WO2013012365A1 - Waterborne homo or copolymer dispersion - Google Patents
Waterborne homo or copolymer dispersion Download PDFInfo
- Publication number
- WO2013012365A1 WO2013012365A1 PCT/SE2012/000100 SE2012000100W WO2013012365A1 WO 2013012365 A1 WO2013012365 A1 WO 2013012365A1 SE 2012000100 W SE2012000100 W SE 2012000100W WO 2013012365 A1 WO2013012365 A1 WO 2013012365A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer dispersion
- dispersion according
- crotonate
- isocrotonate
- waterborne polymer
- Prior art date
Links
- 239000006185 dispersion Substances 0.000 title description 11
- 229920001577 copolymer Polymers 0.000 title description 9
- 229920001519 homopolymer Polymers 0.000 title description 6
- -1 alkyl crotonate Chemical compound 0.000 claims abstract description 32
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012736 aqueous medium Substances 0.000 claims abstract description 8
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 claims abstract description 8
- 239000004815 dispersion polymer Substances 0.000 claims abstract 22
- ZFDIRQKJPRINOQ-HYXAFXHYSA-N ethyl (2Z)-but-2-enoate Chemical compound CCOC(=O)\C=C/C ZFDIRQKJPRINOQ-HYXAFXHYSA-N 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000004816 latex Substances 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 229940117958 vinyl acetate Drugs 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 2
- XTUAWCZYONBWON-UHFFFAOYSA-N 1-ethylimidazolidin-2-one;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCN1CCNC1=O XTUAWCZYONBWON-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- XDOWKOALJBOBBL-PLNGDYQASA-N 2-Methylpropyl (2E)-butenoate Chemical compound C\C=C/C(=O)OCC(C)C XDOWKOALJBOBBL-PLNGDYQASA-N 0.000 claims description 2
- QSOMQGJOPSLUAZ-UHFFFAOYSA-N 2-ethenylbuta-1,3-dienylbenzene Chemical compound C=CC(C=C)=CC1=CC=CC=C1 QSOMQGJOPSLUAZ-UHFFFAOYSA-N 0.000 claims description 2
- LINJIWJIUXFXHS-VMPITWQZSA-N 2-ethylhexyl (e)-but-2-enoate Chemical compound CCCCC(CC)COC(=O)\C=C\C LINJIWJIUXFXHS-VMPITWQZSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- GWCTUKHUBWMAMI-GQCTYLIASA-N butyl (e)-but-2-enoate Chemical compound CCCCOC(=O)\C=C\C GWCTUKHUBWMAMI-GQCTYLIASA-N 0.000 claims description 2
- 229930016911 cinnamic acid Natural products 0.000 claims description 2
- 235000013985 cinnamic acid Nutrition 0.000 claims description 2
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- IYNRVIKPUTZSOR-HWKANZROSA-N ethenyl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC=C IYNRVIKPUTZSOR-HWKANZROSA-N 0.000 claims description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical class CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004922 lacquer Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- MCVVUJPXSBQTRZ-ONEGZZNKSA-N methyl (e)-but-2-enoate Chemical compound COC(=O)\C=C\C MCVVUJPXSBQTRZ-ONEGZZNKSA-N 0.000 claims description 2
- MCVVUJPXSBQTRZ-ARJAWSKDSA-N methyl (z)-but-2-enoate Chemical compound COC(=O)\C=C/C MCVVUJPXSBQTRZ-ARJAWSKDSA-N 0.000 claims description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical class C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- QHSPZGZEUDEIQM-WAYWQWQTSA-N tert-butyl (Z)-but-2-enoate Chemical compound C\C=C/C(=O)OC(C)(C)C QHSPZGZEUDEIQM-WAYWQWQTSA-N 0.000 claims description 2
- QHSPZGZEUDEIQM-AATRIKPKSA-N tert-butyl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)(C)C QHSPZGZEUDEIQM-AATRIKPKSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000004160 Ammonium persulphate Substances 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 7
- 235000019395 ammonium persulphate Nutrition 0.000 description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 6
- 238000000113 differential scanning calorimetry Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000001632 sodium acetate Substances 0.000 description 6
- 235000017281 sodium acetate Nutrition 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- 238000006596 Alder-ene reaction Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- 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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Definitions
- the present invention refers to a waterborne homo or copolymer dispersion obtained by homo or copolymerisation in an aqueous medium of at least one alkyl crotonate and/or at least one crotonic acid.
