multifunctional hydrazide to form hydrazone compounds include those of general formula (V):
  • R5 and R 6 are each independently selected from hydrogen and optionally substituted alkyl (e.g. C1-C6), provided that at least one of R5 and R 6 is an optionally substituted alkyl group, or form together a cyclic ketone.
  • aldehyde compounds include, but are not limited to, those selected from formaldehyde, acetaldehyde, butyraldehyde, benzaldehyde, cinnamaldehyde, and toluyldehyde.
  • Suitable ketone compounds include, but are not limited to, those selected from acetone methyl ethyl ketone, diethyl ketone, isopropyl methyl ketone, n-propyl methyl ketone, diisopropyl and di-n-propyl ketone, tert-butyl methyl ketone, isobutyl methyl ketone, sec-butyl methyl ketone and diisobutyl ketone, diacetone alcohol, cyclohexanone, cyclopentanone, 1- propanone, 2-propanone and acetophenone and combinations thereof.
  • the reversibly blocked crosslinking agent may also be derived from a multifunctional amine.
  • Such amines may be reversibly blocked by reaction with carbon dioxide to form a carbamate. Loss of carbon dioxide from the carbamate can reform the multifunctional amine which can react with the polymerised monomer residues of the copolymer that provide a functional group for promoting crosslinking of the copolymer.
  • the aqueous polymer composition in accordance with the invention may comprise a fugitive crosslinking inhibitor for inhibiting crosslinking of the copolymer.
  • fugitive crosslinking inhibitor is intended to mean a compound that can (i) inhibit crosslinking of the copolymer by the reversibly blocked crosslinking agent, and (ii) escape from the composition in accordance with the invention under conditions in which compositions are conventionally used as herein described.
  • the aqueous polymer composition in accordance with the invention comprises a reversibly blocked crosslinking agent for promoting crosslinking of the copolymer.
  • the reversibly blocked nature of the crosslinking agent assists with preventing premature crosslinking of the copolymer during storage of the composition (e.g. where the composition is not in use).
  • use of the reversibly blocked crosslinking agent in accordance with the invention goes some way to preventing such premature crosslinking, use of the reversibly blocked crosslinking agent alone has been found to be ineffective to render the composition storage stable.
  • reversibly blocked crosslinking agents such as those described herein in aqueous emulsion polymer compositions.
  • multifunctional hydrazone compounds have been used as a reversibly blocked crosslinking agent in emulsion coating compositions.
  • the hydrazone crosslinking agent is dissolved in the continuous aqueous liquid phase, while the polymer binder presents as a dispersed phase within the aqueous liquid.
  • the dispersed polymer binder comprises functional groups that can react with the unblocked form of the crosslinking agent.
  • the storage stable character of such crosslinkable compositions stems from (i) use of a reversibly blocked crosslinking agent dissolved in the continuous aqueous liquid phase and having an equilibrium predominantly in favour of the blocked form of the crosslinking agent, and (ii) the polymer binder comprising functional groups for promoting crosslinking being isolated in the continuous aqueous phase in the form of dispersed particles.
  • the reactive form of the crosslinking agent is simply not exposed to sufficient polymer binder bearing the functional groups for promoting crosslinking for any substantive crosslinking to occur. Accordingly, such compositions are said to be storage stable.
  • the lack of storage stability of these developmental aqueous polymer compositions is due to the polymer binder used in accordance with the invention (i.e. the copolymer) being soluble in the aqueous liquid.
  • the copolymer By the copolymer being soluble in the aqueous liquid (in contrast with being a dispersed phase) it of course exposes all of its functional groups for promoting crosslinking of the copolymer to the reversibly blocked crosslinking agent which is also dissolved in the aqueous liquid. This in turn promotes ready access of any unblocked crosslinking agent to react with functional groups of the copolymer to promote crosslinking.
  • removal of unblocked crosslinking agent from the reversibly blocked crosslinking agent equilibrium further drives formation of more unblocked crosslinking agent and the crosslinking reaction propagates.
  • reaction to promote crosslinking between the reversibly blocked crosslinking agent and the copolymer used in accordance with the invention can be inhibited by using a fugitive crosslinking inhibitor in combination with the reversibly blocked crosslinking agent so as to render the composition storage stable.
  • compositions in accordance with the invention comprise a reversibly blocked crosslinking agent for promoting crosslinking of the copolymer in combination with a fugitive crosslinking inhibitor for inhibiting crosslinking of the copolymer by the reversibly blocked crosslinking agent.
  • a fugitive crosslinking inhibitor interacts with the functional group of the copolymer for promoting crosslinking and/or the reversibly blocked crosslinking agent to more effectively and efficiently prevent premature crosslinking of the copolymer. It is believed a fugitive crosslinking inhibitor can cause the reversibly blocked crosslinking agent to present in the composition substantially entirely in its blocked form by shifting the blocked/unblocked equilibrium further in favour of the blocked form. For example, if the reversibly blocked crosslinking agent is a dihydrazone compound, the equilibrium in favour of the dihydrazone (blocked) can be promoted by including in the composition a ketone such as acetone.
  • the fugitive crosslinking inhibitor e.g. acetone
  • a fugitive crosslinking inhibitor can also interact with functional groups of the copolymer that promote crosslinking to in effect render such groups incapable of undergoing crosslinking until the composition is put into use.
  • the crosslinking functionality of the copolymer is a ketone or aldehyde
  • such functional groups may be temporarily rendered incapable of undergoing crosslinking via reaction with a fugitive crosslinking inhibitor that provides for an amine.
  • the amine can react with the ketone or aldehyde functional group to form an imine that can reversibly form back into the ketone or aldehyde.
  • the so formed imine can revert back to the ketone or aldehyde, followed by release the amine which in turn can escape the composition therefore removing a barrier to crosslinking of the copolymer.
  • the fugitive crosslinking inhibitor is a compound that chemically interacts with functionality of the copolymer which promotes crosslinking and/or of the reversibly blocked crosslinking agent so as to inhibit crosslinking of the copolymer.
  • Scheme (a) above conceptually illustrates the pronated copolymer in aqueous solution as a storage stable crosslinkable composition according to the invention.
  • Acetic acid is being used as the fugitive non-gas acid and protonates tertiary amine basis functional groups of the copolymer to promote its solubility in the aqueous liquid.
  • the copolymer contains ketone groups for promoting crosslinking of the copolymer.
  • the crosslinking agent is ADH which reversibly reacts with ketone groups (in this case acetone) to produce hydrazones.
  • the reversibly blocked crosslinking agent is therefore a reversibly blocked hydrazide.
  • Scheme (b) above conceptually illustrates how a composition of the invention generates a crosslinked polymer mass or film.
  • a storage stable crosslinkable aqueous polymer composition of the invention such as that shown above in scheme (a)
  • water, acetone and acetic acid will evaporate from the applied composition.
  • the loss of acetone (fugitive crosslink inhibitor) will result in unblocking of hydrazide groups that now increase in concertation and are available to react with carbonyl groups of the copolymer, being the only ketone groups now available for reaction.
  • a given fugitive crosslinking inhibitor will typically be selected based on the nature of (i) the reversibly blocked crosslinking agent being used, and (ii) the functional groups of the copolymer for promoting crosslinking being used in the composition. Those skilled in the art will be able to select a suitable fugitive crosslinking inhibitor having regard to the crosslinking chemistry being employed.
  • a given fugitive crosslinking inhibitor can itself directly interact with the functional group of the copolymer for promoting crosslinking and/or the reversibly blocked crosslinking, or it can produce in situ within the composition a compound that interacts with the functional group of the copolymer for promoting crosslinking and/or the reversibly blocked crosslinking agent to more effectively and efficiently prevent premature crosslinking of the copolymer.
