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WO1994026697A1 - Composes oximes utilises comme agents de reticulation pour des copolymeres - Google Patents

Composes oximes utilises comme agents de reticulation pour des copolymeres Download PDF

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Publication number
WO1994026697A1
WO1994026697A1 PCT/EP1994/001324 EP9401324W WO9426697A1 WO 1994026697 A1 WO1994026697 A1 WO 1994026697A1 EP 9401324 W EP9401324 W EP 9401324W WO 9426697 A1 WO9426697 A1 WO 9426697A1
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Prior art keywords
atoms
dispersion
groups
alkyl
carbon atoms
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Ceased
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PCT/EP1994/001324
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German (de)
English (en)
Inventor
Gerhard Bauer
Karl Haeberle
Roland Baumstark
Kaspar Bott
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BASF SE
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BASF SE
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Priority to AU66491/94A priority Critical patent/AU6649194A/en
Publication of WO1994026697A1 publication Critical patent/WO1994026697A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/8077—Oximes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
    • C07C251/54—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/12—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
    • 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
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C08K5/33—Oximes

Definitions

  • the invention relates to a compound of the formula
  • R 1 and R 2 independently of one another for C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, Cs-Cio-cycloalkyl or a Cs-Cio-aryl radical, which also includes 1 to 3 non-adjacent nitrogen or oxygen radicals - Or contain sulfur atoms as heteroatoms in the carbon chain or carbon ring and can be substituted by 1 to 3 C 1 -C 4 -alkyl or -alkoxy groups, R 1 or R 2 can stand for a hydrogen atom, or R 1 and R 2 together form a bridge of 2 to 14 carbon atoms, where some of the carbon atoms can also be part of an aromatic ring system,
  • a and B represent an n- or m-valent organic radical
  • X the meaning of a linear or branched hydrocarbon chain of 2 to 12 carbon atoms, which may be replaced by 1 to 3 non-adjacent oxygen atoms, sulfur atoms or nitrogen atoms or a Cs-Cio -Cycloalkylene- or one Cs-Cio-arylene ring can be interrupted
  • n or m stand for an integer greater than 1.
  • the invention relates to dispersions or solutions of radical polymers, polycondensates or polyadducts which contain compounds of the formula I, II or III.
  • Copolymers which are used in coating compositions or adhesives are in many cases crosslinkable copolymers.
  • Networking can e.g.
  • a crosslinking agent which reacts with functional groups in the copolymer is generally added to the copolymers.
  • crosslinking agents are e.g. Polyisocyanates which react with hydroxyl or amino groups.
  • aqueous adhesive preparations are known from DE-A-35 21 618, in which polyisocyanates dispersed in water are added to aqueous dispersions as free-radical polymerized copolymers as crosslinking agents. Similar adhesive preparations are also described in US Pat. No. 4,396,738 and DE-A-31 12 117.
  • the polyisocyanate may therefore only be dispersed in water and mixed with the copolymer shortly before it is used as a crosslinking aid.
  • Increased storage stability can be achieved by reacting the isocyanate groups with blocking agents, e.g. Oximes, caprolactam, phenols, dialkyl maleate can be achieved.
  • blocking agents e.g. Oximes, caprolactam, phenols, dialkyl maleate
  • the so-called blocked polyisocyanates obtained hydrolyze only to a minor extent in aqueous dispersion.
  • DE-A-38 07 555 relates to such a diisocyanate blocked with oximes, which is dispersed in water and is suitable as an additive for polymers dispersed in water.
  • Crosslinking reactions only occur after the blocking agent has been split off at temperatures above approx. 130 ° C.
  • Previously known aqueous adhesive preparations with polyisocyanates as crosslinking aids are therefore either not stable in storage and can therefore only be used as a two-component system or crosslink only at high temperatures.
  • Storage-stable aqueous dispersions which crosslink at room temperature after removal of the solvent are known from EP-A-3516. These dispersions contain polyhydrazides which react with monomers having carbonyl groups copolymerized in the copolymer.
  • EP-A-516 074 describes aminooxy derivatives as crosslinking agents for copolymers containing keto or aldehyde groups.
  • EP-A-522 306 describes polyisocyanates blocked with oximes as crosslinking agents for polymers containing carbonyl groups.
  • German patent applications P 4219385.0 and P 4219384.2 also relate to crosslinkers for polymers containing carbonyl groups.