- Emulsion polymerisation is well known in the art and frequently disclosed and discussed in the patent literature, in handbooks and encyclopaedias. Emulsion polymerisation is typically performed in an aqueous medium in the presence of a surfactant and a water-soluble initiator and is usually rapidly giving high molecular weight homo or copolymers at high solids content, typically 30-60%, and low dispersion viscosity.
- a surfactant typically a surfactant and a water-soluble initiator
- Traditional applications for these aqueous dispersions are mainly adhesives, binders for fibres, protective and decorative coatings, foam, paper coatings and thread and textile modifiers.
- the present invention accordingly refers to a novel waterborne homo or preferably copolymer dispersion obtained by homo or preferably copolymerisation in an aqueous medium of at least one alkyl crotonate or isocrotonate, preferably a Ci-Cis alkyl crotonate or isocrotonate, such as methyl crotonate, ethyl crotonate, n-butyl crotonate, isobutyl crotonate, t-butyl crotonate, 2-ethylhexyl crotonate, 2-propylheptyl crotonate, neopentyl crotonate, glycidyl crotonate, vinyl
- alkyl crotonates include alkyl dicrotonates and alkyl diisocrotonates of diols, such as ethylene glycol, 1 ,2-propanediol, 1,3-propanediol, butylene glycols, and 2-alkyl-l ,3-propanediols, 2,2-dialkyl-l,3-propanediols, such as neopentyl glycol and 2-ethyl-2-butyl- 1 ,3-propanediol.
- diols such as ethylene glycol, 1 ,2-propanediol, 1,3-propanediol, butylene glycols, and 2-alkyl-l ,3-propanediols, 2,2-dialkyl-l,3-propanediols, such as neopentyl glycol and 2-ethyl-2-butyl- 1 ,
- mono(iso)crotonates of diols mono, di and tri(iso)crotonates of triols and mono di, tri and higher (iso)crotonates of polyols can be included, such as trimethylolpropane mono, di or tricrotonate or isocrotonate.
- alkyl acrylates and/or alkyl methacrylates preferably Ci-C 18 alkyl acrylates or methacrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and/or acrylic acid and/or methacrylic acid, and/or polymerisable allyl, vinyl, maleic and/or diene monomers, such as, but not limited to, itaconic acid, cinnamic acid, maleic anhydride, fumaric acid, glycidyl acrylates, glycidyl methacrylates, acrylamides, methacrylamides, ethyl imidazolidon methacrylates, ethylene, propylene, styrene, divinylstyrene, vinylacetate, vinyl propionates, vinyl versatates, dibutyl
- the homo or copolymer dispersion of the present invention is yielded in either a one stage or a multistage emulsion homo or copolymerisation.
- Said emulsion polymerisation may for instance yield latex particles having a heterogeneous morphology, such as a core-shell morphology.
- core-shell morphologies are possible.
- spherical core-shell particles are made when a polymer made from a first monomer is more hydrophobic than a polymer made from a second monomer.
- dispersion according to the present invention include species comprising at least one polymerisable surfactant, such as a surfactant comprising at least one alkenyl group, and/or a conventional surfactant.
- a polymerisable surfactant such as a surfactant comprising at least one alkenyl group, and/or a conventional surfactant.
- a copolymer according to the present invention is such that the crotonate based content of the total content, with water and/or other solvents excluded, is 0.1-99.9%, such as 5-60%, 5-30% or 10-25%), by weight.
- Storage stability, glass transition temperature and particle size distribution are important parameters whose optima are to be found within the monomer content levels given above.
- crotonic acid and crotonic acid derivatives can be used together with mercaptans in the so called thiol-ene reaction to produce a crosslinked system.
