NO802786L - IRRIGATION SOLUTION OR DISPERSION OF A STYRENE / MALEIC ACID ANHYDRID COPOLYMER, PROCEDURE FOR ITS PREPARATION AND ITS USE - Google Patents
IRRIGATION SOLUTION OR DISPERSION OF A STYRENE / MALEIC ACID ANHYDRID COPOLYMER, PROCEDURE FOR ITS PREPARATION AND ITS USEInfo
- Publication number
- NO802786L NO802786L NO802786A NO802786A NO802786L NO 802786 L NO802786 L NO 802786L NO 802786 A NO802786 A NO 802786A NO 802786 A NO802786 A NO 802786A NO 802786 L NO802786 L NO 802786L
- Authority
- NO
- Norway
- Prior art keywords
- copolymer
- dispersion
- solution
- styrene
- maleic anhydride
- Prior art date
Links
- 229920001577 copolymer Polymers 0.000 title claims description 78
- 239000006185 dispersion Substances 0.000 title claims description 59
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 32
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title 1
- 229940113601 irrigation solution Drugs 0.000 title 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 title 1
- 239000011976 maleic acid Substances 0.000 title 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 title 1
- 239000000243 solution Substances 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 239000012874 anionic emulsifier Substances 0.000 claims description 2
- 238000012674 dispersion polymerization Methods 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000003995 emulsifying agent Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 239000000178 monomer Substances 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000003863 ammonium salts Chemical class 0.000 description 8
- 229920001567 vinyl ester resin Polymers 0.000 description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- -1 vinyl halides Chemical class 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 125000005396 acrylic acid ester group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 235000019395 ammonium persulphate Nutrition 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 2
- ICCVOKMKWYGITK-UHFFFAOYSA-N 1-(2-methylprop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C(C)=C ICCVOKMKWYGITK-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- JJULABXIXFRDCQ-UHFFFAOYSA-N 2,3,4-tritert-butylphenol Chemical class CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1C(C)(C)C JJULABXIXFRDCQ-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- TURPNXCLLLFJAP-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl hydrogen sulfate Chemical compound OCCOCCOCCOS(O)(=O)=O TURPNXCLLLFJAP-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- QWYXNPUTSOVWEA-UHFFFAOYSA-N 2-octylphenol;sodium Chemical compound [Na].CCCCCCCCC1=CC=CC=C1O QWYXNPUTSOVWEA-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005157 alkyl carboxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- QJQZEJFUIOWFMS-UHFFFAOYSA-N formaldehyde;sulfanediol Chemical class O=C.OSO QJQZEJFUIOWFMS-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NUGJFLYPGQISPX-UHFFFAOYSA-N peroxydiphosphoric acid Chemical class OP(O)(=O)OOP(O)(O)=O NUGJFLYPGQISPX-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical class OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
Description
Oppfinnelsen vedrører en vandig oppløsning eller dispersjon av en styren/maleinsyreanhydrid-kopolymer, en fremgangsmåte til dens fremstilling og dens anvendelse. The invention relates to an aqueous solution or dispersion of a styrene/maleic anhydride copolymer, a method for its preparation and its use.
Fremstillingen av kopolymerer av maleinsyreanhydrid med vinylforbindelser som styren har vært kjent lenge (sml. f.eks. Ind. Eng. Chem 41 (1949), s. 1509). The preparation of copolymers of maleic anhydride with vinyl compounds such as styrene has been known for a long time (cf. e.g. Ind. Eng. Chem 41 (1949), p. 1509).
Disse kopolymerer oppløses under alkalitilsetning i vann,These copolymers dissolve under the addition of alkali in water,
da deres virkning som pigmentdispergeringsmiddel, beskyttel-seskolloid, fortykningsmiddel eller klister forutsetter en saltdannelse. since their action as a pigment dispersant, protective colloid, thickener or glue requires salt formation.
Videre er det kjent kopolymer av styren og maleinsyreanhydrid som har et styren/maleinsyreanhydrid-molforhold fra 1:1 til 4:1, en gjennomsnittlig molekylvekt fra 400 til 100.000 og et smeltepunkt fra 80 til 300°C (sml. US patent 34 44 151). Disse kopolymerer omsettes med aminer til nitro-genholdige kopolymerer som omtrent er uoppløselige i vann eller vandige, alkaliske medier, de anvendes som emulgatorer ved emulsjonspolymerisasjon av vinylmonomerer. Furthermore, copolymers of styrene and maleic anhydride are known which have a styrene/maleic anhydride molar ratio of 1:1 to 4:1, an average molecular weight of 400 to 100,000 and a melting point of 80 to 300°C (cf. US patent 34 44 151 ). These copolymers are reacted with amines to nitrogen-containing copolymers which are approximately insoluble in water or aqueous, alkaline media, they are used as emulsifiers in the emulsion polymerization of vinyl monomers.
Videre det er kjent at ved fremstillingen av klebestoffer på stivelsesbasis anvendes styren/maleinsyre-anhydr id-kopolymer er , hvis styren/maleinsyreanhydrid-molforhold utgjør 1:1 til 3:1 og hvis molekylvekt varierer mellom 1600 og 50000 (sml. US patent 39 39 108). Disse kopolymerer fremstilles vanligvis ved oppløsningspolymerisasjon i et aromatisk hydrokarbon i nærvær av en radikaldanner som kata-lysator ved en temperatur fra 75 til 300°C. De kan etter tilsetning av ammoniakk eller alkalihydroksyd inntil en pH-verdi fra 8 til 11 oppløses under oppvarming i vann. Furthermore, it is known that in the production of starch-based adhesives, styrene/maleic anhydride copolymers are used, whose styrene/maleic anhydride molar ratio amounts to 1:1 to 3:1 and whose molecular weight varies between 1,600 and 50,000 (cf. US patent 39 39 108). These copolymers are usually prepared by solution polymerization in an aromatic hydrocarbon in the presence of a radical generator as a catalyst at a temperature from 75 to 300°C. After adding ammonia or alkali hydroxide, they can be dissolved under heating in water until a pH value of 8 to 11 is reached.
Oppfinnelsens oppgave er tilveiebringelse av en vandig oppløsning eller dispersjon av en maleinsyreanhydrid-kopolymer som ikke viser alkalisk reaksjon og som er egnet som emulgatoroppløsning eller -dispersjon for kunststoffdispersjoner. The object of the invention is to provide an aqueous solution or dispersion of a maleic anhydride copolymer which does not show an alkaline reaction and which is suitable as an emulsifier solution or dispersion for plastic dispersions.
Oppfinnelsen vedrører nå en vandig oppløsning eller dispersjon av en hydrolysert kopolymer av styren og maleinsyreanhydrid med et styren/maleinsyreanhydrid-molforhold på større enn 1:1 og en molekylvekt (tallgjennomsnitt) på mer enn 400 og oppløsningen eller dispersjonen erkarakterisert vedat molforholdet ligger i området fra 1,5:1 The invention now relates to an aqueous solution or dispersion of a hydrolyzed copolymer of styrene and maleic anhydride with a styrene/maleic anhydride molar ratio of greater than 1:1 and a molecular weight (number average) of more than 400 and the solution or dispersion is characterized by the molar ratio being in the range from 1.5:1
til 6:1, molekylvekten utgjør 500 til 80000, 1 til 60% av karboksylgruppen av kopolymeren er nøytralisert og oppløs-ningens eller dispersjonens pH-verdi er mindre enn 7. to 6:1, the molecular weight is 500 to 80,000, 1 to 60% of the carboxyl group of the copolymer is neutralized and the pH value of the solution or dispersion is less than 7.
