CN1188486A - 以金属盐水溶胶作为种子基础的聚乙烯酯分散体系 - Google Patents
以金属盐水溶胶作为种子基础的聚乙烯酯分散体系 Download PDFInfo
- Publication number
- CN1188486A CN1188486A CN96194859A CN96194859A CN1188486A CN 1188486 A CN1188486 A CN 1188486A CN 96194859 A CN96194859 A CN 96194859A CN 96194859 A CN96194859 A CN 96194859A CN 1188486 A CN1188486 A CN 1188486A
- Authority
- CN
- China
- Prior art keywords
- acid
- water
- sol
- alpha
- polymerization
- 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.)
- Pending
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 49
- 150000003839 salts Chemical class 0.000 title claims abstract description 24
- 229920001290 polyvinyl ester Polymers 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 title claims abstract description 14
- 239000008131 herbal destillate Substances 0.000 title 1
- 238000001556 precipitation Methods 0.000 title 1
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- 230000000737 periodic effect Effects 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 41
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 36
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 36
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 239000002152 aqueous-organic solution Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 8
- 239000008199 coating composition Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 239000002245 particle Substances 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000084 colloidal system Substances 0.000 description 15
- -1 metal complex salt Chemical class 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 13
- 230000001681 protective effect Effects 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- AUCNMQYOQYTGPE-UHFFFAOYSA-N n-(hydroxymethyl)-n-methylprop-2-enamide Chemical compound OCN(C)C(=O)C=C AUCNMQYOQYTGPE-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 239000011118 polyvinyl acetate Substances 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 3
- NDGXZYRXRPWLOE-UHFFFAOYSA-N 2-(prop-2-enoylamino)oxyacetic acid Chemical compound OC(=O)CONC(=O)C=C NDGXZYRXRPWLOE-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HBJUDHILVBLZJL-UHFFFAOYSA-L [Na+].[Na+].O=C.[O-]S(=O)S([O-])=O Chemical compound [Na+].[Na+].O=C.[O-]S(=O)S([O-])=O HBJUDHILVBLZJL-UHFFFAOYSA-L 0.000 description 2
- 239000008351 acetate buffer Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001246 colloidal dispersion Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 150000002688 maleic acid derivatives Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- MOOYVEVEDVVKGD-UHFFFAOYSA-N oxaldehydic acid;hydrate Chemical class O.OC(=O)C=O MOOYVEVEDVVKGD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000007415 particle size distribution analysis Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002689 polyvinyl acetate 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
- GOPSAMYJSPYXPL-UHFFFAOYSA-N prop-2-enyl n-(hydroxymethyl)carbamate Chemical compound OCNC(=O)OCC=C GOPSAMYJSPYXPL-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 239000001605 (5-methyl-2-propan-2-ylcyclohexyl) acetate Substances 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- HLOUDBQOEJSUPI-UHFFFAOYSA-N 1-ethenyl-2,3-dimethylbenzene Chemical compound CC1=CC=CC(C=C)=C1C HLOUDBQOEJSUPI-UHFFFAOYSA-N 0.000 description 1
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- YFCIQZMEGLCRKA-UHFFFAOYSA-N 4-ethenylbenzamide Chemical compound NC(=O)C1=CC=C(C=C)C=C1 YFCIQZMEGLCRKA-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 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