- Thiol-enes can be part of hybrid systems that involve both thiol-enes and other types of systems, such as radical polymerised unsaturations. By this, the property range of the coatings can be expanded.
- Thiol-ene networks due to their almost perfect network structure that is much more uniform than even epoxy networks, can be fabricated to exhibit a wide range of benchmark properties including rubber-like materials with resiliencies of greater than 95%o, glassy materials with properties resembling traditional rubbery materials (i.e.
- cellulose can be modified, preferably covalently bonded, with crotonic acid and crotonic acid derivatives to obtain increased stability and/or a crosslinked structure.
- the present invention refers to the use of said novel waterborne homo or copolymer dispersion, as disclosed above, in binders for coatings, such as decorative and/or protective paints and lacquers, adhesives and glues.
- binders for coatings such as decorative and/or protective paints and lacquers, adhesives and glues.
- Initiator solution 25% by weight of ammonium persulphate in water, room temperature.
- Example 1 Performed as Example 1 with the difference that the monomer mixture consisted of ethyl crotonate, methyl methacrylate and acrylic acid.
- Example 1 Performed as Example 1 with the difference that the monomer mixture consisted of ethyl crotonate, methyl methacrylate, butyl acrylate and acrylic acid.
- Ammonium persulphate 2 Yielded product exibited following properties:
- Example 1 Performed as Example 1 with the difference that the monomer mixture consisted of ethyl crotonate, methyl methacrylate and acrylic acid.
- Example 1 Performed as Example 1 with the difference that the monomer mixture consisted of ethyl crotonate, methyl methacrylate and acrylic acid. Material Parts by weig
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
Disclosed is a waterbome polymer dispersion is obtained by homo or preferably copolymerisation, together with one or more other polymerisable monomer(s), in an aqueous medium of at least one alkyl crotonate, alkyl isocrotonate, crotonic acid and/or isocrotonic acid.
Description
WATERBOR E HOMO OR COPOLYMER DISPERSION
The present invention refers to a waterborne homo or copolymer dispersion obtained by homo or copolymerisation in an aqueous medium of at least one alkyl crotonate and/or at least one crotonic acid.
The most important industrial method for the manufacture of aqueous dispersion polymers is emulsion polymerisation. Emulsion polymerisation is well known in the art and frequently disclosed and discussed in the patent literature, in handbooks and encyclopaedias. Emulsion polymerisation is typically performed in an aqueous medium in the presence of a surfactant and a water-soluble initiator and is usually rapidly giving high molecular weight homo or copolymers at high solids content, typically 30-60%, and low dispersion viscosity. Traditional applications for these aqueous dispersions are mainly adhesives, binders for fibres, protective and decorative coatings, foam, paper coatings and thread and textile modifiers.
It has now quite unexpectedly been found that alkyl crotonates and/or crotonic acids can, despite previous assumptions and disclosures negating the possibility, yield excellent waterborne homo and copolymer dispersions for use as disclosed above. The present invention accordingly refers to a novel waterborne homo or preferably copolymer dispersion obtained by homo or preferably copolymerisation in an aqueous medium of at least one alkyl crotonate or isocrotonate, preferably a Ci-Cis alkyl crotonate or isocrotonate, such as methyl crotonate, ethyl crotonate, n-butyl crotonate, isobutyl crotonate, t-butyl crotonate, 2-ethylhexyl crotonate, 2-propylheptyl crotonate, neopentyl crotonate, glycidyl crotonate, vinyl crotonate, methyl isocrotonate, ethyl isocrotonate, n-butyl isocrotonate, isobutyl isocrotonate, t-butyl isocrotonate, 2-ethylhexyl isocrotonate, 2-propylheptyl isocrotonate, neopentyl isocrotonate, glycidyl isocrotonate, vinyl isocrotonate and/or at least one crotonic acid, such as crotonic acid and/or isocrotonic acid.