Videre vedrører oppfinnelsen en fremgangsmåte til fremstilling av en vandig oppløsning eller dispersjon av et hydrolysert kopolymer av styren og maleinsyreanhydrid, som har et styren/maleinsyreanhydrid-molforhold på større enn 1:1 og en molekylvekt (tallgjennomsnitt) på mer enn 400 ved hydrolyse av en styren/maleinsyreanhydrid-kopolymer og delvis nøytralisering med et uorganisk nøytraliseringsmiddel, idet fremgangsmåten erkarakterisert vedat en kopolymer Furthermore, the invention relates to a method for producing an aqueous solution or dispersion of a hydrolyzed copolymer of styrene and maleic anhydride, which has a styrene/maleic anhydride molar ratio of greater than 1:1 and a molecular weight (number average) of more than 400 upon hydrolysis of a styrene/maleic anhydride copolymer and partial neutralization with an inorganic neutralizing agent, the method being characterized by a copolymer
med et styren/maleinsyreanhydrid-molforhold fra 1,5:1 til 6:1 og en molekylvekt fra 500 til 80000 oppvarmes i nærvær av vann og i nærvær av så meget ammoniakk eller et alkalihydroksyd eller et jordalkalihydroksyd eller sinkoksyd til en temperatur fra 75 til 250°C at 1 til 60% av kopolymerens karbpksylgrupper nøytraliseres. with a styrene/maleic anhydride molar ratio of from 1.5:1 to 6:1 and a molecular weight of from 500 to 80,000 is heated in the presence of water and in the presence of so much ammonia or an alkali hydroxide or an alkaline earth hydroxide or zinc oxide to a temperature of from 75 to 250°C that 1 to 60% of the copolymer's carboxyl groups are neutralized.
Endelig vedrører oppfinnelsen også anvendelsen av ovennevnte oppløsning eller dispersjon som stabilisator-oppløsning eller -dispersjon for vandige dispersjoner og ved dispersjonspolymerisering av vinylforbindelser. Finally, the invention also relates to the use of the above-mentioned solution or dispersion as a stabilizer solution or dispersion for aqueous dispersions and in the dispersion polymerization of vinyl compounds.
Den ifølge oppfinnelsen anvendte styren/malein-syreanhydr id-kopolymer har en molekylvekt (tallgjennomsnitt) fra 500 til 80000, fortrinnsvis fra 800 til 30000. Styren/ maleinsyreanhydrid-molforholdet utgjør 1,5:1 til 6:1, fortrinnsvis 1,6:1 til 4:1. The styrene/maleic anhydride copolymer used according to the invention has a molecular weight (number average) from 500 to 80,000, preferably from 800 to 30,000. The styrene/maleic anhydride molar ratio amounts to 1.5:1 to 6:1, preferably 1.6: 1 to 4:1.
Styren/maleinsyreanhydr id-kopolymeren oppvarmes ifølge oppfinnelsen i nærvær av vann og i nærvær av et uorganisk nøytralisasjonsmiddel ved en temperatur fra 75 til 250°C, fortrinnsvis 85 til 180°C og hydrolyseres. De derved dannede frie karboksylgrupper av kopolymeren nøytraliseres derved til 1 til 60%, fortrinnsvis 6 til 50%. Ved denne alkaliske behandling av den kopolymere utgjør dens konsentrasjon 5 til 50 vekt-%, fortrinnsvis 10 til 30 vekt-% According to the invention, the styrene/maleic anhydride copolymer is heated in the presence of water and in the presence of an inorganic neutralizing agent at a temperature from 75 to 250°C, preferably 85 to 180°C and hydrolyzed. The resulting free carboxyl groups of the copolymer are thereby neutralized to 1 to 60%, preferably 6 to 50%. In this alkaline treatment of the copolymer, its concentration is 5 to 50% by weight, preferably 10 to 30% by weight
(referert til samlet mengde av vann og kopolymer). Alt etter konsentrasjon og sammensetning av den kopolymere samt den (referred to total amount of water and copolymer). Depending on the concentration and composition of the copolymer as well as the
anvendte temperatur varer behandlingen 5 minutter til 5 timer, fortrinnsvis 10 til 200 minutter. En høy styrenmengde i kopolymeren, en høy kopolymerkonsentrasjon og en lav behandlingstemperatur krever generelt en øket behandlingstid, temperature used, the treatment lasts 5 minutes to 5 hours, preferably 10 to 200 minutes. A high amount of styrene in the copolymer, a high copolymer concentration and a low treatment temperature generally require an increased treatment time,
ved variasjon av de angitte parametere kan følgelig behand-lingstiden endres. Arbeidet under inertgass, f.eks. nitrogen er å anbefale. by varying the specified parameters, the treatment time can therefore be changed. Work under inert gas, e.g. nitrogen is recommended.
Styren/maleinsyreanhydr id-kopolymeren inneholder eventuelt dessuten en eller flere ytterligere monomerer i en mengde inntil 20 mol-% (referert til den samlede monomer-mengde) innpolymerisert. Egnet er olefinisk umettede forbindelser som vinylester, vinyleter, akrylsyreester og umettede karboksylsyrer som akrylsyre, metakrylsyre, itakon-syre, krotonsyre, vinylsulfonsyre og N-metakryloylamino-propansulfonsyre. The styrene/maleic anhydride copolymer optionally also contains one or more additional monomers in an amount of up to 20 mol-% (referred to the total monomer amount) polymerized. Suitable are olefinically unsaturated compounds such as vinyl ester, vinyl ether, acrylic acid ester and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, vinylsulfonic acid and N-methacryloylamino-propanesulfonic acid.
Som uorganisk nøytral iseringsmiddel tjener ammoniumhydroksyd eller et alkalihydroksyd, f.eks. litiumhydroksyd, natriumhydroksyd og kaliumhydroksyd eller et jordalkalihydroksyd, f.eks. magnesiumhydroksyd og kalsium-hydroksyd, samt sinkoksyd. Istedenfor et enkelt nøytrali-ser ingsmiddel kan det også anvendes en blanding av flere nøytraliseringsmidler. De anvendte mengder av nøytraliserings-middel er å velge således at det fås den ønskede nøytrali-seringsgrad, den ligger i området fra 0,02 til 1,2 baseekvivalent, fortrinnsvis 0,12 til 1 baseekvivalent (referert til et mol maleinsyreanhydrid i kopolymeren). Alt etter nøytraliseringsmidlet pluss type og mengde fås en kopolymer-oppløsning eller -dispersjon, for fremstillingen av en opp-løsning anvendes en høyere mengde nøytraliseringsmiddel enn for fremstilling av en dispersjon. Ammonium hydroxide or an alkali hydroxide, e.g. lithium hydroxide, sodium hydroxide and potassium hydroxide or an alkaline earth hydroxide, e.g. magnesium hydroxide and calcium hydroxide, as well as zinc oxide. Instead of a single neutralizing agent, a mixture of several neutralizing agents can also be used. The amounts of neutralizing agent used are to be chosen so that the desired degree of neutralization is obtained, it lies in the range from 0.02 to 1.2 base equivalent, preferably 0.12 to 1 base equivalent (referred to a mole of maleic anhydride in the copolymer) . Depending on the neutralizing agent plus type and amount, a copolymer solution or dispersion is obtained, for the preparation of a solution a higher amount of neutralizing agent is used than for the preparation of a dispersion.
