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WO2009146995A1 - Mélanges de monomères, polymères, ainsi que compositions de revêtement - Google Patents

Mélanges de monomères, polymères, ainsi que compositions de revêtement Download PDF

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Publication number
WO2009146995A1
WO2009146995A1 PCT/EP2009/055573 EP2009055573W WO2009146995A1 WO 2009146995 A1 WO2009146995 A1 WO 2009146995A1 EP 2009055573 W EP2009055573 W EP 2009055573W WO 2009146995 A1 WO2009146995 A1 WO 2009146995A1
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WIPO (PCT)
Prior art keywords
monomer mixture
monomers
meth
monomer
radical
Prior art date
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Ceased
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PCT/EP2009/055573
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German (de)
English (en)
Inventor
Christine Breiner
Mario Gomez
Thorben SCHÜTZ
Ina Bundrock
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Roehm GmbH Darmstadt
Original Assignee
Evonik Roehm GmbH
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Filing date
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Priority claimed from DE102008002254A external-priority patent/DE102008002254A1/de
Priority claimed from DE102009001217A external-priority patent/DE102009001217A1/de
Application filed by Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Publication of WO2009146995A1 publication Critical patent/WO2009146995A1/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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate

Definitions

  • the present invention relates to a monomer mixture as well as polymers obtainable from this monomer mixture. Furthermore, the present invention is directed to coating compositions comprising these polymers. Furthermore, the present invention relates to a process for producing these monomers.
  • Coating agents in particular paints, have been produced synthetically for a long time.
  • Many of these coating compositions are based on so-called alkyd resins, which are prepared using polybasic acids, alcohols and fatty acids and / or fatty acid derivatives.
  • a particular group of these alkyd resins form crosslinked films upon exposure to oxygen, with crosslinking being by oxidation involving unsaturated groups.
  • Many of these alkyd resins include organic solvents or dispersants to coat the resins in a thin layer on coating bodies.
  • the use of these solvents should be omitted for reasons of environmental protection and occupational safety. Therefore, corresponding resins based on aqueous dispersions have been developed, but their storage stability is limited.
  • the water absorption of many alkyd resins is too high or their solvent resistance and hardness is too low. Accordingly, attempts have been made to modify or replace the alkyd-based conventional paints set forth above.
  • compositions comprising an alkyd resin modified with (meth) acrylate polymers, which is subsequently used in an emulsion polymerization.
  • the preparation of the compositions described is carried out over several steps, so that the described resins are very expensive to produce.
  • a solution polymer based coating composition based on vinyl monomers is described for example in DE-A-101 06 561.
  • this composition comprises a high proportion of organic solvents.
  • aqueous dispersions based on (meth) acrylate polymers are also known.
  • the document DE-A-41 05 134 describes aqueous dispersions which can be used as binders in paints.
  • the preparation of these binders is carried out over several stages, initially a solution polymer is produced, which is used after neutralization in an emulsion polymerization.
  • DE-A-25 13 516 describes aqueous dispersions which comprise polymers based on (meth) acrylates, some of the (meth) acrylates being derived from unsaturated alcohol radicals.
  • a disadvantage of the described dispersions is in particular their complicated preparation, wherein the polymers based on (meth) acrylates are obtained by solution polymerization. In this case, these polymers have a high proportion of acid groups, which is in the range of 5 to 20 wt .-%, based on the solution polymer.
  • the document DE-A-26 38 544 describes oxidatively drying aqueous dispersions which comprise emulsion polymers based on (meth) acrylates, some of the (meth) acrylates used being derived from unsaturated alcohol radicals.
  • chain transfer agents have been used to prepare the emulsion polymers so that the emulsion polymer shows high solubility.
  • aqueous dispersions comprising oxidatively drying polymers are disclosed in F.-B. Chen, G. Bufkin, "Crosslinkable Emulsion Polymers by Autooxidation II", Journal of Applied Polymer Science, Vol. 30, 4551-4570 (1985)
  • the polymers contain from 2 to 8% by weight of units derived from (meth The durability of these dispersions and the hardness of the coatings are not sufficient for many applications.
  • US Pat. No. 5,750,751 describes polymers based on vinyl monomers which can crosslink at room temperature. The polymers can be obtained both by solution polymerization and by emulsion polymerization.
  • the monomer mixtures to be polymerized may include, inter alia, (meth) acrylates whose alcohol residues are modified by unsaturated fatty acids.
  • the polymers obtained by solution and emulsion polymerization of modified (meth) acrylates show high solubility since chain transfer agents have been used.
  • a disadvantage of the coating compositions described in US Pat. No. 5,750,751, however, is that softening solvents must be added which are to be avoided for reasons of environmental protection.
  • document WO 2006/013061 describes dispersions comprising particles based on (meth) acrylates.
  • the monomer mixtures used to prepare the particles include (meth) acrylates which have been modified by unsaturated fatty acids.
  • the examples do not polymerize monomers comprising acid groups.
  • the proportion of (meth) acrylates modified with unsaturated fatty acids is very high.
  • Disadvantages of the dispersions described in WO 2006/013061 are in particular their complex preparation and the high proportion of residual monomers.
  • the coatings obtained from the dispersions show a low stability against some solvents.
  • dispersions are known from the prior art which, in addition to polymers based on (meth) acrylates, may also comprise alkyd resins.
  • document WO 98/22545 describes polymers with units derived from (meth) acrylates having unsaturated alcohol radicals. These polymers can be used together with alkyd resins.
  • solvents are used to prepare paints from the described polymers.
  • Aqueous dispersions are not described in WO 98/22545. Accordingly, these compositions suffer from the disadvantages set out above.
  • Japanese Patent JP 59011376 describes emulsion polymers based on (meth) acrylates.
  • the dispersions have a solids content of about 40% to a dynamic viscosity of at least 200 mPas.
  • a particle size is not mentioned in this document. Due to the high viscosity of the dispersion, however, it can be assumed that the emulsion polymers have a particle size below 40 nm.
  • a disadvantage of the dispersions described in this document is their low storage life. In addition, it has been found that the coatings obtained do not have sufficient stability for all requirements compared to all solvents.
  • US Pat. No. 6,599,972 discloses coating compositions based on polymers based on (meth) acrylates whose alcohol residue is derived from unsaturated fatty acid derivatives.
  • a disadvantage of the coating compositions explicitly set forth herein is their shelf life and the stability of the coatings obtainable from the described compositions.
  • the monomer mixtures should become dispersions or
  • Process polymers for example emulsion polymers, which have a very low residual monomer content.
  • the present invention to provide a coating composition which has a particularly long shelf life and durability. Furthermore, the hardness of the coatings obtainable from the coating compositions should be able to be varied over a wide range. In particular, particularly hard, scratch-resistant coatings should be able to be obtained.
  • a further object is to provide polymers, by the use of which coating compositions without volatile organic solvents are obtainable.
  • the coatings obtainable from the aqueous dispersions should have a high weather resistance, in particular a high UV resistance.
  • the films obtainable from the aqueous dispersions should have a low tackiness after a short time.
  • the coatings obtainable from the polymers or monomer mixtures should have a particularly high resistance to solvents. This stability should be high compared to many different solvents.
  • the present invention accordingly provides a monomer mixture comprising at least one monomer A of the general formula (I)
  • R is hydrogen or a methyl group
  • X 1 and X 2 are independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, with the proviso that at least one of the groups X 1 and X 2 represents a group of the formula NR ', in which R' represents hydrogen or a radical having 1 to 6 carbon atoms, Z represents a linking group, and R 1 is an unsaturated radical having 9 to 25 carbon atoms, and at least one monomer B of the general formula ( II),
  • R is hydrogen or a methyl group
  • X 1 and X 2 are independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, with the proviso that at least one of the groups X 1 and X 2 a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, and R 2 is a saturated radical having 9 to 25 carbon atoms.
  • the monomer mixtures according to the invention can be processed into polymers, coating compositions and coatings which have a very low residual monomer content.
  • the hardness of the coatings obtainable from coating compositions according to the invention can be varied over a wide range. According to a preferred
  • Modification according to the invention can be obtained in particular particularly hard, scratch-resistant coatings.
  • the coatings obtainable from the coating compositions of the present invention show a surprisingly high solvent resistance, which is particularly evident in tests with methyl isobutyl ketone (MIBK), ammonia solutions or ethanol.
  • MIBK methyl isobutyl ketone
  • the coatings obtained, in particular in tests according to the furniture test DIN 68861 -1 an excellent classification.
  • Coating agents obtainable using the monomer mixtures of the present invention generally do not require volatile organic solvents.
  • the coating compositions of the invention show a high storage stability, a high durability and a very good shelf life. In particular, hardly any aggregate formation occurs.