  • An example of the later case might be where a fugitive crosslinking inhibitor such as ammonium acetate is introduced into the composition where it produces in situ ammonia and the ammonia interacts with the functional group of the copolymer for promoting crosslinking and/or the reversibly blocked crosslinking agent.
  • fugitive crosslinking inhibitors include, but are not limited to ketones such as acetone, methyl ethyl ketone, isopropyl methyl ketone, diethylketone and combinations thereof.
  • the fugitive crosslinking inhibitor is acetone. If present, the fugitive crosslinking inhibitor will generally be used in the compositions according to the invention in an amount ranging from 0.5 to 10 molar equivalents to the functional groups that participate in crosslinking of the copolymer. Dispersed particulate material
  • compositions described herein may also comprise dispersed particulate material having the reversibly blocked crosslinking agent adsorbed thereon.
  • particulate material being dispersible in the composition is meant the particulate material is substantially insoluble in the composition and forms a dispersed phase therein.
  • the dispersible particulate material will typically be solid particulate material.
  • the dispersed or dispersible particulate material may be non-polymeric.
  • dispersed or dispersible particulate material examples include, but are not limited to, inorganic pigments, organic pigments, extenders, solid fillers and combinations thereof.
  • inorganic pigments include, but are not limited to, carbon black, titanium dioxide, iron oxide, zinc chromate, azurite, chromium oxide, cadmium sulphite, lithopone, calcium carbonate, hydrated magnesium silicate, barium sulphate, hydrated aluminium silicate, silica, hydrous aluminium potassium silicate and combinations thereof.
  • organic pigments include, but are not limited to, azo dyes, polycyclic pigments and combinations thereof.
  • the dispersed or dispersible particulate material may have an average particle size dictated by the intended commercial application for the composition.
  • the dispersed or dispersible particulate material may be solid and non-porous or solid and porous.
  • the term "porous" is intended to mean holes or voids within the particulate material that have the effect of increasing its surface area.
  • the dispersed or dispersible particulate material having the reversibly blocked crosslinking agent adsorbed thereon is intended to mean that the reversibly blocked crosslinking agent is physically associated with the particulate material and substantially remains in that state during storage of the composition and at least up until the composition is used.
  • the particulate material may be provided with adsorbed reversibly blocked crosslinking agent using techniques known in the art.
  • the reversibly blocked crosslinking agent can be combined with the particulate material and conventional dispersing aids and milled to provided the desired size or the particulate material.
  • aqueous polymer compositions according to the invention comprising only the reversibly blocked crosslinking agent per se have been found to undergo premature crosslinking and are not storage stable.
  • Including a fugitive crosslinking inhibitor in the composition has surprisingly been found to prevent such premature crosslinking and impart storage stability to the composition.
  • Such premature crosslinking and imparting storage stability to the compositions might also be achieved by presenting the reversibly blocked crosslinking agent in the composition as being adsorbed on the particulate material. Without wishing to be limited by theory, it is believed that adsorbing the reversibly blocked crosslinking agent on the particulate material could limit access of unblocked crosslinking agent to the solubilised copolymer and thereby prevents premature crosslinking.
  • water can escape from the composition and in effect increase the concentration of the copolymer and particulate material in the composition.
  • This concentrating effect places the copolymer in more intimate contact with the dispersed particulate material, which in turn promotes reaction of unblocked crosslinking agent adsorbed on the particulate material and propagates crosslinking of the copolymer.
  • the reversibly blocked crosslinking agent is not present "free" in solution (i.e. the reversibly blocked crosslinking agent is bound to the particulate material).
  • Two or more different reversibly blocked crosslinking agents may be used.
  • Two or more different fugitive crosslinking inhibitors may be used.
  • composition in accordance with the invention further comprises dispersed particulate material that does not have reversibly blocked crosslinking agent adsorbed thereon.
  • composition in accordance with the invention is prepared using dispersible particulate material that does not have reversibly blocked crosslinking agent adsorbed thereon.
  • particulate material will generally be used in the compositions according to the invention in an amount dictated by the intended commercial application of the composition. Preparing the composition
  • the storage stable crosslinkable aqueous polymer composition is prepared by combining or forming in an aqueous liquid the copolymer and also combining or forming in the aqueous liquid (i) a reversibly blocked crosslinking agent for promoting crosslinking of the copolymer and, (ii) a fugitive crosslinking inhibitor for inhibiting crosslinking of the copolymer by the reversibly blocked crosslinking agent.
  • the copolymer may be formed separately from the composition and then combined with the other components in the aqueous liquid.
  • the copolymer may be prepared or formed in an aqueous liquid as described herein and the other components of the composition combined with the so formed copolymer solution.
  • the method of preparing the storage stable crosslinkable aqueous polymer composition comprises a step of forming the copolymer in the aqueous liquid, that step comprising polymerising in the aqueous liquid comprising fugitive non-gas acid ethylenically unsaturated monomer selected from:
  • ethylenically unsaturated monomer comprising a basic functional group that is protonated by the fugitive non-gas acid, that monomer being used in an amount of less than 25 mol%, relative to the total number of mols of ethylenically unsaturated monomers introduced during polymerisation to prepare the copolymer;
  • the reversibly blocked crosslinking agent may of course be combined with or formed in the aqueous liquid separate from and/or in addition to any particulate material combined in the composition which may or may not have reversibly blocked crosslinking agent adsorbed thereon.
  • Polymer derived from the composition may of course be combined with or formed in the aqueous liquid separate from and/or in addition to any particulate material combined in the composition which may or may not have reversibly blocked crosslinking agent adsorbed thereon.
  • compositions according to the invention and polymer mass/film derived therefrom can provide a number of advantages.
  • the compositions are environmentally friendly being largely water based and substantially free of relatively toxic reagents used in conventional solvent based polymer compositions.
  • Polymer derived from the compositions can advantageously be very hard and have a relatively high Tg.
  • polymer derived from emulsion compositions are typically required to have a relatively low Tg to allow coalescence of the dispersed polymer particles and formation of a continuous polymer mass or film.
  • polymer film derived from conventional emulsion compositions is typically quite soft and on hot days can result in painted surfaces sticking together such as in the case of doors and windows sticking to their frames.
  • Polymer derived from compositions according to the invention can have a relatively high Tg (e.g. >70C) as the polymer in the composition is soluble in the aqueous liquid and the need for coalescence of the dispersed polymer particles is not relevant. Polymer derived from compositions according to the invention can therefore be more durable due to their hardness.
  • Tg e.g. >70C
  • compositions according to the invention when used as clear coat, can readily penetrate and wet timber surfaces.
  • the resultant polymer film provides a hard glossy coating that accentuates the grain of the wood and gives a desirable "wet look”.
  • Traditional solvent based gloss enamel paints undergo an oxidative cure process to cure the film. However, the cure process never stops and the film becomes increasing hard until cracking, delamination or other stress related failure mechanisms occur.
  • polymer derived from compositions according to the invention does not undergo a constant cure as the "cure” is limited by the amount of crosslinking functional groups of the copolymer.
  • polymer derived from compositions according to the invention is expected to have a longer useful life than that derived from solvent based polymer compositions.
  • polymer film/mass derived from compositions according to the invention can advantageously be reconstituted back into liquid form by applying to the so formed polymer film/mass a composition comprising a fugitive non-gas acid and a suitable fugitive crosslinking inhibitor.
  • the crosslinking chemistry of the polymer film/mass can be reversed so as to re-solubilise the polymer into an aqueous liquid.
  • a composition comprising a fugitive non-gas acid and a fugitive crosslinking inhibitor can therefore advantageously be used as a form of "paint stripper" to remove the polymer film/mass from a substrate.
  • the ability to reconstitute dried crosslinked polymer composition means that cured compositions according to the invention can be shipped as dried solid and reconstituted at the required destination. Thus cost of transportation is greatly reduced as one is not paying for the transport of water.