For fremstilling av en sur oppløsning av en hydro-lyser t styren/maleinsyreanhydrid-kopolymer lønner det seg å gjennomføre den alkaliske behandling i nærvær av en emulgator fortrinnsvis en anionisk emulgator. Som emulgatorer egner det seg spesielt alkalisalter eller ammoniumsalter av alkylsulfonsyrer, arylsulfonsyrer eller alkylarylsulfonsyrer samt de tilsvarende svovelsyrer, forsforsyrer eller fosfon-syrer, idet de nevnte forbindelser eventuelt har oksyetylen- enheter•mellom den eventuelle hydrokarbonrest, fortrinnsvis lo til 18 karbonatomer og en anionisk gruppe, de oksetylerte forbindelser inneholder fortrinnsvis 5 til 30 etylenoksyd-enheter. Eksempler på egnede emulgatorer er natriumlauryl-sulfat, natriumoktylfenolglykoletersulfat, natriumdodecyl-benzensulfonat, natriumlauryldiglykolsulfat såmt ammonium-saltene av oksetylerte og sulfaterte tri-t-butylfenol, t-butylfenol og nonylfenol. For the preparation of an acidic solution of a hydrolyser t styrene/maleic anhydride copolymer, it pays to carry out the alkaline treatment in the presence of an emulsifier, preferably an anionic emulsifier. Alkaline salts or ammonium salts of alkylsulfonic acids, arylsulfonic acids or alkylarylsulfonic acids and the corresponding sulfuric acids, phosphoric acids or phosphonic acids are particularly suitable as emulsifiers, the compounds mentioned possibly having oxyethylene units between the possible hydrocarbon residue, preferably up to 18 carbon atoms and an anionic group , the oxyethylated compounds preferably contain 5 to 30 ethylene oxide units. Examples of suitable emulsifiers are sodium lauryl sulfate, sodium octylphenol glycol ether sulfate, sodium dodecyl benzene sulfonate, sodium lauryl diglycol sulfate as well as the ammonium salts of oxytylated and sulfated tri-t-butylphenol, t-butylphenol and nonylphenol.
Emulgatoren anvendes i en mengde fra 3 til 100 vekt-%, fortrinnsvis 5 til 25 vekt-% (referert til styren/ maleinsyreanhydrid-kopolymeren). The emulsifier is used in an amount from 3 to 100% by weight, preferably 5 to 25% by weight (referred to the styrene/maleic anhydride copolymer).
Kopolymer-dispersjonen ifølge oppfinnelsen kari også overføres i en oppløsning, idet den etter tilsetning av en, emulgator av ovennevnte type oppvarmes til en temperatur innen området av ovennevnte behandlingstemperatur. The copolymer dispersion according to the invention is also transferred in a solution, since after the addition of an emulsifier of the above-mentioned type, it is heated to a temperature within the range of the above-mentioned treatment temperature.
Den vandige oppløsning eller dispersjon av en hydrolysert kopolymer ifølge oppfinnelsen av styren og maleinsyreanhydrid viser en sur reaksjon. Dens pH-verdi er mindre enn 7 og fortrinnsvis mindre enn 6, spesielt fordelaktig er en oppløsning eller dispersjon med en pH-verdi fra 2,0 til 5,7. Kopolymerinnholdet av oppløsningen eller dispersjonen ligger i området fra 5 til 50 vekt-%, fortrinnsvis 10 til 30 vekt-%. Viskositeten av oppløsningen eller dispersjonen utgjør 20 til 20000 mPa•s, fortrinnsvis 50 til 3000 mPa•s (målt ifølge Epprecht). The aqueous solution or dispersion of a hydrolyzed copolymer according to the invention of styrene and maleic anhydride shows an acidic reaction. Its pH value is less than 7 and preferably less than 6, particularly advantageous is a solution or dispersion with a pH value of from 2.0 to 5.7. The copolymer content of the solution or dispersion is in the range from 5 to 50% by weight, preferably 10 to 30% by weight. The viscosity of the solution or dispersion is 20 to 20,000 mPa•s, preferably 50 to 3,000 mPa•s (measured according to Epprecht).
Kopolymeroppløsningen eller -dispersjonen ifølge oppfinnelsen anvendes som emulgeringsmiddel, dispergerings-middel, klister, limingsmiddel, fortykningsmiddel, floknings-middel og hydrofoberingsmiddel og på tekstil-, påstryknings-, klebestoff- og papirsektoren som belegnings- og bindemiddel. På materialer som tre, papir, keramikk, metall eller kunst-stoff påføres den oppløste eller dispergerte kopolymer etter påføring av oppløsningen eller dispersjonen ved fjerning av vann eller ved elektrokjemisk utskillelse. The copolymer solution or dispersion according to the invention is used as an emulsifier, dispersant, adhesive, adhesive, thickener, flocculant and hydrophobic agent and in the textile, coating, adhesive and paper sectors as a coating and binding agent. On materials such as wood, paper, ceramics, metal or plastic, the dissolved or dispersed copolymer is applied after application of the solution or dispersion by removal of water or by electrochemical separation.
Oppløsningen eller dispersjonen egner seg utmer-ket til stabilisering av vandige dispersjoner av naturlige eller syntetiske, uorganiske eller organiske stoffer, f.eks. cellulose, kunststoffer, pigmenter og fyllstoffer. Kopolymer-oppløsningen eller -dispersjonen anvendes videre ved suspensjons- eller emulsjonspolymerisasjon av vinylforbindelser, spesielt vinylester og akrylsyreester. De således stabiliserte kunststoffdispersjoner viser en øket stabilitet overfor skjærekrefter og pigmenter. Tilsetningstidspunktet av stabilisatoroppløsningen eller -dispersjonen er derved av underordnet betydning, tilsetningen kan med samme resultat foregå under fremstillingen av dispersjonen som skal stabi-liseres eller senere. The solution or dispersion is excellently suited for stabilizing aqueous dispersions of natural or synthetic, inorganic or organic substances, e.g. cellulose, plastics, pigments and fillers. The copolymer solution or dispersion is further used in suspension or emulsion polymerization of vinyl compounds, especially vinyl esters and acrylic acid esters. The thus stabilized plastic dispersions show an increased stability against cutting forces and pigments. The time of addition of the stabilizer solution or dispersion is therefore of secondary importance, the addition can with the same result take place during the preparation of the dispersion to be stabilized or later.