Further suitable alkyl crotonates include alkyl dicrotonates and alkyl diisocrotonates of diols, such as ethylene glycol, 1 ,2-propanediol, 1,3-propanediol, butylene glycols, and 2-alkyl-l ,3-propanediols, 2,2-dialkyl-l,3-propanediols, such as neopentyl glycol and 2-ethyl-2-butyl- 1 ,3-propanediol. Of course, also mono(iso)crotonates of diols, mono, di and tri(iso)crotonates of triols and mono di, tri and higher (iso)crotonates of polyols can be included, such as trimethylolpropane mono, di or tricrotonate or isocrotonate.
Further suitable monomers in a copolymerisation include, but are not limited to alkyl acrylates and/or alkyl methacrylates, preferably Ci-C18 alkyl acrylates or methacrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and/or acrylic acid and/or methacrylic acid, and/or polymerisable allyl, vinyl, maleic and/or diene monomers,
such as, but not limited to, itaconic acid, cinnamic acid, maleic anhydride, fumaric acid, glycidyl acrylates, glycidyl methacrylates, acrylamides, methacrylamides, ethyl imidazolidon methacrylates, ethylene, propylene, styrene, divinylstyrene, vinylacetate, vinyl propionates, vinyl versatates, dibutyl maleate and/or butadiene or isoprene.
The homo or copolymer dispersion of the present invention is yielded in either a one stage or a multistage emulsion homo or copolymerisation. Said emulsion polymerisation may for instance yield latex particles having a heterogeneous morphology, such as a core-shell morphology. When monomers of different solubility or hydrophobicity are used or when staged polymerisations are carried out, core-shell morphologies are possible. In staged polymerisations, spherical core-shell particles are made when a polymer made from a first monomer is more hydrophobic than a polymer made from a second monomer.
Further embodiments of the dispersion according to the present invention include species comprising at least one polymerisable surfactant, such as a surfactant comprising at least one alkenyl group, and/or a conventional surfactant.
A copolymer according to the present invention is such that the crotonate based content of the total content, with water and/or other solvents excluded, is 0.1-99.9%, such as 5-60%, 5-30% or 10-25%), by weight. Storage stability, glass transition temperature and particle size distribution are important parameters whose optima are to be found within the monomer content levels given above.
Furthermore, crotonic acid and crotonic acid derivatives can be used together with mercaptans in the so called thiol-ene reaction to produce a crosslinked system. Thiol-enes can be part of hybrid systems that involve both thiol-enes and other types of systems, such as radical polymerised unsaturations. By this, the property range of the coatings can be expanded. Thiol-ene networks, due to their almost perfect network structure that is much more uniform than even epoxy networks, can be fabricated to exhibit a wide range of benchmark properties including rubber-like materials with resiliencies of greater than 95%o, glassy materials with properties resembling traditional rubbery materials (i.e. glasses that bounce better than conventional crosslinked super balls), and high energy absorbing materials for personal protection. These properties can be advantageous also for coating applications. Yet furthermore, cellulose can be modified, preferably covalently bonded, with crotonic acid and crotonic acid derivatives to obtain increased stability and/or a crosslinked structure.
In a further aspect, the present invention refers to the use of said novel waterborne homo or copolymer dispersion, as disclosed above, in binders for coatings, such as decorative and/or protective paints and lacquers, adhesives and glues.
The following specific embodiments, Examples 1 -5, relating to preparations of polymers according to the present invention, are to be construed as merely illustrative and not limitative in any way whatsoever.
Example 1
Mixtures a), b) and c) were prepared according to the following:
a) Water, emulsifier Disponil® AES 72 (alkylaryl polyglycol ether sulphate, sodium salt, Cognis) and sodium acetate as buffer (calculated on 35% by weight on ammonium persulphate), heated to 80°C.
b) Monomer mixture: Ethyl crotonate, styrene and acrylic acid, room temperature.
c) Initiator solution: 25% by weight of ammonium persulphate in water, room temperature.
Procedure: a) was heated to 80°C and 10% of b) and c) were charged. Portions of b) and c) were every 20 minutes (during 4 hrs.) added. After completed addition, stirring at 80°C was carried out for one hour. Equipment: Teflon stirrer 100-150 rpm, oil bath and reaction vessel equipped with cooler and nitrogen inlet.
