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WO2015150508A1 - Compositions aqueuses polymériques - Google Patents

Compositions aqueuses polymériques Download PDF

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Publication number
WO2015150508A1
WO2015150508A1 PCT/EP2015/057282 EP2015057282W WO2015150508A1 WO 2015150508 A1 WO2015150508 A1 WO 2015150508A1 EP 2015057282 W EP2015057282 W EP 2015057282W WO 2015150508 A1 WO2015150508 A1 WO 2015150508A1
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Prior art keywords
polymer
monomers
groups
formula
monoethylenically unsaturated
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German (de)
English (en)
Inventor
Peter Nesvadba
Matthias ZORN
Olof Wallquist
Bernd Reck
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/26—Nitrogen
    • C08F212/28—Amines

Definitions

  • the present invention relates to aqueous polymer composition containing at least a first, built up from ethylenically unsaturated monomers
  • Polymer P1 which has on average more than 2 functional groups of the formula -O-NR 1 R 2 , and the use of these polymers for crosslinking polymers P2 which have functional groups F which are bonded to the groups of the formula -O-NR 1 R 2 can react to form a covalent bond.
  • Aqueous polymer compositions in particular aqueous polymer dispersions, are widely used for the production of coatings or as adhesive raw materials.
  • the polymer films forming upon removal of the water are typically uncrosslinked and therefore have only limited mechanical strength or cohesion and only limited chemical resistance, in particular limited resistance to organic solvents.
  • aqueous polymer compositions are then admixed with a low molecular weight, water-soluble crosslinking agent having a reactivity complementary to the functional groups of the film-forming polymer and thus drying the polymer film with the functional groups of the film-forming polymer to form a covalent bond or bond
  • EP 519074 describes aqueous polymer compositions based on aqueous dispersions of polymers which comprise copolymerized ethylenically unsaturated monomers with keto or aldehyde groups, the aqueous polymer compositions containing a low molecular weight compound which has 2 aminoxy groups or one aminox group and one hydrazide group. Similar compositions are known from DE 42 19 384 and DE 43 14 623. MR Hill et al. Polym. Chem., 3 (2012), 1758 describe homopolymers of O- (4-vinylbenzyl) hydroxylamine ethers and its copolymers with styrene.
  • low molecular weight compounds have the disadvantage that they can easily be washed out of the polymer film if they are not completely crosslinked. In addition, they generally have a comparatively high volatility, which is disadvantageous from the point of view of occupational hygiene. In addition, the low molecular weight compounds are often toxic. In addition, the cross-linking effect is not always satisfactory.
  • R a and R b independently of one another are hydrogen or C 1 -C 4 Alkyl or together with the carbon atom to which they are attached, form a Cs-Cs Cycloalkylidenement.
  • hydrolysis of the ketimine groups occurs, releasing the aminoxy groups, which then cause crosslinking.
  • a first aspect of the invention relates to aqueous
  • Polymer compositions comprising: a) at least one first polymer P1 made up of ethylenically unsaturated monomers which has on average more than 2 functional groups of the formula
  • R a and R b independently of one another are hydrogen or C 1 -C 6 -alkyl or together with the carbon atom to which they are attached form a C 5 -C 8 -cycloalkylidene group; b) and at least a second, preferably from ethylenically unsaturated
  • Monomeric polymer P2 having functional groups F which can react with the groups of formula -O-NR 1 R 2 to form a covalent bond.
  • Some of the polymers P1 are new, namely copolymers which on average have more than 2 functional groups of the formula -O-NR 1 R 2 and which are composed of the following repeat units MA and MB:
  • MA repeating units MA which are derived from a monoethylenically unsaturated monomer A which carries a functional group of the formula -O-NR 1 R 2 , in which R 1 and R 2 have the meanings given in Claim 1 or 2;
  • Monomers B are derived, which are not a functional group of the formula
  • Repeat units include MBI, monoethylenically
  • unsaturated monomers B1 having a water solubility of at least 50 g / l, at 20 ° C and 1 bar, are derived.
  • Copolymers of this kind which are also referred to below as copolymers P1 ', are particularly suitable as crosslinking agents for the abovementioned polymers P2 and are therefore themselves also the subject of the present invention.
  • the invention also relates to the use of polymers P1 and of
  • Copolymers P1 ' as described in more detail here and in the following and in the claims, as crosslinkers for polymers P2, the functional groups F, which with the groups of formula -0-NR 1 R 2 of the polymer P1 to form a covalent Binding can react.
  • aqueous polymer compositions of the invention have a number of advantages.
  • the polymers P1 or the copolymers P1 ' it is possible to achieve improved crosslinking in comparison to low molecular weight crosslinkers. This gives polymer films increased mechanical strength and less susceptible to exposure to chemicals such as organic
  • the property profile of the polymer films obtained can be better controlled via the modification of the polymers P1 and adapted to the desired application by modifying the polymer structure, rather than by low molecular weight crosslinkers.
  • such polymers have a significantly less pronounced potential to be sensitizing and toxic.
  • Polymer P1 or the copolymer PV react during drying of the polymer composition to form covalent bonds and thus effect an intermolecular crosslinking of the polymers P2 and the polymers P1 or copolymers PV.
  • the crosslinking is more pronounced than when using low molecular weight crosslinking agents such as dicarboxylic acid dihydrazides, alkylenediamines or Bisaminoxyalkane.
  • alkyl includes straight-chain and branched alkyl groups, preferably having 1 to 6 and in particular 1 to 4 carbon atoms (C 1 -C 6 -alkyl or C 1 -C 4 -alkyl), such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl, 1, 1-dimethylpropyl, 2,2- Dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl,
  • Suitable long-chain alkyl groups are, for example, straight-chain and branched alkyl groups having up to 30 carbon atoms and in particular up to 20 carbon atoms, for.
  • Fatty acids and fatty alcohols and Oxoalkoholen occur. These include, for example, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-nonadecyl.
  • branched alkyl radicals having 7 to 30 C atoms, in particular 7 to 20 C atoms, such as 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, 2-ethylhexyl, isononyl, 2-propylheptyl, isotridecyl and the same.
  • cycloalkylidene in the context of the present invention represents a cyclic hydrocarbon radical bonded via a double bond and preferably having 5 to 8 C atoms, such as cyclopentylidene, cyclohexylidene, cycloheptylidene and cyclooctylidene.
  • alkylene in the context of the present invention represents straight-chain or branched alkanediyl groups having 1 to 12 carbon atoms, such as, for example, methylene, 1-ethane-1,2-diyl, 1,2-propanediyl, 2-methyl-1,2 propanediyl or 1,2,3,3 or 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octanediyl, 1,9-nonanediyl, 1 , 10-decanediyl, 1,1,1-undecanediyl or 1,12-dodecanediyl etc.
  • R a and R b are preferably methyl or ethyl or together with the carbon atom to which they are attached form a cyclopentylidene or cyclohexylidene ring.
  • the functional groups of the formula -O-NR 1 R 2 may be bonded to the carbon backbone directly or via a linker A. Where A stands
  • X represents a chemical bond or is a bivalent radical which is bonded to a carbon atom of the polymer backbone and which is selected from phenylene, phenylene-CH 2 -, C (O), CH 2 , 0-C 2 -C 2 -alkanediyl and
  • n is a number from 0 to 20, where n is other than 0, when X is C (O) and n is in particular 0;
  • n is other than 0 when X is a chemical bond.