- BAYVWWSKYAZXRE-UHFFFAOYSA-N C(C)(=O)OC=C.C(C)(C)(C)C1=CC=C(C(=O)O)C=C1 Chemical compound C(C)(=O)OC=C.C(C)(C)(C)C1=CC=C(C(=O)O)C=C1 BAYVWWSKYAZXRE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XHXUANMFYXWVNG-UHFFFAOYSA-N D-menthyl acetate Natural products CC(C)C1CCC(C)CC1OC(C)=O XHXUANMFYXWVNG-UHFFFAOYSA-N 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XHXUANMFYXWVNG-ADEWGFFLSA-N Menthyl acetate Natural products CC(C)[C@@H]1CC[C@@H](C)C[C@H]1OC(C)=O XHXUANMFYXWVNG-ADEWGFFLSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical class OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- ATGMJWZIFGYPJD-UHFFFAOYSA-N OC1=C(N(C(C=C)=O)C)C=CC=C1 Chemical compound OC1=C(N(C(C=C)=O)C)C=CC=C1 ATGMJWZIFGYPJD-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 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 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011438 discrete method Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- IYNRVIKPUTZSOR-HWKANZROSA-N ethenyl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC=C IYNRVIKPUTZSOR-HWKANZROSA-N 0.000 description 1
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical group CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 description 1
- HLMAOUJZLUOWAH-UHFFFAOYSA-N ethenyl acetate 2-methylpropanoic acid Chemical compound C(=C)OC(C)=O.C(C(C)C)(=O)O HLMAOUJZLUOWAH-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000002650 habitual effect Effects 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N mandelic acid Chemical compound OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- XWQDTJROXGIDKW-UHFFFAOYSA-N n-(1-hydroxy-2,2-dimethoxyethyl)prop-2-enamide Chemical compound COC(OC)C(O)NC(=O)C=C XWQDTJROXGIDKW-UHFFFAOYSA-N 0.000 description 1
- VYHUMZYFJVMWRC-UHFFFAOYSA-N n-(2-hydroxyethyl)-n-methylprop-2-enamide Chemical compound OCCN(C)C(=O)C=C VYHUMZYFJVMWRC-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ZZVLIBHWOSPNQW-UHFFFAOYSA-N n-(3-hydroxy-2,2-dimethylpropyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCC(C)(C)CO ZZVLIBHWOSPNQW-UHFFFAOYSA-N 0.000 description 1
- ZZGCWICUHCMQAR-UHFFFAOYSA-N n-(3-hydroxypropyl)-n-methylprop-2-enamide Chemical compound C=CC(=O)N(C)CCCO ZZGCWICUHCMQAR-UHFFFAOYSA-N 0.000 description 1
- SXMHECGYSOUMFN-UHFFFAOYSA-N n-benzyl-n-methylprop-2-enamide Chemical compound C=CC(=O)N(C)CC1=CC=CC=C1 SXMHECGYSOUMFN-UHFFFAOYSA-N 0.000 description 1
- OWVWGCVNBQLTDH-UHFFFAOYSA-N n-butyl-n-methylprop-2-enamide Chemical compound CCCCN(C)C(=O)C=C OWVWGCVNBQLTDH-UHFFFAOYSA-N 0.000 description 1
- LHLLNIZKYYRADT-UHFFFAOYSA-N n-cyclohexyl-n-methylprop-2-enamide Chemical compound C=CC(=O)N(C)C1CCCCC1 LHLLNIZKYYRADT-UHFFFAOYSA-N 0.000 description 1
- CSGOAFRNKNQONI-UHFFFAOYSA-N n-dodecyl-n-methylprop-2-enamide Chemical compound CCCCCCCCCCCCN(C)C(=O)C=C CSGOAFRNKNQONI-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- AXLMPTNTPOWPLT-UHFFFAOYSA-N prop-2-enyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCC=C AXLMPTNTPOWPLT-UHFFFAOYSA-N 0.000 description 1
- OCAAZRFBJBEVPS-UHFFFAOYSA-N prop-2-enyl carbamate Chemical compound NC(=O)OCC=C OCAAZRFBJBEVPS-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 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
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 150000005672 tetraenes Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/147—Saturated compounds having only one carboxyl group and containing —CHO groups
- C07C59/153—Glyoxylic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
- C07C59/06—Glycolic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
- C07C59/08—Lactic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
- C07C59/255—Tartaric acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
- C07C59/265—Citric acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/42—Unsaturated compounds containing hydroxy or O-metal groups
