CN111836841B - 水溶性共聚物 - Google Patents
水溶性共聚物 Download PDFInfo
- Publication number
- CN111836841B CN111836841B CN201880090606.5A CN201880090606A CN111836841B CN 111836841 B CN111836841 B CN 111836841B CN 201880090606 A CN201880090606 A CN 201880090606A CN 111836841 B CN111836841 B CN 111836841B
- Authority
- CN
- China
- Prior art keywords
- water
- monomers
- ethylenically unsaturated
- weight
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 96
- 239000000178 monomer Substances 0.000 claims abstract description 132
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000003368 amide group Chemical group 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims description 64
- 239000000084 colloidal system Substances 0.000 claims description 51
- 229920000642 polymer Polymers 0.000 claims description 42
- 239000006185 dispersion Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 31
- -1 sulfoalkyl itaconate Chemical compound 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 8
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 5
- 239000001530 fumaric acid Substances 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920003176 water-insoluble polymer Polymers 0.000 claims description 5
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 4
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 claims description 4
- DMZPTAFGSRVFIA-UHFFFAOYSA-N 3-[tris(2-methoxyethoxy)silyl]propyl 2-methylprop-2-enoate Chemical compound COCCO[Si](OCCOC)(OCCOC)CCCOC(=O)C(C)=C DMZPTAFGSRVFIA-UHFFFAOYSA-N 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 4
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 4
- UXYBXUYUKHUNOM-UHFFFAOYSA-M ethyl(trimethyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(C)C UXYBXUYUKHUNOM-UHFFFAOYSA-M 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 4
- UOKUUKOEIMCYAI-UHFFFAOYSA-N trimethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C(C)=C UOKUUKOEIMCYAI-UHFFFAOYSA-N 0.000 claims description 4
- NFUDTVOYLQNLPF-UHFFFAOYSA-M trimethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCCC[N+](C)(C)C NFUDTVOYLQNLPF-UHFFFAOYSA-M 0.000 claims description 4
- CVZIDTRJINIGGZ-UHFFFAOYSA-N 2-methoxypropan-2-yloxysilane Chemical compound COC(C)(C)O[SiH3] CVZIDTRJINIGGZ-UHFFFAOYSA-N 0.000 claims description 3
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 239000008199 coating composition Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000123 paper Substances 0.000 claims description 3
- 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
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000010954 inorganic particle Substances 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-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
- 239000004576 sand Substances 0.000 claims description 2
- 238000004513 sizing Methods 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000004964 sulfoalkyl group Chemical group 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- YVLFRAOEBHFMTI-UHFFFAOYSA-N trimethyl-[2-[(prop-2-enoylamino)methoxy]ethyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOCNC(=O)C=C YVLFRAOEBHFMTI-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 101100041681 Takifugu rubripes sand gene Proteins 0.000 claims 1
- 239000008394 flocculating agent Substances 0.000 claims 1
- 229920005601 base polymer Polymers 0.000 description 24
- 239000007787 solid Substances 0.000 description 16
- 239000003995 emulsifying agent Substances 0.000 description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- 125000002091 cationic group Chemical group 0.000 description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 11
- 150000003863 ammonium salts Chemical class 0.000 description 10
- 125000000129 anionic group Chemical group 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 description 10
- 229920001567 vinyl ester resin Polymers 0.000 description 10
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 150000001340 alkali metals Chemical class 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical class CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 8
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 6
- IOMDIVZAGXCCAC-UHFFFAOYSA-M diethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](CC)(CC)CC=C IOMDIVZAGXCCAC-UHFFFAOYSA-M 0.000 description 6
- 239000004815 dispersion polymer Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920003169 water-soluble polymer Polymers 0.000 description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 5