  • X is a chemical bond or CH 2 and n is an integer from 1 to 20, especially 1 to 10, where n can also be 0 when X is CH 2 .
  • X is phenylene and n is 0 or an integer from 1 to 20, in particular 1 to 10 and in particular 0.
  • X is phenylene-Ch - and n is 0 or a whole Number from 1 to 20, in particular 1 to 10 and in particular for 0.
  • X is C (O) and n is an integer from 1 to 20, in particular 1 to 10 and especially for 1.
  • X is C (O) -NR C - ( C 2 -C 10 -alkanediyl), where R c has the abovementioned meanings and in particular denotes hydrogen, and n is 0 or an integer from 1 to 20, in particular 1 to 10 and in particular for O.
  • X is C 2 -C 12 -alkanediyl or O-C 2 -C 12 -alkanediyl and n is 0 or 1.
  • X is phenylene-Ch - and n is 0.
  • the content of functional groups of the formula -O-NR 1 R 2 can be varied over wide ranges and in principle allows adaptation of the polymer P1 or of the copolymer P1 'to the desired degree of crosslinking.
  • the polymers P1 and the copolymers P1 ' have on average (number average) more than 2, preferably at least 2.5 and in particular at least 3 groups of the formula -O-NR 1 R 2 .
  • the upper limit of the number of functional groups of the formula -O-NR 1 R 2 is limited only by the molecular weight of the polymers P1 or the copolymers P1 'and may be, for example, up to 1000 or more.
  • the weight-average molecular weight M w of the polymers P1 and the copolymer P1 ' is typically in the range from 550 to 5 ⁇ 10 6 g / mol, frequently in the range from 900 to 2 ⁇ 10 6 g / mol and in particular in the range from 1200 to 10 6 g / mol.
  • the ratio of weight average molecular weight to number average molecular weight M w / M n is typically in the range of 1 to 1 to 10, and more preferably in the range of 1 to 2 to 5.
  • the glass transition temperature T g of the polymer P1 is of minor importance and is usually in the range of -60 ° C to 150 ° C, especially in the range of -50 ° C to 150 ° C and especially in the range of -40 ° C to 120 ° C. Under the
  • Glass transition temperature is understood as the so-called midpoint temperature according to ASTM 3418/82, as can be determined by differential scanning calorimetry (DSC).
  • the glass transition temperature of a polymer can also be determined by dynamic mechanical analysis (DMTA) as described in connection with the examples
  • the glass transition temperature can be adjusted by suitable choice of the monomers B1 and B2.
  • the polymers P1 as well as the copolymers P1 ' are composed of ethylenically unsaturated monomers. Accordingly, they have on average more than 2
  • Repeat units MA which are derived from a monoethylenically unsaturated monomer A, which carries a functional group of the formula -O-NR 1 R 2 .
  • the polymers P1 may be homopolymers or copolymers.
  • the monoethylenically unsaturated monomer A has the formula I:
  • R 1 , R 2 have the meanings given above and in particular for
  • R 3 is hydrogen or methyl
  • A is a group of the formula X- [O-Alk] n , where X, Alk and n are the above
  • A is O-CH 2 CH 2 or CH 2 -OCH 2 CH 2 .
  • X is Ci-Ci2-alkanediyl, in particular CH2, or 0-C 2 -Ci2-alkanediyl, in particular 0-C 2 -C 4 -alkanediyl, such as 0- (1, 2-ethanediyl ), O- (1, 2-propanediyl), O- (2-methyl-1,2-propanediyl) or O- (1,2,3,3 or 1,4 butanediyl), and n is 0 or 1 stands.
  • Alk if present, is especially for ethane-1, 2-diyl
  • polymers P1 and copolymers P1 'and those polymers are selected in which the repeating units MA derived from the monomers A are derived from the monomer type 3).
  • the monomers A are selected from the monomers of the formula I in which R 1 , R 2 and R 3 are hydrogen and A is phenylene-Ch.
  • polymers P1 and copolymers P1 'and those polymers are selected in which those of the monomers A derived repeat units MA of the monomer type 1) are derived.
  • the monomers A are selected from the monomers of the formula I in which R 1 , R 2 and R 3 are hydrogen and A is O-CH 2 CH 2 or CH 2 -OCH 2 CH 2.
  • copolymers which, in addition to the repeat units MA, have one or more further repeat units MB which are derived from monoethylenically unsaturated monomers B which have no functional group of the formula -O-NR 1 R 2 .
  • polymers which in addition to the repeat units MA repeating units MB ', which are derived from vinyl alcohol, and optionally repeating units MB.
  • all monomers B are suitable as comonomers which have an ethylenically unsaturated group.
  • the monomers B may be neutral, basic, acidic, nonionic, anionic or cationic.
  • the molar ratio of repeat units MA to repeat units MB is generally in the range from 1: 100 to 10: 1, in particular in the range from 1:80 to 2: 1 and especially in the range from 1: 75 to 1: 1.
  • the proportion of repeating units MA is generally at least 5% by weight, preferably at least 10% by weight and in particular at least 15% by weight.
  • the proportion of repeating units MA in the polymers P1 is generally in the range of 10 to 100 wt .-% or 5 to 90 wt .-%, in particular in the range of 10 to 100 wt .-% or in the range of 10 bis 80 wt .-%, especially in the range of 15 to 100 wt .-% or in the range of 15 to 50 wt .-%, each based on the total amount of the polymer P1 constituent
  • the proportion of repeating units MB or ⁇ is generally in the range from 10 to 95% by weight, in particular in the range from 20 to 90% by weight or in the range from 50 to 85% by weight. , in each case based on the total amount of repeating units constituting the polymer P1.
  • the proportion of the monomers A based on the total amount of the monomers constituting the polymer P1 or the copolymer P1', is generally at least 5% by weight, preferably at least 10% by weight and in particular at least 15% by weight. Accordingly, the proportion of the monomers A in the polymers P1 is generally in the range from 10 to 100% by weight.
  • wt .-% in particular in the range of 10 to 100 wt .-% or in the range of 10 to 80 wt .-%, especially in the range of 15 to 100 wt .-% or in the range of 15 to 50 %
  • the proportion of monomers B is generally in the range from 10 to 95% by weight, in particular in the range from 20 to 90% by weight or in the range from 50 to 85% by weight, in each case based on the total amount of the monomers P1 and B constituting the polymer P1.
  • the proportion of the monomers A is generally in the range of 5 to 90 wt .-%, in particular in the range of 10 to 80 wt .-% and especially in
  • the repeating units MB or MB 'of the polymers P1 comprise one or more repeat units which comprise monomers B1 having a water solubility of at least 50 g / l, in particular at least 100 g / l at 20 ° C. and 1 bar, or derived from vinyl alcohol.
  • comonomers B of the polymers P1 comprise one or more monomers B1 which have a water solubility of at least 50 g / l, in particular at least 100 g / l at 20 ° C. and 1 bar.