  • the object of the present invention was therefore storage-stable dispersions or solutions of crosslinkable copolymers which contain a crosslinking agent and can be crosslinked at room temperature.
  • the compounds of the formula I, II or III are suitable as crosslinking agents or adhesion promoters in dispersions or solutions of free-radical polymers, polycondensates or polyadducts.
  • Crosslinking of free-radical polymers, polycondensates or polyadducts containing keto or aldehyde groups with crosslinking agents of the formula I, II or III occurs when the liquid phase of the dispersion or solution is removed.
  • crosslinking agents of the formula I, II or III occurs when the liquid phase of the dispersion or solution is removed.
  • oxime ether alcohols The production of oxime ether alcohols is known and e.g. in G.B. Bachmann et al. T. Hokama, J. Am. Chem. Soc. 81, 4223 (1959).
  • R 1 , R 2 and X have the meaning given above.
  • variable X is preferably a linear or branched hydrocarbon chain of 2 to 12, in particular 2 to 8 carbon atoms, which may be replaced by 1 to 3, in particular 1 to 2, non-adjacent oxygen atoms or a Cs-Cio-cycloalkylene or a Cs -Cio arylene ring can be interrupted. It is particularly preferably a linear or branched hydrocarbon chain of 2 to 8 carbon atoms.
  • R 1 and R 2 preferably independently of one another represent a hydrogen atom, a C 1 -C 8 -alkyl group, C 1 -C 6 -alkoxy group or a Cs-Cio-aryl radical, in particular a phenyl ring.
  • R 1 and R 2 preferably independently of one another represent a hydrogen atom, a C 1 -C 8 -alkyl group, C 1 -C 6 -alkoxy group or a Cs-Cio-aryl radical, in particular a phenyl ring.
  • the hydrogen atom only one of the two radicals R 2 and R 3 can be a hydrogen atom.
  • the oxime ether alcohols can be converted to the compounds II or III by addition to polyisocyanates to give compounds I (urethane formation of the hydroxyl group in IV with isocyanate) or by transesterification with polycarboxylic esters or carbonic acid esters.
  • the oxime ether alcohols can be reacted with polyisocyanates by customary methods for the production of urethanes or polyurethanes.
  • the reaction takes place at a temperature between 20 and 160 ° C., in particular between 40 and 100 ° C.
  • the reaction can be carried out using solvents which are not reactive with isocyanate or without solvents. Solvents are preferably not used.
  • the customary catalysts such as, for example, dibutyltin dilaurate, tin (II) octoate or diazabicyclo (2,2,2) octane can also be used.
  • Suitable polyisocyanates are organic compounds which have at least two free isocyanate groups.
  • Diisocyanates (X (NCO) 2 ) are preferably used, where X is an aliphatic hydrocarbon radical with 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon radical with 6 to 15 carbon atoms, an aromatic hydrocarbon radical with 6 to 15 carbon atoms or an araliphatic one Hydrocarbon radical having 7 to 15 carbon atoms.
  • diisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanate-cyclohexane, l-isocyanato-3,5,5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI), 4,4'-diisocyanato-dicyclohexyl HMDI), 4,4'-diisocyanatodicyclohexylpropane- (2,2), 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, p -Xylylene diisocyanate, tetramethylxylylene diisocyanate and mixtures consisting of these compounds.
  • IPDI 1,4-diis
  • polyfunctional isocyanates known per se or else modified polyisocyanates known per se for example carbodiimide, allophanate, isocyanurate, urethane and / or biuret groups.
  • polyisocyanates containing isocyanurate or biuret groups in particular those based on 1,6-diisocyanatohexane and / or l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane or reaction products of the polyisocyanates with polyvalent ones, in particular 2- to 5-valent alcohols.
  • Aliphatic alcohols with a total of 2 to 8 carbon atoms such as ethylene glycol, 1,4-butanediol, 1,2-propanediol, glycerol, triethylol-propane or pentaerythritol, are preferred.
  • Hydrophilically modified polyisocyanates are also suitable. These are self-dispersible in water, so that emulsifiers and dispersing aids can largely be dispensed with for dispersion.
  • Self-dispersible polyisocyanates with nonionic groups are known, in particular reaction products of polyisocyanates with polyalkylene ether alcohols, such as those e.g. are described in EP-A-206 059.
  • Polyisocyanates also become self-dispersible by incorporating ionic groups or groups which can be converted into ionic groups. The latter are e.g. known from DE-A-4 113 160 or DE-A-4 001 783.