  • the coatings obtainable from the coating compositions of the invention show a high weather resistance, in particular a high UV resistance. Furthermore, the films obtainable from the coating compositions have a low tackiness after a short time.
  • the monomer mixtures, polymers and coating compositions according to the invention can be produced inexpensively on a large scale.
  • the coating compositions according to the invention are environmentally friendly and can be processed and produced safely and without great effort.
  • the coating compositions of the invention show a very high shear stability.
  • Monomer mixture comprises at least one monomer A of the general formula (I)
  • R is hydrogen or a methyl group
  • X 1 and X 2 are independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, with the proviso that at least one of the groups X 1 and X 2 a group of formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, and R 1 is an unsaturated radical having 9 to 25 carbon atoms.
  • the monomer mixture comprises at least one monomer A of the general formula
  • R is hydrogen or a methyl group
  • X 1 is oxygen or a group of the formula NR ', in which R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a R is hydrogen or a radical having 1 to 6 carbon atoms and R 1 is an unsaturated radical having 9 to 25 carbon atoms.
  • radical having 1 to 6 carbon atoms means a group having 1 to 6 carbon atoms and includes aromatic and heteroaromatic groups as well as alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl groups
  • the groups mentioned may be branched or unbranched, and these groups may also have substituents, in particular halogen atoms or hydroxyl groups.
  • the radicals R ' are preferably alkyl groups.
  • the preferred alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl group.
  • the group Z preferably represents a linking group comprising 1 to 10, preferably 1 to 5 and most preferably 2 to 3 carbon atoms. These include in particular linear or branched, aliphatic or cycloaliphatic radicals, such as a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexylene group, wherein the Ethylene group is particularly preferred.
  • monomer A of the general formula (I) in which the group Z comprises at least one hydroxyl group has surprising advantages.
  • These groups preferably comprise 5 or 6 carbon atoms.
  • the linking group Z may correspond to at least one hydroxy group of the formula (Ia) wherein X 3 is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms and Z 1 represents a linking group which preferably comprises 1 to 5, preferably 2 or 3 and most preferably 2 carbon atoms.
  • R' is hydrogen or a radical having 1 to 6 carbon atoms
  • Z 1 represents a linking group which preferably comprises 1 to 5, preferably 2 or 3 and most preferably 2 carbon atoms.
  • These include in particular linear or branched, aliphatic or cycloaliphatic radicals, such as, for example, a methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, t-butylene or cyclopentylene group, where the Ethylene group is particularly preferred.
  • the linking groups having at least one hydroxy group include, but are not limited to, 2-hydroxy-4-oxa-hexylene, 2-hydroxymethyl-3-oxa-pentylene and 2-hydroxy-4-oxa-5-methyl-hexylene the 2-hydroxy-4-oxa-hexylene group is particularly preferred.
  • the group R 1 in formula (I) is an unsaturated radical having 9 to 25 carbon atoms.
  • These groups include in particular alkenyl, cycloalkenyl, alkenoxy, cycloalkenoxy, alkenoyl and heteroalipatic groups. Furthermore, these groups may have substituents, in particular halogen atoms or hydroxyl groups.
  • the preferred groups include in particular alkenyl groups, such as, for example, the nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, , Docosenyl, octanediazyl, nonanediazyl, decanediazyl, undecanedienyl, dodecanedienyl, tridecanediazyl, tetradecanedienyl , Pentadecanediazyl, hexadecanediazyl, heptadecane-diene-yl, octadecanediazyl, nonadecan-diene-yl, eicosane-diene
  • the preferred monomers A according to formula (I) or (III) include, but are not limited to, heptadecenyloyloxy-2-ethyl (meth) acrylamide, heptadecan-dien-yloyloxy-2-ethyl- (meth) acrylamide, heptadecan-triene-yloyloxy- 2-ethyl (meth) acrylamide, hepadecenyloyloxy-2-ethyl (meth) acrylamide, (meth) acryloyloxy-2-ethyl-palmitoleic acid amide, (meth) acryloyloxy-2-ethyl-oleic acid amide, (meth) acryloyloxy-2 ethyl icosenoic acid amide, (meth) acryloyloxy-2-ethyl cetoleic acid amide, (meth) acryloyloxy-2-ethyl
  • monomers A of the general formula (I) or (III) in which the group Z comprises at least one hydroxyl group are furthermore monomers A of the general formula (V)
  • R is hydrogen or a methyl group
  • X 1 and X 3 are independently oxygen or a group of formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z 1 is a linking group having 1 to 5 carbon atoms, R is hydrogen or a radical having 1 to 6 carbon atoms and R 1 is an unsaturated radical having 9 to 25 carbon atoms.
  • the monomers A of the general formula (I) or (V) in which the group Z comprises at least one hydroxy group include, inter alia, (meth) acryloyloxy-2-hydroxypropyloxy-2-ethyl-palmitoleic acid amide, (meth) acryloyloxy-2 hydroxypropyloxy-2-ethyl-oleic acid amide, (meth) acryloyloxy-2-hydroxypropyloxy-2-ethyl-icosenoic acid amide, (meth) acryloyloxy-2-hydroxypropyloxy-2-ethyl-cetoleic acid amide, (meth) acryloyloxy-2-hydroxypropyloxy-2-one ethyl-erucic acid amide, (meth) acryloyloxy-2-hydroxypropyloxy-2-ethyl-linoleic acid amide, (meth) acryloyloxy-2-hydroxypropyloxy-2-ethyl-lin
  • the notation (meth) acryl stands for acrylic and methacrylic radicals, with methacrylic radicals being preferred.
  • Particularly preferred monomers A according to formula (I) or (III) are methacryloyloxy-2-ethyl-oleic acid amide, methacryloyloxy-2-ethyl-linolenic acid amide and / or methacryloyloxy-2-ethyl-linolenic acid amide.
  • the monomers A according to formula (I) can have an iodine value in the range from 50 to 300 g of iodine / 100 g, more preferably in the range from 100 to 200 g of iodine / 100 g.
  • At least some of the monomers A according to formula (I) have exactly one double bond in the unsaturated radical R 1 .
  • at least a portion of the monomers A of the formula (I) may have two or more double bonds in the unsaturated group R 1 .
  • Preferably mixtures of the monomers A can be used, whereby these mixtures can contain both monomers A with exactly one double bond in the remainder of R 1 as well as monomers A with two or more double bonds in the remainder of R 1 .
  • the weight ratio of the monomers A of the formula (I) which have exactly one double bond in the unsaturated radical R 1 to the monomers A of the formula (I) which have two or more double bonds in the unsaturated radical R 1 can be in the range from 100: 1 to 1:10, more preferably in the range of 10: 1 to 1: 5.
  • the monomers A according to formula (I) or (III) can be obtained in particular by multi-stage processes.
  • a first stage for example, one or more unsaturated fatty acids or fatty acid esters can be reacted with an amine, for example ethylenediamine, ethanolamine, propylenediamine or propanolamine, to form an amide.
  • an amine for example ethylenediamine, ethanolamine, propylenediamine or propanolamine
  • the hydroxy group or the amine group of the amide is reacted with a (meth) acrylate, for example methyl (meth) acrylate, to obtain the monomers of the formula (I) or (III).
  • Valuable information on the preparation of these monomers can be found, inter alia, in the example of the present application. be taken.
  • Particularly preferred monomers A of the general formula (I) in which the group Z comprises at least one hydroxy group can be obtained in particular by reacting glycidyl (meth) acrylate with an unsaturated fatty acid amide having a hydroxyl or an amino group and by the previously described Reaction of a fatty acid or a fatty acid ester with an amine, for example ethylenediamine, ethanolamine, propylenediamine or propanolamine was obtained.
  • the molar ratio of (meth) acrylic anhydride to OH group or NH group of the fatty acid amide is preferably in the range from 2: 1 to 1: 1, particularly preferably in the range of 1.5 : 1 to 1, 05: 1.
  • the reaction can be carried out at overpressure or underpressure. According to a particularly expedient modification of the present invention, the reaction can be carried out at a pressure in the range from 200 to 2000 mbar, more preferably in the range from 500 to 1300 mbar.
  • the reaction temperature is preferably at least 60 0 C. According to a particular embodiment of the present invention, the reaction is preferably at a temperature in the range from 70 0 C to 120 ° C, more preferably in the range from 80 0 C to 100 ° C.
  • the reaction can be carried out in the presence of a catalyst.
  • Metal compounds and / or amines often catalyze the reactions of (meth) acrylic anhydride with hydroxyl or amine groups.
  • Metal compounds and amines are known in the art and set forth, for example, in Ullmann's Encyclopedia of Industrial Chemistry (6th edition), Verlag Wiley-VCH, Weinheim 2003 or Römpp Chemielexikon, 2nd edition on CD-ROM.