  • Examples of monomers B1 are the following monomer classes B1 -a to B1 -j:
  • B1-a monoethylenically unsaturated Cs-Cs monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid or vinylacetic acid, and salts thereof, in particular their alkali metal salts and ammonium salts;
  • B1 -b monoethylenically unsaturated C4-C8 dicarboxylic acids, such as fumaric acid,
  • Itaconic acid citraconic acid or maleic acid, and their salts, in particular their alkali metal salts and ammonium salts;
  • B1 -c monoethylenically unsaturated sulfonic acids, such as vinylsulfonic acid,
  • Phosphonopropyl methacrylate, and 2-acrylamido-2-methyl-propanephosphonic acid and the salts, in particular the alkaline earth or alkali metal salts of the abovementioned acids;
  • B1 -e amides of monoethylenically unsaturated Cs-Cs monocarboxylic acids such as
  • B1 -f hydroxy-C2-C4-alkyl esters of monoethylenically unsaturated Cs-Cs monocarboxylic acids, in particular the hydroxy-C2-C4-alkyl esters of
  • Acrylic acid and methacrylic acid such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate,
  • Poly-C2-C4-alkylene oxide esters of monoethylenically unsaturated Cs-Cs monocarboxylic acids in particular the esters of acrylic acid or the
  • Methacrylic acid for example monomers of the following formula A ' wherein
  • R a is hydrogen or C 1 -C 4 -alkyl and R b is hydrogen or methyl.
  • B1 -h-di-C 1 -C 4 -alkylamino-C 2 -C 4 -alkyl esters of monoethylenically unsaturated C 3 -C 8 -monocarboxylic acids in particular the dimethylamino-C 2 -C 4 -alkyl esters and the diethylamino-C 2 -C 4 -alkyl esters, especially of acrylic acid or of
  • Methacrylic acid such as 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl methacrylate, 2- (dimethylamino) propyl acrylate, 2- (diethylamino) propyl methacrylate, 3- (dimethylamino) propyl acrylate, 3- (diethylamino) propyl methacrylate and their acid addition salts;
  • N-vinyllactams such as N-vinylpyrrolidone or N-vinylcaprolactam
  • B1 -j Olefinically unsaturated nitriles such as acrylonitrile or methacrylonitrile.
  • the monomers B1 -a to B1-h are the monomers B1 -a, B1-c, B1 -d, B1 -e, B1 -f and B1 -g and especially the monomers B1 -a, B1 -e and B1 - f is preferred.
  • the abovementioned repeating units used by the
  • the repeating units MB can also include such repeating units derived from monomers B2, which have only a low solubility in water, which typically does not exceed 40 g / L and in particular 30 g / L at 20 ° C. ,
  • B2-a esters and diesters of monoethylenically unsaturated Cs-Cs-mono- and C4-C8-dicarboxylic acids with C 1 -C 30 -alkanols, in particular with C 1 -C 10 -alkanols,
  • B2-b esters of vinyl or allyl alcohol with C 1 -C 8 -monocarboxylic acids
  • B2-d amides of monoethylenically unsaturated Cs-Cs monocarboxylic acids with C 1 -C 30 -alkylamines or C 1 -C 30 -alkylamines, in particular with C 1 -C 10 -alkylamines or C 1 -C -alkylamines, and mixtures thereof;
  • B2-f olefins and conjugated diolefins.
  • Suitable esters and diesters of monoethylenically unsaturated Cs-Cs-mono- and C4-C8-dicarboxylic acids with C 1 -C 30 -alkanols, in particular with C 1 -C 10 -alkanols, are, above all, the esters of monoethylenically unsaturated C 3 -C 5 -monocarboxylic acids,
  • Tridecyl (meth) acrylate Tridecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate,
  • Arachinyl (meth) acrylate behenyl (meth) acrylate, lignoceryl (meth) acrylate,
  • Cerotinyl (meth) acrylate Cerotinyl (meth) acrylate, melissinyl (meth) acrylate, palmitoleinyl (meth) acrylate,
  • (meth) acrylate encompasses both the corresponding ester of acrylic acid and the corresponding esters of methacrylic acid.
  • Suitable esters of vinyl alcohol and allyl alcohol with Ci-C3o monocarboxylic acids are, for. Vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl versatate, allyl formate, allyl acetate, allyl propionate, allyl butyrate, allyl laurate and mixtures thereof.
  • Suitable vinyl aromatics are styrene, 2-methylstyrene, 4-methylstyrene, 2- (n-butyl) styrene, 4- (n-butyl) styrene, 4- (n-decyl) styrene, in particular styrene.
  • Suitable amides of monoethylenically unsaturated Cs-Cs monocarboxylic acids with C 1 -C 30 -alkylamines or C 1 -C 30 -alkylamines, in particular with C 1 -C 10 -alkylamines or C 1 -C -alkylamines, are, above all, the amides of acrylic acid and of methacrylic acid with Ci-C3o-alkylamines or di-Ci-C3o-alkylamines, in particular with C1-C10-alkylamines or di-Ci-Cio-alkylamines, such as.
  • N- (n-nonyl) (meth) acrylamide N- (n-decyl) (meth) acrylamide
  • N-heptadecyl (meth) acrylamide N-nonadecyl (meth) acrylamide
  • N-palmitoleinyl (meth) acrylamide N-oleyl (meth) acrylamide, N-linolyl (meth) acrylamide, N-linolenyl (meth) acrylamide, N-stearyl (meth) acrylamide, N-lauryl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamides.
  • (meth) acrylamide includes both the corresponding amide of acrylic acid and the corresponding amide of methacrylic acid.
  • Suitable vinyl halides and vinylidene halides are vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
  • Suitable olefins and conjugated diolefins are ethene, propene, 1-butene, isobutene, 1-hexene, butadiene and isoprene.
  • B2 is selected from the monomers B2-a, B2-b and B2-c, especially among the esters of monoethylenically unsaturated C3-C8 monocarboxylic acids, in particular the esters of acrylic acid (acrylates) and the esters of methacrylic acid (methacrylates), with Ci -Cio-alkanols and vinylaromatics, more preferably from C 1 -C 10 -alkyl acrylates and C 1 -C 10 -alkyl methacrylates and vinylaromatics, and especially from methyl acrylate, ethyl acrylate, n-propyl acrylate,
  • the monomers B comprise at least one monomer B1 or a combination of at least one monomer B1 with at least one monomer B2.
  • the molar fraction of the monomers B1, based on the total number of monomers B is at least 10 mol% and in particular at least 20 mol%, and is in particular in the range from 10 to 100 mol% and especially in the range from 20 to 100 mol%, based on the total amount of monomers B.
  • polymers P1 and the copolymers P1 ' are those which are soluble or at least dispersible in water.
  • the polymers P1 and the copolymers P1 ' are those polymers which are soluble in water at least at pH> 10 and 20 ° C and especially those which are already at pH 8 and 20 ° C or pH ⁇ 8 and 20 ° C are soluble.
  • Copolymers P1 usually contain at least 10 wt .-%, in particular at least 20 wt .-% and especially at least 30 wt .-%, based on the
  • Monomers A and B at least one monomer B1 polymerized in particular among the monomers B1 -a, B1 -c, B1 -d, B1e, B1 -f and Bi g is selected.
  • Monomers B1 -a, B1 -c, B1 -d, B1e, B1 -f and Bi g is selected; 0 to 85% by weight, or 5 to 85% by weight, in particular 0 to 70% by weight or 5 to 70% by weight and especially 0 to 55% by weight or 5 to 55% by weight one or more monomers B2, which is selected in particular from the monomers B2-a and B2-c;
  • copolymerized form all stated in wt .-% on the total amount of the polymer P1 or the copolymer PV constituent monomers A and B are based.