  • Hexamethylene diisocyanate, IPDI, HMDI, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane and mixtures thereof are preferably used.
  • the radical A in formula I is accordingly preferably derived from one of the polyisocyanates mentioned.
  • the transesterification of the polycarboxylic acid esters or the carbonic acid esters with the oxime ether alcohols is carried out in the temperature range from 70 to 150 ° C, preferably at 100 to 130 ° C, using as catalysts e.g. can use the above-mentioned tin salts or titanium esters.
  • polycarboxylic acid esters and carbonic acid esters which are preferably used for the transesterification are esterified with lower alcohols such as methanol or ethanol.
  • the oxime ether alcohols IV can also be reacted with the corresponding polycarboxylic acid chlorides or with phosgene. In this way, the reaction temperatures can be reduced to values lower than room temperature.
  • Preferred polycarboxylic acid esters for the reaction are diesters, in particular C 2 -C alkanedioic acid esters or benzene or naphthol dicarboxylic acid esters.
  • m is therefore preferably 2.
  • the statements made above apply to the radicals R 1 , R 2 and X.
  • the radical B in formula II is preferably derived from one of the polycarboxylic acid esters mentioned.
  • the dispersion or solution to which compounds I or II are added as crosslinking agents preferably contains a polymer, polycondensate or polyadduct which comprises 0.001 to 20% by weight, preferably 0.01 to 10% by weight and in its entirety more preferably 0.05 to 4 wt .-% consists of aldehyde groups -CHO- or keto groups -CO- be ⁇ .
  • It can e.g. are a free-radically polymerized copolymer, a polyester as a polycondensate or a polyurethane as a polyadduct.
  • the aldehyde or keto groups are preferably polymerized in by ethylenically unsaturated compounds which contain these groups.
  • monomer a ethylenically unsaturated compounds with one or two aldehyde or keto groups or one aldehyde and one keto group and a free-radically polymerizing bar olefinic double bond
  • polyester for example: monoalcohols, diols, monocarboxylic acids or dicarboxylic acids
  • polyurethane it can be e.g. are mono-, diisocyanates or also monoalcohols or diols which contain aldehyde or keto groups.
  • monoalcohols examples include Hydroxyacetone, hydroxybenzaldehyde, acetoin and benzoin.
  • Suitable monocarboxylic acids are e.g. Ketocarboxylic acids such as pyruvic acid or levulinic acid.
  • Polyurethane dispersions containing keto groups are known, e.g. from DE-A-3 837 519, EP-A-332 326 and EP-A-442 652.
  • compounds having aldehyde or keto groups in the polymers, polycondensates or polyadducts can be bound to the polymers, polycondensates or polyadducts not only as part of the main chain, but also by reaction with reactive groups in the main polymer chain.
  • a free-radically polymerized copolymer which consists of the monomers a) which contain aldehyde or keto groups and monomers b) and c).
  • Examples of monomers a) are Acrolein, methacrolein, vinyl alkyl ketones with 1 to 20, preferably 1 to 10 carbon atoms in
  • Alkyl radical formylstyrene, (meth) acrylic acid alkyl ester with one or two keto or aldehyde or one aldehyde and one keto group in the alkyl radical, the alkyl radical preferably comprising a total of 3 to 10 carbon atoms, e.g. (Meth) acryloxyalkylpropanals, as described in DE-A-27 22 097.
  • N-oxoalkyl (meth) acrylamides such as those e.g. from US-A-4 226 007, DE-A-20 61 213 or DE-A-22 07 209 are known.
  • Acetoacetyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate and in particular diacetone acrylamide are particularly preferred.
  • the main monomers b) are present in the copolymer in particular in an amount of from 20 to 99.99, preferably from 60 to 99.9 and particularly preferably from 80 to 99.5% by weight, based on the copolymer.
  • Suitable monomers b) are esters of acrylic or methacrylic acid of alkyl alcohols containing 1 to 20 carbon atoms. Such alcohols are methanol, ethanol, n- or i-propanol, n-, s- and t-butanol, n-pentanol, isoamyl alcohol, n-hexanol, octanol, 2-ethylhexanol, lauryl and stearyl alcohol.
  • (meth) -acrylic acid alkyl esters with a -C-C ⁇ o-alkyl radical such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • Vinyl esters of carboxylic acids with 1 to 20 carbon atoms such as vinyl laurate, stearate, vinyl propionate and vinyl acetate, are also suitable.