Kopolymer-oppløsningen eller -dispersjonen ifølge oppfinnelsen anvendes fremfor alt ved polymer isasjon av vinylforbindelser som polymeriseres i vandig medium under sure betingelser. Spesielt egnede monomerer er olefiniske umettede forbindelser med formel The copolymer solution or dispersion according to the invention is used above all in the polymerization of vinyl compounds which are polymerized in an aqueous medium under acidic conditions. Particularly suitable monomers are olefinic unsaturated compounds of the formula
1 2 hvor R betyr et hydrogenatom eller en metylrest og R betyr (a) en alkylkarboksyrest med 2-18, fortrinnsvis 2-12 karbonatomer, (b) en alkoksyrest med 1-4 karbonatomer, (c) en nitrilgruppe, (d) et halogenatom, fortrinnsvis et klor-atom, (e) en karboksylgruppe eller sulfogruppe, (f) en alkoksykarbonylrest med 2-12, fortrinnsvis 2-9 karbonatomer, (g) en aminokarbonylrest, (h) et hydrogenatom, (i) en fenyl-rest eller (k) en vinylrest. Som eksempler for slike olefiniske umettede forbindelser skal nevnes (a) vinylestere av alifatiske karboksylsyrer med 2-18, fortrinnsvis 2-12 karbonatomer, f.eks. vinylacetat, vinyl-propionat, vinylbutyrat, vinylpivalat, vinylisononat, vinyllaurat og vinyldekanat samt vinylester av en blanding av monokarboksylsyrer med 9-11 karbonatomer, (b) vinyletere, f.eks. vinylmetyleter, vinyletyleter og 1 2 where R means a hydrogen atom or a methyl residue and R means (a) an alkylcarboxy residue with 2-18, preferably 2-12 carbon atoms, (b) an alkoxy acid residue with 1-4 carbon atoms, (c) a nitrile group, (d) a halogen atom, preferably a chlorine atom, (e) a carboxyl group or sulfo group, (f) an alkoxycarbonyl radical with 2-12, preferably 2-9 carbon atoms, (g) an aminocarbonyl radical, (h) a hydrogen atom, (i) a phenyl- residue or (k) a vinyl residue. Examples of such olefinic unsaturated compounds should be mentioned (a) vinyl esters of aliphatic carboxylic acids with 2-18, preferably 2-12 carbon atoms, e.g. vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl isononate, vinyl laurate and vinyl decanate as well as vinyl esters of a mixture of monocarboxylic acids with 9-11 carbon atoms, (b) vinyl ethers, e.g. vinyl methyl ether, vinyl ethyl ether and
vinyl-n-butyleter,vinyl n-butyl ether,
(c) akrylnitril og metakrylnitril,(c) acrylonitrile and methacrylonitrile,
(d) vinylhalogenider, f.eks. vinylklorid og allylklorid,(d) vinyl halides, e.g. vinyl chloride and allyl chloride,
(e) umettede monokarboksylsyrer, f.eks. akrylsyre, metakrylsyre og vinylsulfonsyre, (f) akrylsyreestere eller metakrylsyreestere av enverdige alkanoler med 1-11, fortrinnsvis 1-8 karbonatomer, f.eks. metylakrylat, etylakrylat, butylakrylåt, 2-etylheksyl-akrylat, metylmetakrylat, etylmetakrylat, butylmetakry-lat, heksylmetakr-ylat, oktylmetakrylat og 2-etylheksyl-metakrylat, (g) akrylsyreamider og metakrylsyreamider, f.eks. akrylsyre-amid, N-metylolakrylsyreamid, metakrylsyreamid og (e) unsaturated monocarboxylic acids, e.g. acrylic acid, methacrylic acid and vinyl sulphonic acid, (f) acrylic acid esters or methacrylic acid esters of monovalent alkanols with 1-11, preferably 1-8 carbon atoms, e.g. methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate and 2-ethylhexyl methacrylate, (g) acrylic acid amides and methacrylic acid amides, e.g. acrylic acid amide, N-methylolacrylic acid amide, methacrylic acid amide and
N-metylolmetakrylsyreamid,N-methylol methacrylic acid amide,
(h) etylen,(h) ethylene,
(i) styren og metylstyren eller(i) styrene and methylstyrene or
(k) butadien og isopren.(k) butadiene and isoprene.
Spesielt egnede monomerer er vinylesterne (a), vinyleterene (b), vinylhalogenidene (d) og akrylsyreestere og metakrylsyreestere (f). De monomere anvendes enkeltvis eller i blanding med hverandre, monomerkombinasjoner dannes eksempelvis av et akrylsyreester og en metakrylsyreester, Particularly suitable monomers are the vinyl esters (a), the vinyl ethers (b), the vinyl halides (d) and acrylic acid esters and methacrylic acid esters (f). The monomers are used individually or in a mixture with each other, monomer combinations are formed, for example, from an acrylic acid ester and a methacrylic acid ester,
en akryl- eller metakrylsyreester og en vinylester samt en blanding av forskjellige vinylestere, spesielt vinylacetat og vinylester av en blanding av monokarboksylsyre med 9-11 karbonatomer, videre av vinyl og etylen samt av vinylacetat, etylen og vinylklorid. an acrylic or methacrylic acid ester and a vinyl ester as well as a mixture of different vinyl esters, especially vinyl acetate and vinyl ester of a mixture of monocarboxylic acid with 9-11 carbon atoms, further of vinyl and ethylene as well as of vinyl acetate, ethylene and vinyl chloride.
Polymer isasjonen foregår vanligvis i nærvær avThe polymerization usually takes place in the presence of
en radikaldannende initiator, fortrinnsvis en peroksydfor-bindelse eller en alifatisk azoforbindelse. Initiatoren er oljeoppløselig eller fortrinnsvis vannoppløselig, den anvendes i en mengde på 0,05 til 2 vekt-%, fortrinnsvis 0,1 til 1 vekt-% (referert til samlet mengde monomer). Det egner seg spesielt hydrogenperoksyd, alkali- eller ammoniumsalter av persvovelsyre, peroksydisvovelsyre, eller peroksy-difosfor syre, f.eks. natriumpersulfat, kaliumperoksydisulfat og ammoniumperoksydisulfat, videre alkylhydroperoksyder som t-butylhydroperoksyd, dialkylperoksyder som di-t-butylperoksyd, diacylperoksyder som diacetylperoksyd, dilauroylperoksyd og a radical-forming initiator, preferably a peroxide compound or an aliphatic azo compound. The initiator is oil-soluble or preferably water-soluble, it is used in an amount of 0.05 to 2% by weight, preferably 0.1 to 1% by weight (referred to the total amount of monomer). Hydrogen peroxide, alkali or ammonium salts of persulfuric acid, peroxydisulfuric acid or peroxy-diphosphoric acid are particularly suitable, e.g. sodium persulfate, potassium peroxydisulfate and ammonium peroxydisulfate, further alkyl hydroperoxides such as t-butyl hydroperoxide, dialkyl peroxides such as di-t-butyl peroxide, diacyl peroxides such as diacetyl peroxide, dilauroyl peroxide and
dibenzoylperoksyd, samt azodiisosmørsyrenitril, azodikarbon-amid og azo-Y/Y<1->bis(4-cyanvaleriansyre). Initiatoren anvendes eventuelt sammen med et reduksjonsmiddel, spesielt med et ammoniumsalt, alkalisalt eller jordalkalisalt av en reduserende virkende svovelholdig syre, fortrinnsvis egner det seg sulfiter, bisulfiter, pyrosulfiter, ditioniter, tio-sulfater og formaldehydsulfoksylater. Mengden av reduksjons-midlet utgjør 0,05 til 20 vekt-%, fortrinnsvis 0,5 til 10 vekt-% (referert til styren/maleinsyreanhydrid-kopolymer). dibenzoyl peroxide, as well as azodiisobutyric nitrile, azodicarbonamide and azo-Y/Y<1->bis(4-cyanvaleric acid). The initiator is optionally used together with a reducing agent, especially with an ammonium salt, alkali salt or alkaline earth salt of a reducing-acting sulphurous acid, preferably sulphites, bisulphites, pyrosulphites, dithionites, thiosulphates and formaldehyde sulphoxylates are suitable. The amount of the reducing agent amounts to 0.05 to 20% by weight, preferably 0.5 to 10% by weight (referred to styrene/maleic anhydride copolymer).