  • B1 -d, B1 -e, B1-f and Bi g is selected;
  • the polymers P1 and the copolymer P1 ' are usually uncrosslinked, d. H. they contain substantially no copolymerized monomers which have two or more non-conjugated double bonds. In particular, the proportion is
  • the preparation of the polymers P1 and the copolymers P1' can be carried out in analogy to known methods of polymer synthesis.
  • the polymers P1 and the copolymers P1 ' are prepared by free-radically initiated polymerization of monomers A or by copolymerization of the monomers A with the monomers B produce.
  • Both classical methods of free radical initiated polymerization and methods of controlled radical polymerization, such as RAFT, SFRP or ATRP can be used.
  • the polymerization of the monomers A or the copolymerization of the monomers A with the monomers B can both as a solution or precipitation, as
  • Emulsion polymerization or be carried out as a polymerization in bulk.
  • the preparation of the polymers P1 and the copolymers PV can also be carried out by polymer-analogous reaction.
  • polymers which have a plurality of nucleophilically displaceable groups for example halogen atoms bound to aliphatic carbon atoms or sulfate or sulfonate groups bonded to aliphatic carbon atoms, eg.
  • tosylate or mesylate groups for example a
  • polymers containing hydroxyl groups bonded to aliphatic C atoms can be prepared by reaction with chloramine in the presence of a strong base, for example in the presence of an alkali metal hydride, such as
  • the preparation of the polymers P1 or the copolymers P1 ' is carried out by free-radically initiated homo- or copolymerization of the at least one monomer A with optionally the monomer (s) B, preferably in an aqueous reaction medium.
  • the free-radically initiated homopolymerization or copolymerization of the at least one monomer A with the monomer (s) B can be carried out analogously to known processes and is preferably carried out by the solution polymerization method or method
  • Emulsion polymerization The free-radical initiated polymerization is typically carried out in the presence of a polymerization initiator or a polymerization initiator system.
  • Suitable radical polymerization initiators are, in particular, initiators and initiator systems which form free radicals on their decomposition. These include in particular:
  • Peroxo compounds for example alkali metal or ammonium peroxidisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl permalate, cumene hydroperoxide, diisopropyl peroxydicarbamate, tert Butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide,
  • alkali metal or ammonium peroxidisulfates diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-but
  • Azo compounds such as 2,2'-azo-bis-isobutyronitrile, azo-bis (2-amidinopropane) dihydrochloride, azobis (2,4-dimethylvaleronitrile) or 2,2'-azobis (2-methylbutyronitrile) ;
  • the amount of polymerization initiator used to prepare the polymer P1 or the copolymer PV is typically in the range of 0.2 to 5 wt .-%, in particular in the range of 0.3 to 3 wt .-%, based on the total amount of monomers to be polymerized. If necessary, it is advantageous to
  • Polymerization during the polymerization over a longer period for example, in parallel with the addition of the monomers A and B, admit.
  • the addition can then take place at a continuous feed rate or increasing or decreasing feed rate.
  • the preparation of the polymer P1 or of the copolymer PV takes place in the presence of at least one regulator.
  • molecular weight of the polymer P1 or of the copolymer PV is controlled.
  • regulators especially compounds with a thiol group are suitable, such as tert-butylmercaptan,
  • the amount of mercapto group regulator used to prepare the polymer P1 or the copolymer PV is preferably in the range from 0.5 to 20% by weight, in particular in the range from 1 to 15% by weight, based on the total amount of monomers to be polymerized.
  • Organic solvents with OH groups can also be used in larger amounts, since they have only a weakly regulating action.
  • the homopolymerization of the monomers A or the copolymerization of the monomers A and B can be carried out as a batch process and is preferably carried out as a monomer feed, d. H. the major amount, preferably at least 80% and especially at least 90% of the monomers A and B to be polymerized in the course of polymerization under polymerization in the
  • the addition can be continuous or stepwise.
  • the monomer composition can be changed once, repeatedly or continuously (gradient procedure).
  • aqueous reaction medium is understood as meaning water or a mixture of water and one or more water-miscible organic solvents, water forming the main constituent of the reaction medium.
  • Water-miscible organic solvents are, for example, C 1 -C 4 -alkanols, eg. As methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol or tert.
  • Butanol, glycols such as ethylene glycol, diethylene glycol.
  • aqueous reaction media contain at least 60% by weight of water, based on the total amount of water and organic solvents.
  • an alcoholic reaction medium is meant
  • Reaction medium consisting mainly of one or more alcoholic solvent
  • Solvents in particular one or more of the aforementioned Ci-C4 alkanols and may still contain water, wherein the alcoholic solvent forms the main component of the reaction medium.
  • Copolymerization of the monomers A and B in the presence of one or more surfactants perform, especially when the
  • Polymerization is carried out as aqueous emulsion polymerization.
  • emulsifiers are understood as meaning surface-active substances whose molecular weight (number average) is usually below 2000 g / mol and especially below 1500 g / mol.
  • protective colloids are usually water-soluble polymers having a number average molecular weight above 2000 g / mol, eg. B. in the range of 2000 to 100000 g / mol and in particular in the range of 5000 to 50,000 g / mol.
  • protective colloids and emulsifiers can be used in the mixture.
  • anionic emulsifiers include usually aliphatic, araliphatic and aromatic sulfonic acids having generally at least 6 carbon atoms and their salts, in particular their ammonium and
  • Alkali metal salts sulfuric acid semi-esters ethoxylated alkanols and alkylphenols and salts thereof, in particular their ammonium and alkali metal salts and alkyl, aralkyl and aryl phosphates including phosphoric monoesters of
  • suitable anionic emulsifiers are: alkali metal and ammonium salts of dialkyl esters of sulfosuccinic acid, alkali metal and ammonium salts of alkyl sulfates (alkyl group: Cs to Cie), alkali metal and
  • Ammonium salts of sulfuric monoesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: Cs to Cie), alkali metal and ammonium salts of
  • Sulfuric acid semi-esters of ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 - to Ci6), alkali metal and ammonium salts of alkylsulfonic (alkyl: Cs to Cie) and of alkylarylsulfonic (alkyl: C 4 - to Cis).
  • alkylsulfonic alkyl: Cs to Cie
  • alkylarylsulfonic alkyl: C 4 - to Cis
  • suitable anionic emulsifiers are also the compounds of the general formula given below
  • R 1 and R 2 is hydrogen or C 4 - to C 4 represent alkyl and are not simultaneously hydrogen
  • X and Y can be alkali metal ions and / or ammonium ions.
  • R 1 and R 2 are hydrogen or linear or branched alkyl radicals having 6 to 18 C atoms and in particular having 6, 12 and 16 C atoms, wherein R 1 and R 2 are not both simultaneously hydrogen.
  • X and Y are preferably sodium, potassium or ammonium ions, with sodium being particularly preferred. Particularly advantageous are compounds in which X and Y are sodium, R 1 is a branched alkyl radical having 12 C atoms and R 2 is hydrogen or one of those indicated for R 1 , of Hydrogen has different meanings.
  • nonionic emulsifiers include typically ethoxylated alkanols having 8 to 36 carbon atoms in the alkyl radical, ethoxylated mono-, di- and trialkylphenols having typically 4 to 12 carbon atoms in the alkyl radicals, wherein the ethoxylated alkanols and alkylphenols typically have a degree of ethoxylation in the range of 3 to 50 exhibit.