  • a formulation consisting DMAEMA (0.15 mole), MMA (0.45) and BMA (0.30) and DAAM (0.10) with acetic acid (0.15), acetone (5ME to DAAM, 0.5 mole) and ADH (0.4 ME to DAAM, 0.04 mole) is dried either as a coating or en-mass it can advantageously be reconstituted by the addition of a solution comprising water (88% wt), acetic acid (2.9% wt) and acetone (9.1% wt).
  • composition according to the invention can be "thinned” also by adding to that composition a composition comprising a fugitive non-gas acid and a suitable fugitive crosslinking inhibitor.
  • a composition according to the invention can be "thinned” also by adding to that composition a composition comprising a fugitive non-gas acid and a suitable fugitive crosslinking inhibitor.
  • compositions according to the invention may be used in a variety of applications such as coatings and adhesives applications.
  • Coatings may be in the form of paints and clear coats for cosmetic, domestic or industrial use.
  • Decorative paints for domestic application is a suitable application due high gloss and durability of the applied paint film being important required properties.
  • Domestic high gloss applications are typically edging, windows, doors, furniture, masonry and floors (as clear coats).
  • high gloss can be a feature of polymer derived from compositions according to the invention, the compositions may be formulated to provide semi-gloss, satin or matt finishes.
  • compositions according to the invention can be applied to a substrate in the same manner as conventional adhesives or paints are applied such as by caulking gun, spatula, brush, roller or spray gun.
  • typical surface preparation used for traditional paints can be used for compositions of this invention.
  • compositions according to the invention can be used as an adhesive or a component of an adhesive.
  • the compositions can provide good bonding to and between substrate surfaces.
  • compositions according to the invention may be used as a nail varnish.
  • the present invention also provides an adhesive, varnish or paint comprising an aqueous polymer composition according to the invention.
  • alkyl used either alone or in compound words denotes straight chain, branched or cyclic alkyl, preferably C 1-2 o alkyl, e.g. CM O or C 1-6 .
  • straight chain and branched alkyl examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, ft-pentyl, 1,2-dimethylpropyl, 1,1-dimethyl-propyl, hexyl, 4-methylpentyl, 1-methylpentyl, 2- methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2- dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2-trimethylpropyl, heptyl, 5- methylhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2- dimethylpentyl, 1,3-dimethylpentyl
  • cyclic alkyl examples include mono- or polycyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. Where an alkyl group is referred to generally as "propyl", butyl” etc, it will be understood that this can refer to any of straight, branched and cyclic isomers where appropriate. An alkyl group may be optionally substituted by one or more optional substituents as herein defined.
  • alkenyl denotes groups formed from straight chain, branched or cyclic hydrocarbon residues containing at least one carbon to carbon double bond including ethylenically mono-, di- or polyunsaturated alkyl or cycloalkyl groups as previously defined, preferably C2-20 alkenyl (e.g.
  • alkenyl examples include vinyl, allyl, 1- methylvinyl, butenyl, iso-butenyl, 3-methyl-2-butenyl, 1-pentenyl, cyclopentenyl, 1 -methyl - cyclopentenyl, 1-hexenyl, 3-hexenyl, cyclohexenyl, 1-heptenyl, 3-heptenyl, 1-octenyl, cyclooctenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 3-decenyl, 1,3-butadienyl, 1,4- pentadienyl, 1,3-cyclopentadienyl, 1,3-hexadienyl, 1,4-hexadienyl, 1,3-cyclohexadienyl, 1,4- cyclohexadienyl, 1,3-cyclohept
  • alkenyl group may be optionally substituted by one or more optional substituents as herein defined.
  • alkynyl denotes groups formed from straight chain, branched or cyclic hydrocarbon residues containing at least one carbon-carbon triple bond including ethylenically mono-, di- or polyunsaturated alkyl or cycloalkyl groups as previously defined. Unless the number of carbon atoms is specified the term preferably refers to C2-20 alkynyl (e.g. C2-10 or C 2 -6)- Examples include ethynyl, 1-propynyl, 2-propynyl, and butynyl isomers, and pentynyl isomers.
  • An alkynyl group may be optionally substituted by one or more optional substituents as herein defined.
  • halogen denotes fluorine, chlorine, bromine or iodine (fluoro, chloro, bromo or iodo). Preferred halogens are chlorine, bromine or iodine.
  • aryl denotes any of single, polynuclear, conjugated and fused residues of aromatic hydrocarbon ring systems (e.g C 6 -i8 aryl).
  • aryl include phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl, phenanthrenyl, fluorenyl, pyrenyl, idenyl, azulenyl, chrysenyl.
  • aryl include phenyl and naphthyl.
  • An aryl group may or may not be optionally substituted by one or more optional substituents as herein defined.
  • arylene is intended to denote the divalent form of aryl.
  • carbocyclyl includes any of non-aromatic monocyclic, polycyclic, fused or conjugated hydrocarbon residues, preferably C 3 -20 (e.g. C 3 -10 or C 3 -8).
  • the rings may be saturated, e.g. cycloalkyl, or may possess one or more double bonds (cycloalkenyl) and/or one or more triple bonds (cycloalkynyl).
  • Particularly preferred carbocyclyl moieties are 5-6- membered or 9-10 membered ring systems.
  • Suitable examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, cyclopentadienyl, cyclohexadienyl, cyclooctatetraenyl, indanyl, decalinyl and indenyl.
  • a carbocyclyl group may be optionally substituted by one or more optional substituents as herein defined.
  • the term "carbocyclylene" is intended to denote the divalent form of carbocyclyl.
  • heterocyclyl when used alone or in compound words includes any of monocyclic, polycyclic, fused or conjugated hydrocarbon residues, preferably C 3 _2o (e.g. C 3 _io or C 3 _ 8 ) wherein one or more carbon atoms are replaced by a heteroatom so as to provide a non- aromatic residue.
  • Suitable heteroatoms include O, N, S, P and Se, particularly O, N and S. Where two or more carbon atoms are replaced, this may be by two or more of the same heteroatom or by different heteroatoms.
  • the heterocyclyl group may be saturated or partially unsaturated, i.e. possess one or more double bonds.
  • heterocyclyl are 5-6 and 9-10 membered heterocyclyl.
  • Suitable examples of heterocyclyl groups may include azridinyl, oxiranyl, thiiranyl, azetidinyl, oxetanyl, thietanyl, 2H-pyrrolyl, pyrrolidinyl, pyrrolinyl, piperidyl, piperazinyl, morpholinyl, indolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, thiomorpholinyl, dioxanyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydropyrrolyl, tetrahydrothiophenyl, pyrazolinyl, dioxalanyl, thiazolidinyl, isoxazolidinyl, dihydropyranyl, oxazinyl, thiazin
  • heteroaryl includes any of monocyclic, polycyclic, fused or conjugated hydrocarbon residues, wherein one or more carbon atoms are replaced by a heteroatom so as to provide an aromatic residue.
  • Preferred heteroaryl have 3-20 ring atoms, e.g. 3-10.
  • Particularly preferred heteroaryl are 5-6 and 9-10 membered bicyclic ring systems.
  • Suitable heteroatoms include, O, N, S, P and Se, particularly O, N and S. Where two or more carbon atoms are replaced, this may be by two or more of the same heteroatom or by different heteroatoms.
  • heteroaryl groups may include pyridyl, pyrrolyl, thienyl, imidazolyl, furanyl, benzothienyl, isobenzothienyl, benzofuranyl, isobenzofuranyl, indolyl, isoindolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, quinolyl, isoquinolyl, phthalazinyl, 1,5-naphthyridinyl, quinozalinyl, quinazolinyl, quinolinyl, oxazolyl, thiazolyl, isothiazolyl, isoxazolyl, triazolyl, oxadialzolyl, oxatriazolyl, triazinyl, and furazanyl.