For økning av polymer isasjonshastigheten er det fordelaktig å anvende en oppløsning eller dispersjon av en hydrolysert styren/maleinsyreanhydrid-kopolymer, hvis fremstilling er gjennomført i nærvær av et sulfit. Som sulfiter er det egnet nøytrale eller sure salter av svovelsyrling eller pyrosvovelsyrling, spesielt ammoniumsalter, alkalisalter og jordalkalisalter. Sulfitet anvendes eventuelt i en mengde fra 0,05 til 20 vekt-%, fortrinnsvis 0,5 til 10 vekt-% To increase the polymerization rate, it is advantageous to use a solution or dispersion of a hydrolyzed styrene/maleic anhydride copolymer, the preparation of which is carried out in the presence of a sulphite. Suitable sulphites are neutral or acidic salts of sulfuric acid or pyrosulphuric acid, especially ammonium salts, alkali salts and alkaline earth salts. Sulfite is optionally used in an amount from 0.05 to 20% by weight, preferably 0.5 to 10% by weight
(referert til styren/maleinsyreanhydrid-kopolymer).(referred to styrene/maleic anhydride copolymer).
Ved emulsjonspolymerisasjon anvendes oppløsningen eller dispersjonen av den hydrolyserte styren/maleinsyreanhydrid i en slik mengde at kopolymeren foreligger i en mengde fra 0,1 til 10 vekt-%, fortrinnsvis 0,5 til 5 vekt-% In emulsion polymerization, the solution or dispersion of the hydrolyzed styrene/maleic anhydride is used in such an amount that the copolymer is present in an amount of from 0.1 to 10% by weight, preferably 0.5 to 5% by weight
(referert til den samlede mengde monomer). Ved suspensjons-polymerisasjon er det nok med 0,01 til 2 vekt-%, fortrinnsvis 0,01 til 1 vekt-% av komonomer (referert til samlet mengde monomer). Polymer isasjonen foregår hver gang ved en temperatur fra 25 til 90°C, fortrinnsvis 40 til 75°C. Alt etter type og mengde av de deltagende monomerer ligger polymerisa-sjonstiden i området fra 2-8 timer, fortrinnsvis 2,5 til 5 timer. (referred to the total amount of monomer). In suspension polymerization, 0.01 to 2% by weight, preferably 0.01 to 1% by weight, of comonomer (referred to the total amount of monomer) is sufficient. The polymerization takes place each time at a temperature from 25 to 90°C, preferably 40 to 75°C. Depending on the type and quantity of the participating monomers, the polymerization time is in the range from 2 to 8 hours, preferably 2.5 to 5 hours.
De resulterende polymerdispersjoner er i høy grad stabile overfor skjaerekrefter og viser meget godt pig-mentbindeevne. De finner derfor fremfor alt anvendelse som .bindemiddeldispersjoner i påstrykningsmidler, spesielt dis-per sjonsmalinger og papirstrykemasser. Det dermed behandlede papir utmerker seg ved høy nuppefasthet og strykevannfasthet. The resulting polymer dispersions are highly stable against shear forces and show very good pigment binding ability. They are therefore primarily used as binder dispersions in coating agents, especially dispersion paints and paper coating compounds. The paper treated in this way is distinguished by high pilling resistance and ironing water resistance.
Oppfinnelsen skal forklares nærmere ved hjelp av noen eksempler hvor prosentangivelsene hver gang refererer The invention will be explained in more detail with the help of some examples to which the percentages each time refer
seg til vekt.to weight.
Eksempel 1Example 1
150 g av en kopolymer av styren og maleinsyreanhydrid (molforhold 2:1), som har en midlere molekylvekt 150 g of a copolymer of styrene and maleic anhydride (molar ratio 2:1), which has an average molecular weight
på 1700, oppvarmes sammen med 790 g vann og 7,05 g etsnatron i et rørekar med tilbakeløpskjøler i 2 timer ved en temperatur på 95-100°C og avkjøles deretter til værelsestemperatur. Man får en klar oppløsning med en pH-verdi på 4,7 og et polymer innhold på 16,5%. Den hydrolyserte kopolymers karboksylgrupper er nøytralisert til 18%. of 1700, is heated together with 790 g of water and 7.05 g of caustic soda in a stirrer with a reflux condenser for 2 hours at a temperature of 95-100°C and then cooled to room temperature. You get a clear solution with a pH value of 4.7 and a polymer content of 16.5%. The hydrolyzed copolymer's carboxyl groups are neutralized to 18%.
Eksempel 2Example 2
a) Eksempel 1 gjentas, imidlertid anvendes istedenfor 7,05 g etsnatron nå 3,52 g etsnatron og istedenfor 790 g vann, 720 g vann. Dessuten filtreres reaksjons-blandingen etter avkjøling til værelsestemperatur, derved blir det tilbake et residuum på 30,9 g (etter tørkning). Man får som filtrat en dispersjon med en pH-verdi på 4,1 og et polymer innhold på 14,9%. b) 8 g av den ifølge a) dannede dispersjon oppvarmes sammen med 2 g av en 15 %-ig vandig oppløsning av natrium-laurylsulfat ved 70°C, idet den kopolymere går i oppløs-ning. c) 8 g av den ifølge a) dannede dispersjon oppvarmes sammen med 2 g av en 15 %-ig vandig oppløsning av ammoniumsaltet av en med 25 mol etylenoksyd oksetylert og deretter sulfatert nonylfenol som emulgator ved 80°C, idet den a) Example 1 is repeated, however, instead of 7.05 g of caustic soda, 3.52 g of caustic soda is now used and instead of 790 g of water, 720 g of water. In addition, the reaction mixture is filtered after cooling to room temperature, thereby leaving a residue of 30.9 g (after drying). A dispersion with a pH value of 4.1 and a polymer content of 14.9% is obtained as filtrate. b) 8 g of the dispersion formed according to a) is heated together with 2 g of a 15% aqueous solution of sodium lauryl sulfate at 70°C, the copolymer dissolving. c) 8 g of the dispersion formed according to a) is heated together with 2 g of a 15% aqueous solution of the ammonium salt of a nonylphenol oxyethylated with 25 mol of ethylene oxide and then sulfated as an emulsifier at 80°C, the
kopolymere går i oppløsning.copolymers dissolve.
Eksempel 3Example 3
300 g av en kopolymer av styren og maleinsyreanhydrid (molforhold 3:1) med en midlere molekylvekt på 300 g of a copolymer of styrene and maleic anhydride (molar ratio 3:1) with an average molecular weight of
1900 oppvarmes sammen med 1680 g vann og 29,3 g etsnatron i et rørekar med tilbakeløpskjøler i 2 timer ved en temperatur på 96°C og avkjøles deretter til værelsestemperatur. Man får en oppløsning med en pH-verdi på 6,8 og et polymer innhold på 16,7%. Den hydrolyserte kopolymers karboksylgrupper 1900 is heated together with 1680 g of water and 29.3 g of caustic soda in a stirrer with a reflux condenser for 2 hours at a temperature of 96°C and then cooled to room temperature. A solution with a pH value of 6.8 and a polymer content of 16.7% is obtained. The carboxyl groups of the hydrolyzed copolymer
er nøytralisert til 50%.is neutralized to 50%.
Eksempel 4Example 4
I et rørekar med tilbakeløpskjøler oppvarmesHeat in a mixing vessel with reflux condenser
150 g av en kopolymer av styren og maleinsyreanhydrid (molforhold 3:1) med en midlere molekylvekt på 1900 sammen med 790 g vann og 25 g av en 25 %-ig vandig ammoniakkoppløsning i 2 timer ved en temperatur på 100°C og avkjøles deretter til værelsestemperatur. Man får en oppløsning med en pH-verdi på 6,8 og et polymer innhold på 16,1%. Den hydrolyserte kopolymers karboksylgrupper er nøytralisert til 50%. 150 g of a copolymer of styrene and maleic anhydride (molar ratio 3:1) with an average molecular weight of 1900 together with 790 g of water and 25 g of a 25% aqueous ammonia solution for 2 hours at a temperature of 100°C and then cooled to room temperature. A solution with a pH value of 6.8 and a polymer content of 16.1% is obtained. The hydrolyzed copolymer's carboxyl groups are neutralized to 50%.
Eksempel 5Example 5
a) 150 g av en kopolymer av styren og maleinsyreanhydrid (molforhold 3:1) med en midlere molekylvekt på a) 150 g of a copolymer of styrene and maleic anhydride (molar ratio 3:1) with an average molecular weight of
1900 oppvarmes sammen med 720 g vann og 7,3 g etsnatron i et rørekar med tilbakeløpskjøler i 3 timer ved en temperatur på 97°C og avkjøles deretter til værelsestemperatur. Man får en dispersjon med en pH-verdi på 5,6 og et polymer innhold på 17,6%. Den hydrolyserte kopolymers karboksylgrupper er nøytralisert til 25%. Den midlere diameter av de dispergerte polymerpartikler utgjør 0,038 ym. b) 8 g av den ifølge a) dannede dispersjon oppvarmes med 2 g av en 15 %-ig vandig oppløsning av natriumlauryl-sulfat ved 85°C, derved går den kopolymere i oppløsning. c) 8 g av den ifølge a) dannede dispersjon oppvarmes med 2 g av en 15 %-ig vandig oppløsning av emulgatoren fra 1900 is heated together with 720 g of water and 7.3 g of caustic soda in a stirrer with a reflux condenser for 3 hours at a temperature of 97°C and then cooled to room temperature. A dispersion with a pH value of 5.6 and a polymer content of 17.6% is obtained. The carboxyl groups of the hydrolyzed copolymer are neutralized to 25%. The average diameter of the dispersed polymer particles is 0.038 µm. b) 8 g of the dispersion formed according to a) is heated with 2 g of a 15% aqueous solution of sodium lauryl sulfate at 85°C, whereby the copolymer dissolves. c) 8 g of the dispersion formed according to a) is heated with 2 g of a 15% aqueous solution of the emulsifier from
eksempel 2 c) til 90°C, derved går kopolymeren i oppløs-ning. example 2 c) to 90°C, whereby the copolymer dissolves.
Eksempel. 6 til 8Example. 6 to 8
Hver gang 150 g av en kopolymer av styren og maleinsyreanhydrid (molforhold 3:1) med midlere molekylvekt på 1900 oppvarmes sammen med hver gang 720 g vann og forskjellige mengder litiumhydroksyd i et rørekar med tilbake-løpskjøler av forskjellig lengde ved en temperatur på 97°C Each time 150 g of a copolymer of styrene and maleic anhydride (molar ratio 3:1) with an average molecular weight of 1900 is heated together with each time 720 g of water and different amounts of lithium hydroxide in a stirrer with a reflux condenser of different lengths at a temperature of 97° C
og avkjøles deretter til værelsestemperatur. Detaljer og and then cooled to room temperature. Details and
egenskaper av den hver gang oppnådde oppløsning eller dispersjon fremgår av tabell 1. properties of the solution or dispersion obtained each time are shown in table 1.
Eksempel 9 Example 9
150 g av en kopolymer av styren og maleinsyreanhydrid (molforhold 3:1) med en midlere molekylvekt på 150 g of a copolymer of styrene and maleic anhydride (molar ratio 3:1) with an average molecular weight of
1900 oppvarmes sammen med 1300 g vann, 7,3 g etsnatron,1900 is heated together with 1300 g of water, 7.3 g of caustic soda,
125 g av en 30 %-ig oppløsning av emulgatoren fra eksempel 2 c) og 12 g natriumpyrosulfit under nitrogenoverleir ing i et rørekar med tilbakeløpskjøler i 2 timer ved en temperatur på 96°C og avkjøles deretter til værelsestemperatur. 125 g of a 30% solution of the emulsifier from example 2 c) and 12 g of sodium pyrosulphite under a nitrogen overlay in a stirring vessel with a reflux condenser for 2 hours at a temperature of 96°C and then cooled to room temperature.
Man får en oppløsning med en pH-verdi på 5,3 og et polymer-innhold 13,3%. Den hydrolyserte kopolymers karboksylgrupper er nøytralisert til 25%. You get a solution with a pH value of 5.3 and a polymer content of 13.3%. The carboxyl groups of the hydrolyzed copolymer are neutralized to 25%.
Oppløsninger blir for anvendelse ved polymerisa-sjon av vinylacetat innstilt med vann til en konsentrasjon på 7,8%. For use in the polymerization of vinyl acetate, solutions are adjusted with water to a concentration of 7.8%.
Eksempel 10Example 10
150 g av kopolymer av styren og maleinsyreanhydrid (molforhold 2:1) med en midlere molekylvekt på 1700 oppvarmes sammen med 1300 g vann, 7,3 g etsnatron, 125 g av en 30 %-ig vandig oppløsning av emulgatoren fra eksempel 2 c) og 12 g 150 g of copolymer of styrene and maleic anhydride (molar ratio 2:1) with an average molecular weight of 1700 is heated together with 1300 g of water, 7.3 g of caustic soda, 125 g of a 30% aqueous solution of the emulsifier from example 2 c) and 12 g
natriumpyrosulfit under nitrogenoverleir ing i et rørekar med tilbakeløpskjøler i 2 timer ved en temperatur på 96°C og avkjøles deretter til værelsestemperatur. Man får en oppløs-ning med en pH-verdi på 4,3 og et polymer innhold på 13%. sodium pyrosulphite under a blanket of nitrogen in a stirrer with a reflux condenser for 2 hours at a temperature of 96°C and then cooled to room temperature. A solution with a pH value of 4.3 and a polymer content of 13% is obtained.
Den hydrolyserte kopolymers karboksylgrupper er nøytralisert til 18,6%. The hydrolyzed copolymer's carboxyl groups are neutralized to 18.6%.
Oppløsningen blir for anvendelse ved polymerisa-sjon av vinylacetat innstilt med vann til en konsentrasjon på 7,8%. For use in the polymerization of vinyl acetate, the solution is adjusted with water to a concentration of 7.8%.
Anvendelseseksempel 1Application example 1
I et rørekar has 510 g vann, 1,77 g av en 6 %-ig vandig natriumalkylsulfonatoppløsning (midlere kjedelengde i alkylgruppen: 12-14 karbonatomer) og 2 g av en 30 %-ig vandig oppløsning av ammoniumsaltet av en med 25 mol etylenoksyd oksetylerte og deretter sulfatert nonylfenol og spyles med nitrogen. Etter tilsetning av en oppløsning av 2,25 g ammoniumpersulfat i 20 g vann oppvarmes blandingen til en temperatur på 50°C. Under overholdelse av denne temperatur tilføres jevnt til blandingen i løpet av 3 timer adskilt fra hverandre 750 g vinylacetat og en oppløsning av 0,39 g natriumformaldehydsulfoksylat i 50 g vann. Under den første time tilsettes i tillegg igjen samme mengde av emulgator-kombinasjonen i løpet av de derpå følgende to timer tildoseres dessuten 100 g av den ifølge eksempel 9 dannede kopolymer-oppløsning samt 1,87 g av ovennevnte alkylsulfonatoppløsning og 21,2 g av ovennevnte 30 %-ig ammoniumsaltoppløsning. Deretter blandes blandingen med en oppløsning av 0,75 g ammoniumpersulfat i 30 g vann og oppvarmes i 30 minutter ved en temperatur på 75°C og avkjøles deretter til værelsestemperatur. In a mixing vessel there are 510 g of water, 1.77 g of a 6% aqueous sodium alkylsulfonate solution (average chain length in the alkyl group: 12-14 carbon atoms) and 2 g of a 30% aqueous solution of the ammonium salt of one with 25 mol of ethylene oxide oxyethylated and then sulfated nonylphenol and flushed with nitrogen. After adding a solution of 2.25 g of ammonium persulphate in 20 g of water, the mixture is heated to a temperature of 50°C. While maintaining this temperature, 750 g of vinyl acetate and a solution of 0.39 g of sodium formaldehyde sulfoxylate in 50 g of water are added evenly to the mixture over the course of 3 hours, separated from each other. During the first hour, the same amount of the emulsifier combination is added again, during the following two hours, 100 g of the copolymer solution formed according to example 9 is added, as well as 1.87 g of the above-mentioned alkylsulfonate solution and 21.2 g of the above-mentioned 30% ammonium salt solution. The mixture is then mixed with a solution of 0.75 g of ammonium persulphate in 30 g of water and heated for 30 minutes at a temperature of 75°C and then cooled to room temperature.
Man får en koagulatfri polyvinylacetat-dispersjon som innstilles med 3,2 g 12,5 % ammoniakkoppløsning på en pH-verdi på 6. Dispersjonens faststoffinnhold utgjør 50,8%, og polymerpartiklene har en midlere diameter på 0,22 ym. Dispersjonen er skjærestabil, for etter 2 minutters omrøring med en hurtigrører (5000 omdr./min.) trer ingen koagulat-dannelse og den polymeres midlere partikkelstørrelse endrer seg ikke. A coagulate-free polyvinyl acetate dispersion is obtained which is adjusted with 3.2 g of 12.5% ammonia solution to a pH value of 6. The solids content of the dispersion amounts to 50.8%, and the polymer particles have an average diameter of 0.22 um. The dispersion is shear stable, because after 2 minutes of stirring with a high-speed stirrer (5000 rpm) no coagulate formation occurs and the average particle size of the polymer does not change.
Anvendelseseksempel 2Application example 2
Anvendelseseksempel 1 gjentas, imidlertid anvendes istedenfor den ifølge eksempel 9 dannede kopolymeroppløsning nå den ifølge eksempel 10 dannede kopolymeroppløsning. Den hver gang dannede vinylacetatdispersjon er koagulatfri. Dispersjonens faststoffinnhold utgjør 50,4% og polymerpartiklene har en midlere diameter på 0,18 ym. Dispersjonen er skjærestabil (prøve analog anvendelseseksempel 1). Application example 1 is repeated, however, instead of the copolymer solution formed according to example 9, the copolymer solution formed according to example 10 is now used. The vinyl acetate dispersion formed each time is coagulant-free. The solids content of the dispersion amounts to 50.4% and the polymer particles have an average diameter of 0.18 um. The dispersion is shear stable (sample analogous to application example 1).
Sammenligningseksempel 1Comparative example 1
1620 g av den i eksempel 3 anvendte styren/malein-syreanhydr id-kopolymer omrøres i 8024 g vann under tilsetning av 316 g etsnatron 6 3/4 timer ved en temperatur på 80°C. 1620 g of the styrene/maleic anhydride copolymer used in example 3 is stirred in 8024 g of water with the addition of 316 g of caustic soda for 6 3/4 hours at a temperature of 80°C.
Den etter avkjøling til værelsestemperatur dannede suspensjon filtreres, derved fremkommer et fast residuum på 47 g. Filtratet har en pH-verdi på 10,0 og et polymer innhold på 18,7%. Den hydrolyserte kopolymers karboksylgrupper er nøytralisert til 100%. The suspension formed after cooling to room temperature is filtered, resulting in a solid residue of 47 g. The filtrate has a pH value of 10.0 and a polymer content of 18.7%. The carboxyl groups of the hydrolyzed copolymer are neutralized to 100%.
Sammenligningseksempel 2Comparative example 2
Eksempel 4 gjentas, idet oppvarmingstemperaturen imidlertid bare utgjør 70°C. Derved går bare 50% av styren/ maleinsyreanhydrid-kopolymeren i oppløsning. Oppløsningen viser en pH-verdi på 5,2. Example 4 is repeated, but the heating temperature is only 70°C. Thereby, only 50% of the styrene/maleic anhydride copolymer dissolves. The solution shows a pH value of 5.2.
Sammenligningseksempel 3Comparative example 3
Eksempel 4 gjentas, idet oppvarmingstemperaturen imidlertid bare utgjør 70°C og det anvendes en dobbelt ammo-niakkoppløsningsmengde. Den dannede oppløsning viser en pH-verdi på 9,3. Example 4 is repeated, however, the heating temperature is only 70°C and a double amount of ammonia solution is used. The formed solution shows a pH value of 9.3.
Sammenligningseksempel 4Comparative example 4
Anvendelseseksempel 1 gjentas, idet den ifølge eksempel 9 dannede kopolymeroppløsning erstattes med vann. Den dannede polyvinylacetat-dispersjon koagulerer ved under-søkelse på skjærestabilitet. Application example 1 is repeated, replacing the copolymer solution formed according to example 9 with water. The polyvinyl acetate dispersion formed coagulates when tested for shear stability.