  • emulsifiers can be found, for example, in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208. Polymerization temperature and polymerization pressure are of secondary importance
  • the emulsion polymerization is typically carried out at temperatures in the range of 30 to 130, preferably in the range of 50 to 100 ° C.
  • Polymerization pressure is usually in the range of atmospheric pressure, d. H. at ambient pressure, but may also be slightly above or below, z. B. in the range of 800 to 1500 mbar.
  • the polymers P1 and the copolymers P1 ' are typically obtained in the polymerization in the form of a solution or dispersion, which, optionally after replacement of organic solvents by water, directly in the aqueous according to the invention
  • compositions can be used.
  • the compositions of the invention also contain a polymer P2 having functional groups F which can react with the groups of the formula -O-NR 1 R 2 to form a covalent bond.
  • the functional groups F include, in particular, aldehyde groups, keto groups, eg. B.
  • the number of functional groups can be varied over wide ranges and is preferably in the range of 0.01 to 2 mol / kg, in particular in the range of 0.05 to 1 mol / kg and especially in the range of 0, 1 to 0.5 mol / kg of polymer P2.
  • the polymers P2 can in principle be selected from any polymer groups and in principle include all polymers which are in the form of aqueous
  • compositions are used, for.
  • polyurethanes polyether urethanes, polyethers, polyesters, polyester urethanes, polyether esters and in particular polymers which are composed of ethylenically unsaturated monomers M.
  • the functional groups F can be bound directly, that is via a chemical bond, the polymer backbone or via a bivalent linker L, z.
  • B a radical of the formula Y- [Alk'0] p -Z.
  • Y, Z, Alk 'and p have the following
  • Ci-Ci2-alkanediyl represents a chemical bond or Ci-Ci2-alkanediyl, which may optionally be substituted by 1 or 2 OH groups,
  • polymers P2 which are composed of ethylenically unsaturated
  • Monomers M are constructed, in particular those in which the monomers P1 constituting the polymer P1 comprise the following monomers M1 and M2:
  • Monomers at least one monoethylenically unsaturated monomer M1, which has no functional groups F and which has a water solubility of less than 50 g / l, at 20 ° C and 1 bar;
  • Suitable monomers M1 are in principle all monomers which are suitable as
  • Monomers B2 in connection with the polymers P1 and the copolymers P1 ' were called.
  • M1 is selected from the monomers B2-a, B2-b and B2-c, especially among the esters of monoethylenically unsaturated C3-C8 monocarboxylic acids, in particular the esters of acrylic acid (acrylates) and the esters of methacrylic acid (methacrylates), with Ci -Cio-alkanols and vinylaromatics, more preferably from C 1 -C 10 -alkyl acrylates and C 1 -C 10 -alkyl methacrylates and vinylaromatics, and especially from methyl acrylate, ethyl acrylate, n-propyl acrylate,
  • Suitable monomers M2 are compounds of the formula (II):
  • R 4 is hydrogen or methyl
  • L is a radical of the formula Y- [Alk'0] p -Z, in which Y, Z, Alk 'and p have the abovementioned meanings and in which L is in particular C (O) O-Z, C (O) O -Alk'0-Z, C (0) -NR d -Alk'0-Z or C (0) -NR d -Z, wherein Z is a chemical bond or Ci-Ci2-alkanediyl, which is optionally substituted by 1 or 2 OH groups may be substituted;
  • F is a functional group which can react with the groups of the formula -O-NR 1 R 2 to form a covalent bond and which preferably represents an aldehyde group, a keto group, for.
  • B a group of the formula
  • Aldehyd tendency carrying monomers such as acrolein, methacrolein, formylstyrene (vinylbenzaldehyde), esters of acrylic acid with hydroxyaldehydes and the corresponding esters of methacrylic acid, for example
  • Keto-containing monomers such as vinyl alkyl ketones and allyl alkyl ketones wherein the alkyl radicals each have 1 to 20 carbon atoms, acetylstyrene
  • esters of acrylic acid with hydroxy ketones and the corresponding esters of methacrylic acid eg. B. 1, 1-dimethyl-3-oxobutyl acrylate and 1, 1-dimethyl-3-oxobutyl methacrylate, amides of acrylic acid with
  • HOC (0) -CH 2 -C (O) -Ci-C 4 -alkyl e.g. Acetoacetoxyethyl acrylate and
  • Monomers having an oxirane group e.g. B. glycidyl allyl ether,
  • the monomers M constituting the polymer P1 may comprise one or more further, different ethylenically unsaturated monomers M3, which have no functional group F and which are different from the monomers M1 and M2.
  • the total amount of the monomers of other monomers will usually not exceed 30% by weight, in particular 20% by weight and especially 15% by weight and, if present, is in the range from 0.01 to 40% by weight, in particular in the range of 0.05 to 20 wt .-% and especially in the range of 0.1 to 15 wt .-%, based on the total amount of the monomers M. It is understood that the total amount of monomers M1, M2 and M3 added to 100 wt .-%.
  • Suitable monomers M3 are monoethylenically unsaturated monomers having an increased water solubility of at least 50 g / l, in particular at least 100 g / l at 20 ° C and 1 bar. These monomers are referred to below as monomers M3a
  • Suitable monomers M3a are the abovementioned monomers B1.
  • the monomers B1-a, B1-c, B1 -d, B1-e, B1 -f and Bi g are preferred.
  • the proportion of these monomers M3a is usually 30 wt .-%,
  • the proportion of these monomers M3b will generally not exceed 10 wt .-%, in particular 5 wt .-% and especially 1 wt .-%, based on the total amount of the monomers M.
  • the monomers constituting the polymer P2 comprise no or less than 0.1% by weight, based on the total amount of the monomers M, of monomers M3b.
  • the polymers P2 generally have a weight-average molecular weight M w in the range of about 10,000 to 20,000,000 and in particular in the range of about 50,000 to 10,000,000.
  • the molar mass determination can by
  • the glass transition temperature T g of the polymer P2 depends on the desired use and is usually in the range of -60 ° C to 60 ° C, preferably in the range of -50 ° C to 50 ° C and more preferably in the range of -40 ° C to 40 ° C.
  • the glass transition temperature is understood to be the so-called midpoint temperature according to ASTM 3418/82, as can be determined by differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the glass transition temperature of a polymer can also be determined by dynamic mechanical analysis (DMTA) according to the method given in connection with the examples.
  • DMTA dynamic mechanical analysis
  • the glass transition temperature can be adjusted by suitable choice of the monomers M1.
  • the polymers P2 are known, for. B. from the documents cited above
  • EP 516074, DE 4219384 or DE 4314623 or can be prepared in analogy to known polymerization, for. B. in analogy to those for the
  • the aqueous polymer dispersion of the polymer P2 may be the direct product of a free-radical, aqueous emulsion polymerization of the monomers M or a secondary dispersion, ie the polymer P2 suspended or dispersed in water following its preparation.
  • the free-radical, aqueous emulsion polymerization may also be referred to as so-called
  • the monomers to be polymerized are used in the form of an aqueous miniemulsion, wherein the monomer droplets have very small diameters (volume-average
  • a secondary dispersion is understood as meaning an aqueous polymer dispersion whose polymer is first prepared in a solution polymerization or in another manner and subsequently dispersed or emulsified in an aqueous medium, optionally with removal of organic solvent from the solution polymerization.