- 239000003125 aqueous solvent Substances 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical class OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000151 polyglycol Polymers 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229920004482 WACKER® Polymers 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical class OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NEYTXADIGVEHQD-UHFFFAOYSA-N 2-hydroxy-2-(prop-2-enoylamino)acetic acid Chemical compound OC(=O)C(O)NC(=O)C=C NEYTXADIGVEHQD-UHFFFAOYSA-N 0.000 description 2
- YHSYGCXKWUUKIK-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C=C YHSYGCXKWUUKIK-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 2
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- KCTMTGOHHMRJHZ-UHFFFAOYSA-N n-(2-methylpropoxymethyl)prop-2-enamide Chemical compound CC(C)COCNC(=O)C=C KCTMTGOHHMRJHZ-UHFFFAOYSA-N 0.000 description 2
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
- GOPSAMYJSPYXPL-UHFFFAOYSA-N prop-2-enyl n-(hydroxymethyl)carbamate Chemical compound OCNC(=O)OCC=C GOPSAMYJSPYXPL-UHFFFAOYSA-N 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 2
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- IDXCKOANSQIPGX-UHFFFAOYSA-N (acetyloxy-ethenyl-methylsilyl) acetate Chemical compound CC(=O)O[Si](C)(C=C)OC(C)=O IDXCKOANSQIPGX-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- KNJOXNMRJUPXJT-UHFFFAOYSA-N 12,12-dimethoxydodecoxy(ethenyl)silane Chemical compound COC(OC)CCCCCCCCCCCO[SiH2]C=C KNJOXNMRJUPXJT-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- GWRKYBXTKSGXNJ-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxyperoxy)propane Chemical compound CC(C)COOOCC(C)C GWRKYBXTKSGXNJ-UHFFFAOYSA-N 0.000 description 1
- TWYISXLZCIVDDW-UHFFFAOYSA-N 2-methyl-n-(2-methylpropoxymethyl)prop-2-enamide Chemical compound CC(C)COCNC(=O)C(C)=C TWYISXLZCIVDDW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- UMSFRTCUQPFZFA-UHFFFAOYSA-N 3-(3-sulfopropoxycarbonyl)but-3-enoic acid Chemical compound OC(=O)CC(=C)C(=O)OCCCS(O)(=O)=O UMSFRTCUQPFZFA-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- NYUTUWAFOUJLKI-UHFFFAOYSA-N 3-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-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
- SJIBSEBLLOLBMW-UHFFFAOYSA-N 8,8-dimethoxyoctoxy(ethenyl)silane Chemical compound COC(OC)CCCCCCCO[SiH2]C=C SJIBSEBLLOLBMW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229920000945 Amylopectin Polymers 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000011632 Caseins Human genes 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GHTLTFFZHMSQSC-UHFFFAOYSA-N N-(2-trimethoxysilylethyl)prop-2-enamide Chemical compound C(C=C)(=O)NCC[Si](OC)(OC)OC GHTLTFFZHMSQSC-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- XRLWQTOZMISADO-UHFFFAOYSA-N [diacetyloxy(prop-2-enyl)silyl] acetate Chemical compound CC(=O)O[Si](CC=C)(OC(C)=O)OC(C)=O XRLWQTOZMISADO-UHFFFAOYSA-N 0.000 description 1
- VITIHTHZBVSMSI-UHFFFAOYSA-N [diacetyloxy-[3-(prop-2-enoylamino)propyl]silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)CCCNC(=O)C=C VITIHTHZBVSMSI-UHFFFAOYSA-N 0.000 description 1
- KTVHXOHGRUQTPX-UHFFFAOYSA-N [ethenyl(dimethyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(C)C=C KTVHXOHGRUQTPX-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 229940071162 caseinate Drugs 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 1
- OTFXLPHXAADAKO-UHFFFAOYSA-N didodecoxy(prop-2-enoxy)silane Chemical compound C(=C)CO[SiH](OCCCCCCCCCCCC)OCCCCCCCCCCCC OTFXLPHXAADAKO-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical class OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- QMUOYZCDQUNRJS-UHFFFAOYSA-N dioctoxy(prop-2-enoxy)silane Chemical compound C(=C)CO[SiH](OCCCCCCCC)OCCCCCCCC QMUOYZCDQUNRJS-UHFFFAOYSA-N 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002118 epoxides Chemical group 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
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- MLVRYXJUYPBRSQ-UHFFFAOYSA-N ethenyl(trihexoxy)silane Chemical compound CCCCCCO[Si](OCCCCCC)(OCCCCCC)C=C MLVRYXJUYPBRSQ-UHFFFAOYSA-N 0.000 description 1
- NNBRCHPBPDRPIT-UHFFFAOYSA-N ethenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C=C NNBRCHPBPDRPIT-UHFFFAOYSA-N 0.000 description 1
- QZOSZICRWGJQRX-UHFFFAOYSA-N ethenyl-dimethoxy-(2-methylpropyl)silane Chemical compound CO[Si](C=C)(OC)CC(C)C QZOSZICRWGJQRX-UHFFFAOYSA-N 0.000 description 1
- JEWCZPTVOYXPGG-UHFFFAOYSA-N ethenyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)C=C JEWCZPTVOYXPGG-UHFFFAOYSA-N 0.000 description 1
- NUFVQEIPPHHQCK-UHFFFAOYSA-N ethenyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)C=C NUFVQEIPPHHQCK-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000005670 ethenylalkyl group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229940014259 gelatin Drugs 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000004569 hydrophobicizing agent Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NQVJUHCFWKRBCA-UHFFFAOYSA-N methyl 2-hydroxy-2-(2-methylprop-2-enoylamino)acetate Chemical compound COC(=O)C(O)NC(=O)C(C)=C NQVJUHCFWKRBCA-UHFFFAOYSA-N 0.000 description 1