  • the metal compounds include in particular salts, such as, for example, halides, hydroxides or oxides of alkali metals, such as LiOH, KOH, or zirconium Links.
  • the amines include, for example, ammonia, triethylamine, tributylamine and others
  • polymerization inhibitors such as, for example, hydroquinones, hydroquinone ethers, such as hydroquinone monomethyl ether or di-tert-butyl catechol, phenothiazine, 4-hydroxy-2, 2,6,6-tetramethylpiperidine-1-oxyl, methylene blue or hindered phenols, for example 2,4 Dimethyl-6-tert-butylphenol are well known in the art. These compounds can be used singly or in the form of mixtures and are generally available commercially. For further details, reference is made to the usual technical literature, in particular to the Rompp-Lexikon Chemie; Publisher: J. Falbe, M. Regitz; Stuttgart, New York; 10th edition (1996); Reference "Antioxidants" and cited references cited here.
  • phenols are preferably used as the polymerization inhibitor.
  • Hydroquinone monomethyl ether to 2,4-dimethyl-6-tert-butylphenol here in the range of 2: 1 to 1: 2. Based on the weight of the entire reaction mixture, the
  • Proportion of the inhibitors individually or as a mixture is generally 0.01-0.5% (wt / wt).
  • polymerization inhibitors may be added to the reaction mixture before or at the beginning of the reaction.
  • parts of the accompanying polymerization inhibitors may also be added during the reaction.
  • the reaction may preferably be effected in the presence of oxygen, in particular atmospheric oxygen.
  • oxygen in particular atmospheric oxygen.
  • the reaction can continue under an oxygen depleted atmosphere, especially under nitrogen.
  • the reaction can be carried out both continuously and batchwise.
  • the process according to the invention can be carried out in bulk, i. be carried out without the use of another solvent.
  • an inert solvent can also be used. These include, among others, gasoline, benzene, toluene, n-hexane, cyclohexane and methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK).
  • the reaction mixture used contains at least 90% by weight of unsaturated fatty acid amide having a hydroxyl or an amino group and (meth) acrylic anhydride, particularly preferably at least 95% by weight % Fatty acid amide and (meth) acrylic anhydride. Therefore, according to this preferred embodiment of the method according to the invention only small amounts, more preferably no solvents are used.
  • all components, such as the fatty acid amide are (meth) acrylic anhydride and the polymerization inhibitor mixed, after which this reaction mixture in the presence of air or under an inert gas atom sphere, for example, under nitrogen, preferably at least 60 0 C, preferably about 80 to 100 0 C is heated.
  • the reaction times depend, among other things, on the selected parameters, such as pressure and temperature. However, they are generally in the range of 1 to 24 hours, preferably from 2 to 20 hours, and most preferably 4 to 8 hours. In continuous
  • the residence times are generally in the range of 0.5 to 24 hours, preferably from 1 to 12 hours and most preferably 4 to 8 hours.
  • the reaction may take place with stirring, wherein the stirring speed may be more preferably in the range of 50 to 2000 rpm, most preferably in the range of 100 to 500 rpm.
  • the pH can be in a wide range.
  • (meth) acrylic acid is formed, which leads to a lowering of the pH due to the low content of metal compounds.
  • the reaction may be carried out at a pH in the range of 0 to 8, preferably 2 to 7, this value being measured by a mixed with a 10-fold excess of water sample of the reaction mixture.
  • a suitable plant for carrying out the present transesterification may comprise, for example, a stirred tank reactor with stirrer and steam heating.
  • stirred tank reactor with stirrer and steam heating.
  • Such systems are known per se and described for example in Ullmann's Encyclopedia of Industrial Chemistry (6th edition), Verlag Wiley-VCH, Weinheim 2003, Volume 10, page 647.
  • the present process can be carried out both on a laboratory scale and on an industrial scale.
  • the stirred tank reactor can accordingly have a boiler volume in the range of 1 m 3 to 30 m 3 , preferably 3 m 3 to 20 m 3 .
  • the agitator of the reactor vessel may be designed in particular in the form of an anchor agitator, impeller, blade or Inter-MIG stirrer.
  • the (meth) acrylic acid or a salt of this acid present in the reaction mixture can in many cases remain in the reaction mixture obtained, without this having a disadvantageous influence on the polymers obtainable therefrom.
  • the obtained (meth) acrylic acid can also be separated by extraction process or distillation from the reaction mixture.
  • compositions obtainable by the present process can be used in many cases without separation of the released (meth) acrylic acid.
  • the released (meth) acrylic acid can be separated from the composition.
  • the (meth) acrylate obtained in each case often already meets the above-described high requirements, so that further purification is often unnecessary.
  • the resulting mixture can be purified by known methods.
  • the product mixture obtained can be purified by filtration.
  • filtration aids such as bleaching earth and aluminum silicates (perlite) can be used.
  • continuously operable filters can be used for precoat filtration, among others.
  • intermediates obtained according to the different processes for example carboxamides which have hydroxyl groups in the alkyl or amide radical
  • intermediates obtained can be converted to the monomers A according to formula (I) without expensive purification.
  • a costly purification means in particular a purification, which is associated with relatively high use of energy or investment costs. These include in particular extraction steps or distillation steps for purification of the product obtained. Filtration, which is associated with relatively low cost, in comparison to the examples mentioned no complicated purification.
  • a complex purification can be surprisingly especially when using fatty acid esters derived from alcohols having 1 to 4 carbon atoms, in particular by the use of Fatty acid methyl esters, which are commercially available under the name Biodiesel, be avoided.
  • unsaturated fatty acids which can be used to prepare the present monomers A according to formula (I) include undecylenic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, icosenoic acid, cetoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid , Clupanodonic acid and / or cervonic acid.
  • These acids can preferably also be used as esters of alcohols having 1 to 4 carbon atoms, for example as ethyl, propyl, butyl and especially methyl esters.
  • fatty acid esters of alcohols having 1 to 4 carbon atoms set out above, in particular the methyl esters of these fatty acids, are commercially available under the name biodiesel, in particular in admixture with saturated fatty acids.
  • biodiesel according to the standard EN 14214 or ASTM D 6751 can be used for the preparation of preferred monomers A according to formula (I) or inventive monomer mixtures.
  • oils include palm oil, rapeseed oil, coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, palm kernel oil, coconut oil, and mustard seed oil, among others.
  • the preferred fatty acid alkyl esters can be obtained from these oils by methods known in the art.
  • Preferred oils are those which have a high proportion of unsaturated, particularly preferably polyunsaturated fatty acids, such as, for example, linseed oil or rapeseed oil.
  • fatty acid esters derived from alcohols having 1 to 4 carbon atoms in particular fatty acid methyl ester (FAME)
  • FAME fatty acid methyl ester
  • the preferred amines for the reaction of the fatty acid or of the fatty acid ester include, in particular, ethylenediamine, ethanolamine, propanolamine and propylenediamine.
  • a monomer mixture comprising at least 2, preferably at least 5% by weight and more preferably at least 10% by weight of monomers A having 17 to 21 carbon atoms in the unsaturated group Have R 1 , based on the total weight of the monomer mixture.
  • a monomer mixture according to the invention comprises at least one monomer B of the general formula
  • R is hydrogen or a methyl group
  • X 1 and X 2 are independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, with the proviso that at least one of the groups X 1 and X 2 represents a group of formula NR ', wherein R' represents hydrogen or a radical of 1 to 6 carbon atoms, Z represents a linking group, and R 2 represents a saturated radical of 9 to 25 carbon atoms.
  • the monomer mixture comprises at least one monomer B according to the general formula (IV) wherein R is hydrogen or a methyl group, X 1 is oxygen or a group of formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, R is hydrogen or a radical having 1 to 6 carbon atoms and R 2 is a saturated Is residue with 9 to 25 carbon atoms.
  • R is hydrogen or a methyl group
  • X 1 is oxygen or a group of formula NR '
  • R' is hydrogen or a radical having 1 to 6 carbon atoms
  • Z is a linking group
  • R is hydrogen or a radical having 1 to 6 carbon atoms
  • R 2 is a saturated Is residue with 9 to 25 carbon atoms.
  • the group R 2 in formula (II) or (IV) is a saturated radical having 9 to 25 carbon atoms.
  • These groups include in particular alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkanoyl, alkoxycarbonyl and heteroaliphatic groups. Furthermore, these groups may have substituents, in particular halogen atoms or hydroxyl groups.
  • the preferred groups include in particular alkyl groups, such as, for example, the nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl , Docosyl group.
  • alkyl groups such as, for example, the nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl , Docosyl group.