  • preferred are polymer dispersions prepared by free radical aqueous emulsion polymerization. Polymer dispersions are preferred in which the dispersed polymer particles have an average particle diameter, determined by hydrodynamic fractionation, in the range from 0.01 to 1.5 ⁇ m and in particular in the range from 0.02 to 1 ⁇ m.
  • the polymers P2 are preferably those which are obtained by a free-radical, aqueous emulsion polymerization of the ethylenically unsaturated
  • Monomers M are available. If the aqueous dispersions of the polymer P2 are prepared by free-radical aqueous emulsion polymerization, this can be carried out in a manner known per se, and preferably according to a monomer feed process. The free-radical, aqueous emulsion polymerization is typically carried out in
  • emulsifiers are used in the process according to the invention.
  • it has proven to be a combination of at least one
  • anionic and at least one nonionic emulsifier to use as a surfactant.
  • the surface-active substances are used in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.2 to 5% by weight, based on the weight of the monomers M to be polymerized.
  • the initiators used for free-radical emulsion polymerization are usually water-soluble, radical-forming substances.
  • Water-soluble initiators for the emulsion polymerization are organic or inorganic peroxide compounds, ie compounds having at least one peroxide or hydroperoxide group, for.
  • Peroxodisulfuric acid e.g., sodium peroxodisulfate, hydrogen peroxide or organic peroxides, z. B. tert-butyl hydroperoxide.
  • the redox initiator systems consist of at least one mostly inorganic reducing agent and one inorganic or organic oxidizing agent.
  • the oxidation component is z. B. to the above-mentioned peroxide.
  • the reduction components are, for. B. to alkali metal salts of sulfurous acid, such as.
  • the red-ox initiator systems can be used with the concomitant use of soluble metal compounds whose metallic component can occur in multiple valence states. Usual redox initiator systems are z.
  • the initiators mentioned are usually used in the form of aqueous solutions, the lower concentration being determined by the amount of water acceptable in the dispersion and the upper concentration by the solubility of the compound in question in water.
  • the concentration is 0.1 to 30 wt .-%, preferably 0.5 to 20 wt .-%, particularly preferably 1, 0 to 10 wt .-%, based on the solution.
  • the amount of initiators is generally 0.1 to 10 wt .-%, preferably 0.2 to 5 wt .-%, based on the monomers to be polymerized. It is also possible to use a plurality of different initiators in the emulsion polymerization.
  • M regulators can be used, for. B. in amounts of 0 to 1 wt .-%, based on the monomers to be polymerized M. This reduces the molecular weight of the polymer.
  • the process of the invention is preferably carried out as feed process, d. H. At least 90% of the monomers M to be polymerized are added to the polymerization reactor in the course of the polymerization under polymerization conditions. The addition can be continuous or stepwise. In the course of the polymerization, the monomer composition can be changed once, repeatedly or continuously (gradient procedure).
  • seed polymer is understood by the person skilled in the art to mean a finely divided polymer in the form of an aqueous polymer dispersion.
  • the weight-average particle size of the seed polymers used in the process according to the invention is typically below 200 nm, frequently in the range from 10 to 150 nm and in particular in the range from 20 to 120 nm.
  • the monomer composition of the seed polymers is of secondary importance. Suitable are both seed polymers, which are predominantly vinyl aromatic
  • Monomers and in particular of styrene are constructed (so-called styrene seed), as well as seed polymers, mainly from Ci-Cio-alkyl acrylates and / or C1-C10 alkyl methacrylates, eg. B. are composed of a mixture of butyl acrylate and methyl methacrylate.
  • the seed polymers may also contain various monomers, especially those having an increased water solubility, e.g. B. monomers having at least one
  • Acid function and / or neutral monomers with increased water solubility, and / or monomers with two or more ethylenically unsaturated double bonds in copolymerized form (monomers M3b).
  • the proportion of such monomers will typically not exceed 20% by weight, and more preferably 10% by weight, and, if present, is typically in the range of 0.1 to 10% by weight, based on the total amount of the seed polymer constituting monomers.
  • Subset of the monomers M and / or an externally produced seed polymer in the form of an aqueous dispersion presents.
  • the seed polymer may pass through in situ
  • Emulsion polymerization preferably using a small subset of the monomers M, be prepared in advance. Then it will open
  • Polymerization initiator e.g. B. 1 to 20 wt .-% and in particular 5 to 15 wt .-%, based on the total amount of the initiator added. It is also possible to proceed by first adding the partial amount of the polymerization initiator and
  • the polymerization reactor less than 5 wt .-% of the monomers to be polymerized M.
  • the addition of the monomers to be polymerized in the polymerization reactor is carried out under polymerization conditions.
  • the addition is usually over a longer period of usually at least 30 minutes, z. B. 30 minutes to 10 hours, especially over a period of 1 h to 6 h.
  • the addition can be carried out with a constant, increasing or decreasing rate of addition.
  • the addition takes place at the beginning of the polymerization with increasing feed rate.
  • the addition takes place at a constant rate of addition.
  • the monomers can be added as such.
  • the addition of the monomers takes place in the form of an aqueous monomer emulsion which typically comprises at least a portion, preferably at least 70% by weight of those employed in the emulsion polymerization
  • this monomer emulsion contains surface-active substances.
  • this monomer emulsion has a monomer content in the range of 60 to 85 weight percent, and more preferably in the range of 65 to 80 weight percent. It is possible in principle, the monomers or the
  • Monomer emulsion over multiple feeds in the polymerization reactor wherein the monomer composition of the individual feeds may be different from each other. In general, however, it is sufficient to give the monomers as a mixture via an inlet in the polymerization reactor. If the monomers are added to the polymerization reactor in the form of an aqueous emulsion, it may be advantageous to freshly emulsify the monomers immediately prior to their addition and according to their addition in the polymerization reactor, for example by a continuous process. It is also possible first to prepare the monomer emulsion and then add it to the desired addition rate in the
  • polymerization reactor Usually, the addition of at least one partial amount or the total amount of the polymerization initiator takes place in parallel with the monomer addition. Typically, at least 80% of that required for emulsion polymerization will be needed
  • Polymerization initiator in particular 85 to 95% of the polymerization initiator in the course of the polymerization reaction in the polymerization reactor.
  • the addition of the polymerization initiator may be carried out at a constant rate or with a varying, e.g. B. a decreasing or increasing rate of addition.
  • the polymerization medium may consist of water only, as well as of mixtures of water and thus miscible liquids such as methanol.
  • Polymerization temperature and polymerization pressure are of secondary importance.
  • the emulsion polymerization is typically carried out at temperatures in the range of 30 to 130, preferably in the range of 50 to 100 ° C.
  • Polymerization pressure is usually in the range of atmospheric pressure, d. H. at ambient pressure, but may also be slightly above or below, z. B. in the range of 800 to 1500 mbar.
  • z. B. in the range of 800 to 1500 mbar.
  • Polymerization reaction d. H. after completion of the addition of the monomers to be polymerized or after a conversion of the monomers present in the polymerization reactor of at least 95%, a chemical and / or physical
  • Chemical deodorization to remove unpolymerized monomers.
  • at least one chemical deodorization will be carried out.