- JMSTYCQEPRPFBF-UHFFFAOYSA-N methyl 2-methoxy-2-(prop-2-enoylamino)acetate Chemical compound COC(=O)C(OC)NC(=O)C=C JMSTYCQEPRPFBF-UHFFFAOYSA-N 0.000 description 1
- LDTLDBDUBGAEDT-UHFFFAOYSA-N methyl 3-sulfanylpropanoate Chemical compound COC(=O)CCS LDTLDBDUBGAEDT-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- WOSHDWLEPRMIPR-UHFFFAOYSA-N n-(3-aminopropyl)prop-2-enamide;hydrochloride Chemical compound [Cl-].[NH3+]CCCNC(=O)C=C WOSHDWLEPRMIPR-UHFFFAOYSA-N 0.000 description 1
- JUGMHUQFSYYJTB-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)prop-2-enamide Chemical compound CCO[Si](OCC)(OCC)CCCNC(=O)C=C JUGMHUQFSYYJTB-UHFFFAOYSA-N 0.000 description 1
- XGHNWFFWGDCAHZ-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)prop-2-enamide Chemical compound CO[Si](OC)(OC)CCCNC(=O)C=C XGHNWFFWGDCAHZ-UHFFFAOYSA-N 0.000 description 1
- VERHEKWGDRQWPH-UHFFFAOYSA-N n-(trimethoxysilylmethyl)prop-2-enamide Chemical compound CO[Si](OC)(OC)CNC(=O)C=C VERHEKWGDRQWPH-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- GUNSHNXZPCSGAU-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]prop-2-enamide Chemical compound CO[Si](C)(OC)CCCNC(=O)C=C GUNSHNXZPCSGAU-UHFFFAOYSA-N 0.000 description 1
- AGRSZGPFUNJIPW-UHFFFAOYSA-N n-[3-[methoxy(dimethyl)silyl]propyl]prop-2-enamide Chemical compound CO[Si](C)(C)CCCNC(=O)C=C AGRSZGPFUNJIPW-UHFFFAOYSA-N 0.000 description 1
- BQHUUHKPGWUHNS-UHFFFAOYSA-N n-[[dimethoxy(2-methylpropyl)silyl]oxymethyl]prop-2-enamide Chemical compound CC(C)C[Si](OC)(OC)OCNC(=O)C=C BQHUUHKPGWUHNS-UHFFFAOYSA-N 0.000 description 1
- XFOBMOZBCGIRDL-UHFFFAOYSA-N n-[[dimethoxy(propyl)silyl]oxymethyl]prop-2-enamide Chemical compound CCC[Si](OC)(OC)OCNC(=O)C=C XFOBMOZBCGIRDL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 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
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940001941 soy protein Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- FYOWZTWVYZOZSI-UHFFFAOYSA-N thiourea dioxide Chemical compound NC(=N)S(O)=O FYOWZTWVYZOZSI-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- CAAIULQYGCAMCD-UHFFFAOYSA-L zinc;hydroxymethanesulfinate Chemical compound [Zn+2].OCS([O-])=O.OCS([O-])=O CAAIULQYGCAMCD-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
-
- 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
- C08F228/00—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 bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—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 bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0021—Preparation of sols containing a solid organic phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0034—Additives, e.g. in view of promoting stabilisation or peptisation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
-
- 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
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- 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
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
- C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D141/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/24—Homopolymers or copolymers of amides or imides
- C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J141/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/22—Materials not provided for elsewhere for dust-laying or dust-absorbing
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/21—Efflorescence resistance
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/29—Frost-thaw resistance
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2341/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
Abstract
本发明涉及基于a)50至97wt.%的一种或多种含有烯属不饱和酰胺基团的非离子性单体,b)0.1至10wt.%的一种或多种含有烯属不饱和硅烷基团的单体,和c)1至30wt.%的一种或多种离子性的烯属不饱和单体以及可选的一种或多种其他烯属不饱和单体的水溶性共聚物,以wt%计的量总和为100wt%。
Description
技术领域
本发明涉及基于含酰胺基团的非离子性单体和离子性单体的水溶性共聚物、其生产方法和用途,例如,作为水性聚合物分散体或在水中可再分散的粉末的保护性胶体。
背景技术
水溶性聚合物用作例如保护胶体,用于稳定水不溶性聚合物的水性分散体或用于生产在水中可再分散的聚合物粉末。这种聚合物分散体或聚合物粉末可以用于,例如,建筑化学品中。常见的保护性胶体是聚乙烯醇、聚乙烯吡咯烷酮、纤维素或淀粉,如EP-A133899,WO-A 84/00369或EP-B 62106中描述的。为了获得足够的稳定化效果,有时必须大量使用此类保护性胶体,这可能与以下缺点有关:通过添加保护性胶体,分散体的粘合剂含量降低,这可能会导致流变学缺陷,并且最后添加保护性胶体可能会使分散体生产的聚合物薄膜对水敏感。在基于(甲基)丙烯酸酯和/或芳族化合物如苯乙烯的水不溶性共聚物的保护胶体的情况下,这些问题特别明显。另外,保护性胶体也相对昂贵。
为了改善相应聚合物薄膜的耐水性,EP-A 727441建议使用基于5至50%的酸(酐)官能共聚单体、0.1至80%长链(甲基)丙烯酸酯和至多达94.9%的水不溶性主要单体,如(甲基)丙烯酸酯或乙烯基酯的水溶性保护性胶体。缺点在于这些保护性胶体是通过在有机溶剂中聚合产生的,并必须通过蒸馏费力地除去溶剂。DE-A 2618898描述了基于疏水性单体单元如甲基丙烯酸甲酯和亲水性单体单元如烯属不饱和磺酸酯共聚单体的保护性胶体,其制备也通过在有机溶剂中的聚合进行。
对于用于喷雾干燥保护性胶体稳定的聚合物分散体的干燥剂,EP-A 629650推荐磺酸官能的共聚单体和水不溶性共聚单体的共聚物,EP-A 671435推荐使用丙烯酸烷基酯与磺酸酯或羧酸酯取代的单体的共聚物。
由DE-A 19608911已知具有含磺酸盐、含N-羟甲基和疏水性单体单元的可交联保护胶体。缺点是当在酸性环境中或在热应力下使用时,这种保护性胶体稳定的聚合物会发生交联并因此变脆。这与许多应用(密封浆,密封组合物,裂纹桥接涂料)中要求的弹性性能背道而驰。