  • Suitable vinyl aromatic compounds with up to 20 carbon atoms are vinyl toluene, a- and p-styrene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • Examples of ethylenically unsaturated nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are chlorine, fluorine or bromine-substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • butadiene, isoprene and chloroprene may be mentioned as non-aromatic hydrocarbons with 2 to 8 carbon atoms and at least two conjugated olefinic double bonds.
  • the monomers b) can in particular also be used in a mixture, especially in order to set the desired glass transition temperatures of the copolymer.
  • Copolymerizable monomers c) not falling under a) and b) come e.g. Esters of acrylic and methacrylic acid of alcohols having 1 to 20 carbon atoms which, in addition to the oxygen atom in the alcohol group, contain at least one further heteroatom and / or which contain an aliphatic or aromatic ring.
  • Examples include 2-ethoxyethyl acrylate, 2-butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylic acid aryl, alkaryl or cycloalkyl esters, such as cyclohexyl (meth) acrylate , Phenyl ethyl (meth) acrylate, phenylpropyl (meth) acrylate or acrylic acid ester of heterocyclic alcohols such as furfuryl (meth) acrylate.
  • Hydroxy-functional comonomers e.g. (Meth) acrylic acid Ci-C s-alkyl esters which are substituted by one or two hydroxyl groups.
  • hydroxy-functional comonomers are (meth) acrylic acid-Ci-C ⁇ -hydroxyalkyl esters, such as n-hydroxyethyl, n-hydroxypropyl or n-hydroxybutyl (meth) acrylate.
  • comonomers with salt-forming groups are in particular itaconic acid, acrylic acid and methacrylic acid.
  • the proportion by weight of the further comonomers in the copolymer can be, in particular, 0 to 50%, preferably 0 to 20% and very particularly preferably 0 to 10% by weight.
  • the proportions of the monomers a), b) and c) add up to 100% by weight.
  • the proportion of monomers a) is chosen so that the above-mentioned content of aldehyde or keto groups is present in the copolymer.
  • the copolymer is generally prepared by radical polymerization. Suitable polymerization methods, such as bulk, solution, suspension or emulsion polymerization, are known to the person skilled in the art.
  • the copolymer is preferably prepared by solution polymerization with subsequent dispersion in water or particularly preferably by emulsion polymerization, the copolymer being obtained as an aqueous dispersion.
  • the comonomers can be polymerized in the emulsion polymerization, as usual, in the presence of a water-soluble initiator and an emulsifier at preferably 30 to 95 ° C.
  • Suitable initiators are, for example, sodium, potassium and ammonium persulphate, tert-butyl hydroperoxides, water-soluble azo compounds or redox initiators.
  • Suitable emulsifiers are reaction products of alkylene oxides, in particular ethylene oxide or propylene oxide, with fatty alcohols, acids or phenol, or alkylphenols.
  • the copolymer is first prepared by solution polymerization in an organic solvent and then with the addition of salt formers, e.g. from copolymers containing ammonia to carboxylic acid groups, dispersed in water without the use of an emulsifier or dispersing aid.
  • the organic solvent can be distilled off.
  • the preparation of aqueous secondary dispersions is known to the person skilled in the art and e.g. described in DE-A-37 20 860.
  • Regulators can be used in the polymerization to adjust the molecular weight. Suitable are e.g. -SH-containing compounds such as mercaptoethanol, mercaptopropanol, thiophenol, thioglycerin, ethyl thioglycolate, methyl thioglycolate and tert-dodecyl mercaptan.
  • -SH-containing compounds such as mercaptoethanol, mercaptopropanol, thiophenol, thioglycerin, ethyl thioglycolate, methyl thioglycolate and tert-dodecyl mercaptan.
  • the type and amount of the comonomers is expediently chosen so that the copolymer obtained has a glass transition temperature between preferably -60 and + 140 ° C. Depending on whether hard or soft coatings are desired, high or low glass transition temperatures are set by the choice of the monomers.
  • the glass transition temperature of the copolymer can be determined using customary methods such as differential thermal analysis or differential scanning calorimetry (see, for example, ASTM 3418/82, so-called "midpoint temperature").
  • the dispersion or solution contains a compound of the formula I or II as an adhesion promoter or as a crosslinking agent.
  • the solids content of the dispersion or solution according to the invention is preferably between 20 and 90% by weight, in particular between 30 and 70% by weight.