  • Chemical deodorization is understood as meaning a postpolymerization phase which is triggered by the addition of at least one further polymerization initiator, in particular one of the abovementioned redox initiator systems. Methods for this purpose are known, for example from DE-A-4435422, DE-A-4435423 and DE-A-4419518.
  • Reduction of the residual monomers can also be carried out by combined measures of chemical and physical deodorization, wherein preferably the physical deodorization is carried out after the chemical deodorization.
  • the polymer dispersions obtained in this way preferably contain less than 1500 ppm, in particular less than 1000 ppm and more preferably less than 500 ppm of volatile organic components TVOC.
  • TVOC Total Volatile Organic Compounds
  • the determination of the residual volatile content is typically carried out according to DIN 55649.
  • aqueous polymer compositions according to the invention contain
  • the polymer P1 can be dissolved in the aqueous composition in dissolved form or in dispersed form, i. H. in the form of an aqueous polymer dispersion.
  • the polymer particles of the dispersion preferably have an average particle diameter, determined by hydrodynamic fractionation of not more than 500 nm, and in particular not more than 300 nm, z. B. in the range of 5 to 500 nm or in the range of 10 to 300 nm.
  • mean particle diameter is meant the hydrodynamic mean diameter, d. H. the hydrodynamic particle diameter determined by hydrodynamic fractionation according to the method of large exclusion of dilute polymer dispersions (absorption of 0.03 AU / ⁇ , 22 ° C).
  • the polymer P2 may in principle be in dissolved or disperse form.
  • the polymer P2 in the aqueous polymer compositions according to the invention is the polymer P2 in disperse form, d. H. as a heterogeneous phase in the form of finely divided
  • Polymer particles which are dispersed in a homogeneous aqueous phase or
  • polymer dispersions in which the dispersed polymer particles of the polymer P2 have an average particle diameter, determined by hydrodynamic fractionation, in the range from 0.01 to 1.5 ⁇ m and in particular in the range from 0.02 to 1 ⁇ m, are preferred.
  • the polymer particles can have both a monomodal particle size distribution, ie a
  • Particle size distribution with only one maximum, or a polymodal distribution having at least two distinct maxima, which differ in the rule by at least 0.05 ⁇ have.
  • the polymer P1 and the polymer P2 will be used in an amount ratio such that the molar ratio of the groups of the formula -O-NR 1 R 2 to the functional groups F is in the range from 10: 1 to 1:10 and in particular in the range from 1: 5 to 5: 1.
  • the weight ratio of polymer P1 to polymer P2 is preferably in the range from 1: 500 to 2: 1, in particular in the range from 1: 100 to 1: 1 and especially in the range from 1:50 to 1: 2.
  • the concentration of polymer P1 in the aqueous polymer composition is typically in the range of 0.1 to 50% by weight, in particular in the range of 0.5 to 30% by weight and especially in the range of 1 to 20% by weight, based on the
  • the concentration of polymer P2 in the aqueous polymer composition is typically in the range of 4.9 to 69.9% by weight, in particular in the range of 10 to 64.5% by weight and especially in the range of 10 to 54% by weight. %, based on the total weight of the polymer composition.
  • the total content of polymers P1 and P2 in the aqueous polymer composition is usually from 5 to 70 wt .-%, preferably 10 to 65 wt .-% and especially from 30 to 55 wt .-%, wherein the polymer composition prior to its application with water to a suitable for the application
  • Concentration can be diluted.
  • the aqueous polymer compositions according to the invention also have a coherent aqueous phase in which the polymer P1 and the polymer P2 are present in dissolved or dispersed form.
  • the aqueous phase may include
  • the amount of surface-active substances will generally not exceed 20% by weight, in particular 10% by weight, based on the total weight of the polymers P1 and P2, and is typically in the range from 0.1 to 20% by weight, in particular in the range of 0.2 to 10 wt .-%, based on the total weight of the polymers P1 and P2.
  • Solvents is usually less than 1 wt .-%, in particular less than 0.2 wt .-%, based on the total weight of the aqueous
  • the pH of the aqueous polymer composition according to the invention is preferably in the range of pH 3 to pH 9, in particular in the range of pH 5 to pH 8.5 and especially in the range of pH 6 to pH 8.
  • the other ingredients are especially biocides (preservatives ), which the aqueous polymer composition against infestation with
  • Stabilize microorganisms include, for example, alkyl esters of para-hydroxybenzoic acid, sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, ortho-phenylphenol, dichlorophene, benzyl alcohol hemiformal, pentachlorophenol,
  • Ci-Cio-Alkylisothiazolinone 5-chloro-2-methyl-4-isothiazolinone and
  • Benzoisothiazolinones e.g. B. the products sold under the names Proxel ® the Fa. Avecia (or Fa. Arch) or Acticide ® the company Thor Chemie products.
  • Preservatives are usually used in amounts of from 0.01 to 10 grams per liter of the polymer dispersion.
  • ingredients are mainly dependent on the nature of the desired application and include, for example, means for adjusting the pH,
  • Film-forming aids thickeners, defoamers, dispersing agents, leveling agents, colorants, in particular pigments, fillers, tackifiers and tackifier resins.
  • the binder compositions according to the invention are suitable for a multiplicity of applications in which aqueous polymer dispersions are usually used as binders, eg.
  • aqueous polymer dispersions are usually used as binders, eg.
  • coating agents such as in paints for interior and exterior applications, in paper coating slips, in coating systems for leather and textiles, in printing inks, in coating systems for mineral moldings, in primers for coating metals, as a binder in the production of polymer-bonded fiber webs, as sticking raw materials , as additives for inorganic, hydraulic binders such as CaSCv O, 5 H2O, anhydride or cement, and the hydraulic binding compositions prepared therefrom such as gypsum or concrete, as additives for clay or earth building materials, for the production of membranes and the like.
  • the molecular weight of the polymers was determined by size exclusion chromatography.
  • the eluent used was tetrahydrofuran.
  • the sample was present of the injection on Macherey-Nagel PTFE.20 / 25 (0.2 pm) and filtered over a separation column combination (Pl-gel precolumn (PI Gel 5pm, ID: 7.5 mm, L: 5 cm), PLgel MIXED B (PL gel 10 pm, ID: 7.5 mm, L: 30 cm)).
  • Elution time is calibrated with polystyrene calibration latices. The measurement is carried out in the range from 20 nm to 1200 nm. Detection is carried out with a UV detector at a wavelength of 254 nm.
  • the glass transition temperature was determined by differential scanning calorimetry according to ASTM 3418/82.
  • ASTM 3418/82 For conditioning, the polymers were poured out, dried overnight, then dried for 1 h in a vacuum oven at 120 ° C. In the measurement, the sample is heated to 150 ° C, cooled rapidly and then measured at 20 K / min heating. Indicated is the so-called mid-point temperature.
  • 4-aminoxymethylstyrene A monomer of the formula I in which R1, R2 and R are H and A is 4-phenylene-CH2, prepared according to the instructions of Wen-Jing Zhou, Mark E. Wilson, Mark J. Kurth, You-Lo Hsieh, John M. Krochta, Charles F. Shoemaker Macromolecules 1997, 30, 7063-7068.
  • Emulsifier Composition 1 32% solution of a C12 / C14 alkyl
  • Emulsifier Composition 2 45% solution of a dodecyldiphenyl ether disulfonic acid sodium salt in water
  • Emulsifier Composition 3 15% solution of sodium lauryl sulfate in water
  • Emulsifier Composition 4 20% solution of a C16 / C18 alkyl
  • Polyethylene glycol having an ethoxylation degree of 18 in water Polystyrene seed latex: 33% polystyrene latex in water, mean particle size of 30 nm.