为了改善聚合物改性的涂料或建筑产品的耐水性,WO A 98/49205建议使用基于5至95wt%的含磺酸或磺酸酯基团的单体、5至95wt%的非可交联的水溶性单体和0至5wt%的疏水性单体的保护性胶体。US 7968642推荐低分子量或低粘度聚丙烯酰胺用于可再分散性聚合物粉末的保护胶体。EP-B 206814描述了(甲基)丙烯酸、磺酸酯官能单体和乙烯基酯的三元共聚物用于稳定包含溶解或悬浮的固体的水性体系,如冷却水或锅炉水。
在这种背景下,目的在于为水分散体或在水中可再分散粉末的形式的聚合物提供作为保护性胶体的水溶性聚合物,由此可以解决上述问题。
发明内容
本发明涉及基于以下的水溶性共聚物:
a)50至97wt%的一种或多种含有酰胺基团的非离子性烯属不饱和单体,
b)0.1至10wt%的一种或多种含硅烷基团的烯属不饱和单体,
c)1至30wt%的一种或多种离子性烯属不饱和单体,和
可选地,其他的烯属不饱和单体,
其中以wt%计的数值总和为100wt%。
包含酰胺基团的非离子性烯属不饱和单体a)的实例有包含酰胺基团(-CONH2)的烯属不饱和化合物。因此,单体a)通常不带有阴离子性或阳离子性基团如酸或铵基团。单体a)优选不带有硅烷基团或不带有离子性基团,尤其是不带有阴离子性或阳离子性基团。
优选的单体a)是(甲基)丙烯酰胺、乙烯基吡咯烷酮和双丙酮丙烯酰胺。特别优选的是甲基丙烯酰胺,且尤其是丙烯酰胺。
单体a)也可以是交联单体如,例如,包含N-羟甲基(-NH-CH2OH)或其醚化衍生物(NH-CH2OR,其中R=C1-至C6-烷基)的丙烯酰胺,尤其是N-羟甲基丙烯酰胺(NMA)、N-羟甲基甲基丙烯酰胺(NMMA)、N-(异丁氧基甲基)丙烯酰胺(IBMA)、N-(异丁氧基甲基)甲基丙烯酰胺、N-(正丁氧基甲基)丙烯酰胺(NBMA)。优选的交联单体a)是N-羟甲基丙烯酰胺和N-(异丁氧基甲基)丙烯酰胺。
基于单体a)的总重量,单体a)优选是≥50wt%,特别优选≥80wt%且最优选≥95wt%的程度的非交联单体。基于水溶性共聚物的总重量,交联单体a)的分数优选≤3wt%,而特别优选≤1wt%。最优选的水溶性共聚物不包含任何交联单体a)的单元。
优选地,基于水溶性共聚物的总重量,水溶性共聚物基于60至95wt%,特别优选70至94wt%,而最优选80至92wt%的范围的单体a)。
含有硅烷基团的烯属不饱和单体b)是,例如,式R1SiR2 0-2(OR3)1-3的烯属不饱和硅酮化合物,其中R1具有定义CH2=CR4-(CH2)0-1或CH2=CR4CO2(CH2)1-3,R2具有定义C1-至C3-烷基基团、C1-至C3-烷氧基基团或卤素,优选Cl或Br,R3是直链或支链的、可选取代的、具有1至12个碳原子,优选1至3个碳原子的烷基基团,或是具有2至12个碳原子的酰基基团,其中R3可以可选地被醚基团中断,而R4是H或CH3。
含硅烷基团的优选单体b)是γ-丙烯酰基或γ-甲基丙烯酰氧基丙基三(烷氧基)硅烷、α-甲基丙烯酰氧基甲基三(烷氧基)硅烷、γ-甲基丙烯酰氧基丙基甲基二(烷氧基)硅烷;乙烯基硅烷如乙烯基烷基二(烷氧基)硅烷和乙烯基三(烷氧基)硅烷,其中例如甲氧基、乙氧基、甲氧基亚乙基、乙氧基亚乙基、甲氧基丙二醇醚或乙氧基丙二醇醚基团可以用作烷氧基。
含有硅烷基团的优选单体b)的实例有3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基甲基二甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基甲基二甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基甲基二乙氧基硅烷、乙烯基三丙氧基硅烷、乙烯基三异丙氧基硅烷、乙烯基三-(1-甲氧基)异丙氧基硅烷、乙烯基三丁氧基硅烷、乙烯基三乙酰氧基硅烷、甲基丙烯酰氧基甲基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三(2-甲氧基乙氧基)硅烷、乙烯基三氯硅烷、乙烯基甲基二氯硅烷、乙烯基三-(2-甲氧基乙氧基)硅烷、三乙酰氧基乙烯基硅烷、烯丙基乙烯基三甲氧基硅烷、烯丙基三乙酰氧基硅烷、乙烯基二甲基甲氧基硅烷、乙烯基二甲基乙氧基硅烷、乙烯基甲基二乙酰氧基硅烷、乙烯基二甲基乙酰氧基硅烷、乙烯基异丁基二甲氧基硅烷、乙烯基三异丙氧基硅烷、乙烯基三丁氧基硅烷、乙烯基三己氧基硅烷、乙烯基甲氧基二己氧基硅烷、乙烯基三辛氧基硅烷、乙烯基二甲氧基辛氧基硅烷、乙烯基甲氧基二辛氧基硅烷、乙烯基甲氧基二(十二烷氧基)硅烷、乙烯基二甲氧基十二烷氧基硅烷和聚乙二醇改性的乙烯基硅烷。
最优选的作为含硅烷基团的单体b)是乙烯基三甲氧基硅烷、乙烯基甲基二甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基甲基二乙氧基硅烷、乙烯基三(1-甲氧基)异丙氧基硅烷、甲基丙烯酰氧基丙基三(2-甲氧基乙氧基)硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基甲基二甲氧基硅烷和甲基丙烯酰氧基甲基三甲氧基硅烷及其混合物。
合适的含硅烷基团单体b)还有包含硅烷基团的(甲基)丙烯酰胺,其通式为CH2=CR5-CO-NR6-R7-SiR8 n-(R9)3-m,其中n=0至4,m=0至2,R5是H或甲基,R6是H或具有碳原子数1-5的烷基;R7是具有碳原子数1-5的亚烷基或其中碳链被O或N原子间断的二价有机基团,R8是具有碳原子数1-5的烷基,R9是具有碳原子数1-40的烷氧基,其可以被其他杂环取代。在其中存在两个或更多个R5或R9基团的单体中,这些可以相同或不同。
这种(甲基)丙烯酰胺基烷基硅烷的实例有:3-(甲基)丙烯酰胺基丙基三甲氧基硅烷,3-(甲基)丙烯酰胺基丙基三乙氧基硅烷,3-(甲基)丙烯酰胺基丙基三(β-甲氧基乙氧基)硅烷,2-(甲基)丙烯酰胺基-2-甲基丙基三甲氧基硅烷,2-(甲基)丙烯酰胺基-2-甲基乙基三甲氧基硅烷,N-(2-(甲基)丙烯酰胺基乙基)氨基丙基三甲氧基硅烷,3-(甲基)丙烯酰胺基丙基三乙酰氧基硅烷,2-(甲基)丙烯酰胺基乙基三甲氧基硅烷,1-(甲基)丙烯酰胺基甲基三甲氧基硅烷,3-(甲基)丙烯酰胺基丙基甲基二甲氧基硅烷,3-(甲基)丙烯酰胺基丙基二甲基甲氧基硅烷,3-(N-甲基(甲基)丙烯酰胺基)丙基三甲氧基硅烷,3-((甲基)丙烯酰胺基甲氧基)-3-羟丙基三甲氧基硅烷,3-((甲基)丙烯酰胺基甲氧基)丙基三甲氧基硅烷,N,N-二甲基-N-三甲氧基甲硅烷基丙基-3-(甲基)丙烯酰胺基丙基氯化铵和N,N-二甲基-N-三甲氧基甲硅烷基丙基-2-(甲基)丙烯酰胺基-2-甲基丙基氯化铵。
优选地,基于水溶性共聚物的总重量,该水溶性共聚物基于0.2至7wt%,特别优选0.3至5wt%,而最优选0.5至3wt%的范围的单体b)。
离子性烯属不饱和单体c)可以是,例如阴离子性烯属不饱和单体或阳离子性烯属不饱和单体。
烯属不饱和阴离子性单体c)是另外带有例如羧酸、磺酸、硫酸酯或膦酸基团的烯属不饱和单体。烯属不饱和羧酸可以是例如单或二羧酸,优选丙烯酸、甲基丙烯酸、衣康酸、富马酸、马来酸、富马酸和马来酸的单和二酯如二乙基和二异丙基酯。烯属不饱和磺酸的实例是乙烯基磺酸、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、苯乙烯基磺酸、(甲基)丙烯酸磺基烷基酯、衣康酸磺基烷基酯,优选在每种情况下具有C1-至C6-烷基基团,以及乙烯基磺酸。特别优选的是2-丙烯酸酰胺基-2-甲基丙磺酸(AMPS)、苯乙烯基磺酸、丙烯酸磺基丙基酯、衣康酸磺基丙基酯、乙烯基磺酸。
特别优选的单体c)是丙烯酸、甲基丙烯酸和乙烯基磺酸。
阴离子性单体c)也可以是其盐的形式,例如,其碱金属、碱土金属或铵盐,优选钠、钾、钙或铵盐。
阳离子性单体c)的实例有二烯丙基二乙基氯化铵(DADEAC)、(3-甲基丙烯酰氧基)丙基三甲基氯化铵(MPTAC)、(3-甲基丙烯酰氧基)乙基三甲基氯化铵(METAC)、(3-甲基丙烯酰胺基)丙基三甲基氯化铵(MAPTAC)、三甲基-3-(1-丙烯酰胺基-1,1-二甲基丙基)氯化铵、三甲基-3-(1-丙烯酰胺基-1,1-二甲基丁基)氯化铵、二甲基丙烯酰胺基丙基-4-三甲基铵丁烯基-2-氯化铵、2-(丙烯酰胺基甲氧基)乙基三甲基氯化铵,且尤其是二烯丙基二甲基氯化铵(DADMAC)。
优选的阳离子性单体c)是二烯丙基二甲基氯化铵(DADMAC)、二烯丙基二乙基氯化铵(DADEAC)、(3-甲基丙烯酰氧基)丙基三甲基氯化铵(MPTAC)、(3-甲基丙烯酰氧基)乙基三甲基氯化铵(METAC)和(3-甲基丙烯酰氨基)丙基三甲基氯化铵(MAPTAC)。
优选地,基于水溶性共聚物的总重量,水溶性共聚物基于3至25wt%,特别优选5至20wt%,而最优选7至15wt%的范围的单体c)。
可选地,水溶性共聚物可以另外基于一种或多种疏水性的烯属不饱和单体d)。单体d)优选在23℃下在水中溶解程度小于2wt%。
疏水性烯属不饱和单体d)优选选自包括乙烯基酯、(甲基)丙烯酸酯、乙烯基芳族化合物、烯烃、1,3-二烯和乙烯卤化物的组。
合适的乙烯基酯是例如具有1至20个碳原子,尤其是2至15个碳原子的羧酸的那些,如乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯、乙酸1-甲基乙烯酯、新戊酸乙烯酯和具有9至11个碳原子的α-支化单羧酸的乙烯基酯。
来自由丙烯酸或甲基丙烯酸的酯的组的合适单体是,例如,具有1至15个碳原子的直链或支链醇的酯,如丙烯酸甲酯、甲基丙烯酸甲酯,丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸2-乙基己酯。
乙烯基芳族化合物的实例是苯乙烯、甲基苯乙烯和乙烯基甲苯。卤乙烯的实例是氯乙烯。烯烃的实例是乙烯和丙烯。二烯的实例是1,3-丁二烯和异戊二烯。
优选的是,基于水溶性共聚物的总重量,水溶性共聚物基于≤10wt%,更优选≤5wt%,而特别优选≤1wt%的范围的单体d)。最优选的水溶性共聚物不包含任何单体d)的单元。
可选地,可以另外共聚一种或多种烯属不饱和辅助单体e)。辅助单体e)的实例是烯属不饱和腈,优选丙烯腈和乙酰基乙酰氧基-乙基丙烯酸酯或甲基丙烯酸酯。辅助单体e)也可以是烯属不饱和的交联单体e),如预交联或后交联单体e)。预交联单体e)的实例是多烯属不饱和单体,例如,己二酸二乙烯基酯,马来酸二烯丙基酯,甲基丙烯酸烯丙酯,异氰脲酸三烯丙基酯或氰尿酸三烯丙基酯。后交联单体e)的实例是环氧官能单体,如甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯。还可以提及的有具有羟基的单体,如甲基丙烯酸羟烷基酯和丙烯酸羟烷基酯,特别是丙烯酸或甲基丙烯酸的羟乙酯、羟丙酯或羟丁酯。辅助单体e),特别是交联单体e)通常与上述单体a)至d)或a)至c)不同,特别是也与上述交联单体a)不同。