- C07C59/48—Unsaturated compounds containing hydroxy or O-metal groups containing six-membered aromatic rings
- C07C59/50—Mandelic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl 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
- 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
-
- 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
- C09D131/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
-
- 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
- C09J131/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
- Catalysts (AREA)
Abstract
包括元素周期第Ⅳb族金属和有机α-羟基和/或α-氧代酸的配盐水溶胶作为种子基础的聚乙烯酯分散体系。水溶胶包括一表面活性物质。该分散体系适于作为粘合剂和涂料组成。
Description
本发明涉及包含表面活性物质的金属配盐水溶胶;也涉及在这些作为种子基础的水溶胶存在下的乙烯酯自由基乳液聚合的特别方法。本发明另外还涉及用此法制备的聚乙烯酯分散体系用作多孔和半多孔基体的粘合剂的用途。
聚乙烯酯水分散体系(特别是聚醋酸乙烯酯水分散体系)是用作粘合木材和其它多孔基体的所谓白胶。这种粘合剂在文献中已有叙述,例如Handbook of Adhesives(粘合剂手册)3rdEd.,Chap.21,VanNostrand Reinhold,New York,1990和Wood Adhesives-Chemistryand Technology(木材粘合剂-化学和技术)Vol 1,Chap.7,MarcelDekker,New York,1983。
这些粘合剂通常是在聚合稳定剂(所谓的保护胶体,特别是聚乙烯醇)存在下用乙烯酯的自由基乳液聚合制备的。此方法在技术文献中是广泛讨论的,其述评可见于下述文献中,例如Wood Adhesives-Chemistry and Technology,Vol.2,Chap.2,Marcel Dekker,NewYork,1989。
乙烯酯、特别是醋酸乙烯酯在聚乙烯醇存在下的乳液聚合通常产生粘度相对高的分散体系。与仅借助于纯乳化剂稳定的分散体系比较,其粒度分布也是较宽的。再者,决定于聚合的方法、引发剂类型、稳定剂类型和其它参数,观察到颗粒附聚的情况也是常有的。此现象特别是分散体系粘度进一步增加的起因,直至产生糊状的粘稠度并影响了流动性,此现象也使剪切稳定性受到损害,并且一般说来对于窄粘度范围分散体系的重复制备起着负作用。
聚乙烯酯分散体系的一个亚类是由其粘合键提高了抗水性的那些化合物形成的。在这些分散体系中,用作保护胶体的聚乙烯醇的亲水性常常因与具有交联作用的乙烯基化合物(诸如N-羟甲基(甲基)丙烯酰胺)共聚而降低。
例如专利文献US-A3,301,809、DE-C2620738和DE-A3942628中的方法是被建议使用的。结合使用酸性固化剂(诸如无机酸或酸性金属盐水溶液,例如三氯化铝水溶液),就可得到抗水的粘合剂。
此方法的一个已知的缺点是,共聚合增加量的交联剂N-羟甲基(甲基)丙烯酰胺时,其结果是观察到了粘度的进一步剧烈增加。再者,在贮存时此分散体系(特别是酸催化形式)趋向于粘度和结构的增加。因此,酸催化的胶料配方的适用期通常是短的。
文献DE-C2620738和DE-A3942628叙述了一个二步聚合法,其中单体混合物的一部分先加入到水液中,另一部分是计量加入的。所加入的单体主要是醋酸、新戊酸和Versatic酸(α,α-二烷基羧酸,Shell-Chemie)的乙烯酯,也有N-羟甲基丙烯酰胺。取决于乙烯酯的类型和相继加入的酸性催化剂的类型,所得到的胶料配方至少有4周的适用期。
US-A4085074建议用诸如氨、单-、双-或三(羟)烷基胺、特别是三乙醇胺之类的挥发性含氮碱作为诸如三氯化铝之类的酸性金属盐的交联抑制剂。该碱是随后加入胶料配方的。用此方法改性的配方贮存稳定性超过了3个月,其粘度明显低于现今市场对此种体系的要求(至少7Pa·s),虽然其贮存前的粘度<1.5Pa·s。再者,包括含氮碱的分散体系在贮存时经常有变黄的趋向。
另外,上述的两种试尝方法均未能解决使用增量N-羟甲基(甲基)丙烯酰胺制备的聚乙烯酯分散体系的粘度急剧增加的问题。
DE-C2620738和DE-A3942628中采用的方法显然包括在颗粒种子上的接枝反应,种子是在聚合的初始阶段中产生的并由已经预交联和用聚乙烯醇稳定的聚合物组成。
常规方法接种聚合的基本原理是,在水液中进行乳液聚合前,加入事先已经制备好的某一定量分散体系作为初始加料。在此方法中,在已有颗粒存在下以控制量的乳化剂和引发剂进行聚合反应,由此使得到特定的粒度分布成为可能(见J.W.Vanderhoff,Chem.En-gin.Sci.48,203(1993))。但这种方法的缺点是制备这种分散体系需要有两个聚合步骤。
另外,文献中包括了接种聚合的许多变体,代替聚合物种子乳胶的是在乳液聚合前加入无机颗粒种子,例如颜料。这种颗粒的实例是细分的碳酸钙、二氧化钛或硅胶颗粒,它们在聚合中被在其上生长的聚合物所包裹。A.Revillon等在Double Liaison431-432,285(1991)中做了文献述评。
EP-B0337672叙述了用氧化还原引发剂体系在高比例二氧化钛颜料颗粒存在下的乙烯酯乳液聚合,主要在诸如羟乙基纤维素和聚丙烯酸之类的聚合稳定剂存在下和在阴离子乳化剂存在下进行,其结果是颜料颗粒未被包裹而是分离的颗粒形式,周围是聚合物颗粒,形成了似花结的形式。这种分散体系有改进的不透明度和相对的高剪切粘度,被用作表面涂料。
从文献(A.Clearfield,Rev.Pure and Appl.Chem.(纯粹和应用化学述评),14,91(1964))可知,用锆(IV)和二齿氧配位体稳定的配合物是可以制取的,它是在加低分子量α-羟基羧酸(例如羟基乙酸)后从锆(IV)盐的酸性水溶液中以胶凝状的非晶形式沉淀的。这些化合物也包括螯合配合物,其中的α-羟基羧酸是作为二齿氧配位体出现的。
本发明的目的是开发一种自由基乳液聚合的方法以制备主要由保护胶体(诸如聚乙烯醇)稳定的聚乙烯酯分散体系,这种方法提供了降低的颗粒附聚倾向,并由此改进终产品的流变控制并赋予较低的乳胶粘度,甚至是在相对大量的交联共聚单体(诸如N-羟甲基(甲基)丙烯酰胺)共聚时。而且在加入酸***联催化剂(例如三氯化铝水溶液)后,给予了用此方法催化的胶料配方以延长的贮存稳定性。
现惊人地发现,本发明目的的这两个方面可用一乳液聚合新方法来完成。该方法包括进行接种聚合,是在聚合前的含水聚合液中进行预先加入一有机酸和元素周期表IVb族金属(特别是锆)的胶态分散配盐作为颗粒种子,配盐以至少一种表面活性物质(特别是聚乙烯醇)进行稳定。
本发明提供一种由元素周期表IVb族金属(特别是锆)和有机α-羟基和/或α-氧代酸形成的配盐水溶胶,这种水溶胶包括一表面活性物质,优选占主要部分的聚合稳定剂,特别是聚乙烯醇。
适合于作为其后的乳液聚合颗粒种子的水溶胶的颗粒粒度通常是在200nm-5μm范围内。电子显微镜揭示,水溶胶颗粒本身又是粒度约为20nm的甚至更小的初级颗粒的集聚体。
优选的在本发明水溶胶中存在的稳定剂是聚乙烯醇,其水解度为60-100(摩尔)%,特别是70-98(摩尔)%;其4(重量)%浓度的水溶液的粘度在20℃下最好是2-70mPa·s。适合的聚乙烯醇最好与其后在含水聚合液中稳定聚乙烯酯分散体系的相同。因此采用有不同水解度和分子量的不同产品的混合物也是可能的。
如果在胶态分散配盐中使用不同的或附加的聚合稳定剂,则适合的保护胶体是没有游离羧基或其它与锆离子形成强配合物的官能基的保护胶体。在本文中可述及的例子有羟乙基纤维素、淀粉、淀粉衍生物、糊精和聚乙烯吡咯烷酮。
增用少量的阴离子、非离子或阳离子乳化剂是允许的。增用的最好是非离子乳化剂,诸如乙氧基化的脂肪醇。其量最好是使其在随后的聚合中的总量为0-3(重量)%,优选0.005-2(重量)%(基于单体量计算)。