  • Reaction temperature maintained at 80 ° C for a further 30 min. Subsequently, 80 g of water were added within 15 min while iso-propanol was completely distilled off. The resulting dispersion had a solids content of 16.6%, an average particle size of 918 nm and a pH of 8.6. The resulting polymer had a weight average molecular weight Mw of 20400 g / mol.
  • Emulsifier composition 2 19.8 g (0.097 mol) of 2-ethylhexyl thioglycollate, 33.00 g (0.221 mol) of 4-aminoxymethylstyrene and 99 g (0.989 mol) of methyl methacrylate were prepared as a monomer emulsion.
  • the dispersion had a solids content of 37.4%.
  • the particle size was 137 nm.
  • the glass transition temperature was 25.9 ° C.
  • Example 5 Alkali-soluble dispersion
  • the dispersion had a solids content of 40.6%
  • the particle size was 380 nm, the glass transition temperature was 60 ° C.
  • Example 6 Copolymer of 4-vinylbenzenesulfonic acid sodium salt and 4-aminoxymethylstyrene
  • Preparative Example D1 Polymer dispersion with diacetone acrylamide (DAAM) From 182.5 g of water, 55.2 g of emulsifier composition 3, 276 g (2.757 mol) of methyl methacrylate, 300 g (2.341 mol) of n-butyl acrylate and 120 g of a 20% solution of diacetone acrylamide in water (0.142 mol), a monomer emulsion was prepared.
  • DAAM diacetone acrylamide
  • the dispersion had a solids content of 49.4%, the particle size was 1 14 nm.
  • the glass transition temperature was 12.1 ° C.
  • Acetoacetoxyethyl methacrylate a monomer emulsion was prepared.
  • the dispersion had a solids content of 49.1%, the particle size was 120 nm.
  • the glass transition temperature was 12.3 ° C.
  • Preparation D3 Polymer dispersion with glycidyl methacrylate (GMA) From 293.96 g of water, 28.13 g of emulsifier composition 1, 15.0 g
  • Emulsifier composition 4 276 g (2.757 mol) of methymethacrylate, 300 g (2.341 mol) of n-butyl acrylate and 24 g (0.169 mol) of glycidyl methacrylate became a
  • thermocouple Introduced thermocouple and reflux condenser and stirred at 90 ° C for 10 min.
  • Preparation Example D4 Polymer dispersion with glycerol carbonate acrylate (GCA) From 277.75 g of water, 28.13 g of emulsifier composition 1, 15.0 g
  • Emulsifier Composition 4 12 g (0.169 mol) acrylamide, 270 g (2.697 mol) Methyl methacrylate, 300 g (2.341 mol) of n-butyl acrylate and 24 g of glycerol carbonate acrylate (20% solution in water) was prepared as a monomer emulsion.
  • thermocouple Introduced thermocouple and reflux condenser and stirred at 90 ° C for 10 min.
  • Molar ratio of the reactive groups to the functional groups of the crosslinker was 1: 1.
  • the following low molecular weight crosslinkers were used:
  • Adipic dihydrazide ADHT
  • HMDA hexamethylenediamine
  • BAOB 1,4-bisaminoxybutane
  • aqueous polymer compositions thus obtained were then diluted to a solids content of 20% and then in a silicone mold 170h at
  • the films were placed on a laboratory shaker at room temperature for 24 h

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition aqueuse polymérique, comprenant au moins un premier polymère P1 constitué de monomères éthylèniquement insaturés, qui présente en moyenne plus de 2 groupes fonctionnels de formule -O-NR1R2 et l'utilisation de ces polymères pour la réticulation de polymères P2, qui présentent des groupes fonctionnels qui peuvent réagir avec les groupes de formule -O-NR1R2 en formant une liaison covalente. Les compositions polymériques comprennent : a) au moins un premier polymère P1 constitué de monomères éthylèniquement insaturés, qui présente en moyenne plus de 2 groupes fonctionnels de formule -O-NR1R2, dans laquelle R1 R2 représentent l'hydrogène ou conjointement un groupe =CRaRb, dans lequel Ra et Rb, indépendamment l'un de l'autre, représentent l'hydrogène ou un groupe alkyle en C1-C6 ou conjointement avec l'atome de carbone auquel ils sont reliés forment un groupe cycloalkylidène en C5-C8; b) et au moins un deuxième polymère P2 constitué de préférence de monomères éthyléniquement insaturés qui présente des groupes fonctionnels F pouvant réagir avec les groupes de formule -O-NR1R2 en formant une liaison covalente.
PCT/EP2015/057282 2014-04-04 2015-04-02 Compositions aqueuses polymériques Ceased WO2015150508A1 (fr)

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EP14163568.0 2014-04-04

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018118221A1 (fr) 2016-12-19 2018-06-28 Celanese International Corporation Dispersions aqueuses acryliques présentant un contenu biorenouvelable élevé
US10329372B2 (en) 2014-06-13 2019-06-25 Basf Se Polyurethanes with reduced aldehyde emission
US11021560B2 (en) 2015-11-19 2021-06-01 Basf Se Catalyst for the preparation of polyurethanes

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0394787A2 (fr) * 1989-04-27 1990-10-31 Bayer Ag Compositions contenant esters de l'acide (méta)acrylique contenant des groupes carbamides pour utilisation comme composants adhésifs pour le traitement de matériaux collagènes médicaux, et préparation des compositions
EP0516074A1 (fr) * 1991-05-28 1992-12-02 Wacker-Chemie Gmbh Dispersions aqueuses de copolymères à groupes carbonyle, contenant des agents de réticulation aminoxy
DE4314623A1 (de) * 1993-05-04 1994-11-10 Basf Ag Carbamoylhydroxylamine
DE10063263A1 (de) * 1999-12-23 2001-06-28 Hyundai Electronics Ind Organisches nicht reflektierendes Beschichtungspolymer und dessen Herstellungsverfahren

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0394787A2 (fr) * 1989-04-27 1990-10-31 Bayer Ag Compositions contenant esters de l'acide (méta)acrylique contenant des groupes carbamides pour utilisation comme composants adhésifs pour le traitement de matériaux collagènes médicaux, et préparation des compositions
EP0516074A1 (fr) * 1991-05-28 1992-12-02 Wacker-Chemie Gmbh Dispersions aqueuses de copolymères à groupes carbonyle, contenant des agents de réticulation aminoxy
DE4314623A1 (de) * 1993-05-04 1994-11-10 Basf Ag Carbamoylhydroxylamine
DE10063263A1 (de) * 1999-12-23 2001-06-28 Hyundai Electronics Ind Organisches nicht reflektierendes Beschichtungspolymer und dessen Herstellungsverfahren

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10329372B2 (en) 2014-06-13 2019-06-25 Basf Se Polyurethanes with reduced aldehyde emission
US11021560B2 (en) 2015-11-19 2021-06-01 Basf Se Catalyst for the preparation of polyurethanes
WO2018118221A1 (fr) 2016-12-19 2018-06-28 Celanese International Corporation Dispersions aqueuses acryliques présentant un contenu biorenouvelable élevé

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