优选的是,基于水溶性共聚物的总重量,该水溶性共聚物基于0至20wt%,特别优选0.5至10wt%,而最优选1至5wt%的范围的辅助单体e)。
具体地,水溶性共聚物基于60至95wt%,特别是70至94wt%的(甲基)丙烯酰胺;0.2至7wt%,尤其是0.3至5wt%的一种或多种含有硅烷基团并选自由以下组成的组的烯属不饱和单体:乙烯基三甲氧基硅烷、乙烯基甲基二甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基甲基二乙氧基硅烷、乙烯基三(1-甲氧基)-异丙氧基硅烷、甲基丙烯酰氧基丙基三(2-甲氧基乙氧基)硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基甲基二甲氧基硅烷和甲基丙烯酰氧基甲基三甲氧基硅烷;3至25wt%,特别是5至15wt%的一种或多种选自由丙烯酸、甲基丙烯酸和乙烯基磺酸组成的组的阴离子性单体c)或一种或多种选自由以下组成的组的阳离子性单体c):二烯丙基二甲基氯化铵(DADMAC)、二烯丙基二乙基氯化铵(DADEAC)、(3-甲基丙烯酰氧基)丙基三甲基氯化铵(MPTAC)、(3-甲基丙烯酰氧基)乙基三甲基氯化铵(METAC)和(3-甲基丙烯酰胺基)丙基三甲基氯化铵(MAPTAC);其中水溶性共聚物优选以指定的量可选地另外包含疏水性的烯属不饱和单体d)和/或辅助单体e);其中以wt%计的数值总和为100wt%。
水溶性共聚物在23℃下在水中的溶解度优选至少10wt%。
水溶性共聚物的具有20%固体含量的水溶液的粘度优选为10至10000mPas,特别优选50至5000mPas,最优选100至1000mPas。该粘度使用布鲁克菲尔德(Brookfield)粘度计(使用轴1,在25℃和20rpm下)测定。
本发明进一步涉及通过自由基引发的聚合,优选在水性溶剂中,生产根据本发明的水溶性共聚物的方法。
水溶性共聚物优选通过溶液聚合法生产。
该水性溶剂可以可选地包括一种或多种有机溶剂。有机溶剂优选是水溶性有机溶剂,优选是醇,尤其是具有1-6个碳原子的二醇、聚乙二醇或脂族醇;酮,尤其是丙酮或甲乙酮;酯,尤其是乙酸甲酯,乙酸乙酯,乙酸丙酯或乙酸丁酯;或醚。最优选的有机溶剂是甲醇、异丙醇、乙酸甲酯、乙酸乙酯和乙酸丁酯。基于水性溶剂的总重量,该水性溶剂优选包含≤20wt%,更优选≤10wt%,特别优选≤5wt%的有机溶剂。最优选的是,该水性溶剂不包含任何有机溶剂。
溶液聚合可以使用常见的氧化还原引发剂组合引发。单体转化率可以通过计量加入引发剂控制。通常总体上计量加入引发剂使得确保连续聚合。合适的氧化引发剂的实例是过二硫酸的钠、钾和铵盐,过氧化氢,过氧化叔丁基,叔丁基过氧化氢,过二磷酸钾,过氧新戊酸叔丁酯,枯烯过氧化氢,偶氮二异丁腈。优选的是过二硫酸的钠,钾和铵盐和过氧化氢。指定的引发剂通常以基于单体总重量的0.01至2.0wt%的量使用。合适的还原剂是碱金属和铵的亚硫酸盐和亚硫酸氢盐例如亚硫酸钠,次硫酸的衍生物如甲醛次硫酸锌或甲醛次硫酸碱金属盐,例如甲醛合次硫酸钠(Brüggolit)和(异)抗坏血酸。优选甲醛合次硫酸钠和(异)抗坏血酸。基于单体的总重量,还原剂的量优选为0.015至3wt%。所指定的氧化剂,尤其是过二硫酸的盐,也可以单独用作热引发剂。
聚合温度优选为40至100℃,特别优选60至90℃。气态共聚单体如乙烯、1,3-丁二烯或氯乙烯的共聚也可以在压力下,通常在5巴至100巴的压力下进行。
为了在溶液聚合期间控制分子量,可以使用调节物质。如果使用这种链转移剂,则基于待聚合的单体,其通常以0.01至5.0wt%的量使用,并且例如分开计量加入或与反应组分预混合。这种物质的实例是正十二烷基硫醇、叔十二烷基硫醇、巯基丙酸、巯基丙酸甲酯、异丙醇和乙醛。优选不使用调节物质。
溶液聚合过程也可以在乳化剂或保护性胶体的存在下进行。基于单体的总重量,乳化剂和保护性胶体优选至多10wt%,尤其是0.1至10wt%。特别优选在不存在乳化剂和/或尤其在不存在保护性胶体的情况下进行聚合。
乳化剂的实例是阴离子性、阳离子性或非离子性乳化剂,如阴离子表面活性剂,特别是烷基硫酸盐,烷基或烷基芳基醚硫酸盐,烷基或烷基芳基磺酸盐,磺基琥珀酸(单)酯或非离子表面活性剂,如具有8至40个环氧乙烷单元的烷基聚乙二醇醚或烷基芳基聚乙二醇醚。保护性胶体的实例是聚乙烯醇,如部分水解的聚乙烯醇;纤维素醚如甲基纤维素、甲基羟丙基纤维素、羟乙基纤维素、羧甲基纤维素。
当进行溶液聚合过程时,聚合通常进行至固含量10至70wt%,优选至固含量15至60wt%。
聚合完成后,残余单体的去除可以通过使用已知方法的后聚合,例如,通过氧化还原催化剂引发的后聚合实现。挥发性残余单体还可以通过蒸馏或汽提方法,优选在减压下,以及可选地使惰性夹带气体如空气、氮气或蒸汽通过或穿过而除去。
为了将水溶性共聚物转化为水溶性聚合物粉末,通常通过例如流化床干燥、辊式干燥、冷冻干燥或喷雾干燥来干燥水溶性共聚物的水溶液。溶液优选喷雾干燥。优选地,不向待干燥溶液中加入干燥助剂,特别是不加入保护性胶体如聚乙烯醇。喷雾干燥可以通过常规的喷雾干燥系统进行,其中雾化可以通过一个、两个或多个流体喷嘴或使用旋转盘进行。出口温度通常根据系统或期望的干燥度在45℃至120℃的范围内,优选在60℃至90℃的范围内选择。
在雾化期间,基于水溶性共聚物,至多达1.5wt%的消泡剂含量被证实是有利的。为了通过改善粘连稳定性而延长保质期,可以向获得的粉末提供基于水溶性共聚物的总重量优选至多30wt%的抗粘连剂(抗结块剂)。抗粘连剂的实例是粒度优选处于10nm至10μm范围内的碳酸钙或镁、滑石、石膏、二氧化硅、高岭土、硅酸盐。
通过固体含量调节待雾化的进料的粘度,从而获得<500mPas(在20rpm和23℃下的Brookfield粘度),优选<250mPas的值。待雾化的分散体的固含量通常>35%,优选>40%。
为了改善性能,在雾化期间可以添加其他添加剂。存在于优选实施方式中的聚合物粉末组合物的其他组分是,例如,颜料,填料,泡沫稳定剂,疏水剂。
因此,通过根据本发明的方法生产的水溶性共聚物优选是水溶性聚合物粉末形式,特别优选是水溶液形式。水溶液优选是澄清的,但可选地也可以是稍微混浊的,但通常并不是分散体形式。例如,具有20wt%根据本发明的水溶性共聚物的固含量的水溶液的浊度优选为≤700EBC,特别优选≤600EBC,更加优选≤400EBC,而最优选≤200EBC(使用Metrisa的TA6FS/251型浊度测量仪,在室温下根据DIN 38404的Formazin标准测定)。
水性分散体和/或聚合物粉末优选不含乳化剂和/或尤其是不含与根据本发明的水溶性共聚物不同的保护性胶体。
本发明的水溶性共聚物优选用作水性聚合物分散体或在水中可再分散的粉末的保护性胶体。
本发明还涉及以水性分散体或可再分散于水中的粉末形式的保护性胶体稳定的聚合物,其特征在于一种或多种保护性胶体是根据本发明的水溶性共聚物。
用一种或多种根据本发明的水溶性共聚物作为保护性胶体稳定的聚合物在下面也称为基础聚合物。
基础聚合物优选不溶于水。基础聚合物在23℃水中的溶解度优选至多5wt%,特别优选至多1wt%。聚合物的溶解性能取决于例如其单体组成。本领域技术人员可以基于一些定向实验提供水不溶性或水溶性聚合物。
基础聚合物通常不同于根据本发明的水溶性共聚物。
基础聚合物优选基于来自包括具有1至18个碳原子的直链或支链羧酸的乙烯基酯、丙烯酸和甲基丙烯酸与具有1至18个碳原子的直链或支链醇的酯、乙烯基芳烃、乙烯基卤化物和烯烃的组的一种或多种单体。这些单体可以认为是以上指定的优选和特别优选的实施方式。基于基础聚合物的总重量,基础聚合物基于优选≥50wt%,特别优选≥75wt%,而最优选≥90wt%的范围的以上提及的疏水性单体d)。
可选地,基础聚合物可以基于在每种情况下基于基础聚合物的总重量0.05至30.0wt%,优选0.5至15wt%的范围的一种或多种辅助单体。辅助单体的实例有烯属不饱和一元和二元羧酸,优选丙烯酸、甲基丙烯酸、富马酸和马来酸;烯属不饱和酰胺和腈,优选丙烯酰胺和丙烯腈;富马酸和马来酸的单酯和二酯,如二乙基和二异丙基酯,以及马来酸酐、烯属不饱和磺酸或其盐,优选乙烯基磺酸、2-丙烯酰胺基-2-甲基丙磺酸。实例还有烯属不饱和阳离子单体,尤其是以上指定的阳离子单体。进一步的实例还有预交联共聚单体,如聚烯属不饱和共聚单体,例如己二酸二乙烯酯、马来酸二烯丙酯、甲基丙烯酸烯丙酯或氰尿酸三烯丙酯,或后交联共聚单体,例如丙烯酰胺基乙醇酸(AGA)、甲基丙烯酰胺基乙醇酸甲基酯(MAGME)、N-羟甲基丙烯酰胺(NMA)、N-羟甲基甲基丙烯酰胺(NMMA)、N-羟甲基烯丙基氨基甲酸酯,烷基醚如异丁氧基醚或N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺和N-羟甲基烯丙基氨基甲酸酯的酯。环氧官能的共聚单体如甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯也是合适的。进一步的实例是硅酮官能性单体如丙烯酰氧基丙基三(烷氧基)硅烷和甲基丙烯酰氧基丙基三(烷氧基)硅烷、乙烯基三烷氧基硅烷和乙烯基甲基二烷氧基硅烷(其中,例如,乙氧基和乙氧基丙二醇醚基团可以作为烷氧基存在)、(3-环氧丙氧基丙基)三乙氧基硅烷和(3-环氧丙氧基丙基)三甲氧基硅烷。还可以提及的是具有羟基或CO基团的单体,例如,甲基丙烯酸羟烷基酯和丙烯酸羟烷基酯如丙烯酸或甲基丙烯酸羟乙基酯、羟丙基酯或羟丁基酯,以及诸如二丙酮丙烯酰胺和丙烯酸乙酰乙酰氧基乙酯或甲基丙烯酸乙酰乙酰氧基乙酯。进一步的实例还有乙烯基醚如甲基、乙基或异丁基乙烯基醚。
用于基础聚合物的优选辅助单体是含环氧基团的单体如甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯,特别是(3-环氧丙氧基丙基)三乙氧基硅烷和(3-环氧丙氧基丙基)三甲氧基硅烷。优选基于基础聚合物的总重量,该基础聚合物基于0.01至5wt%,特别优选0.05至2wt%,且最优选0.1至1wt%的范围的含环氧基团的单体。包含含环氧基团的单体单元的基础聚合物可以与例如根据本发明的水溶性共聚物交联。
在包含阳离子性单体c)的单元的根据本发明的水溶性共聚物的情况下,还优选将含酸基团的单体如羧酸或磺酸作为基础聚合物的辅助单体。在包含阴离子性单体c)的单元的根据本发明的水溶性共聚物的情况下,阳离子性单体也优选作为基础聚合物的辅助单体。同样在该实施方式中,根据本发明的水溶性共聚物和基础聚合物可以以有利的相互作用彼此结合。
合适的基础聚合物的实例是乙酸乙烯酯均聚物、乙酸乙烯酯与乙烯的共聚物、乙酸乙烯酯与乙烯和一种或多种其他乙烯基酯的共聚物、乙酸乙烯酯与乙烯和丙烯酸酯的共聚物、乙酸乙烯酯与乙烯和氯乙烯的共聚物、苯乙烯-丙烯酸酯共聚物、苯乙烯-1,3-丁二烯共聚物。