  • a heteroaryl group may be optionally substituted by one or more optional substituents as
  • Preferred acyl includes C(0)-R e , wherein R e is hydrogen or an alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl residue.
  • R e is hydrogen or an alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl residue.
  • Examples of acyl include formyl, straight chain or branched alkanoyl (e.g.
  • Ci-20 such as acetyl, propanoyl, butanoyl, 2-methylpropanoyl, pentanoyl, 2,2- dimethylpropanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl and icosanoyl; cycloalkylcarbonyl such as cyclopropylcarbonyl cyclobutylcarbonyl, cyclopentylcarbonyl and cyclohexylcarbonyl; aroyl such as benzoyl, toluoyl and naphthoyl; aralkanoyl such as
  • phenylacetyl phenylpropanoyl, phenylbutanoyl, phenylisobutylyl, phenylpentanoyl and phenylhexanoyl
  • naphthylalkanoyl e.g. naphthylacetyl, naphthylpropanoyl and naphthylbutanoyl]
  • aralkenoyl such as phenylalkenoyl (e.g.
  • phenylpropenoyl e.g., phenylbutenoyl, phenylmethacryloyl, phenylpentenoyl and phenylhexenoyl and naphthylalkenoyl (e.g.
  • aryloxyalkanoyl such as phenoxyacetyl and phenoxypropionyl
  • arylthiocarbamoyl such as phenylthiocarbamoyl
  • arylglyoxyloyl such as phenylglyoxyloyl and naphthylglyoxyloyl
  • arylsulfonyl such as phenylsulfonyl and napthylsulfonyl
  • heterocycliccarbonyl heterocyclicalkanoyl such as thienylacetyl, thienylpropanoyl, thienylbutanoyl, thienylpentanoyl, thienylhexanoyl, thiazolylacetyl, thiadiazolylacetyl and tetrazolylacetyl
  • sulfoxide refers to a group -S(0)R wherein R is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and aralkyl.
  • R is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and aralkyl.
  • R is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and aralkyl.
  • R is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and aralkyl.
  • Examples of preferred R include Ci_ 2 oalkyl, phenyl and benzyl.
  • sulfonyl refers to a group S(0) 2 -R , wherein R is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl and aralkyl. Examples of preferred R include Ci_ 2 oalkyl, phenyl and benzyl.
  • sulfonamide refers to a group S(0)NR f R f wherein each R is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and aralkyl.
  • R is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and aralkyl.
  • preferred R include Ci_ 2 oalkyl, phenyl and benzyl.
  • at least one R is hydrogen.
  • both R are hydrogen.
  • amino is used here in its broadest sense as understood in the art and includes groups of the formula NR a R b wherein R a and R b may be independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, arylalkyl, and acyl. R a and R b , together with the nitrogen to which they are attached, may also form a monocyclic, or polycyclic ring system e.g. a 3-10 membered ring, particularly, 5-6 and 9-10 membered systems. Examples of “amino” include NH 2 , NHalkyl (e.g.
  • Ci_ 2 oalkyl NHaryl (e.g. NHphenyl), NHaralkyl (e.g. NHbenzyl), NHacyl (e.g. NHC(O)C 1 _ 20 alkyl, NHC(O)phenyl), Nalkylalkyl (wherein each alkyl, for example Ci_ 2 o, may be the same or different) and 5 or 6 membered rings, optionally containing one or more same or different heteroatoms (e.g. O, N and S).
  • NHaryl e.g. NHphenyl
  • NHaralkyl e.g. NHbenzyl
  • NHacyl e.g. NHC(O)C 1 _ 20 alkyl, NHC(O)phenyl
  • Nalkylalkyl wherein each alkyl, for example Ci_ 2 o, may be the same or different
  • 5 or 6 membered rings optionally containing one or more same or different heteroatoms (e
  • amido is used here in its broadest sense as understood in the art and includes groups having the formula C(0)NR a R b , wherein R a and R b are as defined as above.
  • Examples of amido include C(0)NH 2 , C(0)NHalkyl (e.g. Ci_ 20 alkyl), C(0)NHaryl (e.g. C(O)NHphenyl), C(0)NHaralkyl (e.g. C(O)NHbenzyl), C(0)NHacyl (e.g.
  • C(0)NHC(0)Ci_ 2 oalkyl C(0)NHC(0)phenyl
  • C(0)Nalkylalkyl wherein each alkyl, for example C 1-2 o, may be the same or different
  • 5 or 6 membered rings optionally containing one or more same or different heteroatoms (e.g. O, N and S).
  • carboxy ester is used here in its broadest sense as understood in the art and includes groups having the formula C0 2 R g , wherein R g may be selected from groups including alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, aralkyl, and acyl.
  • R g may be selected from groups including alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, aralkyl, and acyl.
  • Examples of carboxy ester include C0 2 Ci_ 2 oalkyl, C0 2 aryl (e.g.. C0 2 phenyl), C0 2 aralkyl (e.g. C0 2 benzyl).
  • a group may or may not be substituted or fused (so as to form a condensed polycyclic group) with one, two, three or more of organic and inorganic groups, including those selected from: alkyl, alkenyl, alkynyl, carbocyclyl, aryl, heterocyclyl, heteroaryl, acyl, aralkyl, alkaryl, alkheterocyclyl, alkheteroaryl, alkcarbocyclyl, halo, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, halocarbocyclyl, haloheterocyclyl, haloheteroaryl, haloacyl, haloaryalkyl, hydroxy, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, hydroxycarbocyclyl, hydroxyaryl, hydroxyaryl, hydroxy
  • Optional substitution may also be taken to refer to where a -CH 2 - group in a chain or ring is replaced by a group selected from -0-, -S-, - NR a -, -C(O)- (i.e. carbonyl), -C(0)0- (i.e. ester), and -C(0)NR a - (i.e. amide), where R a is as defined herein.
  • Preferred optional substituents include alkyl, (e.g. Ci_ 6 alkyl such as methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), hydroxyalkyl (e.g. hydroxymethyl, hydroxyethyl, hydroxypropyl), alkoxyalkyl (e.g. methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl etc) alkoxy (e.g.
  • alkyl e.g. Ci_ 6 alkyl such as methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl
  • hydroxyalkyl e.g. hydroxymethyl, hydroxyethyl, hydroxypropyl
  • C 1-6 alkoxy such as methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, cyclobutoxy
  • halo trifluoromethyl, trichloromethyl, tribromomethyl, hydroxy, phenyl (which itself may be further substituted e.g., by Ci- 6 alkyl, halo, hydroxy, hydroxyCi- 6 alkyl, C 1-6 alkoxy, haloCi_ 6 alkyl, cyano, nitro OC(0)Ci_ 6 alkyl, and amino)
  • benzyl wherein benzyl itself may be further substituted e.g., by Ci_ 6 alkyl, halo, hydroxy, hydroxyCi_ 6 alkyl, Ci_ 6 alkoxy, haloCi_ 6 alkyl, cyano, nitro OC(0)Ci_ 6 alkyl, and amino
  • phenoxy wherein phenyl itself may be further substituted e.g., by Ci_
  • Ci_ 6 alkyl such as methylamino, ethylamino, propylamino etc
  • dialkylamino e.g. C 1-6 alkyl, such as dimethylamino, diethylamino, dipropylamino
  • acylamino e.g.
  • NHC(0)CH 3 NHC(0)CH 3
  • phenylamino wherein phenyl itself may be further substituted e.g., by Ci_ 6 alkyl, halo, hydroxy, hydroxyCi_6 alkyl, Ci_ 6 alkoxy, haloCi_6 alkyl, cyano, nitro OC(0)Ci_ 6 alkyl, and amino
  • nitro, formyl, -C(0)-alkyl e.g. Ci_ 6 alkyl, such as acetyl
  • 0-C(0)-alkyl e.g.