  • the preferred monomers B according to formula (II) or (IV) include inter alia pentadecyloyloxy-2-ethyl (meth) acrylamide, heptadecyloyloxy-2-ethyl-
  • R is hydrogen or a methyl group
  • X 1 and X 3 are independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z 1 is a linking group having 1 to 5 carbon atoms, R is hydrogen or a radical with 1 to 6 carbon atoms and R 2 is a saturated radical having 9 to 25 carbon atoms.
  • the monomers B of the general formula (II) or (VI), wherein the group Z comprises at least one hydroxy group include (meth) acryloyloxy-2-hydroxypropyloxy-2-ethyl-laurinklareamid, (meth) acryloyloxy-2 hydroxypropyloxy-2-ethyl-myristic acid amide, (meth) acryloyloxy-2-hydroxypropyloxy-2-ethyl-palmitic acid amide, (meth) acryloyloxy-2-hydroxypropyloxy-2-ethylstearic acid amide, (meth) acryloyloxy-2-hydroxypropyloxy-2- propyl lauric acid amide, (meth) acryloyloxy-2-hydroxypropyloxy-2-propylmyristinamide, (meth) acryloyloxy-2-hydroxypropyloxy-2-propyl palmitic acid amide and (meth) acryloyloxy-2-hydroxypropyl
  • Particularly preferred monomers B according to formula (II) or (IV) include methacryloyloxy-2-ethyl-palmitic acid amide and methacryloyloxy-2-ethylstearic acid amide.
  • monomers B according to formula (II) which have 15 or 17 carbon atoms in the radical R 2 are preferably used.
  • 2 or more monomers B of the formula (II) are used in the monomer mixture, which differ in the number of carbon atoms in the radical R 2 .
  • the weight ratio of the monomers B according to formula (II), which have 15 carbon atoms in the saturated radical R 2 , to the monomers B according to formula (II), the 17 carbon atoms in the saturated radical R 2 is preferably in the range of 100: 1 to 1:10, particularly preferably in the range of 10: 1 to 1: 2.
  • the monomer mixture may have at least 0.5, preferably at least 1, and particularly preferably at least 3,% by weight of monomers B having 11 to 17 carbon atoms in the saturated radical R 2 , based on the Total weight of the monomer mixture.
  • Monomers B of the formula (II) or (IV) can be prepared in a similar manner as the previously stated monomers A according to formula (I), but using saturated fatty acids or fatty acid esters.
  • the preferred fatty acids include, among others, capnic acid, lauric acid, myristic acid, palmitic acid, margaric acid, arachic acid, behenic acid, lignoceric acid, cerotic acid and stearic acid. These acids can preferably also be used as esters of alcohols having 1 to 4 carbon atoms, for example as ethyl, propyl, butyl and especially methyl esters.
  • Monomer mixtures comprising monomers A according to formula (I) and monomers B according to formula (II) can be obtained by mixing monomers A and monomers B.
  • these mixtures can be further obtained by reacting a fatty acid mixture or a fatty acid ester mixture which comprises unsaturated and saturated fatty acids or fatty acid esters with an amine and then with a (meth) acrylate or with a (meth) acrylamide in the manner described above a hydroxy group is reacted in the alkyl radical.
  • the monomers B according to formula (II) or the monomer mixtures according to the invention can be prepared particularly simply by reacting fatty acid esters of alcohols having 1 to 4 carbon atoms, which are commercially available in particular under the name "biodiesel”.
  • a preferred monomer mixture according to the invention can accordingly be obtained in a particularly cost-effective manner by the following steps:
  • step B) can in this case take place in particular in the form of a transesterification with an alkyl (meth) acrylate, in particular of ethyl or methyl (meth) acrylate. Furthermore, this reaction can be carried out using (meth) acrylic anhydride, as stated above.
  • Monomers B of the formula (II) or (VI) which have a hydroxy group in the linking group Z can be obtained by reacting glycidyl (meth) acrylates with saturated fatty acid amides having at least one hydroxy group or one amine group.
  • the weight ratio of the monomers A to the monomers B is not critical per se. However, surprising advantages can be achieved if the weight ratio of the monomers A to the monomers B is in the range from 100: 1 to 1:10, preferably in the range from 10: 1 to 1: 3 and more preferably in the range from 3: 1 to 1 : 1 is.
  • a monomer mixture according to the invention may comprise further monomers which are copolymerizable with the monomers A and B.
  • copolymerizable monomers include, but are not limited to, monomers having an acid group, monomers C comprising ester groups other than the monomers of formulas I or II, and styrenic monomers.
  • Acid group-containing monomers are compounds which can preferably be free-radical copolymehsieren with the above-described monomers A and B. These include, for example, monomers having a sulfonic acid group, such as vinylsulfonic acid; Monomers having a phosphonic acid group, such as vinylphosphonic acid and unsaturated carboxylic acids, such as methacrylic acid, acrylic acid, fumaric acid and maleic acid. Particularly preferred are methacrylic acid and acrylic acid.
  • the acid group-containing monomers can be used individually or as a mixture of two, three or more acid group-containing monomers.
  • Particularly preferred monomers C comprising ester groups include (meth) acrylates which differ from the monomers A or B, fumarates, maleate and / or vinyl acetate.
  • the term (meth) acrylates include methacrylates and acrylates as well as mixtures of both. These monomers are well known.
  • (meth) acrylates having 1 to 6 carbons in the alkyl radical which are derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate , n-butyl (meth) acrylate, tert-butyl (meth) acrylate and pentyl (meth) acrylate, hexyl (meth) acrylate; Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate; and (meth) acrylates derived from unsaturated alcohols, such as 2-propynyl (meth) acrylate, allyl (meth) acrylate and vinyl (meth) acrylate.
  • saturated alcohols such as methyl (meth) acrylate, ethyl
  • mixtures comprising methacrylates and acrylates.
  • mixtures of methyl methacrylate and acrylates with 2 to 6 carbons such as ethyl acrylate, butyl acrylate and hexyl acrylate.
  • these comonomers include, for example, (meth) acrylates having at least 7 carbon atoms in the alkyl radical which are derived from saturated alcohols, for example 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate,
  • the monomers C comprising ester groups furthermore include vinyl esters, such as vinyl acetate;
  • Maleic acid derivatives such as, for example, maleic anhydride, esters of maleic acid, for example dimethyl maleate, methylmaleic anhydride; and fumaric acid derivatives such as dimethyl fumarate.
  • styrene monomeric such as styrene, substituted styrenes having an alkyl substituent in the side chain, such as styrene.
  • styrene substituted styrenes having an alkyl substituent in the side chain
  • styrene substituted styrenes having an alkyl substituent on the ring, such as vinyltoluene and p-methylstyrene
  • halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.
  • polymers according to the invention which are obtained by the polymerization of monomer mixtures may comprise further monomers.
  • monomers include, for example, heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, Vinyl thiolane, vinyl thiazoles and hydrogenated vinyl thiazoles, vinylo
  • Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride.
  • Preferred monomer mixtures of the present invention comprise from 0.1% to 50%, preferably from 0.5% to 30%, by weight of monomer A; 0.1 to 50% by weight, preferably 0.5 to 30% by weight of monomer B; From 30 to 95% by weight, preferably from 40 to 90% by weight, of monomers having ester groups C; 0 to 10 wt .-%, preferably 1 to 8 wt .-% of monomer having an acid group, 0 to 50 wt .-% styrene monomers and 0 to 50 wt .-% further comonomer, wherein the information is based on the total weight of the monomers Respectively.
  • monomer mixtures which have a very small proportion of (meth) acrylates which have two or more carbon-carbon double bonds which have a reactivity identical to a (meth) acrylate group.
  • the proportion of compounds having two or more (meth) acrylate groups is preferably at most 5% by weight, especially at most 2% by weight, particularly preferred at most 1% by weight, particularly preferably at most 0.5% by weight and very particularly preferably at most 0.1% by weight, based on the total weight of the monomers.
  • the monomer mixtures according to the invention are used in particular for the preparation or modification of polymers.
  • the abovementioned monomers or monomer mixtures can be reacted, for example, by solution polymerizations, bulk polymerizations or emulsion polymerizations, it being possible to achieve surprising advantages by free-radical emulsion polymerization.
  • an aqueous phase is prepared for this purpose, which may comprise, in addition to water, customary additives, in particular emulsifiers and protective colloids, for stabilizing the emulsion.
  • Monomers are then added to this aqueous phase and polymethylated in the aqueous phase.
  • a monomer mixture can be added continuously or batchwise over a period of time.