优选的是乙酸乙烯酯均聚物;乙酸乙烯酯与1至40wt%的乙烯的共聚物;乙酸乙烯酯与1至40wt%的乙烯和1至50wt%的一种或多种来自在羧酸基团中具有1-12个碳原子的乙烯基酯如丙酸乙烯酯、月桂酸乙烯酯,具有5-13个碳原子的α-支化羧酸的乙烯基酯如VeoVa9R、VeoVa10R、VeoVa11R的组的其他共聚单体的共聚物;乙酸乙烯酯、1至40wt%的乙烯和优选1至60wt%的具有1-15个碳原子的直链或支链醇的丙烯酸酯,特别是丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚物;和具有30至75wt%的乙酸乙烯酯、1至30wt%的月桂酸乙烯酯或具有5-13个碳原子的α-支化羧酸的乙烯基酯以及1至30wt%具有1-15个碳原子的无支链或支链醇的丙烯酸酯,尤其是丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚物,其还可以包含1至40wt%的乙烯;乙酸乙烯酯、1至40wt%的乙烯和1至60wt%的氯乙烯的共聚物;其中聚合物在每种情况下还可以包含指定的量的辅助单体,并且在每种情况下以wt%计的数值总加和为100wt%。
还优选的是(甲基)丙烯酸酯聚合物如丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚物或甲基丙烯酸甲酯与丙烯酸正丁酯和/或丙烯酸2-乙基己酯和可选的乙烯的共聚物;苯乙烯-丙烯酸酯与一种或多种来自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯的组的单体的共聚物;乙酸乙烯酯-丙烯酸酯与一种或多种来自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯和可选的乙烯的组的单体的共聚物;苯乙烯-1,3-丁二烯共聚物;其中该聚合物还可以包含指定量的辅助单体,并且在每种情况下以wt%计的数值总加和为100wt%。
用根据本发明的水溶性共聚物作为保护性胶体稳定的聚合物的水性分散体在固含量为50%下可以具有优选为10-10000mPas,特别优选15-1000mPas,且最优选20-100mPas的粘度。可替换地,在固体含量为50%下上述水性分散体,特别是用作絮凝剂时,可以具有优选为4 000-20000 000mPas,特别优选10 000-5 000 000mPas,且最优选20 000-1 000000mPas的粘度。该粘度用布鲁克菲尔德(Brookfield)粘度计(使用轴1,在25℃和20rpm下)测定。
在这种情况下,进行单体的选择或共聚单体的重量比例的选择,以通导致-50℃至+50℃,优选-30℃至+40℃的玻璃化转变温度Tg。聚合物的玻璃化转变温度Tg可以通过差示扫描量热法(DSC)以已知的方式测定。Tg也可以通过Fox方程近似地预测。根据文献FoxT.G.,Bull.Am.Physics Soc.1,3,p 123(1956):1/Tg=x1/Tg1+x2/Tg2+...+xn/Tgn,其中xn是单体n的质量分数(wt%/100),Tgn是单体n均聚物以开尔文为单位的玻璃化转变温度。均聚物的Tg值列于Polymer Handbook 2nd Edition,J.Wiley&Sons,New York(1975)中。
本发明进一步涉及通过悬浮液或乳液聚合方法通过自由基引发的烯属不饱和单体基团聚合以及可选的随后的干燥而制备水性分散体或在水中可再分散的粉末的形式的保护性胶体稳定的聚合物的方法,其特征在于,聚合在一种或多种根据本发明的水溶性共聚物作为保护性胶体的存在下进行。
基础聚合物的水性分散体通过水性悬浮液聚合或优选通过水性乳液聚合在优选0.1至20wt%,特别优选0.5至10wt%,最优选1至7.0wt%的一种或多种根据本发明的水溶性共聚物存在下制备,在每种情况下基于用于生产基础聚合物的单体的总重量。
聚合温度通常为35-95℃,优选40-80℃。聚合可以以间歇法进行,其中首先将所有组分装入反应器中,或以计量加入法(其中在聚合期间进料单个或两种或更多种组分)进行。采用初始装料和计量添加的混合类型是优选的。
计量添加可以分开(在空间和时间上)进行,或待计量加入的组分可以经过全部或部分预乳化而计量加入。
保护性胶体,特别是根据本发明的水溶性共聚物,可以首先加入或计量加入,或可以分为初始装料和计量加入。水溶性共聚物,尤其是水性溶液形式的水溶性共聚物,优选计量加入。
如果,例如使用气态单体如氯乙烯或乙烯,则乳液聚合也可以在高压下进行。如果在压力下操作,优选5巴至100巴的压力。
根据本发明的用作保护性胶体的水溶性共聚物可以单独使用或与乳化剂和/或其他保护性胶体组合使用。
适合作为乳化剂的有阴离子型、阳离子型或非离子型乳化剂。如果聚合在乳化剂的存在下进行,其量基于单体的总重量优选至多4wt%。优选使用阴离子型和非离子型乳化剂。非离子型乳化剂的实例是如具有8-40个氧化烯单元的烷基聚二醇醚或烷基芳基聚二醇醚的表面活性剂。优选由C2-至C4-氧化烯,特别是氧化乙烯和氧化丙烯或其混合物烷氧基化的烷氧基化C8-至C16-烷醇。其它实例有C8-C12烷基硫酸酯的碱金属或铵盐、具有C12-C18烷基基团和EO度为3-30的乙氧基化的烷醇的碱金属或铵盐、具有EO度3-50的乙氧基化的C4-C10烷基酚的碱金属或铵盐、C12-C18烷基磺酸的碱金属或铵盐、C9-C18烷基芳基磺酸的碱金属或铵盐和具有EO度3-50的乙氧基化的直链或支链C8-C36烷基醇的磺酸酯的碱金属或铵盐。
除了根据本发明的水溶性共聚物以外还可以可选地使用的合适保护性胶体是聚乙烯醇,如部分水解的聚乙烯醇;纤维素醚,如甲基纤维素、甲基羟丙基纤维素、羟乙基纤维素、羧甲基纤维素。
聚合可以例如用上述引发剂或引发剂组合,优选以此处提及的量引发。可选地,在聚合期间也可以优选以指定的量使用上述的用于控制分子量的调节物质。
由此可以获得的水性分散体具有优选30至75wt%,特别优选40至65wt%的固体含量。
基于水性聚合物分散体的干重,基础聚合物的水性聚合物分散体优选包含0.1至20wt%,特别优选0.5至10wt%,且最优选1至7.0wt%的根据本发明的水溶性共聚物。
基于水性聚合物分散体干重,基础聚合物的水性聚合物分散体优选包含≤20wt%,更优选≤10wt%,且特别优选≤5wt%,更加优选≤0.9wt%的不同于根据本发明的水溶性共聚物的乳化剂和/或特别是保护性胶体。最优选的,基础聚合物的水性聚合物分散体不包含任何乳化剂和/或特别是不包含任何不同于根据本发明的水溶性共聚物的保护性胶体。
为了制备用本发明的水溶性共聚物作为保护胶体稳定的在水中可再分散的粉末形式的基础聚合物,基础聚合物的水性分散体在可选地添加保护胶体作为干燥助剂之后,优选如上进一步对于干燥水溶性共聚物的水溶液描述的干燥。通常,基于分散体的聚合物成分,干燥助剂(保护胶体)以3至30wt%的总量使用。基于聚合物的比例,优选使用5至20wt%。
干燥助剂的实例有:部分水解的聚乙烯醇;聚乙烯吡咯烷酮;水溶性形式的多糖如淀粉(直链淀粉和支链淀粉)、纤维素及其羧甲基、甲基、羟乙基和羟丙基衍生物;蛋白质如酪蛋白或酪蛋白酸盐,大豆蛋白,明胶;木质素磺酸盐;合成聚合物如聚(甲基)丙烯酸、(甲基)丙烯酸酯与羧基官能性共聚单体单元的共聚物、聚(甲基)丙烯酰胺、聚乙烯基磺酸及其水溶性共聚物;三聚氰胺甲醛磺酸盐、萘甲醛磺酸盐、苯乙烯-马来酸共聚物和乙烯基醚-马来酸共聚物。
基于可再分散粉末的总重量,根据本发明的可再分散粉末优选包含0.1至20wt%,特别优选0.5至10wt%,且最优选1至7.0wt%根据本发明的水溶性共聚物。
基于可再分散粉末的总重量,根据本发明的可再分散粉末优选包含1至20wt%,特别优选2至15wt%的不同于根据本发明的水溶性共聚物的保护性胶体。
出乎意料的是,与常规的保护性胶体如聚乙烯醇相比,根据本发明的水溶性共聚物用作保护性胶体更加有效。这通过例如稳定的分散体可以具有更高的固含量或较少量的保护性胶体的事实证明。
这尤其适用于基于(甲基)丙烯酸酯和/或芳族化合物如苯乙烯的聚合物,使用保护胶体对其的稳定化在特定程度上是要求苛刻的。
因此,根据本发明的水溶性共聚物适合用作例如水不溶性聚合物的保护胶体,特别是用作烯属不饱和单体的水性乳液或悬浮聚合的保护胶体,或用作干燥聚合物水性分散体的干燥助剂。
水溶性共聚物也可以用作无机颗粒如颜料或填料的分散剂。
有利的是,根据本发明的水溶性共聚物,当用作水不溶聚合物的保护性胶体或用作分散剂时,导致分散体具有出乎意料的低粘度,因此即使在较高固含量下,本发明的分散体与常规稳定的分散体相比也具有期望的粘度。
采用根据本发明的水溶性共聚物的应用产品具有有利的性能,如高耐水性。与相应的具有常规保护性胶体的建筑产品相比,采用根据本发明的水溶性共聚物的建筑产品在热应力后或在冷冻/融解循环储存后更稳定,并且在水中储存之后,具有更低的风化(efflorescence)形成趋势。使用根据本发明的水溶性共聚物可以抵消建筑产品中的裂纹形成。根据本发明的水溶性共聚物还有利地以高水泥相容性和对矿物建筑材料的高粘附性为特征。
包含根据本发明的水溶性共聚物的聚合物分散体或由其获得的聚合物粉末也适合作为涂料组合物如砂浆、填充组合物、流平组合物、灰泥、建筑粘合剂或油漆,特别是油漆的粘合剂;作为例如用于木材、纸张、纺织品和无纺布的粘合剂或粘合剂;作为造纸中的粘合剂以及用于生产模制组合物或模制品的粘合剂;作为粘结沙子或粉尘的粘合剂;作为粘合剂或涂料组合物的添加剂,例如,用于涂层纺织品、膜、金属或特别是纸张的添加剂;作为涂料的底漆;作为絮凝剂、增稠剂、纤维上浆剂、交联剂或防尘剂。
具体实施方式
以下实施例用于进一步说明本发明:
水溶性共聚物的生产:
实施例1:
首先在氮气气氛中将269g去离子水和0.74g过二硫酸钾的混合物装入2升体积的反应器中,并将该混合物在搅拌下加热至80℃。在该温度下将680g的包括593.3g丙烯酰胺(在水中30%)、80g乙烯基磺酸酯(在水中25%)和2.0g的Geniosil GF 56(Wacker Chemie的商品名;乙烯基三乙氧基硅烷)的单体混合物在90分钟中计量加入该反应器中并在150分钟中计量加入62g过二硫酸钾(在水中3%)的引发剂溶液。在计量加入引发剂结束时,将混合物在80℃下后聚合1小时。然后将聚合物溶液冷却至室温。
获得的溶液具有20%的固含量和685mPa.s的粘度(使用布鲁克菲尔德粘度计,使用轴2,在25℃和20rpm下测定)。
比较例2:
比较例2类似于实施例1进行,不同之处在于,基于所有单体的总重量,GeniosilGF 56的量增加至15wt%(Wacker Chemie的商品名;乙烯基三乙氧基硅烷)。
未能获得水性聚合物溶液。发生了胶凝。聚合产物不适合作为保护胶体。
使用水溶性聚合物作为保护胶体的聚合物分散体的制备:
实施例3:
将2335g去离子水、86.4g作为保护性胶体的实施例1的水溶性共聚物的聚合物溶液、0.05g Dissolvine Na(乙二胺四乙酸二钠盐)、2.5g FAS(氨基亚氨基甲亚磺酸,10%,在水中)和24.1g TBHP(叔丁基过氧化氢,10%,在水中)在氮气气氛下首先装入2升体积的反应器中,并在搅拌下将该混合物加热至70℃。
在此温度下,在210分钟中向该反应器中计量加入565.2g丙烯酸丁酯、100.3g苯乙烯、2.7g Geniosil GF 56(Wacker Chemie的商标名;乙烯基三乙氧基硅烷)的单体混合物并在300分钟中计量加入83.6g FF6(FF6,Bürgemann Chemical的商标名;在水中12%)和TBHP(叔丁基过氧化氢,在水中10%)。