Sammenligningseksempel 5Comparative example 5
Anvendelseseksempel 1 gjentas, idet den ifølge eksempel 9 dannede kopolymeroppløsning erstattes med en tilsvarende fremstilt oppløsning av en styren/maleinsyreanhydrid-kopolymer (molforhold 1:1) med en midlere molekylvekt på 1600, hvis karboksylgrupper etter hydrolysen er nøytralisert til 12,3%. Den dannede polyvinylacetatdispersjon koagulerer ved undersøkelse'på sk jærestabilitet. Application example 1 is repeated, with the copolymer solution formed according to example 9 being replaced with a correspondingly prepared solution of a styrene/maleic anhydride copolymer (molar ratio 1:1) with an average molecular weight of 1600, whose carboxyl groups have been neutralized to 12.3% after hydrolysis. The formed polyvinyl acetate dispersion coagulates when tested for so-called lime stability.
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| DE19792938429 DE2938429A1 (en) | 1979-09-22 | 1979-09-22 | AQUEOUS SOLUTION OR DISPERSION OF A STYRENE / MALEIC ACID ANHYDRIDE COPOLYMER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
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| DE3631814A1 (en) * | 1986-09-19 | 1988-03-31 | Basf Ag | LIGHTLY CROSSLINKED, WATER-SOLUBLE POLYMAL ACID, METHOD FOR THE PRODUCTION AND USE THEREOF |
| ES2116264T3 (en) * | 1989-06-06 | 1998-07-16 | Pluss Stauffer Ag | VERY CONCENTRATED AQUEOUS SUSPENSION OF MINERALS AND / OR LOADS AND / OR PIGMENTS. |
| IT1236966B (en) * | 1989-10-25 | 1993-05-07 | Ausidet Srl | PROCESS FOR THE PRODUCTION OF AQUEOUS SOLUTIONS OF ANTI-INCRUSTATION AGENTS AND SOLUTIONS SO OBTAINED |
| JPH07157524A (en) * | 1993-11-24 | 1995-06-20 | Union Carbide Chem & Plast Technol Corp | Vinyl copolymer containing macromonomer |
| FI991295A (en) * | 1999-06-07 | 2000-12-08 | Neste Chemicals Oy | A process for preparing styrene-maleic hydride copolymers |
| EP1405865A1 (en) * | 2002-10-04 | 2004-04-07 | DSM IP Assets B.V. | Process for preparing a polymer dispersion |
| JP5207097B2 (en) * | 2006-06-16 | 2013-06-12 | 星光Ｐｍｃ株式会社 | Filler modifier, filler slurry and paper making method |
| JP5515217B2 (en) * | 2008-01-11 | 2014-06-11 | 東洋インキＳｃホールディングス株式会社 | Dispersant, and pigment composition and pigment dispersion using the same |
| JP5614786B2 (en) * | 2013-05-09 | 2014-10-29 | 株式会社Adeka | Novel polymer and non-aqueous electrolyte secondary battery using the polymer |
| KR20160086888A (en) * | 2013-12-27 | 2016-07-20 | 코니카 미놀타 가부시키가이샤 | Acrylic resin film and method for manufacturing same, polarizing plate protective film, and polarizing plate and liquid crystal display device including polarizing plate protective film |
| JP7115427B2 (en) * | 2018-07-11 | 2022-08-09 | 荒川化学工業株式会社 | Tackifying resin emulsion, water-based adhesive/adhesive composition, and adhesive/adhesive sheet |
| WO2023286481A1 (en) * | 2021-07-15 | 2023-01-19 | サンノプコ株式会社 | Dispersant and water-based coating composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2490489A (en) * | 1944-02-03 | 1949-12-06 | Du Pont | Process for copolymerizing maleic anhydride and styrene |
| US3444151A (en) * | 1965-09-07 | 1969-05-13 | Sinclair Research Inc | Styrene-maleic anhydride-amine polymers as emulsifiers in polymerization of vinyl monomers |
| GB1414918A (en) * | 1973-02-14 | 1975-11-19 | Ciba Geigy Uk Ltd | Treatment of water to prevent the deposition of scale |
| US3835122A (en) * | 1973-04-25 | 1974-09-10 | Atomic Energy Commission | Novel polystyrene product having rapid-post-irradiation decay of conductivity and process of making same |
| US3939108A (en) * | 1974-12-16 | 1976-02-17 | National Starch And Chemical Corporation | Cold water resistant starch-based adhesive containing styrene-maleic anhydride resin and fixed alkali |
| JPS5299104A (en) * | 1976-02-17 | 1977-08-19 | Toyo Ink Mfg Co | Composition of water dispersive material |
| JPS54107945A (en) * | 1978-02-14 | 1979-08-24 | Toagosei Chem Ind Co Ltd | Aqueous dispersion of finely granulated polymer |
-
1979
- 1979-09-22 DE DE19792938429 patent/DE2938429A1/en not_active Withdrawn
-
1980
- 1980-09-16 ES ES495100A patent/ES495100A0/en active Granted
- 1980-09-18 FI FI802934A patent/FI72990C/en not_active IP Right Cessation
- 1980-09-18 EP EP80105591A patent/EP0025979B1/en not_active Expired
- 1980-09-18 AT AT80105591T patent/ATE3555T1/en not_active Application Discontinuation
- 1980-09-18 DE DE8080105591T patent/DE3063516D1/en not_active Expired
- 1980-09-19 ZA ZA00805810A patent/ZA805810B/en unknown
- 1980-09-19 IE IE1958/80A patent/IE50353B1/en not_active IP Right Cessation
- 1980-09-19 PT PT71820A patent/PT71820B/en unknown
- 1980-09-19 CA CA000360619A patent/CA1161581A/en not_active Expired
- 1980-09-19 DK DK399380A patent/DK156579C/en active
- 1980-09-19 JP JP12939380A patent/JPS5647412A/en active Granted
- 1980-09-19 BR BR8005999A patent/BR8005999A/en unknown
- 1980-09-19 NO NO802786A patent/NO802786L/en unknown
- 1980-09-19 AR AR282593A patent/AR222101A1/en active
- 1980-09-19 AU AU62551/80A patent/AU537112B2/en not_active Ceased
- 1980-09-22 MX MX184014A patent/MX156364A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0336854B2 (en) | 1991-06-03 |
| FI72990B (en) | 1987-04-30 |
| DK156579B (en) | 1989-09-11 |
| DK399380A (en) | 1981-03-23 |
| ES8105356A1 (en) | 1981-06-16 |
| JPS5647412A (en) | 1981-04-30 |
| FI72990C (en) | 1987-08-10 |
| AR222101A1 (en) | 1981-04-15 |
| CA1161581A (en) | 1984-01-31 |
| EP0025979A1 (en) | 1981-04-01 |
| BR8005999A (en) | 1981-03-31 |
| MX156364A (en) | 1988-08-15 |
| ATE3555T1 (en) | 1983-06-15 |
| PT71820B (en) | 1981-10-23 |
| DE2938429A1 (en) | 1981-04-09 |
| AU537112B2 (en) | 1984-06-07 |
| DE3063516D1 (en) | 1983-07-07 |
| FI802934A (en) | 1981-03-23 |
| ES495100A0 (en) | 1981-06-16 |
| AU6255180A (en) | 1981-04-09 |
| IE50353B1 (en) | 1986-04-02 |
| DK156579C (en) | 1990-01-29 |
| ZA805810B (en) | 1981-10-28 |
| EP0025979B1 (en) | 1983-05-25 |
| PT71820A (en) | 1980-10-01 |
| IE801958L (en) | 1981-03-22 |
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