  • the emulsion polymerization can be carried out, for example, as a miniemulsion or as a microemulsion, described in more detail in Chemistry and Technology of Emulsion Polymerization, AM van Herk (editor), Blackwell Publishing, Oxford 2005 and J. O'Donnell, EW Kaier, Macromolecular Rapid Communications 2007, 28 (14), 1445-1454.
  • a miniemulsion is customary characterized by the use of costabilizers or swelling agents, many of which use long-chain alkanes or alkanols.
  • the droplet size in miniemulsions is preferably in the range of 0.05 to 20 microns.
  • the droplet size in the case of microemulsions is preferably in the range below 1 ⁇ m, whereby particles below a size of 50 nm can be obtained in this way.
  • Microemulsions often use additional surfactants, for example hexanol or similar compounds.
  • the dispersing of the monomer-containing phase in the aqueous phase can be carried out by known means. These include, in particular, mechanical methods and the use of ultrasound.
  • a monomer mixture comprising 10 to 40% by weight of monomers A according to formula (I) may preferably be used.
  • the composition of the monomer mixture can be changed stepwise, wherein before changing the composition, the polymerization is preferably up to a conversion of at least 80 wt .-%, particularly preferably at least 95 wt .-%, each based on the Total weight of the monomer mixture used is polymerized.
  • the monitoring of the progress of the polymerization in each step can be carried out in a known manner, for example gravimetrically or by gas chromatography.
  • the monomer mixture for producing the core preferably comprises from 50 to 100% by weight of (meth) acrylates, with a mixture of acrylates and methacrylates being particularly preferably used.
  • a monomer mixture are grafted or polymerized onto the core, which comprises 15 to 40 wt .-% of monomers A according to formula (I).
  • the emulsion polymerization is preferably carried out at a temperature in the range from 0 to 120 ° C., more preferably in the range from 30 to 100 ° C.
  • Polymerization temperatures in the range from greater than 60 to less than 90 ° C., expediently in the range from greater than 70 to less than 85 ° C., preferably in the range from greater than 75 to less than 85 ° C., have proven to be particularly favorable.
  • Suitable organic initiators are, for example, hydroperoxides, such as tert-butyl hydroperoxide or cumene hydroperoxide.
  • Suitable inorganic initiators are hydrogen peroxide and the alkali metal and ammonium salts of peroxodisulfuric acid, in particular ammonium, sodium and potassium peroxodisulfate.
  • Suitable redox initiator systems are, for example, combinations of tertiary amines with peroxides or sodium disulfite and alkali metal and the ammonium salts of peroxodisulfuric acid, in particular sodium and potassium peroxodisulfate.
  • the initiators mentioned can be used both individually and as a mixture. They are preferably used in an amount of 0.05 to 3.0 wt .-%, based on the total weight of the monomers of each stage. It is also possible with preference to carry out the polymerization with a mixture of different polymerization initiators having a different half-life in order to keep the free radical stream constant during the polymerization and at different polymerization temperatures.
  • the stabilization of the approach is preferably carried out by means of emulsifiers and / or protective colloids. Preferably, the emulsion is stabilized by emulsifiers to obtain a low dispersion viscosity.
  • the total amount of emulsifier is preferably 0.1 to 15 wt .-%, in particular 1 to 10 wt .-% and particularly preferably 2 to 5 wt .-%, based on the total weight of the monomers used. According to a particular aspect of the present invention, a part of the emulsifiers may be added during the polymerization.
  • emulsifiers are anionic or nonionic emulsifiers or mixtures thereof, in particular
  • Alkyl sulfates preferably those having 8 to 18 carbon atoms in the alkyl radical, alkyl and alkylaryl ether sulfates having 8 to 18 carbon atoms in the alkyl radical and 1 to 50 ethylene oxide units; Sulfonates, preferably alkyl sulfonates having 8 to 18 carbon atoms in the alkyl radical, alkylaryl sulfonates having 8 to 18 carbon atoms in the alkyl radical, esters and half-esters of sulfosuccinic acid with monohydric alcohols or alkylphenols having 4 to 15 carbon atoms in the alkyl radical; optionally, these alcohols or alkylphenols may also be ethoxylated with 1 to 40 ethylene oxide units; Partial phosphoric acid esters and their alkali metal and ammonium salts, preferably alkyl and alkylaryl phosphates having 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 1 to 5
  • Alkylpolyglykolether preferably having 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units
  • - Alkylarylpolyglykolether preferably having 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 8 to 40 ethylene oxide units
  • Ethylene oxide / propylene oxide copolymers preferably block copolymers, desirably with 8 to 40 ethylene oxide or propylene oxide units, respectively.
  • the particularly preferred anionic emulsifiers include, in particular, fatty alcohol ether sulfates, diisooctyl sulfosuccinate, lauryl sulfate, C15 paraffin sulfonate, these compounds generally being usable as alkali metal salt, in particular as sodium salt. These compounds can be obtained commercially in particular under the trade names Disponil® FES 32, Aerosol® OT 75, Texapon® K1296 and Statexan® K1 from the companies Cognis GmbH, Cytec Industries, Inc. and Bayer AG.
  • Useful nonionic emulsifiers include tert-octylphenol ethoxylate having 30 ethylene oxide units and fatty alcohol polyethylene glycol ethers preferably having 8 to 20 carbon atoms in the alkyl group and 8 to 40 ethylene oxide units. These emulsifiers are commercially available under the trade names Triton® X 305 (Fluka), Tergitol® 15-S-7 (Sigma-Aldrich Co.), Marlipal® 1618/25 (Sasol Germany), and Marlipal® O 13/400 (Sasol Germany) available.
  • the weight ratio of anionic emulsifier to nonionic emulsifier in the range of 20: 1 to 1: 20, preferably 2: 1 to 1: 10 and more preferably 1: 1 to 1: 5 are.
  • Mixtures comprising a sulfate, in particular a fatty alcohol ether sulfate, a lauryl sulfate, or a sulfonate, in particular a diisooctyl sulfosuccinate or a paraffin sulfonate as anionic emulsifier and an alkylphenol ethoxylate or a fatty alcohol polyethylene glycol ether, each preferably 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units have proven particularly useful as a nonionic emulsifier.
  • the emulsifiers can also be used in admixture with protective colloids.
  • Suitable protective colloids include partially saponified polyvinyl acetates, polyvinylpyrrolidones, carboxymethyl, methyl, hydroxyethyl, hydroxypropyl cellulose, starches, proteins, poly (meth) acrylic acid, poly (meth) acrylamide, polyvinylsulfonic acids, Melamine formaldehyde sulfonates, naphthalene formaldehyde sulfonates, styrene-maleic acid and vinyl ether maleic acid copolymers.
  • protective colloids are used, this is preferably carried out in an amount of 0.01 to 1, 0 wt .-%, based on the total amount of the monomers.
  • the protective colloids can be initially charged or added before the start of the polymerization.
  • the initiator can be initially charged or added. Furthermore, it is also possible to submit a portion of the initiator and to meter in the remainder.
  • the polymerization is preferably started by heating the batch to the polymerization temperature and metering in the initiator, preferably in aqueous solution.
  • the dosages of emulsifier and monomers can be carried out separately or as a mixture.
  • the procedure is such that emulsifier and monomer are premixed in a mixer upstream of the polymerization reactor.
  • the residues of emulsifier and of monomer, which were not initially charged are metered in separately after the start of the polymerization.
  • the dosage can be started 15 to 35 minutes after the start of the polymerization.
  • Preferred emulsion polymers having a high content of insoluble polymers can be obtained in the manner set forth above, the reaction parameters for obtaining a high molecular weight being known.
  • the use of molecular weight regulators can be dispensed with.
  • the adjustment of the particle radii can be influenced inter alia by the proportion of emulsifiers. The higher this proportion, especially at the beginning of the polymerization, the smaller the particles are obtained.
  • the emulsion polymer may have a content of from 2 to 60% by weight, more preferably from 10 to 50% by weight and most preferably from 20 to 40% by weight, based on the weight of the emulsion polymer dissolved in tetrahydrofuran (THF). at 20 0 C is soluble.
  • THF tetrahydrofuran
  • a sample of the polymer dried under exclusion of oxygen is stored in a 200-fold amount of solvent, based on the weight of the sample, at 20 ° C. for 4 hours.
  • the sample can be dried, for example under nitrogen or under vacuum.
  • the solution is separated from the insoluble fraction, for example by filtration.
  • the weight of the residue is determined. For example, a 0.5 g sample of a vacuum-dried emulsion polymer can be stored in 150 ml of THF for 4 hours.
  • an emulsion polymer may have a swelling of at least 1000%, more preferably at least 1400% and most preferably at least 1600% in tetrahydrofuran (THF) at 20 ° C.
  • the upper limit of the swelling is not critical per se, the swelling preferably being at most 5000%, more preferably at most 3000% and most preferably at most 2500%.