在计量加入引发剂结束时,将该混合物在70℃下后聚合1小时。然后将聚合物溶液冷却至室温。
获得的分散体具有58%的固含量和1200mPa.s的粘度(使用布鲁克菲尔德粘度计,使用轴3,在25℃和20rpm下测定)。
实施例4:
实施例4类似于实施例3进行,不同之处在于,在制备聚合物分散体的聚合中未使用Geniosil GF 56(乙烯基三乙氧基硅烷)。
获得的分散体具有58.5%的固含量和1140mPa.s的粘度(使用布鲁克菲尔德粘度计,使用轴3,在25℃和20rpm下测定)。通过Coulter LS 230测定粒度给出1380nm的Dw值。
比较例5:
与实施例4一样,不同之处在于,作为保护性胶体,将实施例1的水溶性共聚物替换为119.7g(在水中20%)聚乙烯醇(Mowiol 5-88,Kuraray)。
获得的分散体具有50.0%的固含量和2980mPa.s的粘度(使用布鲁克菲尔德粘度计,使用轴1,在25℃和20rpm下测定)。
Claims (12)
1.一种水性分散体的形式或在水中可再分散的粉末的形式的保护胶体稳定的聚合物,其特征在于,一种或多种所述保护胶体是水溶性共聚物,基于以下:
a)50至97wt%的一种或多种含有酰胺基团的非离子性烯属不饱和单体,
b)0.1至10wt%的一种或多种含有硅烷基团的烯属不饱和单体,
c)1至30wt%的一种或多种离子性烯属不饱和单体,和
可选的一种或多种其他烯属不饱和单体,
其中以wt%计的数字总和为100wt%。
2.根据权利要求1所述的水性分散体的形式或在水中可再分散的粉末的形式的保护胶体稳定的聚合物,其特征在于,一种或多种含有酰胺基团的非离子性烯属不饱和单体a)选自包括丙烯酰胺、甲基丙烯酰胺、乙烯基吡咯烷酮和双丙酮丙烯酰胺的组。
3.根据权利要求1或2所述的水性分散体的形式或在水中可再分散的粉末的形式的保护胶体稳定的聚合物,其特征在于,一种或多种含有硅烷基团的烯属不饱和单体b)对应于式R1SiR2 0-2(OR3)1-3,其中R1具有定义CH2=CR4-(CH2)0-1或CH2=CR4CO2(CH2)1-3,R2具有定义C1至C3烷基基团、C1至C3烷氧基基团或卤素,R3是具有1至12个碳原子的、直链或支链的、可选取代的烷基基团或是具有2至12个碳原子的酰基基团,其中R3可选地被醚基团中断,并且R4是H或CH3。
4.根据权利要求1或2所述的水性分散体的形式或在水中可再分散的粉末的形式的保护胶体稳定的聚合物,其特征在于,一种或多种含有硅烷基团的烯属不饱和单体b)选自包括γ-(甲基)丙烯酰氧基丙基三(烷氧基)硅烷、α-(甲基)丙烯酰氧基甲基三(烷氧基)硅烷、γ-(甲基)丙烯酰氧基丙基甲基二(烷氧基)硅烷、乙烯基烷基二(烷氧基)硅烷和乙烯基三(烷氧基)硅烷的组。
5.根据权利要求1或2所述的水性分散体的形式或在水中可再分散的粉末的形式的保护胶体稳定的聚合物,其特征在于,一种或多种含有硅烷基团的烯属不饱和单体b)选自包括乙烯基三甲氧基硅烷、乙烯基甲基二甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基甲基二乙氧基硅烷、乙烯基三(1-甲氧基)异丙氧基硅烷、甲基丙烯酰氧基丙基三(2-甲氧基乙氧基)硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基甲基二甲氧基硅烷和甲基丙烯酰氧基甲基三甲氧基硅烷的组。
6.根据权利要求1或2所述的水性分散体的形式或在水中可再分散的粉末的形式的保护胶体稳定的聚合物,其特征在于,基于所述水溶性共聚物总重量,所述水溶性共聚物基于0.5至3wt%的范围的含有硅烷基团的烯属不饱和单体b)。
7.根据权利要求1或2所述的水性分散体的形式或在水中可再分散的粉末的形式的保护胶体稳定的聚合物,其特征在于,一种或多种离子性烯属不饱和单体c)选自包括丙烯酸、甲基丙烯酸、衣康酸、富马酸、马来酸、乙烯基磺酸、2-丙烯酰胺基-2-甲基丙磺酸、苯乙烯磺酸、(甲基)丙烯酸磺基烷基酯、衣康酸磺基烷基酯、二烯丙基二乙基氯化铵、(3-甲基丙烯酰氧基)丙基三甲基氯化铵、(3-甲基丙烯酰氧基)乙基三甲基氯化铵、(3-甲基丙烯酰胺基)丙基三甲基氯化铵、三甲基-3-(1-丙烯酰胺基-1,1-二甲基丙基)氯化铵、三甲基-3-(1-丙烯酰胺基-1,1-二甲基丁基)氯化铵、2-(丙烯酰胺基甲氧基)乙基三甲基氯化铵和二烯丙基二甲基氯化铵的组。
8.根据权利要求1或2所述的水性分散体的形式或在水中可再分散的粉末的形式的保护胶体稳定的聚合物,其特征在于,基于所述水溶性共聚物的总重量,所述水溶性共聚物基于5至20wt%的离子性烯属不饱和单体c)。
9.根据权利要求1所述的水性分散体的形式或在水中可再分散的粉末的形式的保护胶体稳定的聚合物,其特征在于,基于所述水性分散体的干重,或基于所述在水中可再分散的粉末的总重量,存在0.1至20wt%的所述水溶性共聚物。
10.一种通过悬浮液或乳液聚合方法通过自由基引发的烯属不饱和单体的聚合和可选地随后干燥而生产权利要求1至8中任一项所述的水性分散体的形式或在水中可再分散的粉末的形式的保护胶体稳定的聚合物的方法,其特征在于,所述聚合在作为保护胶体的一种或多种所述水溶性共聚物存在下进行。
11.权利要求1至8中任一项限定的水溶性共聚物作为水不溶性聚合物的保护胶体或作为无机颗粒的分散剂的用途。
12.根据权利要求1或9所述的水性分散体的形式或在水中可再分散的粉末的形式的保护胶体稳定的聚合物在粘合剂中,用于生产模制组合物或模制品;或作为涂料组合物的粘合剂,用于造纸、粘合沙或粉尘;作为涂料的底漆;作为絮凝剂、增稠剂、纤维上浆剂、交联剂或除尘剂的用途。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2018/068154 WO2020007467A1 (de) | 2018-07-04 | 2018-07-04 | Wasserlösliche copolymere |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111836841A CN111836841A (zh) | 2020-10-27 |
CN111836841B true CN111836841B (zh) | 2022-07-29 |
Family
ID=62874900
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201880090606.5A Active CN111836841B (zh) | 2018-07-04 | 2018-07-04 | 水溶性共聚物 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20210108013A1 (zh) |
EP (1) | EP3707180B1 (zh) |
CN (1) | CN111836841B (zh) |
WO (1) | WO2020007467A1 (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112813710B (zh) * | 2020-12-31 | 2021-12-14 | 珠海华大浩宏新材料有限公司 | 一种节能省水染色后处理助剂及其制备方法 |
CN113200616B (zh) * | 2021-05-17 | 2022-06-14 | 佛山市天宝利硅工程科技有限公司 | 一种水溶性有机硅三元共聚物及其制备方法和应用 |
CN113583174A (zh) * | 2021-07-23 | 2021-11-02 | 安徽海螺新材料科技有限公司 | 一种混凝土细骨料专用流变剂的制备方法 |
CN117794879A (zh) * | 2021-08-10 | 2024-03-29 | 瓦克化学股份公司 | 包含固体乙烯基酯树脂的建筑材料干混合物 |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE789223A (fr) * | 1971-09-28 | 1973-03-26 | Wacker Chemie Gmbh | Dispersions de polymeres vinyliques |
US3965032A (en) | 1973-04-16 | 1976-06-22 | The Dow Chemical Company | Colloidally stable dispersions |
DE3111602A1 (de) | 1981-03-24 | 1982-10-07 | Wacker-Chemie GmbH, 8000 München | Copolymerisate erhoehter wasserfestigkeit, verfahren zu ihrer herstellung und ihre verwendung |
DE3227090A1 (de) | 1982-07-20 | 1984-01-26 | Wacker-Chemie GmbH, 8000 München | Verfahren zur herstellung von polymerdispersionen und ihre verwendung |
DE3323851A1 (de) | 1983-07-01 | 1985-01-03 | Wacker-Chemie GmbH, 8000 München | Verfahren zur herstellung waessriger polymerdispersionen und ihre verwendung |
US4711725A (en) | 1985-06-26 | 1987-12-08 | Rohm And Haas Co. | Method of stabilizing aqueous systems |
DE4320220A1 (de) | 1993-06-18 | 1994-12-22 | Basf Ag | Verwendung von Polymerisaten I, die spezielle monoethylenisch ungesättigte Sulfonsäuren einpolymerisiert enthalten, als Hilfsmittel bei der Sprühtrocknung wäßriger Dispersionen von Polymerisaten II |
DE4407841A1 (de) | 1994-03-09 | 1995-09-14 | Huels Chemische Werke Ag | Pulverförmige, redispergierbare Bindemittel |
DE19505039A1 (de) | 1995-02-15 | 1996-08-22 | Basf Ag | Verfahren zur Herstellung von emulgatorfreien wäßrigen Polymerdispersionen |