  • Ci_ 6 alkyl such as acetyloxy
  • benzoyl wherein the phenyl group itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy hydroxyCi-6 alkyl, C 1-6 alkoxy, haloCi_6 alkyl, cyano, nitro OC(0)Ci_ 6 alkyl, and amino
  • Ci_6 alkyl such as methyl ester, ethyl ester, propyl ester, butyl ester
  • C0 2 phenyl wherein phenyl itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy, hydroxyl C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkyl, cyano, nitro OC(0)C 1-6 alkyl, and amino
  • CONH 2 CONHphenyl (wherein phenyl itself may be further substituted e.g., by Ci_ 6 alkyl, halo, hydroxy, hydroxyl Ci_ 6 alkyl, Ci_ 6 alkoxy, halo Ci_ 6 alkyl, cyano, nitro OC(0)Ci_ 6 alkyl, and amino)
  • CONHbenzyl wherein benzyl itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy hydroxyl C
  • Ci_ 6 alkyl such as methyl ester, ethyl ester, propyl ester, butyl amide) CONHdialkyl (e.g. Ci_ 6 alkyl) aminoalkyl (e.g., HN Ci_ 6 alkyl-, Ci_ 6 alkylHN-Ci_ 6 alkyl- and (C 1-6 alkyl) 2 N-Ci_6 alkyl-), thioalkyl (e.g., HS C 1-6 alkyl-), carboxyalkyl (e.g., H0 2 CCi_6 alkyl-), carboxyesteralkyl (e.g., C 1-6 alkyl0 2 CCi_6 alkyl-), amidoalkyl (e.g., H 2 N(0)CCi_6 alkyl-, H(Ci_ 6 alkyl)N(0)CCi_ 6 alkyl-), formylalkyl (e.g., OHCCi_ 6 alkyl-), acy
  • heteroatom refers to any atom other than a carbon atom which may be a member of a cyclic organic group.
  • heteroatoms include nitrogen, oxygen, sulfur, phosphorous, boron, silicon, selenium and tellurium, more particularly nitrogen, oxygen and sulfur.
  • groups written as “[group A] [group B]” refer to group A when linked by a divalent form of group B.
  • [group A] [alkyl]” refers to a particular group A (such as hydroxy, amino, etc.) when linked by divalent alkyl, i.e. alkylene (e.g.
  • hydroxyethyl is intended to denote HO-CH 2 -CH-).
  • groups written as “[group]oxy” refer to a particular group when linked by oxygen, for example, the terms “alkoxy” or “alkyloxy”, “alkenoxy” or “alkenyloxy”, “alkynoxy” or alkynyloxy”, “aryloxy” and “acyloxy”, respectively, denote alkyl, alkenyl, alkynyl, aryl and acyl groups as hereinbefore defined when linked by oxygen.
  • alkylthio alkenylthio
  • alkynylthio alkynylthio
  • arylthio alkyl, alkenyl, alkynyl and aryl groups as hereinbefore defined when linked by sulfur.
  • DMAEMA 2-(dimethylamino)ethyl methacrylate
  • MMA methyl methacrylate
  • iBMA isobutyl methacrylate
  • DAAM diacetone acrylamide
  • glacial acetic acid 84.66 g, 1410 mrnol
  • terpinolene 4.80 g, 35.2 mrnol
  • VA-044 13.23 g, 40.9 mrnol dissolved into H 2 0 (100 mL) was injected into the reaction over a 6 hour period using a syringe pump. The reaction became more viscous after the monomer injection and stirring speed was increased to 300 rpm. At 6 hours, after the initiator feed had finished, a single shot of VA-044 (2.21 g, 6.84 mrnol) was added and the stirring increased to 350 rpm. The reaction solution can then be used as is.
  • GPC Gel permeation chromatography
  • N,N-Dimethylacetamide (DMAc) (containing 4.34 g L 1 lithium bromide (LiBr)) was used as an eluent with a flow rate of 1 mL/min at 80 °C.
  • Number ( n ) and weight average ( w ) molar masses were evaluated using Shimadzu LC Solution software.
  • the GPC columns were calibrated with low dispersity polystyrene (PSt) and poly(methyl methacrylate) (PMMA) standards (Polymer Laboratories) ranging from 575 to 3,242,000 g mol ⁇ and 1010 to 2,136,000 g mol ⁇ respectively, and molar masses are reported as PSt and PMMA equivalents.
  • a 3rd-order polynomial was used to fit the log M p vs. time calibration curve, which was near linear across the molar mass ranges. This method was used in the analysis of the polymer made in the other examples.
  • Additional initiator solution was prepared (1.035 g of VA-044 dissolved in 10 g water) and deoxygenated with nitrogen bubbling, of which 9.46 mL of was injected using a syringe pump over a six hour period, the remainder (1.58 mL) being injected in one portion at the six hour mark. Heating was continued to 7 hrs. The reaction became more viscous after the monomer injection and stirring speed was increased to 400 rpm. The reaction was cooled to ambient temperature and decanted into a sealed container.
  • Additional initiator solution was prepared (0.600 g of VA-044 dissolved in 10 mL water), deoxygenated with nitrogen bubbling and injected using a syringe pump over a six hour period. Additional solid initiator (0.100 g of VA-044) was added in one portion at the six hour mark. Heating was continued to 7 hrs. The reaction was cooled to ambient temperature and decanted into a sealed container.
  • Additional initiator solution was prepared (0.600 g of VA-044 dissolved in 10 mL water), deoxygenated with nitrogen bubbling and injected using a syringe pump over a six hour period. Additional solid initiator (0.100 g of VA-044) was added in one portion at the six hour mark. Heating was continued to 7 hrs. The reaction was cooled to ambient temperature and decanted into a sealed container.
  • Additional initiator solution was prepared (0.600 g of VA-044 dissolved in 10 mL water), deoxygenated with nitrogen bubbling and injected using a syringe pump over a six hour period. Additional solid initiator (0.100 g of VA-044) was added in one portion at the six hour mark. Heating was continued to 7 hrs. The reaction was cooled to ambient temperature and decanted into a sealed container.
  • This solution was added to a 500 mL reactor containing seed polymer solution (3 mL of a previously synthesised batch of polymer with a DMAEMA : MM A :iB MA : DAAM 15:50:30:5 ratio (35 wt% solids), under a nitrogen atmosphere. Stirring with an overhead stirrer (half-moon blade) was commenced at 350 rpm and the reaction temperature was raised to 60°C.
  • Additional initiator solution was prepared (1.000 g of VA-044 dissolved in 10 mL water), deoxygenated with nitrogen bubbling and injected using a syringe pump over a six hour period. Additional solid initiator (0.167 g of VA-044) was added in one portion at the six hour mark. Heating was continued to 7 hrs. The reaction was cooled to ambient temperature and decanted into a sealed container. Solids Content: 49% (gravimetrically)
  • Tg (of dry polymer film, heat/cool/heat cycle from -50 °C to 200 °C at lOK/min with N 2 ): 78.14 °C.
  • the polymer solution was then subjected to a post polymerisation monomer reduction procedure to minimise the residual iBMA monomer content.
  • the above polymer solution was heated to 40°C and to this was added teri-Butyl hydroperoxide (0.2 mL of a 70% aqueous solution).
  • a solution of Sodium formaldehyde sulfoxylate (0.0223 g in 1 mL water, 1 mol equivalent with respect to the hydroperoxide) was prepared and deoxygenated by nitrogen bubbling.
  • Ureido methacrylate was a 30% w/w solution in methyl methacrylate.