Following properties on yielded product were determined: Molecular weight (Mn) and molecular weight (Mw) by GPC (General Purpose Chromatography), polydispersity and glass transition temperature (Tg) by DSC (Differential Scanning Calorimetry).
Material Parts by weig
Water 477
Disponir AES 72 54
Sodium acetate 2 x 0.35
Ethyl crotonate 220
Styrene 220
Acrylic acid 25
Ammonium persulphate 2
Yielded product exibited following properties:
Mn, g/mol: 5800
Mw, g/mol: 17000
Polydispersity: 2.9
Tg, °C: 33
Example 2
Performed as Example 1 with the difference that the monomer mixture consisted of ethyl crotonate, methyl methacrylate and acrylic acid.
Material Parts by weig
Water 477
Disponil® AES 72 54
Sodium acetate 2 x 0.35
Ethyl crotonate 220
Methyl methacrylate 220
Acrylic acid 25
Ammonium persulphate 2
Yielded product exibited following properties:
Mn g/mol (GPC): 8500
Mw g/mol (GPC): 22000
Polydispersity: 2.6
Tg °C, (DSC): -2.6
Example 3
Performed as Example 1 with the difference that the monomer mixture consisted of ethyl crotonate, methyl methacrylate, butyl acrylate and acrylic acid.
Material Parts by weight
Water 477
Disponil® AES 72 54
Sodium acetate 2 x 0.35
Ethyl crotonate 86
Methyl methacrylate 225
Butyl acrylate 139
Acrylic acid 14
Ammonium persulphate 2
Yielded product exibited following properties:
Mn g/mol (GPC): 4300
Mw g/mol (GPC): 48000
Polydispersity: 1 1
Tg °C, (DSC): 4
Example 4
Performed as Example 1 with the difference that the monomer mixture consisted of ethyl crotonate, methyl methacrylate and acrylic acid.
Material Parts by weight
Water 477
Disponil® AES 72 54
Sodium acetate 2 x 0.35
Ethyl crotonate 86
methyl methacrylate 225
Butyl acrylate 139
Acrylic acid 14
Ammonium persulphate 2
Yielded product exibited following properties:
Mn g/mol (GPC): 1100
Mw g/mol (GPC): 158000
Polydispersity: 14.5
Tg °C, (DSC): 15
Example 5
Performed as Example 1 with the difference that the monomer mixture consisted of ethyl crotonate, methyl methacrylate and acrylic acid.
Material Parts by weig
Water 477
Disponil® AES 72 54 Sodium acetate 2 x 0.35 Ethyl crotonate 102 Vinyl acetate 348 Acrylic acid 14
Ammonium persulphate 2
Yielded product exibited following properties:
Mn g/mol (GPC): 900
Mw g/mol (GPC): 5400
Polydispersity: 6.3
Tg °C, (DSC): 10
Claims
1. A waterborne polymer dispersion characterised in, that it is obtained by homo or copolymerisation in an aqueous medium of at least one alkyl crotonate, alkyl isocrotonate, crotonic acid and/or isocrotonic acid.
2. A waterborne polymer dispersion according to Claim 1 characterised in, that it is obtained by homo or copolymerisation in an aqueous medium of at least one Ci-Ci8 alkyl crotonate and/or isocrotonate.
3. A waterborne polymer dispersion according to Claim 1 characterised in, that it is obtained by homo or copolymerisation in an aqueous medium of methyl crotonate, ethyl crotonate, n-butyl crotonate, isobutyl crotonate, t-butyl crotonate, 2-ethylhexyl crotonate, 2-propylheptyl crotonate, neopentyl crotonate, glycidyl crotonate, vinyl crotonate, methyl isocrotonate, ethyl isocrotonate, n-butyl isocrotonate, isobutyl isocrotonate, t-butyl isocrotonate, 2-ethylhexyl isocrotonate, 2-propylheptyl isocrotonate, neopentyl isocrotonate, glycidyl isocrotonate, vinyl isocrotonate and/or at least one crotonic acid, such as crotonic acid and/or isocrotonic acid.