  • the dispersions or solutions according to the invention are suitable as coating compositions for different substrates with plastic, wood or metal surfaces or, for example, for textiles, nonwovens, leather or paper. They are also suitable for applications in construction chemistry, for example as adhesives, sealants, binders or the like.
  • the coatings can be, for example, paints, protective coatings or adhesive coatings.
  • An aqueous dispersion of a free-radically polymerized copolymer, in particular a copolymer containing keto and / or aldehyde groups, is particularly suitable for the uses mentioned.
  • the aqueous dispersion can also contain organic, preferably water-miscible, solvents as auxiliary solvents.
  • the dispersion or solution according to the invention can contain customary auxiliaries and additives.
  • these include, for example, fillers such as quartz powder, quartz sand, highly disperse silicic acid, heavy spar, calcium carbonate, chalk, dolomite or talc, which are often combined with suitable wetting agents such as Polyphosphates such as sodium hexamethaphosphate, naphthalenesulfonic acid, ammonium or sodium polyacrylic acid salts are used, the wetting agents being generally added from 0.2 to 0.6% by weight, based on the filler.
  • fillers such as quartz powder, quartz sand, highly disperse silicic acid, heavy spar, calcium carbonate, chalk, dolomite or talc
  • suitable wetting agents such as Polyphosphates such as sodium hexamethaphosphate, naphthalenesulfonic acid, ammonium or sodium polyacrylic acid salts are used, the wetting agents being generally added from 0.2 to 0.6% by weight, based on the
  • fungicides for preservation are generally used in amounts of 0.02 to 1% by weight, based on the entire dispersion or solution.
  • Suitable fungicides are, for example, phenol or cresol derivatives or organotin compounds.
  • the dispersions or solutions according to the invention are particularly suitable, in particular as an aqueous dispersion of a free-radical copolymer, as a sealant or adhesive, in particular, for example, as a laminating adhesive for the production of composite films and gloss films.
  • the dispersions can also contain, as an adhesive, special auxiliaries and additives customary in adhesive technology. These include, for example, thickeners, plasticizers or tackifying resins such as natural resins or modified resins such as rosin esters or synthetic resins such as phthalate resins.
  • Dispersions which are used as adhesives particularly preferably contain alkyl (meth) acrylates as monomers b) in the copolymer.
  • the glass transition temperature of the copolymers is preferably set to values between 0 and -40 ° C.
  • the dispersions When used as an adhesive, the dispersions also surprisingly show very good adhesion, in particular wet adhesion.
  • the pH of the dispersion is preferably adjusted to a value between 2 and 9, since the crosslinking reaction with the copolymers can be catalyzed with acid.
  • the dispersions or solutions according to the invention which contain compounds of the formula I are stable on storage.
  • the crosslinking reaction e.g. with keto and / or aldehyde groups, occurs even at room temperature when the liquid phase is removed, e.g. Volatilization of the water.
  • the volatilization of the water can be accelerated to 30 to 100 ° C.
  • the compounds act as so-called primers.
  • feed 1 200 g of demineralized water, 37 g of feed 1 (see below) and 20 g of feed 2 were placed in a reaction vessel with stirrer and two feed vessels (feed 1 and feed 2) and heated to 85 ° C. After 15 minutes, feed 1 was uniformly added to the reaction vessel over the course of 2 h and feed 2 evenly over the course of 2.5 h. After the last addition of initiator (feed 2), the dispersion was stirred at 85 ° C. for 1 hour. Feed 1: (this feed is stirred during the polymerization)
  • the dispersions D2 to D3 were prepared in a corresponding manner.
  • the composition of the respective copolymers is given in Table 1.
  • Feed 1 (is stirred during the polymerization)
  • demineralized water 50 g 20% by weight aqueous solution of a fatty alcohol etherified with 18 ethylene oxide units (C16 / C18) (emulsifier)
  • the preparation of the copolymer dispersion D5 corresponds to that of D4, with the 38 g of acetoacetoxyethyl methacrylate in feed 1
  • AAEM diacetone acrylamide
  • crosslinked polymers swelling occurs due to the absorption of solvents. As the degree of crosslinking increases, the swelling becomes less since less solvent can be taken up by the closely crosslinked polymer. Polymers that are not or hardly crosslinked are largely dissolved by solvents or swell excessively if a small number of crosslinking sites are present.