  • 10.57 g of UMA 30% w/w in MMA solution was used in addition to 7.02g of pure MMA this results in total MMA mass of 14.42g and total mass of UMA of 3.171g
  • Water (90 mL) was deoxygenated with N 2 bubbling then added to a 500 mL reactor under an N 2 atmosphere, to which was added the initiator 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (known as VA-044) (0.200 g, 0.619 mmol) and seed polymer solution (3 mL of solution with 30% wt solids of a polymer (ca.
  • VA-044 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride
  • Additional initiator solution was prepared (0.696 g of VA-061 dissolved in 9.5 g water containing 0.334 g glacial acetic acid) and deoxygenated with nitrogen bubbling, of which 9.03 mL of was injected using a syringe pump over a six hour period, the remainder (1.5 mL) being injected in one portion at the six hour mark. Heating was continued to 7 hrs. The reaction became more viscous after the monomer injection and stirring speed was increased to 400 rpm. The reaction was cooled to ambient temperature, giving a viscous but easily pourable polymer mixture.
  • Additional initiator solution was prepared (0.932 g of VA-044 dissolved in 10 g water) and deoxygenated with nitrogen bubbling, of which 9.4 mL of was injected using a syringe pump over a six hour period, the remainder (about 1.5 mL) being injected in one portion at the six hour mark. Heating was continued to 7 hrs. The reaction became more viscous after the monomer injection and stirring speed was increased to 400 rpm. The reaction was cooled to ambient temperature, giving a viscous but pourable polymer mixture.
  • Solids Content 41.0 % (gravimetrically).
  • Additional initiator solution was prepared (1.094 g of VA-044 dissolved in 10 mL water), deoxygenated with nitrogen bubbling and injected using a syringe pump over a six hour period. Additional solid initiator (0.182 g of VA-044) was added in one portion at the six hour mark. Heating was continued to 7 hrs. The reaction was cooled to ambient temperature and decanted into a sealed container. Solids Content: 52% (gravimetrically)
  • Tg (of dry polymer film, heat/cool/heat cycle from -50 °C to 200 °C at lOK/min with N 2 ): 79.55 °C.
  • Adipic acid dihydrazide (ADH) 16.0g, 0.09mol was refluxed in acetone (50 mL) for 4 hours, upon cooling the excess acetone was removed in vacuo to give N,N-di(propan-2-ylidene)adipohydrazide (23g, 99%).
  • Example 1 To samples of Example 1 ( ⁇ 10-25g) was added ammonium acetate (0 or 1 molar equivalent (relative to moles of pDMAEMA)), acetone (0-10 molar equivalents (relative to PDAAM)) and ADH (0.4 molar equivalents (relative to PDAAM) (Table 1) . The samples were stirred vigorously for 1 hour. Visual and viscosity measurements were made after 48 hours then weekly, using a Brookfield DV-II + viscometer, S64 spindle, 100, 50 and 30 rpm. Brookfield standard 500 lot number 112801 gave 483.5 at 24°C at lOOrmp S64 spindle (expect 488 at 25°C).
  • Table 2 illustrates a number of important features of the invention.
  • Addition of ammonium acetate only to the polymer solution of the invention (entry 3) reduces the viscosity of the solution (entry 1) from 1494 mPa.s to 1038 mPa.s. Many other salts will do this but the most practical salts to use are those that are volatile otherwise the salt will remain in the coating and may compromise its performance.
  • Ammonium acetate is most preferred with ammonium carbonate being also useable. This viscosity decrease can be of use in the synthesis of solution with high loading of polymer to moderate solution viscosity.
  • the ammonium cation may also contribute to the prevention of premature crosslinking.
  • Samples that contain, ammonium acetate and ADH (entry 5) or ADH only (entry 4) will rapidly gel or solidify within 24 hours (typically much faster) and are examples of unstable formulations.
  • ammonium acetate, ADH and more than 2 molar equivalents of acetone relative to the DAAM content of the polymer is required with 5 molar equivalents providing good stability (entry 8) and 10 molar equivalents (entry 9) providing additional reduction of viscosity.
  • entry 8 When acetone at 2 molar equivalents was insufficient to prevent gelation under the current conditions (entry 7).
  • the use of ADH and acetone (5 molar equivalents) with no ammonium acetate can provide a solution with stability but it will have higher viscosity than formulations with ammonium acetate ADH and acetone.
  • Samples were prepared for crosslinking by taking 20g of the aqueous solution of the reaction described in the relevant example.
  • polymer for tabular entry 2 was that made in example 6.
  • a 20g sample contained 2.23 mmoles of DAAM and 6.71 mmoles of DMAEMA. To this solution was added 0.52g (6.71 mmoles) ammonium acetate and 0.52g (8.94 mmoles) acetone with stirring until dissolved. Following this, 0.16g (0.89 mmoles) of ADH was added, and mixed to provide a homogenous solution.
  • a small amount (1 mL) of the polymer solution prepared as described in the relevant example was coated onto a glass plate and allowed to dry under ambient conditions for 24 h.
  • the dried polymer film was scraped from the plate using a sharp blade, before being analysed in 40 aluminium crucibles with a pierced lid on a Mettler Toledo DSC-3 with Haake EK90/MT intracooler. This was using a gas flow of 40 mL/min under an N 2 inert atmosphere with a temperature profile of heat -50 °C to 200 °C, cool 200 °C to -50 °C, heat -50 °C to 200 °C at 10 °C /min.
  • a small amount (1 mL) of the polymer solution prepared as described in the relevant example was drawn down onto a glass plate using a 152 micron draw-down frame.
  • the film was allowed to dry under ambient conditions before measurement of film gloss using a Star Instruments GRM-2000 gloss meter (Table 3) Table 3. Gloss measurement of films.
  • Entry 1 The polymer synthesised according to the procedure for example 6 with an adjusted monomer feed ratio of DMAEMA:MMA:iBMA:DAAM 20:50:25:5 at 29 wt% solids loading.
  • DMAEMA 2-(dimethylamino)ethyl methacrylate
  • MMA methyl methacrylate
  • HMA hexyl methacrylate
  • DAAM diacetone acrylamide
  • terpinolene 0.218 g, 1.6 mmol
  • DEAEMA 2-(diethylamino)ethyl methacrylate
  • MMA methyl methacrylate
  • iBMA isobutyl methacrylate
  • DAAM diacetone acrylamide
  • terpinolene 0.218 g, 1.6 mmol
  • VA-044 (0.600 g, 1.87 mmol) dissolved into N 2 degassed H 2 0 (10 mL) was injected into the reaction over a 6 hour period using a syringe pump. The reaction became more viscous after the monomer injection and stirring speed was increased to 400 rpm. At 6 hours, after the initiator feed had finished, a single shot of VA-044 (0.100 g, 0.309 mmol) was added and the stirring increased to 450 rpm. The reaction was decanted and used as is.
  • VA-044 (0.600 g, 1.87 mmol) dissolved into N2 degassed H20 (10 mL) was injected into the reaction over a 6 hour period using a syringe pump. The reaction became more viscous after the monomer injection and stirring speed was increased to 400 rpm. At 6 hours, after the initiator feed had finished, a single shot of VA-044 (0.100 g, 0.309 mmol) was added and the stirring increased to 450 rpm. The reaction was decanted and used as is.
  • Example 23 Synthesis of polymer containing IEMA in water, under nitrogen atmosphere without seed polymer. ⁇ :MMA:iBMA:DAAM 20:50:25:5 ratio (29 wt% solids)
  • TMSMMA Trimethylsilylmethyl methacrylate
  • VA-044 (5.14 g, 15.9 mmol) dissolved into N2 degassed H20 (50 mL) was injected into the reaction over a 6 hour period using a syringe pump. The reaction became more viscous after the monomer injection and stirring speed was increased to 350 rpm. At 6 hours, after the initiator feed had finished, a single shot of VA-044 (0.856 g, 2.63 mmol) was added and the stirring increased to 380 rpm. After a further 1 hour the heat was turned off and t- butylhydroperoxide (70wt% in water, 5.00 g, 3.88 mmol) was added. Bruggolite (1.00 g, 5.52 mmol) dissolved into N2 degassed water (10 mL) was injected over the next 15 minutes. Once the reaction had cooled to room temperature (45 minutes) it was decanted and used as is.
  • VA-044 (5.14 g, 15.9 mmol) dissolved into N2 degassed H20 (50 mL) was injected into the reaction over a 6 hour period using a syringe pump. The reaction became more viscous after the monomer injection and stirring speed was increased to 350 rpm. At 6 hours, after the initiator feed had finished, a single shot of VA-044 (0.856 g, 2.63 mmol) was added and the stirring increased to 380 rpm. After a further 1 hour the heat was turned off and t- butylhydroperoxide (70wt% in water, 5.00 g, 3.88 mmol) was added. Bruggolite (1.00 g, 5.52 mmol) dissolved into N2 degassed water (10 mL) was injected over the next 15 minutes. Once the reaction had cooled to room temperature (45 minutes) it was decanted and used as is.
  • the polymer made in part 1 was then used to make aqueous solutions of the copolymer
  • Solutions containing 10, 20 and 30% solids, made up to 20ml with stock solution 1, were prepared from, part I above. The samples were placed on a shaker 400/mm until dissolved. The solids for the 10% solution were effectively dissolved after 2 hours. The 20% solution was partially dissolved some gel particles remained undissolved after 2 hours, whilst the 30% solution appeared to have absorbed the water and formed a gel after two hours. Overnight 80% of the 30% solution had dissolved and the 20% solution had fully dissolved. After 48 hours the 30% sample was dissolved.
  • 1,3,5-Pentanetrihydrazide crosslinker (1.2 g) synthesized above was added to polymer sample of Example 29 (50 g) and acetone at 3 different molar equivalent levels (8, 10 and 15 molar equivalents). The samples were stirred under high shear for 1 hour. Visual measurements were made after 48 hours. It was observed that the variant with 8 molar equivalents acetone gelled completely after 48 hours. Acetone with 10 equivalents and 15 equivalents showed an increase in viscosity but still flowed.
  • a mill base containing Tiona 595, additol VXW 6208, BYK024, BYK1710 and RO water was pre- prepared. It was prepared in the following manner. ADDITOL VXW 6208 (18.02 g), BYK 024 (0.9 g), BYK 1710 (1.025 g), and DOSED RO WATER (13.51 g) are added to a 250 ml paint can and mixed using an overhead stirrer. TIONA 595 (112.58 g) is added to the paint can gradually while increasing the stirring speed up to 800 rpm to provide good dispersion of pigment. 7.5 g DOSED RO WATER is then added to the mill base as wash-out water.
  • Aqueous polymer solution from Example 30 (20 g) was mixed with the mill base (8.71), butyl CARBITOLTM (1.8 g) and acetone (1.07 g). ADH (640 mg) was then added and the solution stirred for 20 minutes to provide a homogenous solution. When painted out as a coating the solution gave a hard, white, opaque, high gloss finish.
  • Calcium carbonate (3.3 g) was added to the formulation A to give hard, white, opaque, matt finish surfaces when used as a coating.
  • Silicon dioxide (1.0 g) was added to the formulation A to give a hard, white, opaque, matt finish surfaces when used as a coating.
  • the pre-prepared mill base (8.71 g) was added to aqueous polymer solution from Example 30 (20 g), butyl CARBITOLTM (1.8 g) and acetone (1.07 g). PTH (602 mg) was then added and the solution stirred for 20 minutes to provide a homogenous solution. When painted out as a coating the solution gave a hard, white, opaque, high gloss finish.
  • Rheology modifiers such as Natrosol Plus 330 could be added to increase viscosity, or alternatively ammonium acetate could be added to reduce viscosity.
  • Example 35 Stain resistance - red wine
  • Entry 1 paint was prepared by mixing a pre-prepared mill base containing Tiona 595, additol VXW 6208, BYK024, BYK1710 and RO water with aqueous polymer solution from Example 2 (20 g) was - I l l - mixed with the mill base (7.47 g), butyl CARBITOLTM (1.5 g) and acetone (296 mg). ADH (177 mg) was then added and the solution stirred for 20 minutes to provide a homogenous solution. When painted out as a coating the solution gave a hard, white, opaque, high gloss finish.
  • Entry 2 paint was prepared by mixing a pre-prepared mill base containing Tiona 595, additol VXW 6208, BYK024, BYK1710 and RO water with aqueous polymer solution from Example 26 (20 g) was mixed with the mill base (7.47 g), butyl CARBITOLTM (1.5 g) and acetone (625 mg). ADH (375 mg) was then added and the solution stirred for 20 minutes to provide a homogenous solution. When painted out as a coating the solution gave a hard, white, opaque, high gloss finish.
  • Entry 3 paint was prepared by mixing a pre-prepared mill base containing Tiona 595, additol VXW 6208, BYK024, BYK1710 and RO water with aqueous polymer solution from Example 27 (20 g) was mixed with the mill base (7.47 g), butyl CARBITOLTM (1.5 g) and acetone (1.07 g). ADH (640 mg) was then added and the solution stirred for 20 minutes to provide a homogenous solution. When painted out as a coating the solution gave a hard, white, opaque, high gloss finish.
  • Entry 4 paint was prepared by mixing a pre-prepared mill base containing Tiona 595, additol VXW 6208, BYK024, BYK1710 and RO water with aqueous polymer solution from Example 28 (20 g) was mixed with the mill base (7.47 g), butyl CARBITOLTM (1.5 g) and acetone (1.19 g). ADH (711 mg) was then added and the solution stirred for 20 minutes to provide a homogenous solution. When painted out as a coating the solution gave a hard, white, opaque, high gloss finish.
  • a contact adhesive can be made from the composition provided by Example 22 by the addition of acetone (5 molar equivalent relative to DAAM content of the composition provided by Example 22) and ADH (0.4 molar equivalent relative to DAAM content of the composition provided by Example 22).
  • the acetone and ADH can be added to the composition provided by Example 22 by first adding the required amount of acetone with stirring followed by the addition of the required amount of ADH with stirring.
  • the resulting formulation may then be applied to the roughened surface of at least two polypropylene substrates (80 grade sandpaper) and allowed to dry (for example over a period of about 5 to 20 hours).
  • the adhesive coated surfaces can be pressed together and allowed to cure for about a 1 hour. Immediately after pressing the substrates together they can be easily separated, repositioned and bought into contact again. However, after about 1 hour the adhesive should have substantially cured and the substrates will not be able to be readily separated without considerable force being applied.
  • Uncrosslinked dried polymer, unformulated or formulated into paint, coatings or adhesive can be reconstituted with the application of mildly acidic solutions.
  • Crosslinked dried polymer, unformulated or formulated into paint, coatings or adhesive can be reconstituted with the application of mildly acidic solutions containing small amounts of acetone.
  • a mill base containing Tiona 595, additol VXW 6208, BYK024, BYK1710 and RO water was pre- prepared.
  • Aqueous polymer solution from Example 28 (20 g) was mixed with the mill base (7.47 g), butyl CARBITOLTM (1.5 g) and acetone (1.19 g).
  • ADH (711 mg) was then added and the solution stirred for 20 minutes to provide a homogenous solution.
  • a portion of the formulated solution (15 g) was allowed to dry for 48 hours and was then mechanically broken up into small pieces.
  • Entry 1 paint was prepared by mixing a pre-prepared mill base containing Tiona 595, additol VXW 6208, BYK024, BYK1710 and RO water with aqueous polymer solution from Example 27 (20 g) was mixed with the mill base (7.47 g), butyl CARBITOLTM (1.5 g) and acetone (1.07 g). ADH (640 mg) was then added and the solution stirred for 20 minutes to provide a homogenous solution. When painted out as a coating the solution gave a hard, white, opaque, high gloss finish.
  • Entry 2 paint was prepared by mixing a pre-prepared mill base containing Tiona 595, additol VXW 6208, BYK024, BYK1710 and RO water with aqueous polymer solution from Example 28 (20 g) was mixed with the mill base (7.47 g), butyl CARBITOLTM (1.5 g) and acetone (1.19 g). ADH (711 mg) was then added and the solution stirred for 20 minutes to provide a homogenous solution. When painted out as a coating the solution gave a hard, white, opaque, high gloss finish.
  • Entry 3 paint was prepared by mixing a pre-prepared mill base containing Tiona 595, additol VXW 6208, BYK024, BYK1710 and RO water with aqueous polymer solution from Example 30 (20 g) was mixed with the mill base (8.71 g), butyl CARBITOLTM (1.8 g) and acetone (913 mg). ADH (548 mg) was then added and the solution stirred for 20 minutes to provide a homogenous solution. When painted out as a coating the solution gave a hard, white, opaque, high gloss finish. The lowest and highest readings were discarded and the rest averaged (Table 5) .
  • Deionised water (521.79 g) and seed polymer solution (51.00 g, 35.86 wt%) was added to a 1 L round bottom reactor under an N 2 atmosphere. Stirring with an overhead stirrer (anchor blade) was commenced at 150 rpm and the reaction temperature was raised to 60°C. 2,2'-Azobis[2-(2-imidazolin- 2-yl)propane] dihydrochloride (known as VA-044) (1.10 g) was dissolved in 10.00 g Deionised water and added as a shot to the reactor at 60°C. The stirring speed was raised to 160 rpm.
  • VA-044 2,2'-Azobis[2-(2-imidazolin- 2-yl)propane] dihydrochloride
  • VA-044 (5.40 g, 16.70 mmol) dissolved into Deionised water (30.00 g) was injected into the reaction over a 4 hour period using a syringe pump. At the end of the monomer/initiator feed, a shot of Rhodoline DF 642 Nl (0.20 ml) was added to the reactor. 1.08 g VA-044 was dissolved in 10.00 g Deionised water and fed to the reactor over 15 minutes. After a further 1 hour and 45 minutes, t-butylhydroperoxide (70wt% in water, 1.00 g) was added as a shot.
  • Bruggolite (l.OOg) was dissolved into Deionised water (20.00 g) and was injected over 15 minutes. The heat was turned off immediately after this. Once the reaction had cooled to room temperature (45 minutes) it was decanted and filtered through an 85 micron filter silk.
  • VA-044 (5.40 g, 16.70 mmol) dissolved into Deionised water (30.00 g) was injected into the reaction over a 4 hour period using a syringe pump. At the end of the monomer/initiator feed, a shot of Rhodoline DF 642 Nl (0.20 ml) was added to the reactor. 1.08 g VA-044 was dissolved in 10.00 g Deionised water and fed to the reactor over 15 minutes. After a further 1 hour and 45 minutes, t-butylhydroperoxide (70wt% in water, 1.00 g) was added as a shot.
  • Bruggolite (l.OOg) was dissolved into Deionised water (20.00 g) and was injected over 15 minutes. The heat was turned off immediately after this. Once the reaction had cooled to room temperature (45 minutes) it was decanted and filtered through an 85 micron filter silk.
  • a mill base was first prepared. Tiona 595 (110.28 g) was dispersed in Additol VXW 6208 (17.64 g), BYK024 (0.88 g), BYK1710 (1.0 g) and RO water (13.24 g) under high shear (1600 rpm) mixing.7.34 g of RO water was used as wash out water. This forms the mill base.
  • Aqueous polymer solution prepared above (containing 60 mol% DMAEMA) (292.78 g) was mixed with the mill base (135.36 g), butyl carbitol (27.33 g), propylene glycol (9.05 g) and acetone (22.38 g). 1,3,5-pentanetrihydrazide crosslinker (9.59 g) was then added. Natrosol PLUS 330 (2.80 g) was dissolved in RO water (27.94 g). After pH adjustment to pH 9, Natrosol-water mixture was added and stirred at 800 rpm.
  • Deionised water (523.90 g) and seed polymer solution (51.00 g, 35.95 wt%) was added to a 1 L round bottom reactor under an N 2 atmosphere. Stirring with an overhead stirrer (anchor blade) was commenced at 150 rpm and the reaction temperature was raised to 60°C. 2,2'-Azobis[2-(2-imidazolin- 2-yl)propane] dihydrochloride (known as VA-044) (1.10 g) was dissolved in 10.00 g Deionised water and added as a shot to the reactor at 60°C. The stirring speed was raised to 160 rpm.
  • VA-044 2,2'-Azobis[2-(2-imidazolin- 2-yl)propane] dihydrochloride
  • VA-044 (5.40 g, 16.70 mmol) dissolved into Deionised water (30.00 g) was injected into the reaction over a 4 hour period using a syringe pump. At the end of the monomer/initiator feed, a shot of Rhodoline DF 642 Nl (0.20 ml) was added to the reactor. 1.08 g VA-044 was dissolved in 10.00 g Deionised water and fed to the reactor over 15 minutes. After a further 1 hour and 45 minutes, t-butylhydroperoxide (70wt% in water, 1.00 g) was added as a shot.
  • Bruggolite (l.OOg) was dissolved into Deionised water (20.00 g) and was injected over 15 minutes. The heat was turned off immediately after this. Once the reaction had cooled to room temperature (45 minutes) it was decanted and filtered through an 85 micron filter silk.
  • a mill base was first prepared. Tiona 595 (133.1 g) was dispersed in Additol VXW 6208 (21.3 g), BYK024 (1.1 g), BYK1710 (1.2 g) and RO water (16.0 g) under high shear (1600 rpm) mixing. 8.9 g of RO water was used as wash out water. This forms the mill base.
  • Aqueous polymer solution from Example 29 (201.1 g) was mixed with the mill base (90.8 g), butyl carbitol (18.3 g), propylene glycol (6.1 g) and acetone (11.0 g). 1,3,5-pentanetrihydrazide crosslinker (example 33) (4.7 g) was then added.
  • Natrosol PLUS 330 (1.9 g) was dissolved in RO water (18.8 g). After pH adjustment to pH 9, the Natrosol PLUS-water mixture was added and stirred at 800 rpm.

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Abstract

La présente invention concerne une composition aqueuse de polymère réticulable stable au stockage comprenant : (a) un liquide aqueux ; (b) un copolymère solubilisé dans le liquide aqueux par un acide non gazeux fugitif, le copolymère comprenant des résidus polymérisés de : (i) monomère à insaturation éthylénique comprenant un groupe fonctionnel basique qui est protoné par l'acide non gazeux fugitif, les résidus polymérisés de ce monomère étant présents en une quantité inférieure à 25 % en moles, par rapport au nombre total de moles de résidus monomères polymérisés du copolymère ; (ii) un monomère à insaturation éthylénique comprenant un groupe fonctionnel permettant de favoriser la réticulation du copolymère ; et (iii) un monomère hydrophobe à insaturation éthylénique ; et (c) (i) un agent de réticulation à blocage réversible permettant de favoriser la réticulation du copolymère, et (ii) un inhibiteur de réticulation fugitif pour inhiber la réticulation du copolymère par l'agent de réticulation à blocage réversible.
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WO2023172864A1 (fr) * 2022-03-08 2023-09-14 Genentech, Inc. Excipients hétéropolymères aléatoires pour formulations à concentration de protéines élevée

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