用以稳定配合物的表面活性物质的量最好是每毫摩尔锆使用0.5-100克、特别是1-20克、更特别优选2-5克表面活性物质。
本发明的水溶胶包括元素周期表IVb族的至少一种元素,特别是锆。IVb族元素与IVb族其它元素或其它的金属元素的混合物也是能够使用的。
在本发明水溶胶中存在的有机α-羟基或α-氧代酸最好是在酸性介质中与水溶性锆(IV)盐形成不溶性配合物的α-羟基或α-氧代酸。按照本发明,在至少一个羧基的α-位上有一个羟基的特别适合的酸是乙醇酸、丙烯酰胺基乙醇酸、乳酸、柠檬酸、扁桃酸和酒石酸。除羧基外还在其α-位上有羰基并因此(以水合形式平衡)相对于羧基的α-位上有两个成对的羟基的其它适合的化合物的优选实例是乙醛酸和丙酮酸。乙醛酸是特别适合的并在本发明水溶胶的制备中作为随后的乳液聚合的颗粒种子是优先选择的。
所用的有机α-羟基和/或α-氧代酸与含水Zr(IV)盐的摩尔比对随后的乳液聚合中观察到的分散体系的粒度分布是有很重要作用的。在本文中,羧酸与锆的摩尔比最好应为0.001-4,特别是0.05-2,更特别优选0.08-1.2。
本发明也提供制备元素周期表IVb族金属(特别是锆)与有机α-羟基和/或α-氧代酸的配盐水溶胶的方法,该方法是在表面活性物质(优选主要是聚合稳定剂,特别是聚乙烯醇)存在下加入有机α-羟基和/或α-氧代酸或此酸的水溶液或有机溶液从均相水溶液中沉淀该金属的水溶性盐。
适合用作随后的乳液聚合的颗粒种子的最优选的用聚乙烯醇稳定的Zr(IV)配盐水溶胶的制备是例如用简单的方式首先制备确定浓度的聚乙烯醇水溶液。制备水溶胶时,聚乙烯醇溶液的浓度最好是1-20(重量)%。溶液的浓度是特别与随后所用的聚合液所具有的浓度相同的。将α-羟基羧酸或α-氧代羧酸溶于此溶液并搅拌,再加入酸性水溶性Zr(IV)盐的水溶液。所用的酸性水溶性Zr(IV)盐包括例如二氯氧化锆、硝酸锆、原硫酸锆和醋酸锆的水溶液。因为醋酸锆的酸性低于强酸性的二氯氧化锆、硝酸锆和原硫酸锆盐,所以前者是特别优选的,因为在加入此溶液后pH已在3-5的水平,适合于随后的乳液聚合,当然也可以在制备后用适合的中和剂(诸如稀氢氧化钠溶液)将水溶胶的pH升高到要求值。在醋酸锆的情况中,由于释放出醋酸而产生缓冲体系,当用于分散体系时能抑制纯粹由pH的改变而引起的任何粘度增加。用其它盐制备的水溶胶可加入适当的缓冲体系进行改性。经过一段时间(取决于反应温度)后,形成了水溶胶,视溶液开始出现乳状混浊的稠度而辨认。适合的反应温度为20-90℃,优选30-80℃,特别优选40-60℃。水溶胶在此温度范围通常几分钟内就可形成。然后可将其加入聚合液或最好是将其在一槽法中用作随后的乳液聚合的聚合液。
依靠所用稳定剂的类型和分子量,根据它在溶液中的浓度并因此而根据稳定剂相对于配合物的质量比,同时也根据反应时的搅拌速度,改变水溶胶的粒度是有可能的。在本发明中,特别是当使用聚乙烯醇时,增加分子量和其在溶液中的浓度并增加搅拌速度,其结果观察到了溶胶粒度的明显降低。
本发明还提供一种聚乙烯醇分散体系,它可在元素周期表第IVb族金属(特别是锆)和有机α-羟基和/或α-氧代酸的配盐水溶胶存在下用至少一种乙烯酯单体和进一步的可共聚单体(如果需要)进行乳液聚合来制取;其中的水溶胶包括表面活性物质,最好是占主要部分的聚合稳定剂,特别是聚乙烯醇。
本发明的均聚或共聚的聚乙烯酯分散体的单体基础可以是甲酸乙烯酯、醋酸乙烯酯、丙酸乙烯酯、异丁酸乙烯酯、新戊酸乙烯酯、2-乙基己酸乙烯酯、酸基中有9-10个碳原子的有α-支链的饱和一元羧酸的乙烯酯、长链饱和或不饱和脂肪酸乙烯酯(例如月桂酸乙烯酯和硬脂酸乙烯酯)以及苯甲酸和苯甲酸取代衍生物的乙烯酯(诸如对叔丁基苯甲酸乙烯酯)。在这些单体中,优选的是醋酸乙烯酯,上述的乙烯酯也可以组合用于聚乙烯醇。上述各乙烯酯在聚合物中的比例最好是至少50(重量)%。在共聚的聚乙烯醇分散体系中醋酸乙烯酯在各种乙烯酯总量中的比例最好是至少50(重量)%,特别是至少75(重量)%。
可与乙烯酯共聚的其它烯属不饱和单体是α,β-不饱和酸(例如丙烯酸和甲基丙烯酸)以及它们与1-18个碳原子的伯和仲饱和一元醇形成的酯,饱和一元醇之例是甲醇、乙醇、丙醇、丁醇、2-乙基己醇、环脂醇和长链脂肪醇。使用α,β-不饱和二元羧酸(例如马来酸、富马酸、衣康酸和柠康酸)以及这些酸与1-8个碳原子的饱和一元脂肪醇形成的单酯或二酯也是可以使用的。在单体总量中这些共聚单体的比例可达25(重量)%,优选0.1-15(重量)%。
适合的共聚单体还有烯属不饱和烃(诸如乙烯或3-18个碳原子的α-烯烃,例如丙烯和丁烯以及苯乙烯、乙烯基甲苯和乙烯基二甲苯)和卤代不饱和脂肪烃(例如氯乙烯、氟乙烯、1,1-二氯乙烯和1,1-二氟乙烯)。在单体总量中这些共聚单体的比例可达50(重量)%,优选1-25(重量)%。
此外,在聚合时聚合物中存在交联的烯属多不饱和单体也是可能的。烯属多不饱和单体的实例有邻苯二甲酸二烯丙酯、马来酸二烯丙酯、氰脲酸三烯丙酯、四烯丙氧基乙烷、二乙烯基苯、1,4-丁二醇的二(甲基丙烯酸)酯、二(甲基丙烯酸)三甘醇酯、己二酸二乙烯酯、(甲基)丙烯酸烯丙酯、巴豆酸乙烯酯、亚甲基双丙烯酰胺、二丙烯酸己二醇酯、二丙烯酸季戊四醇酯、三羟甲基丙烷的三丙烯酸酯。单体总量中的这些共聚单体的比例可达10(重量)%,优选0.01-2(重量)%。
特别适合的共聚单体是那些具有N-官能基的单体,它们特别包括(甲基)丙烯酰胺、氨基甲酸烯丙酯、丙烯腈、N-羟甲基(甲基)丙烯酰胺、N-羟甲基氨基甲酸烯丙酯以及N-羟甲基(甲基)丙烯酰胺或N-羟甲基氨基甲酸烯丙酯的N-羟甲基酯、N-烷基醚或曼尼斯碱,或是丙烯酰胺基乙醇酸、丙烯酰胺基甲氧基乙酸甲酯、N-(2,2-二甲氧基-1-羟乙基)丙烯酰胺、N-二甲基氨基丙基(甲基)丙烯酰胺、N-甲基(甲基)丙烯酰胺、N-丁基(甲基)丙烯酰胺、N-环己基(甲基)丙烯酰胺、N-十二烷基(甲基)丙烯酰胺、N-苄基(甲基)丙烯酰胺、对羟苯基(甲基)丙烯酰胺、N-(3-羟基-2,2-二甲基丙基)甲基丙烯酰胺、乙基咪唑酮甲基丙烯酸酯、N-乙烯基甲酰胺、N-乙烯基乙酰胺、N-羟甲基-N-乙烯基乙酰胺、N-乙烯基吡咯烷酮、N-羟乙基(甲基)丙烯酰胺、N-羟丙基(甲基)丙烯酰胺、N-羟甲基马来酰胺、N-羟甲基马来酰胺酸和它们与C1-18脂肪醇形成的酯,以及芳族乙烯基羧酸的N-羟甲基酰胺,例如N-羟甲基对乙烯基苯甲酰胺。当按本发明制备的分散体系是用作防水粘合剂时,丙烯酸和甲基丙烯酸的N-羟甲基酰胺是特别优选的。这些共聚单体在单体总量中的比例可达10(重量)%,优选0.1-5(重量)%。
适合的共聚单体还有含羟基官能的单体,诸如(甲基)丙烯酸(2-羟乙酯)、(甲基)丙烯酸(3-羟丙酯)和它们与环氧乙烷或环氧丙烷的加合物,这些共聚单体在单体总量中的比例能达10(重量)%,优选0.1-5(重量)%。
适合的共聚单体还有那些具有自动交联基或能通过羰基交联的基团的单体,诸如二丙酮丙烯酰胺、乙酰乙酸烯丙酯、乙酰乙酸乙烯酯和(甲基)丙烯酸乙酰乙酰氧基乙酯。这些共聚单体在单体总量中的比例可达10(重量)%,优选0.01-5(重量)%。
除乙烯酯单元外,在聚合物中含有的共聚单体单元的比例加在一起可达50(重量)%。
按本发明制备的均聚或共聚聚乙烯酯分散体系是用保护胶体稳定的。保护胶体可事先置于含水聚合液中或部分事先加入部分在聚合中计量加入;或者在某些情况中也可以随后加入。所用的保护胶体可以相同于或不同于在水溶胶中所采用的。如果事先制备的锆盐配合物水溶胶是完全在一槽法中直接用作聚合液,那么已溶于水溶胶水相中的保护胶体(特别是聚乙烯醇)自然在聚合前已经加入。再者,如果需要,在聚合前加入或在聚合中逐渐加入或在聚合后进一步加入水溶液形式的保护胶体(特别是聚乙烯醇)当然也是可以的。
优选的制备和稳定聚乙烯酯分散体系的适合化合物是聚乙烯醇,特别是水解度为60-100(摩尔)%、优选70-98(摩尔)%并在20℃下4(重量)%的水溶液粘度为2-70mPa·s的聚乙烯醇。采用官能化的聚乙烯醇作为保护胶体也是可能的。这可被理解为这样的化合物,它们用与适当的化合物相继反应或与适当的单体共聚合而具有诸如氨基、羧基或乙酰乙酰基之类的官能基。可以述及的实例是聚乙烯醇与双烯酮的反应产物或有巴豆酸或乙烯胺单元的共聚聚乙烯醇。
其它可以采用的保护胶体是醚化的纤维素衍生物(例如羟乙基纤维素或羧甲基纤维素)或聚乙烯吡咯烷酮,聚丙烯酸,α-烯烃和马来酸、马来酸衍生物或马来酐的共聚物,以及苯乙烯与马来酸、马来酸衍生物或马来酐的共聚物。它们最好是与聚乙烯醇组合使用。以固体含量为基础,聚合保护胶体(包括已用于制备锆盐配合物水溶胶的聚乙烯醇或其它聚合稳定剂)的比例最好是1-20(重量)%,特别是2-12(重量)%。
除了聚合保护胶体外,在聚合液中使用达3(重量)%(包括可能已用于制备水溶胶的量)基于聚合物计算的非离子和/或离子型乳化剂也是可能的。
本发明还提供制备聚乙烯酯分散体系的方法,该方法是在元素周期表第IVb族金属(特别是锆)与α-羟基和/或α-氧代酸的配盐水溶胶存在下用至少一种乙烯酯单体和另外的可共聚单体(如果需要)进行连续或非连续的乳液聚合,所用的水溶胶包括表面活性物质,最好以聚合稳定剂为主,特别是聚乙烯醇。
在这一方法中,使用了水溶性和/或油溶性引发剂体系,诸如过二硫酸盐、偶氮化合物、过氧化氢、有机氢过氧化物或过氧化二苯甲酰。这些体系可以单独使用,也可与还原性化合物结合使用作为氧化还原催化体系,还原性化合物是诸如Fe(II)盐、焦亚硫酸钠、亚硫酸氢钠、亚硫酸钠、连二亚硫酸钠、甲醛-次硫酸钠或抗坏血酸。包括例如氢过氧化叔丁基与甲醛一次硫酸钠结合使用的氧化还原催化体系是优先选择的。
聚合时的反应温度为20-100℃,特别是50-90℃,更优选60-85℃。
允许使用的聚合方法是普通的非连续或连续自由基乳液聚合法,但优选使用非连续法,诸如批量法、批/供联合法或纯单体供料法。纯单体供料法是特别使用的。在此情况下可在包括锆配盐水溶胶的聚合液中初始加入小比例(低于10(重量)%)的单体以引发聚合。这一聚合过程最好是控制在使反应器中的单体没有明显的聚集。
与常规类型的接种聚合相比,此法也因其简单而受到注意。从工艺安全观点考虑它也是有利的,因为它包括一个纯供料过程。
本发明以简单和安全的步骤,可能由于抑制了聚合时聚合物颗粒附聚,使作为终产物得到的分散体系的流变学的突出控制成为可能。
乳液聚合时水溶胶附聚物大概是被还没有详细研究的过程所破坏。破坏的结果是当分散体系作为薄膜应用时没有能观察到对分散体系的性能破坏。
本发明还提供用聚乙烯酯分散体系作为涂料或粘合剂组成,特别是常用的或抗水的多孔或半多孔基体的粘合剂,例如木材粘合剂或纸张粘合剂的用途,以及用于粘合模压层状材料、纤维革和织物的用途。其适宜性最好是使用的终产品要求高剪切稳定性和贮存稳定性的部门。
为了成型作为粘合剂的终产品,另外可再向聚乙烯醇分散体系加惯用添加剂。这些添加剂的实例是降低成膜温度(MFT)的成膜辅助剂(例如丁基二甘醇的乙酸酯)以及增塑剂、消泡剂、填料和防腐剂。
如果用交联或自动交联共聚单体(例如N-羟甲基(甲基)丙烯酰胺)制备的分散体系是要用作适用期长的防水粘合剂,那么,最好再加pKa<2.5的无机酸(例如磷酸或酸性水溶盐-例如三氯化铝、硝酸铝或二氯氧化锆)的水溶液作为交联催化剂。此后这些粘合剂满足了按DINEN204标准分类的至少是强度D2类,优选强度D3类。
下面的实施例用以说明本发明。实施例中的份数或百分数均以重量计,除非另外指明。
实施例
用聚乙烯醇稳定的Zr(IV)配盐水溶胶的制备
实施例H1-H7
用水解度为88(摩尔)%并在20℃其4%的水溶液具有如表1所示粘度的部分水解的聚乙烯醇制备各重500克并有表1所示浓度的水溶液。在50℃下于各溶液中溶解1.56克(10.5毫摩尔)二羟乙酸(浓度为50%),用桨式搅拌器搅拌(100rpm)。10分钟后,在每一溶液中计量加入5.88克(10.5毫摩尔Zr)市售乙酸锆溶液(浓度22%,基于ZrO2计算),历时10分钟。再经30分钟后,冷却至室温,其间该批料成为乳白混浊状稠料。
水溶胶新制样品的粒度测定是用光子关联能谱法。dz的值是单形态分布累积评价中的Z-平均值(仪器:Malvern4700,散射角90℃;其测定方法学见J.P.Fischer和E.Nolken,Progr.Colloid &Polymer Science 77,180(1988))所示的范围介定了测定的每种情况中至少2个重复批粒的粒度Z-平均值。
表1:
实施例 | 4%的PVA水溶液的粘度[mpa·s](Mw[g/mol]) | 溶液浓度[%] | 质量PVA/Zr量[g/mmol] | dz[μm](范围) | dz[μm](平均值) |
H1 | 26(160,000) | 1 | 0.5 | 2.1-3.0 | 2.5 |
H2 | 26(160,000) | 7 | 3.3 | 1.2-2.0 | 1.6 |
H3 | 26(160,000) | 13 | 6.2 | 0.8-1.4 | 1.1 |
H4 | 4(31,000) | 7 | 3.3 | 2.6-5.9 | 4.1 |
H5 | 8(67,000) | 7 | 3.3 | 2.6-4.2 | 3.6 |
H6 | 18(130,000) | 7 | 3.3 | 1.7-4.3 | 3,0 |
H7 | 40(205,000) | 7 | 3.3 | 0.9-2.0 | 1.4 |
很明显,在Z-平均值范围和由各分别值(未示出)形成的平均值的一系列基础上,增加稳定剂(聚乙烯醇)的量和(使用相等的量)增加4%浓度溶液的粘度并因而增加聚乙烯醇的分子量,水溶胶的细度性能也有所提高。
在用聚乙烯醇稳定的Zr(IV)配盐水溶胶存在下聚醋酸乙烯酯分散体系的制备
实施例1和2,对比例V1,V2和V3
1)聚合液的制备
在一带有锚式搅拌器(110rpm)并装有计量装置、回流冷凝器、夹套加热和冷却装置的10升玻璃反应器中先加入水解度88(摩尔)%、20℃时4%浓度水溶液的粘度为26mPa·s的部分水解的聚乙烯醇的7%浓度水溶液3440克。
在实施例1和2中,溶液用10.65克二羟乙酸(浓度50%)和40.32克醋酸锆(22%ZrO2)按类似于实施例H2的步骤处理。随后用40.7克浓度为10%的NaOH溶液将水溶胶的pH自3调至5。然后将此溶液直接进一步用于一槽法中。
在对比例V1和V2中(常用步骤,液体不需处理),聚乙烯醇溶液不经进一步处理即用作聚合液。
在对比例V3(用乙酸盐缓冲液缓冲)中,首先用16.56克乙酸固样将pH调至3,然后再用74.3克浓度为10%的NaOH调至5。
2)乳液聚合
于50℃的内部温度下将4克Agitan 280(消泡剂,Munzing-Chemie)、溶于33克水中的0.24克Rongalit C(甲醛-次硫酸钠,BASF)和200克醋酸乙烯酯(5份)此液体中相继加入。内部温度升至60℃并加入1.13克Trigonox AW70(氢过氧化叔丁基,纯度70%,Akzo-Chemie)于20克水中的溶液引发聚合。
初始加料的聚合完全后(内部温度68℃),在3小时的过程中计量加入一方面由3840克(95份)醋酸乙烯酯和3.5克Trigonox AW70(实施例1和V1)或由3760克(93份)醋酸乙烯酯和3.5克Trigonox AW 70和166.7克(2份)N-羟甲基丙烯酰胺于400克水(浓度48%)(实施例2、V2和V3)、另一方面由1.2克Rongalit C于400克水中组成的两批或三批供料。控制夹套温度使内部温度由开始时的68℃缓慢升至大约80℃无回流地进行聚合。然后相继加入0.57克Trigonox AW 70和0.18克Rongalit C分别在10克和80克水中的溶液进行后期聚合。冷却后,将160克醋酸丁基二甘醇酯缓慢搅拌到分散体系中以降低MFT。
分散体系分析
1.粘度:Brookfield RVT(7/20),23℃
2.触变面积是在Rheomat 115型(Contraves公司)旋转式粘度计中在剪切范围D=20-1000S-1测定。测定条件:上向曲线持续时间为1分钟,D=1000S-1时的保留时间为5分钟,下向曲线持续时间为1分钟。
3.粒度分布分析用下列文献中所述的方法:Xe***溶胶光谱法(Xe-LAS)进行:J.P.Fischer,FH Texte der Fachhoch-SchuleAachen,Vol.66(1995)和其中引用的文献(例如KunstharzNachrichten 28,12 ff(1991))。
表2:分散体系的分析数据
实施例 | 共聚单体 | 固体含量[%] | pH | 粘度[Pa·s] | 触变面积[MPa·s-1] |
1 | - | 52.7 | 4.5 | 33 | 0.23 |
V1 | - | 52.2 | 3.8 | 102 | 2.18 |
2 | 2%NMA | 49.6 | 4.5 | 15 | 0.16 |
V2 | 2%NMA | 50.2 | 3.9 | 78 | 3.19 |
V3 | 2%NMA | 50.1 | 4.9 | 53 | 1.01 |
从表中明显可见,本发明的实施例1和2(均有很低的触变面积)有极高的剪切稳定性,并且在有可比的固体含量情况下与实施例V1、V2和V3分别比较有显著低的粘度。纯粹用醋酸缓冲液缓冲(同样施以正效应),如实施例V3,是不可能带来这样作用的。有这种特性的原因是粒度分布的差异。
表3:粒度分布分析
实施例 | 光显微法 | xe-LAS:dw(范围) |
1 | 主要是单颗粒及少量附聚体 | 双形态分布0.4-0.8μm(单颗粒)及1.5-3μm(附聚体) |
V1 | 少量单颗粒,主要是颗粒附聚体 | 双形态分布0.3-0.6μm(单颗粒)及0.9-3μm(附聚体) |
2 | 主要是单颗粒及较少量附聚体 | 双形态分布0.4-0.8μm(单颗粒)及1.5-3μm(附聚体) |
V2 | 主要是颗粒附聚体 | 1.5-4μm(附聚体) |
V3 | 主要是颗粒附聚体 | 1.5-4μm(附聚体) |
实施例2-A,比较例V2-A和V3-A
共聚的聚醋酸乙烯酯分散体与酸性固化剂结合作为防水木材粘合剂的测试
将27重量份浓度为28%的三氯化铝水溶液分别搅拌加入1000重量份实施例2、V2和V3的分散体系中。粘合剂特性以测试标准DIN EN204(以前为DIN68602)为基础进行测定。所需测试试样制备按DIN EN205(以前为DIN53254)的步骤进行。上胶和测试在下列条件下进行:涂胶: 150±20g/m2,施于两面上开放等候时间: 3分钟闭合等候时间: 3分钟加压时间: 2小时加压压力: 0.7±0.1N/mm2每系列试样数 20
在下述贮存周期后测试:按DIN EN204D1/1贮存周期:7天标准条件*)按DIN EN204D3/3贮存周期:7天标准条件
4天于冷水中按D1/80℃贮存周期: 7天标准条件(非DIN EN204部分) 于80℃炉中2小时
(在80℃下测试)
(*)23±2℃和50±5%相对大气湿度)
测试温度: 23℃±2℃
前进速度: 50mm/分钟
撕裂强度≥10N/mm2为强度类D1/1
撕裂强度≥2N/mm2为强度类D3/3
加固化剂后的适用期测定
在室温下的贮存实验中,此时间是在加固化剂后粘合剂分散体系仍然是容易流动的粘度≤75Pa·s(用Brookfield RVT 7120测定)的时间,在该时间以后分散体满足粘合剂的标准值。
所得的测试数据列于下表4中。数据表明,本发明方法的实施例2-A和比较例都满足所要求的标准试验值。而且实施例2-A的适用期有戏剧性的增加,2个月以后继续满足所有的标准试验值。表4
实施例 | 2-A | V2-A | V3-A |
粘度BrookfieldRVT7/20开始[Pa·s] | 9 | 64 | 47 |
D1/1[N/mm2] | 15.8 | 15.4 | 16.9 |
D1/80℃[N/mm2] | 8.3 | 8.4 | 8.5 |
D3/3[N/mm2] | 3.5 | 4.5 | 5.1 |
适用期 | >>6周 | <14天 | <14天 |
D1/1 2月后[N/mm2] | 16.9 | - | - |
D1/80℃2月后[N/mm2] | 7.8 | - | - |
D3/3 2月后[N/mm2] | 5.8 | - | - |
Claims (11)
1.一种元素周期表第IVb族金属和有机α-羟基和/或α-氧代酸的配盐水溶胶,该水溶胶包括一表面活性物质。
2.权利要求1的水溶胶,其中的有机酸是单官能或多官能羧酸,在其至少一个羧基的α-位上有一个羰基,羰基在平衡的水相中是完全或部分水合的。
3.权利要求1的水溶胶,其中有机酸是乙醛酸。
4.权利要求1的水溶胶,其中IVb族金属是锆。
5.权利要求1的水溶胶,其中表面活性物质是聚乙烯醇。
6.一种制备如权利要求1所述的元素周期表IVb族金属和α-羟基和/或α-氧代酸的配盐水溶胶的方法,该方法是在表面活性物质存在下通过加入有机α-羟基和/或α-氧代酸或该有机酸的水溶液或有机溶液从水溶性金属盐的均相水溶液中沉淀而进行。
7.一种聚乙烯酯分散体系,该分散体系是在元素周期表第IVb族金属和有机α-羟基和/或α-氧代酸的配盐水溶胶存在下使至少一种乙烯酯单体和(需要时)其它可共聚单体经乳液聚合得到的,该水溶胶包括一表面活性物质。
8.一种制备聚乙烯酯分散体系的方法,该方法是在元素周期表第IVb族金属和有机α-羟基和/或α-氧代酸的配盐水溶胶存在下使至少一种乙烯酯单体和(需要时)其它可共聚单体经连续或不连续的自由基乳液聚合进行的,该水溶胶包括一表面活性物质。
9.权利要求7的聚乙烯酯分散体系,其中醋酸乙烯酯被用来作为乙烯酯单体。
10.权利要求8的聚乙烯酯分散体系,其中自动交联或随后可交联单体是被用来作为其它可共聚单体的。
11.用权利要求7的聚乙烯酯分散体系作为粘合剂或涂料组成的用途。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN96194859A CN1188486A (zh) | 1995-05-15 | 1996-05-10 | 以金属盐水溶胶作为种子基础的聚乙烯酯分散体系 |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19517777A DE19517777A1 (de) | 1995-05-15 | 1995-05-15 | Polyvinylester-Dispersion mit Metallsalz-Hydrosolen als Saatgrundlage |
DE19517777.0 | 1995-05-15 | ||
CN96194859A CN1188486A (zh) | 1995-05-15 | 1996-05-10 | 以金属盐水溶胶作为种子基础的聚乙烯酯分散体系 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1188486A true CN1188486A (zh) | 1998-07-22 |
Family
ID=7761935
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN96194859A Pending CN1188486A (zh) | 1995-05-15 | 1996-05-10 | 以金属盐水溶胶作为种子基础的聚乙烯酯分散体系 |
Country Status (22)
Country | Link |
---|---|
US (1) | US5889107A (zh) |
EP (1) | EP0826008B1 (zh) |
JP (1) | JP3626201B2 (zh) |
KR (1) | KR19990014792A (zh) |
CN (1) | CN1188486A (zh) |
AR (1) | AR001932A1 (zh) |
AT (1) | ATE182158T1 (zh) |
AU (1) | AU5894796A (zh) |
BR (1) | BR9608786A (zh) |
CA (1) | CA2221144A1 (zh) |
CO (1) | CO4560364A1 (zh) |
CZ (1) | CZ361297A3 (zh) |
DE (2) | DE19517777A1 (zh) |
ES (1) | ES2135232T3 (zh) |
GR (1) | GR3031394T3 (zh) |
HU (1) | HUP9801392A1 (zh) |
NO (1) | NO975248L (zh) |
PL (1) | PL323361A1 (zh) |
TR (1) | TR199701357T1 (zh) |
TW (1) | TW340121B (zh) |
WO (1) | WO1996036648A1 (zh) |
ZA (1) | ZA963803B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110669487A (zh) * | 2019-10-11 | 2020-01-10 | 大庆华营化工有限公司 | 一种流度控制剂及其制备方法 |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6436538B1 (en) | 1998-08-24 | 2002-08-20 | Ciba Specialty Chemicals Corporation | Nitrogen doped carbon-coated effect pigments and their manufacture |
US6869996B1 (en) * | 1999-06-08 | 2005-03-22 | The Sherwin-Williams Company | Waterborne coating having improved chemical resistance |
DE19949332A1 (de) | 1999-10-13 | 2001-05-23 | Clariant Gmbh | Verfärbungsarme Dispersionsklebstoffe mit verlängerter Topfzeit |
WO2001048026A1 (fr) * | 1999-12-27 | 2001-07-05 | Atofina | Latex ayant un haut extrait sec, une faible viscosite et presentant une distribution bimodale |
DE10163586A1 (de) * | 2001-12-21 | 2003-07-03 | Clariant Gmbh | Verwendung von weichmacherfreien, wässrigen copolymeren Poly(vinylester)- Dispersionen in Lebensmittelbeschichtungsmassen |
US20040003892A1 (en) * | 2002-07-08 | 2004-01-08 | Lehman Nicholas C. | One part woodworking adhesive composition |
JP4231309B2 (ja) * | 2003-03-14 | 2009-02-25 | リケンテクノス株式会社 | ゾル状熱可塑性樹脂組成物の製造方法 |
DE10335673B4 (de) | 2003-08-04 | 2007-01-18 | Celanese Emulsions Gmbh | Wässrige Dispersionsklebstoffe, Verfahren zu deren Herstellung und deren Verwendung |
EP1799782B1 (en) * | 2004-10-08 | 2012-12-12 | The Sherwin-Williams Company | Self crosslinking waterborne coatings |
US7960452B2 (en) * | 2005-07-01 | 2011-06-14 | Akzo Nobel Coatings International B.V. | Adhesive composition and method |
US8147979B2 (en) * | 2005-07-01 | 2012-04-03 | Akzo Nobel Coatings International B.V. | Adhesive system and method |
US8048257B2 (en) | 2006-06-23 | 2011-11-01 | Akzo Nobel Coating International B.V. | Adhesive system and method of producing a wood based product |
US20090317651A1 (en) * | 2006-06-23 | 2009-12-24 | Akzo Nobel Coatings International B.V. | Adhesive system and method of producing a wood based product |
DE102007033595A1 (de) | 2007-07-19 | 2009-01-22 | Celanese Emulsions Gmbh | Polyvinylesterdispersionen, Verfahren zu deren Herstellung und deren Verwendung |
DE102007033596A1 (de) | 2007-07-19 | 2009-01-22 | Celanese Emulsions Gmbh | Beschichtungsmittel mit hoher Bewitterungsbeständigkeit, Verfahren zu deren Herstellung und deren Verwendung |
CN104718225A (zh) | 2012-06-22 | 2015-06-17 | 塞拉尼斯乳液有限公司 | 疏水性乙烯基酯共聚物分散体 |
JP6753333B2 (ja) * | 2017-02-24 | 2020-09-09 | 三菱ケミカル株式会社 | 架橋構造体の製造方法、及びインクジェット記録媒体 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2455937A (en) * | 1944-10-23 | 1948-12-14 | Eastman Kodak Co | Preparation of hardened polyvinyl alcohol coatings |
US3301809A (en) * | 1965-04-23 | 1967-01-31 | Nat Starch Chem Corp | Nu-methylol acrylamide-vinyl acetate copolymer emulsions containing polyvinyl alcohol |
US3941730A (en) * | 1972-06-05 | 1976-03-02 | E. I. Du Pont De Nemours And Company | Polyvinyl alcohol microgel precursor blends |
US4085074A (en) * | 1976-03-29 | 1978-04-18 | National Casein Of New Jersey | Pre-mixed catalyzed vinyl acetate polymer adhesive composition |
DE2620738C2 (de) * | 1976-05-11 | 1983-04-28 | Wacker-Chemie GmbH, 8000 München | Verfahren zur Herstellung wäßriger Copolymerdispersionen und deren Verwendung in Vermischung mit sauren, wasserlöslichen Härtezusätzen für Klebemittel |
DE3126201A1 (de) * | 1981-07-03 | 1983-01-20 | Hoechst Ag, 6000 Frankfurt | Verfahren zur herstellung einer polyvinylalkohol-komplexverbindung und danach hergestellte polyvinylalkohol-komplexverbindung |
GB8808755D0 (en) * | 1988-04-13 | 1988-05-18 | Crown Decorative Prod Ltd | Aqueous surface coatings |
DE3942628A1 (de) * | 1989-12-22 | 1991-06-27 | Wacker Chemie Gmbh | Verwendung waessriger copolymerdispersionen unter zusatz von sauren metallsalzen oder freien saeuren als klebemittel |
-
1995
- 1995-05-15 DE DE19517777A patent/DE19517777A1/de not_active Withdrawn
-
1996
- 1996-04-29 TW TW085105084A patent/TW340121B/zh active
- 1996-05-06 CO CO96022327A patent/CO4560364A1/es unknown
- 1996-05-10 JP JP53453096A patent/JP3626201B2/ja not_active Expired - Fee Related
- 1996-05-10 CZ CZ973612A patent/CZ361297A3/cs unknown
- 1996-05-10 DE DE59602451T patent/DE59602451D1/de not_active Expired - Fee Related
- 1996-05-10 KR KR1019970708136A patent/KR19990014792A/ko not_active Application Discontinuation
- 1996-05-10 WO PCT/EP1996/001999 patent/WO1996036648A1/de not_active Application Discontinuation
- 1996-05-10 AT AT96916036T patent/ATE182158T1/de not_active IP Right Cessation
- 1996-05-10 AU AU58947/96A patent/AU5894796A/en not_active Abandoned
- 1996-05-10 EP EP96916036A patent/EP0826008B1/de not_active Expired - Lifetime
- 1996-05-10 CA CA002221144A patent/CA2221144A1/en not_active Abandoned
- 1996-05-10 PL PL96323361A patent/PL323361A1/xx unknown
- 1996-05-10 HU HU9801392A patent/HUP9801392A1/hu unknown
- 1996-05-10 ES ES96916036T patent/ES2135232T3/es not_active Expired - Lifetime
- 1996-05-10 TR TR97/01357T patent/TR199701357T1/xx unknown
- 1996-05-10 BR BR9608786A patent/BR9608786A/pt not_active Application Discontinuation
- 1996-05-10 CN CN96194859A patent/CN1188486A/zh active Pending
- 1996-05-10 US US08/930,096 patent/US5889107A/en not_active Expired - Fee Related
- 1996-05-13 AR AR33649696A patent/AR001932A1/es unknown
- 1996-05-14 ZA ZA9603803A patent/ZA963803B/xx unknown
-
1997
- 1997-11-14 NO NO975248A patent/NO975248L/no unknown
-
1999
- 1999-09-30 GR GR990402485T patent/GR3031394T3/el unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110669487A (zh) * | 2019-10-11 | 2020-01-10 | 大庆华营化工有限公司 | 一种流度控制剂及其制备方法 |
CN110669487B (zh) * | 2019-10-11 | 2021-07-23 | 大庆华营化工有限公司 | 一种流度控制剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
TR199701357T1 (xx) | 1998-02-21 |
ZA963803B (en) | 1997-11-14 |
JPH11506482A (ja) | 1999-06-08 |
ATE182158T1 (de) | 1999-07-15 |
DE19517777A1 (de) | 1996-11-21 |
GR3031394T3 (en) | 2000-01-31 |
CZ361297A3 (cs) | 1998-03-18 |
CO4560364A1 (es) | 1998-02-10 |
TW340121B (en) | 1998-09-11 |
AU5894796A (en) | 1996-11-29 |
PL323361A1 (en) | 1998-03-30 |
WO1996036648A1 (de) | 1996-11-21 |
ES2135232T3 (es) | 1999-10-16 |
AR001932A1 (es) | 1997-12-10 |
EP0826008A1 (de) | 1998-03-04 |
DE59602451D1 (de) | 1999-08-19 |
CA2221144A1 (en) | 1996-11-21 |
NO975248D0 (no) | 1997-11-14 |
US5889107A (en) | 1999-03-30 |
JP3626201B2 (ja) | 2005-03-02 |
NO975248L (no) | 1998-01-06 |
KR19990014792A (ko) | 1999-02-25 |
EP0826008B1 (de) | 1999-07-14 |
HUP9801392A1 (hu) | 1998-11-30 |
MX9708866A (es) | 1998-03-31 |
BR9608786A (pt) | 1999-02-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1188486A (zh) | 以金属盐水溶胶作为种子基础的聚乙烯酯分散体系 | |
CN1021053C (zh) | 疏水性改进的羟乙基纤维存在下聚合物水乳胶的制备方法 | |
CN101223234A (zh) | 水性分散液及其制备方法、以及组合物、粘合剂和涂层剂 | |
CN101663330A (zh) | 悬浮聚合用分散稳定剂 | |
CN1146997A (zh) | 吸水树脂的制备方法 | |
EP1358217A2 (en) | Highly functional polymer latex | |
CN1185267C (zh) | 乙烯基化合物的悬浮聚合用分散稳定剂 | |
EP1373324A2 (en) | Highly functional polymer latex | |
CN1183796A (zh) | 木材胶粉 | |
TWI445717B (zh) | Production method of ethylene-based resin | |
TW202005991A (zh) | 改質乙烯醇系聚合物及其製造方法、以及懸浮聚合用分散穩定劑及乙烯系聚合物之製造方法 | |
CN1127528C (zh) | 淀粉降解/接枝聚合组合物、制备方法及其用途 | |
CN1345353A (zh) | 乙烯基化合物的水乳液和悬浮聚合用分散剂 | |
JP4849753B2 (ja) | アクリル系エマルジョンの製造方法 | |
JP4145466B2 (ja) | 合成樹脂エマルジョン粉末 | |
JP3758705B2 (ja) | 乳化分散安定剤 | |
JP3426358B2 (ja) | ポリビニルアルコール系樹脂微粒子の製造法 | |
JP2004300193A (ja) | 水性エマルジョン | |
JP5730123B2 (ja) | 水性エマルション | |
JP4245213B2 (ja) | 酢酸ビニル樹脂系エマルジョン製造用乳化用分散安定剤およびその用途 | |
JPH08193154A (ja) | 不均質ポリビニルエステル分散物および−粉末 | |
CN1281701C (zh) | 单组分木材加工粘合剂组合物 | |
JP2007270002A (ja) | 水性エマルジョンおよびその組成物 | |
JP4627381B2 (ja) | アセト酢酸エステル基含有ポリビニルアルコール系樹脂の製造方法 | |
JP2000063427A (ja) | アセト酢酸エステル基含有ポリビニルアルコール系樹脂の製造法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C01 | Deemed withdrawal of patent application (patent law 1993) | ||
WD01 | Invention patent application deemed withdrawn after publication |