  • a dried under exclusion of oxygen sample of the emulsion polymer is stored at 20 0 C for 4 hours in a 200-fold amount of THF. As a result, the sample swells up. The swollen sample is separated from the supernatant solvent. Subsequently, the solvent is removed from the sample.
  • the particle radius of the emulsion polymers can be in a wide range.
  • emulsion polymers having a particle radius in the range of 1 to 100 nm, preferably 5 to 59 nm can be used.
  • the radius of the particles is preferably in the range of 60 nm to 500 nm, particularly preferably 70 to 150 nm and very particularly preferably 75 to 100 nm.
  • the radius of the particles can be determined by PCS (Photon Correlation Spektroscopy ), the data given refer to the d50 value (50% of the particles are smaller, 50% are larger).
  • PCS Photon Correlation Spektroscopy
  • a Beckman Coulter N5 Submicron Particle Size Analyzer may be used.
  • emulsion polymers having a high swelling factor exhibit a swelling factor of at least 2, in particular at least 4, particularly preferably at least 6 and very particularly preferably at least 8.
  • the particle radius of the emulsion polymers in water is first measured by the method set out above.
  • the measurement is carried out at 20.degree. C., the dispersion being swollen for 5 minutes after addition of the solvent (THF).
  • the quotient of the particle volumes calculated from the obtained particle radii (r Ls gm and r Wa sser) is defined as a swelling factor (QF): ⁇ - 3 Qp _ ' Ls 9 m -r3
  • High swelling factors in particular show emulsion polymers which have a low pre-crosslinking. Under pre-crosslinking is here an undesirable crosslinking of the Emulsionspolymeren understood that takes place before application to an object to be coated. Accordingly, in particular, emulsion polymers obtained from a monomer mixture having a low content of compounds having two or more (meth) acrylate groups show a high swelling factor.
  • Polymers having these properties can preferably be obtained from monomer blends prepared by reacting fatty acid esters derived from alcohols having from 1 to 4 carbon atoms, especially fatty acid methyl esters (FAME), as set forth above.
  • FAME fatty acid methyl esters
  • the glass transition temperature of the polymer according to the invention is preferably in the range of -30 0 C to 70 0 C, more preferably in the range of -20 to 40 0 C and most preferably in the range of 0 to 25 ° C.
  • the glass transition temperature can be influenced by the type and proportion of the monomers used to prepare the polymer.
  • the glass transition temperature Tg of the polymer can be determined in a known manner by means of differential scanning calohmetry (DSC).
  • DSC differential scanning calohmetry
  • the glass transition temperature Tg can also be calculated approximately in advance by means of the Fox equation. After Fox TG, Bull. Am. Physics Soc. 1, 3, page 123 (1956) applies:
  • Tg Tg 1 Tg Tg n 2 wherein X n is the mass fraction designated n (wt .-% / 100) of monomer n and Tg n is the glass transition temperature in Kelvin of the homopolymer of the monomer. Further helpful information can be found by the person skilled in the art in Polymer Handbook 2 nd Edition, J. Wiley & Sons, New York (1975), which indicates Tg values for the most common homopolymers. In this case, the polymer may have one or more different glass transition temperatures. These data therefore apply to a segment which is obtainable by polymerization of a monomer mixture according to the invention.
  • the architecture of the polymer is not critical to many applications and properties.
  • the polymers in particular the emulsion polymers, can represent random copolymers, gradient copolymers, block copolymers and / or graft copolymers.
  • Block copolymers or gradient copolymers can be obtained, for example, by discontinuously changing the monomer composition during chain growth.
  • the emulsion polymer is a random copolymer in which the monomer composition is substantially constant throughout the polymerization. However, since the monomers may have different copolymerization parameters, the exact composition may vary across the polymer chain of the polymer.
  • the polymer may be a homogeneous polymer which, for example, forms particles with a constant composition in an aqueous dispersion.
  • the polymer which is preferably an emulsion polymer, may consist of one or more segments obtainable by polymerization of the monomer mixtures of the invention.
  • the emulsion polymer may be a core-shell polymer which may have one, two, three, or more shells.
  • the segment obtainable by polymerization of the monomer mixture according to the invention preferably forms the outermost shell of the core-shell polymer.
  • the shell may be connected to the core or inner shells via covalent bonds.
  • the shell can also be polymerized on the core or an inner shell.
  • the segment which is obtainable by polymerization of the monomer mixture according to the invention can often be separated from the core by suitable solvents and isolated.
  • the weight ratio of segment obtainable by polymerization of the monomer mixture of the present invention to core may be in the range of 2: 1 to 1: 6, more preferably 1: 1 to 1: 3.
  • the core may preferably be formed from polymers comprising from 50 to 100% by weight, preferably from 60 to 90% by weight, of units derived from (meth) acrylates. Preference is given to esters of (meth) acrylic acid whose alcohol radical preferably comprises 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms and very particularly preferably 1 to 10 carbon atoms.
  • (meth) acrylates which are derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate and pentyl (meth) acrylate, hexyl (meth) acrylate.
  • saturated alcohols such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate and pentyl (meth) acrylate, hexyl (meth) acrylate.
  • a mixture comprising methacrylates and acrylates can be used to produce the core.
  • methacrylates and acrylates having 2 to 6 carbons, such as ethyl acrylate, butyl acrylate and hexyl acrylate can be used.
  • the polymers of the core may include the comonomers set forth above.
  • the core may be crosslinked. This crosslinking can be achieved by the use of monomers having two, three or more free-radically polymerizable double bonds.
  • the shell of an emulsion polymer of the present invention obtainable by polymerization of a monomer mixture according to the invention may preferably comprise 15 to 50% by weight of units derived from monomers A of formula (I) having at least one double bond in the radical R 1 .
  • the core may preferably have a glass transition temperature in the range from -30 to 200 ° C., more preferably in the range from -20 to 150 ° C.
  • the shell of the emulsion polymer according to the invention which is preferably obtainable by polymerization of the monomer mixture according to the invention, may preferably have a glass transition temperature in the range of -30 0 C to 70 0 C, more preferably in the range of -20 to 40 ° C and most preferably in the range of 0 have up to 25 0 C.
  • the glass transition temperature of the core may be greater than the glass transition temperature of the shell.
  • the glass transition temperature of the core at least 10 0 C, preferably at least 20 ° C above the glass transition temperature of the shell.
  • the iodine value of the polymers according to the invention is preferably in the range of 1 to 150 g of iodine per 100 g of polymer, more preferably in the range of 2 to 100 g of iodine per 100 g of polymer and most preferably 5 to 40 g of iodine per 100 g of polymer, measured according to DIN 53241 -1.
  • the iodine number can in particular also be measured by means of a dispersion according to the invention.
  • the polymer may have an acid number in the range of 0.1 to 40 mg KOH / g, preferably 1 to 20 mg KOH / g and most preferably in the range of 2 to 10 mg KOH / g.
  • the acid number can also be determined by dispersion according to DIN EN ISO 2114.
  • the hydroxyl number of the polymer may preferably be in the range from 0 to 200 mg KOH / g, more preferably 1 to 100 mg KOH / g and most preferably in the range from 3 to 50 mg KOH / g.
  • the hydroxyl number can also be determined by dispersion according to DIN EN ISO 4629.
  • the polymers obtainable by polymerization of the monomer mixture according to the invention can be isolated.
  • the dispersions obtainable by emulsion polymerization can be used as such as a coating agent.
  • aqueous dispersions are a further subject of the present invention.
  • the aqueous dispersions preferably have a solids content in the range from 10 to 70% by weight, particularly preferably from 20 to 60% by weight.
  • the dispersion may have a dynamic viscosity in the range of 0.1 to 180 mPas, preferably 1 to 80 mPas and most preferably 10 to 50 mPas, measured according to DIN EN ISO 2555 at 25 ° C (Brookfield).
  • aqueous dispersions according to the invention can be provided in a known manner with additives or further components in order to adapt the properties of the coating agent to specific requirements.
  • additives include in particular drying aids, so-called siccatives, flow improvers, pigments and dyes.
  • coating compositions of the present invention have a minimum film-forming temperature of at most 50 0 C, particularly preferably at most 35 ° C and most preferably at most 25 ° C, which can be sen 2115 measured in accordance with DIN ISO.
  • siccatives can be added to the aqueous dispersions.
  • organometallic compounds for example metal soaps of transition metals, such as cobalt, manganese, lead, zirconium; Alkali or alkaline earth metals, such as lithium, potassium and calcium.
  • transition metals such as cobalt, manganese, lead, zirconium
  • Alkali or alkaline earth metals such as lithium, potassium and calcium.
  • cobalt naphthalate and cobalt acetate can be used singly or as a mixture, whereby in particular shingles containing cobalt, zirconium and lithium salts are particularly preferred.
  • the aqueous dispersions of the present invention can be used in particular as a coating agent or as an additive. These include in particular paints, impregnating agents, adhesives and / or primers.
  • the aqueous dispersions can particularly preferably be used for the production of paints or impregnating agents for applications on wood and / or metal.
  • the coatings obtainable from the coating compositions according to the invention show a high resistance to solvents, with only small amounts in particular being dissolved out of the coating by solvents.
  • Preferred coatings show a high resistance, in particular to methyl isobutyl ketone (MIBK).
  • MIBK methyl isobutyl ketone
  • the weight loss after treatment with MIBK is preferably at most 50% by weight, preferably at most 35% by weight.
  • the uptake of MIBK is preferably at most 300% by weight, particularly preferably at most 250% by weight, based on the weight of the coating used. These values are measured at a temperature of about 25 ° C and an exposure time of at least 4 hours, wherein a completely dried coating is measured. In this case, the drying takes place in the presence of oxygen, for example air, in order to allow crosslinking.
  • the coatings obtained from the coating compositions of the invention show high mechanical resistance.
  • the pendulum hardness is preferably at least 15 s, preferably at least 25 s, measured in accordance with DIN ISO 1522.
  • the dispersions according to the invention may contain other constituents in addition to the emulsion polymers.
  • these include in particular alkyd resins.
  • Alkyd resins have long been known, which are generally understood to mean resins, which are obtained by condensation of polybasic carboxylic acids and polyhydric alcohols, these compounds are generally modified with long-chain alcohols (fatty alcohols), fatty acids or fatty acid-containing compounds, such as fats or oils (DIN 55945, 1968).
  • Alkyd resins are set forth, for example, in Ullmann's Encyclopedia of Industrial Chemistry 5th Edition on CD-ROM. In addition to these classic alkyd resins and resins can be used, which have similar properties.
  • These resins are also characterized by a high content of groups derived from the long-chain alcohols (fatty alcohols), fatty acids or fatty acid-containing compounds described above, for example, fats or oils.
  • fatty alcohols long-chain alcohols
  • fatty acids fatty acids
  • fatty acid-containing compounds for example, fats or oils.
  • these derivatives do not necessarily have polybasic carboxylic acids but can be obtained, for example, by reacting polyols with isocyanates.
  • the usable alkyd resins may preferably be mixed or diluted with water.
  • alkyd resins modified with polymers obtainable by radical polymerization are known inter alia from the publications US 5,538,760, US 6,369,135 and DE-A-199 57 161.
  • the resins set forth in US Pat. No. 5,538,760 filed May 22, 1995 with the United States Patent Office (USPTO) No. 446,130 are incorporated herein for purposes of disclosure.
  • the resins set forth in US Pat. No. 6,369,135 B1 filed Aug. 13, 1996 with the United States Patent Office (USPTO) Serial No. 08 / 696,361 are incorporated herein for purposes of disclosure.
  • alkyd resins are inter alia the acrylate-modified alkyd resins described in DE-A-199 57 161. These alkyd resins have, besides an alkyd core, groups obtained by polymerization of (meth) acrylates.
  • alkyd resins which are obtainable according to the document US Pat. No. 5,096,959 are preferred. These alkyd resins are modified by cycloaliphatic polycarboxylic acid, with cyclohexanedicarboxylic acids and cyclopentanedicarboxylic acids in particular being suitable for the modification.
  • U.S. Patent No. 5,096,959 B1 filed Oct. 30, 1990 at the United States Patent Office
  • alkyd resins modified with polyethylene glycol can be used.
  • a large number of patents describe the preparation of water-emulsifiable alkyd resins by modification with polyethylene glycol (PEG).
  • PEG polyethylene glycol
  • Preferred alkyd resins modified with polyethylene glycol are known inter alia from the document EP-AO 029 145. Those filed in the document EP-AO 029 145 on 30.10.80 at the European Patent Office with the application The resins set forth in EP 80106672.1 are incorporated in the present application for the purposes of disclosure.
  • a polyethylene glycol can first be reacted with epoxide-containing carboxylic acid. The reaction product thus obtained can then be used in the reaction mixture to prepare the alkyd resin.
  • Preferred polyethylene glycols for modifying the alkyd resins have, for example, a number average molecular weight of 500 to 5000 g / mol.
  • alkyd resins modified with polyethylene glycol can be further modified with copolymers obtainable by polymerization of methacrylic acid, unsaturated fatty acids and vinyl and / or vinylidene compounds. According to a particular aspect of the present invention, these alkyd resins may also be modified with copolymers obtainable by the monomer mixtures according to the invention.
  • alkyd resins modified with urethane groups are disclosed inter alia in WO 2006/09221 1 and EP-A-1 533 342.
  • urethane-alkyd resins obtainable by reacting polyhydric alcohols A ', modified fatty acids B', fatty acids C, and polyfunctional isocyanates D '.
  • the modified fatty acids B ' can be prepared by reacting unsaturated fatty acids B1' with unsaturated carboxylic acids B2 '.
  • These urethane alkyds are known inter alia from WO 2006/092211.
  • the resins set forth in document WO 2006/092211 filed on 20.02.06 at the European Patent Office with the application number PCT / EP2006 / 001503 are incorporated in the present application for the purposes of disclosure.
  • the modified fatty acid B ' preferably has an acid number of at least 80 mg / g.
  • the increase in the acid number by the grafting is in the range from 80 mg / g to 250 mg / g and most preferably in the range from 100 mg / g to 150 mg / g, the acid value according to DIN EN ISO 2114 can be determined .
  • the iodine value of the fatty acids C used to prepare the urethane alkyd resins is preferably at least 80 g / 100 g and preferably at least 120 g / 100 g.
  • the components A ', B' and C are generally first reacted, the condensate preferably having a hydroxy functionality of at least 1, 9, more preferably at least 2.
  • the condensate may have groups derived from polybasic carboxylic acids, especially the di- and tricarboxylic acids set forth above. This condensate is then reacted with a polyvalent isocyanate.
  • the preferred polyfunctional isocyanates include, among others, 2,4- and 2,6-toluene diisocyanate and their technical mixtures, bis (4-isocyanatophenyl) methane, isophorone diisocyanate, bis (4-isocyanatocyclohexyl) methane and 1,6-di -isocyanatohexane, and derived from these isocyanurates, allophanes and biurets.
  • alkyd resins for the preparation of which polycarboxylic acids are generally used, it is also possible to use further alkyd resins, as already stated above.
  • these alkyd resins can be obtained, for example, by reacting polyhydric alcohols with polyvalent isocyanates.
  • Preferred urethane resins are known, for example, from EP-A-1 129 147. These can be obtained, for example, by reacting amide ester diols with polyols and polyfunctional isocyanates.
  • Amidesterdiole can be obtained by reacting vegetable oils with N 1 N- dialkanolamines.
  • the monomer mixtures according to the invention can also be used for the modification of alkyd resins.
  • the fatty acid methyl ester mixture comprised 6% by weight of saturated C12 to C16 fatty acid methyl ester, 2.5% by weight of saturated C17 to C20 fatty acid methyl ester, 52% by weight of monounsaturated C18 fatty acid methyl ester, 1.5% by weight of monounsaturated C20 to C24 fatty acid methyl esters , 36% by weight of polyunsaturated C18 fatty acid methyl ester, 2% by weight of polyunsaturated C20 to C24 fatty acid methyl esters.
  • the reaction mixture was heated to 150 0 C. Within 2 h, 19.5 ml of methanol were distilled off. The resulting reaction product contained 86.5% fatty acid ethanolamides. The resulting reaction mixture was further processed without purification.
  • reaction apparatus While stirring, the reaction apparatus was purged with nitrogen for 10 minutes. Thereafter, the reaction mixture was heated to boiling. The methyl methacrylate / methanol azeotrope was separated and then the head temperature gradually increased to 100 0 C. After completion of the reaction, the reaction mixture was cooled to about 70 ° C and filtered. Excess methyl methacrylate was separated on a rotary evaporator. It could be obtained 370 g of product.
  • the fatty acid methyl ester mixture comprised 6% by weight of saturated C12 to C16 fatty acid methyl ester, 2.5% by weight of saturated C17 to C20 fatty acid methyl ester, 52% by weight of monounsaturated C18 fatty acid methyl ester, 1.5% by weight of monounsaturated C20 to C24 fatty acid methyl esters , 36% by weight of polyunsaturated C18 fatty acid methyl ester, 2% by weight of polyunsaturated C20 to C24 fatty acid methyl esters.