4. A waterborne polymer dispersion according to Claim 1 characterised in, that it is obtained by homo or copolymerisation in an aqueous medium of at least one alkyl mono or dicrotonate and/or at least one alkyl mono or diisocrotonate of a diol.
5. A waterborne polymer dispersion according to claim 4 characterised in, that said diol is ethylene glycol, 1,2-propanediol, 1,3-propanediol and/or a butylene glycol.
6. A waterborne polymer dispersion according to claim 4 characterised in, that said diol is a 2-alkyl- 1,3-propanediol and/or a 2,2-dialkyl- 1,3-propanediol.
7. A waterborne polymer dispersion according to claim 4 characterised in, that said diol is neopentyl glycol and/or 2-ethyl-2-butyl-l,3-propanediol.
8. A waterborne polymer dispersion according to any of the Claims 1-7
characterised in, that said copolymerisation further employs at least one alkyl acrylate and/or alkyl methacrylate.
9. A waterborne polymer dispersion according to Claim 8 characterised in, that said alkyl acrylate or methacrylate is a Ci-Ci8 alkyl acrylate or methacrylate.
10. A waterborne polymer dispersion according to any of the Claims 1-7
characterised in, that said copolymerisation further employs methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and/or acrylic acid and/or methacrylic acid.
11. A waterborne polymer dispersion according to any of the Claims 1-10
c h arac t eri s e d i n, that said copolymerisation further employs at least one polymerisable allyl, vinyl, maleic and/or diene monomer.
12. A waterborne polymer dispersion according to any of the Claims 1-10
characteri s ed i n, that said copolymerisation further employs itaconic acid, cinnamic acid, maleic anhydride, fumaric acid, glycidyl acrylates, glycidyl methacrylates, acrylamide, methacrylamide, ethyl imidazolidon methacrylate, ethylene, propylene, styrene, divinylstyrene, vinylacetate, vinyl propionate, vinyl versatate, dibutyl maleate, butadiene and/or isoprene.
13. A waterborne polymer dispersion according to any of the Claims 1-12
c h ar ac t e r i s e d i n, that said copolymerisation further employs at least one polymerisable surfactant and/or a conventional surfactant.
14. A waterborne polymer dispersion according to any of the Claims 1-13
characterised in, that said polymer dispersion is yielded in a one stage emulsion homo or copolymerisation.
15. A waterborne polymer dispersion according to any of the Claims 1-13
c h ar a c t e ri s e d i n, that said polymer dispersion is yielded in a multistage emulsion homo or copolymerisation.
16. A waterborne polymer dispersion according to Claim 14 or 15 characterised in, that said emulsion polymerisation yields latex particles having a heterogeneous morphology.
17. A waterborne polymer dispersion according to Claim 14 or 15 characterised in, that said emulsion polymerisation yields latex particles having a core-shell morphology.
18. Use of a waterborne polymer dispersion according to any of the Claims 1-17, in binders for coatings.
19. Use of a waterborne polymer dispersion according to any of the Claims 1-17, in decorative and/or protective paints and lacquers, adhesives and glues.
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| Application Number | Priority Date | Filing Date | Title |
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| US201161509304P | 2011-07-19 | 2011-07-19 | |
| US61/509,304 | 2011-07-19 |
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| WO2013012365A1 true WO2013012365A1 (en) | 2013-01-24 |
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| PCT/SE2012/000100 WO2013012365A1 (en) | 2011-07-19 | 2012-06-29 | Waterborne homo or copolymer dispersion |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104387515A (en) * | 2014-11-13 | 2015-03-04 | 常熟市万象涂料有限公司 | Interface agent and preparation method thereof |
| CN105085777A (en) * | 2015-07-17 | 2015-11-25 | 中国石油天然气股份有限公司 | Polystyrene 2-ethyl crotonate and preparation method and application thereof |
| CN109868094A (en) * | 2019-01-24 | 2019-06-11 | 东莞泰康聚合物科技有限公司 | A kind of new waterproof lotion and preparation method instead of ethylene-vinyl acetate lotion |
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