  • the extractables were determined by reweighing at room temperature after drying in a drying cabinet at 80 ° C. for 4 hours. In the tests according to Table 3, the drying time of the films was only 4 days instead of one week.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un composé de formule (I), (II) ou (III) où R1 et R2 désignent indépendamment l'un de l'autre un reste alkyle C¿1?-C10, un reste alcoxy C1-C10, un reste cycloalkyle C5-C10 ou un reste aryle C5-C10, qui contiennent également comme hétéroatomes 1 à 3 atomes d'azote, d'oxygène ou de soufre non adjacents, dans la chaîne de carbone ou le composé cyclique de carbone et qui peuvent être substitués par 1 à 3 groupes alkyle C1-C4 ou alcoxy, R?1 ou R2¿ peut désigner un atome d'hydrogène ou R1 et R2 forment conjointement un pont composé de 2 à 14 atomes de carbone, une partie des atomes de carbone pouvant également constituer un composant d'un système cyclique aromatique, A et B désignent un reste organique n-valent ou m-valent, X représente une chaîne hydrocarburée linéaire ou ramifiée composée de 2 à 12 atomes de carbone qui peut être interrompue par 1 à 3 atomes d'oxygène, de soufre ou d'azote non adjacents ou par un composé cyclique cycloalkylène C¿5?-C10 ou un composé cyclique arylène C5-C10, et n ou m est un nombre entier supérieur à 1. L'invention concerne par ailleurs ce composé en dispersion ou en solution et son utilisation comme agent de réticulation pour des polymères.
PCT/EP1994/001324 1993-05-07 1994-04-27 Composes oximes utilises comme agents de reticulation pour des copolymeres Ceased WO1994026697A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU66491/94A AU6649194A (en) 1993-05-07 1994-04-27 Oxime compounds used as crosslinking agents for copolymers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19934315207 DE4315207A1 (de) 1993-05-07 1993-05-07 Oximverbindungen als Vernetzer für Copolymerisate
DEP4315207.4 1993-05-07

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DE (1) DE4315207A1 (fr)
WO (1) WO1994026697A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4219384A1 (de) * 1992-06-13 1993-12-23 Basf Ag Bei Raumtemperatur mit Hydroxylaminen oder Oximethern vernetzbare Dispersion oder Lösung
DE4306392A1 (de) * 1993-03-02 1994-09-08 Basf Ag ß-Hydroxyoximether und bei Raumtemperatur mit ß-Hydroxyoximethern vernetzbare Dispersionen oder Lösungen
DE4309193A1 (de) * 1993-03-22 1994-09-29 Basf Ag Copolymerisierbare Oximether und diese enthaltende Copolymerisate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3807555A1 (de) * 1987-03-12 1988-09-22 Dai Ichi Kogyo Seiyaku Co Ltd Thermoreaktive waessrige zusammensetzung
EP0483060A2 (fr) * 1990-10-22 1992-04-29 Ciba-Geigy Ag Oxime stériquement encombrée comme améliorateur de couleur pour la transformation de polyoléfines
EP0522306A1 (fr) * 1991-07-03 1993-01-13 BASF Aktiengesellschaft Composition aqueuse de résine synthétique durcissable à température ambiante et son utilisation comme adhésif pour stratifiés
DE4219385A1 (de) * 1992-06-13 1993-12-16 Basf Ag Copolymerisierbare Oximether und diese enthaltende Copolymerisate
DE4219384A1 (de) * 1992-06-13 1993-12-23 Basf Ag Bei Raumtemperatur mit Hydroxylaminen oder Oximethern vernetzbare Dispersion oder Lösung

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3807555A1 (de) * 1987-03-12 1988-09-22 Dai Ichi Kogyo Seiyaku Co Ltd Thermoreaktive waessrige zusammensetzung
EP0483060A2 (fr) * 1990-10-22 1992-04-29 Ciba-Geigy Ag Oxime stériquement encombrée comme améliorateur de couleur pour la transformation de polyoléfines
EP0522306A1 (fr) * 1991-07-03 1993-01-13 BASF Aktiengesellschaft Composition aqueuse de résine synthétique durcissable à température ambiante et son utilisation comme adhésif pour stratifiés
DE4219385A1 (de) * 1992-06-13 1993-12-16 Basf Ag Copolymerisierbare Oximether und diese enthaltende Copolymerisate
DE4219384A1 (de) * 1992-06-13 1993-12-23 Basf Ag Bei Raumtemperatur mit Hydroxylaminen oder Oximethern vernetzbare Dispersion oder Lösung

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DE4315207A1 (de) 1994-11-10

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