  • the reaction mixture was heated to 150 0 C. Within 2 h, 19.5 ml of methanol were distilled off. The resulting reaction product contained 86.5% fatty acid ethanolamides. The resulting reaction mixture was further processed without purification. After addition of inhibitor mixture 500 ppm hydroquinone monomethyl ether and 500 ppm of phenothiazine, 108 g (0.70 mol) of methacrylic anhydride were added slowly at a bottom temperature of 80 0 C. The reaction mixture was heated to 90 ° C and stirred for 6 h at this temperature. The resulting methacrylic acid was separated on a thin-film evaporator. A brown, liquid product was obtained.
  • a polymer dispersion was prepared.
  • BA butyl acrylate
  • MMA methyl methacrylate
  • MAS methacrylic acid
  • APS Ammonium peroxodisulfate
  • Disponil FES 32 (30%)
  • 359.18 g of water were emulsified by Ultra-Turrax at 4000 rpm for 3 minutes.
  • the emulsion produced had a solids content of 40 ⁇ 1%, a pH of 5.6, a viscosity of 37 mPas and a rN5 value of 70-75 nm.
  • the properties of the coating composition thus obtained were investigated by various methods. For this purpose, tests on solvent resistance, water absorption and hardness were carried out on dried films.
  • Solvent resistance was determined using methyl isobutyl ketone (MIBK), with a sample swollen with MIBK at room temperature for 4 hours. The sample was then removed from the solvent and excess solvent removed. Subsequently, the sample was dried for 1 hour at about 140 ° C. The weight loss is used to calculate the proportion of the sample removed by the solvent. The weight loss in ethanol reported in Table 1 was determined similarly to the experimental description set out above but using ethanol as the solvent.
  • MIBK methyl isobutyl ketone
  • a test specimen of untreated solid pine wood (dimensions: 45-50mmx45-50mmx17mm) can be used.
  • the test piece was coated and placed in water at room temperature so that only the coated area was in contact with water. From the increase in weight of the specimen, the water absorption is calculated.
  • the dispersions were equimolar to 6 wt.% AAEMA crosslinked with adipic dihydrazide (ADH). To this was added 100 g of dispersion with 6.54 g of 15% strength ADH solution with stirring and stirred for 30 min. The dried films were subjected to solvent resistance, water absorption and scratch resistance tests.
  • the furniture test according to 68861-1 shows that a dispersion according to the invention leads to a coating which is very stable to a large number of different solvents. While the uncrosslinked polymer shows extremely low stability to ethanol, a coating according to the invention is stable to bases, acids and a polar solvent.

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Abstract

La présente invention porte sur un mélange de monomères comportant au moins un monomère A de formule générale (I) dans laquelle R est un atome d'hydrogène ou un groupe méthyle, X1 et X2 représentent chacun indépendamment de l'autre un atome d'oxygène ou un groupe de formule NR' dans laquelle R' est un atome d'hydrogène ou un radical ayant 1 à 6 atomes de carbone, du moment qu'au moins l'un des groupes X1 et X2 représente un groupe de formule NR' dans laquelle R' est un atome d'hydrogène ou un radical ayant 1 à 6 atomes de carbone, Z est un groupe de liaison, et R1 est un radical insaturé ayant 9 à 25 atomes de carbone, et au moins un monomère B de formule générale (II) dans laquelle R est un atome d'hydrogène ou un groupe méthyle, X1 et X2 représentent chacun indépendamment de l'autre un atome d'oxygène ou un groupe de formule NR' dans laquelle R' est un atome d'hydrogène ou un radical ayant 1 à 6 atomes de carbone, à la condition qu'au moins l'un des groupes X1 et X2 représente un groupe de formule NR' dans laquelle R' est un atome d'hydrogène ou un radical ayant 1 à 6 atomes de carbone, Z est un groupe de liaison, et R2 est un radical saturé ayant 9 à 25 atomes de carbone. La présente invention porte en outre sur un procédé de préparation des monomères décrits ci-dessus, des polymères pouvant être obtenus à partir de ce mélange de monomères, ainsi que des compositions de revêtement contenant lesdits polymères.
PCT/EP2009/055573 2008-06-06 2009-05-08 Mélanges de monomères, polymères, ainsi que compositions de revêtement Ceased WO2009146995A1 (fr)

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DE102008002254A DE102008002254A1 (de) 2008-06-06 2008-06-06 Monomermischungen, Polymere sowie Beschichtungszusammensetzungen
DE102009001217.6 2009-02-27
DE102009001217A DE102009001217A1 (de) 2009-02-27 2009-02-27 Monomermischungen, Polymere sowie Beschichtungszusammensetzungen

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Cited By (9)

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WO2012028627A1 (fr) 2010-09-01 2012-03-08 Basf Se Polymères en émulsion aqueuse, leur fabrication et leur utilisation
DE102011088149A1 (de) 2011-12-09 2013-06-13 Evonik Industries Ag Beschichteter Verbundkörper, umfassend ein Verbundmaterial
US8722756B2 (en) 2010-09-01 2014-05-13 Basf Se Aqueous emulsion polymers, their preparation and use
WO2020016037A1 (fr) 2018-07-17 2020-01-23 Evonik Operations Gmbh Esters méthacryliques ch-acides pour la préparation de dispersions polymères aqueuses
WO2022053357A1 (fr) 2020-09-10 2022-03-17 Evonik Operations Gmbh Procédé de préparation de (méth)acrylates de vanilline
RU2777540C2 (ru) * 2018-07-17 2022-08-08 Эвоник Оперейшенс ГмбХ Ch-кислотные сложные метакриловые эфиры для получения водных полимерных дисперсий
US11505520B2 (en) 2018-05-23 2022-11-22 Evonik Operations Gmbh Method for preparing keto-functionalized aromatic (meth)acrylates
US11512043B2 (en) 2018-07-26 2022-11-29 Evonik Operations Gmbh Process for preparing N-methyl(meth)acrylamide
US11912648B2 (en) 2018-07-17 2024-02-27 Evonik Operations Gmbh Method for preparing C-H acidic (meth)acrylates

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US3590016A (en) * 1968-08-08 1971-06-29 Balm Paints Ltd Polymerizable monomers
US4233362A (en) * 1976-12-17 1980-11-11 Rohm And Haas Company Water-soluble air-oxidizing acrylic coatings
US4292220A (en) * 1979-12-20 1981-09-29 Rohm And Haas Company Addition polymer comprising air-curable alkyl diamide

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US3590016A (en) * 1968-08-08 1971-06-29 Balm Paints Ltd Polymerizable monomers
US4233362A (en) * 1976-12-17 1980-11-11 Rohm And Haas Company Water-soluble air-oxidizing acrylic coatings
US4292220A (en) * 1979-12-20 1981-09-29 Rohm And Haas Company Addition polymer comprising air-curable alkyl diamide

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012028627A1 (fr) 2010-09-01 2012-03-08 Basf Se Polymères en émulsion aqueuse, leur fabrication et leur utilisation
JP2013540844A (ja) * 2010-09-01 2013-11-07 ビーエーエスエフ ソシエタス・ヨーロピア 水性のエマルションポリマー、その製造及び使用
US8722756B2 (en) 2010-09-01 2014-05-13 Basf Se Aqueous emulsion polymers, their preparation and use
US9150732B2 (en) 2010-09-01 2015-10-06 Basf Se Aqueous emulsion polymers, their preparation and use
DE102011088149A1 (de) 2011-12-09 2013-06-13 Evonik Industries Ag Beschichteter Verbundkörper, umfassend ein Verbundmaterial
WO2013083362A2 (fr) 2011-12-09 2013-06-13 Evonik Industries Ag Corps composite enrobé comportant un matériau composite
US11505520B2 (en) 2018-05-23 2022-11-22 Evonik Operations Gmbh Method for preparing keto-functionalized aromatic (meth)acrylates
WO2020016037A1 (fr) 2018-07-17 2020-01-23 Evonik Operations Gmbh Esters méthacryliques ch-acides pour la préparation de dispersions polymères aqueuses
RU2777540C2 (ru) * 2018-07-17 2022-08-08 Эвоник Оперейшенс ГмбХ Ch-кислотные сложные метакриловые эфиры для получения водных полимерных дисперсий
US11912648B2 (en) 2018-07-17 2024-02-27 Evonik Operations Gmbh Method for preparing C-H acidic (meth)acrylates
US11512043B2 (en) 2018-07-26 2022-11-29 Evonik Operations Gmbh Process for preparing N-methyl(meth)acrylamide
WO2022053357A1 (fr) 2020-09-10 2022-03-17 Evonik Operations Gmbh Procédé de préparation de (méth)acrylates de vanilline

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