DE19608911A1 (de) | 1996-03-07 | 1997-09-11 | Wacker Chemie Gmbh | Vernetzbare Schutzkolloide |
DE19718289A1 (de) | 1997-04-30 | 1998-11-05 | Wacker Chemie Gmbh | Verfahren zur Herstellung von wässrigen Polymerdispersionen |
NZ330371A (en) * | 1997-06-09 | 1999-10-28 | Kuraray Co | Aqueous emulsion system having as dispersant a polyvinyl alcohol polymer and the condensate of an alkali metal salt of an aromatic sulfonic acid |
DE10335673B4 (de) * | 2003-08-04 | 2007-01-18 | Celanese Emulsions Gmbh | Wässrige Dispersionsklebstoffe, Verfahren zu deren Herstellung und deren Verwendung |
WO2008101297A1 (en) | 2007-02-22 | 2008-08-28 | Acquos Pty Ltd | Redispersible polymers including a protective colloid system |
CN101226994B (zh) * | 2007-12-21 | 2010-06-30 | 成都中科来方能源科技有限公司 | 无纺布增强微孔聚合物隔膜及其制备方法和用途 |
BR112012028282A2 (pt) * | 2010-05-12 | 2016-11-01 | Akzo Nobel Chemicals Int Bv | processo para preparar um polímero através de um processo de polimerização de emulsão ou suspensão aquosa, emulsão, pó de polímero redispensável, uso da emulsão, composição de material de construção, processo para hidrofobizar uma composição de material de construção curada e processo para melhorar a estabilidade de congelamento e descongelamento de uma composição de material de construção curada |
CN102382241B (zh) * | 2010-08-30 | 2013-08-14 | 中国石油化工股份有限公司 | 一种长支链聚丙烯酰胺共聚物及其制备方法 |
EP2812360B1 (en) * | 2012-02-09 | 2022-08-31 | Life Technologies Corporation | Hydrophilic polymeric particles and methods for making same |
DE102012223620A1 (de) * | 2012-12-18 | 2014-06-18 | Wacker Chemie Ag | Verwendung von Hybridcopolymeren als Schutzkolloide für Polymere |
PL2970682T5 (pl) * | 2013-03-14 | 2023-10-09 | Akzo Nobel Coatings International B.V. | Kompozycje powłokowe utworzone z hybrydowych emulsji lateksowych |
DE102013219325A1 (de) * | 2013-09-25 | 2015-03-26 | Wacker Chemie Ag | Verwendung von modifizierten wasserlöslichen Polymeren als Vernetzungshilfsmittel |
DE102013223305A1 (de) * | 2013-11-15 | 2015-05-21 | Wacker Chemie Ag | Verfahren zur Herstellung von in Wasser redispergierbaren Polymerpulver-Zusammensetzungen mit kationischer Funktionalität |
CN105567190A (zh) * | 2014-10-17 | 2016-05-11 | 中国石油化工股份有限公司 | 一种凝胶堵漏剂及其制备方法 |
DE102015209381A1 (de) * | 2015-05-21 | 2016-11-24 | Wacker Chemie Ag | Polymerisate für schmutzabweisende Beschichtungen |
CN109232812A (zh) * | 2018-06-28 | 2019-01-18 | 江苏富淼科技股份有限公司 | 一种交联改性型水溶性固体聚丙烯酰胺及其用途 |
-
2018
- 2018-07-04 WO PCT/EP2018/068154 patent/WO2020007467A1/de unknown
- 2018-07-04 US US16/977,924 patent/US20210108013A1/en active Pending
- 2018-07-04 EP EP18739820.1A patent/EP3707180B1/de active Active
- 2018-07-04 CN CN201880090606.5A patent/CN111836841B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
EP3707180A1 (de) | 2020-09-16 |
CN111836841A (zh) | 2020-10-27 |
US20210108013A1 (en) | 2021-04-15 |
WO2020007467A1 (de) | 2020-01-09 |
EP3707180B1 (de) | 2021-05-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100961241B1 (ko) | 양이온 안정성 및 수재분산성 중합체 분말 조성물의 제조방법 | |
CN111836841B (zh) | 水溶性共聚物 | |
US6863985B2 (en) | Hydrophobicized copolymers | |
US9334388B2 (en) | Dispersion powder compositions comprising gemini surfactants | |
JP5054700B2 (ja) | 脂肪酸無水物を含有する分散粉末 | |
US8217109B2 (en) | Protective-colloid-stabilized polymers in the form of their aqueous dispersions or of their water-redispersible powders | |
US20070037925A1 (en) | Redispersion powder composition with a binding acceleration effect | |
KR100999478B1 (ko) | 실란 개질된 분산 분말 | |
JP5181113B2 (ja) | 保護コロイドで安定化されたポリマーの製造方法及び前記方法を実施するための装置 | |
US7863370B2 (en) | Dispersion powders stabilized by polyvinyl alcohol protective colloids | |
US6734246B2 (en) | Polyvinylacetal-grafted polymers | |
US7381761B2 (en) | Method for producing silicone-treated polymers | |
US6710113B2 (en) | Process for preparing two-phase polymers in the form of their aqueous dispersions and water-redispersible powders | |
US20050250899A1 (en) | Use of copolymers stabilized with a protective colloid in cement-free or low-cement coating materials | |
US9926232B2 (en) | Process for producing water-redispersible polymer powder compositions having cationic functionality | |
WO2020007466A1 (de) | Wasserlösliche copolymere | |
US6727323B2 (en) | Process for reducing odor emission in aqueous polymer dispersions and in polymer powders | |
US9580591B2 (en) | Use of hybrid copolymers as protective colloids for polymers | |
JP2007533785A (ja) | 変性されたポリビニルアルコールを含有するポリマー組成物 | |
US20220135784A1 (en) | Crosslinkable polymer-powder compositions redispersible in water | |
US11339228B2 (en) | Dispersion powder composition containing vinyl alcohol copolymerisate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |