CN1088940A - 可生物降解的水分散液 - Google Patents
可生物降解的水分散液 Download PDFInfo
- Publication number
- CN1088940A CN1088940A CN93120849A CN93120849A CN1088940A CN 1088940 A CN1088940 A CN 1088940A CN 93120849 A CN93120849 A CN 93120849A CN 93120849 A CN93120849 A CN 93120849A CN 1088940 A CN1088940 A CN 1088940A
- Authority
- CN
- China
- Prior art keywords
- weight
- biodegradable
- weight parts
- acid
- ester
- 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 34
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 26
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 23
- 239000000084 colloidal system Substances 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 12
- 239000004902 Softening Agent Substances 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000004815 dispersion polymer Substances 0.000 claims abstract description 4
- 238000010556 emulsion polymerization method Methods 0.000 claims abstract description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 3
- -1 alkyl carboxylic acid Chemical class 0.000 claims description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 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 claims description 3
- BQCXFGVWPFXMKD-UHFFFAOYSA-N 2,2-dimethylpropanoic acid;ethenyl acetate Chemical compound CC(=O)OC=C.CC(C)(C)C(O)=O BQCXFGVWPFXMKD-UHFFFAOYSA-N 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000004375 Dextrin Substances 0.000 claims description 3
- 229920001353 Dextrin Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 235000019425 dextrin Nutrition 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000151 polyglycol Polymers 0.000 claims description 3
- 239000010695 polyglycol Substances 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000005018 casein Substances 0.000 claims description 2
- 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 claims description 2
- 235000021240 caseins Nutrition 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 235000019395 ammonium persulphate Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 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 2
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000012874 anionic emulsifier Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229920002988 biodegradable polymer Polymers 0.000 description 2
- 239000004621 biodegradable polymer Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000001177 diphosphate Substances 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000005385 peroxodisulfate group Chemical group 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-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
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical class OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 125000003047 N-acetyl group Chemical group 0.000 description 1
- 229920006197 POE laurate Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- ZLXPLDLEBORRPT-UHFFFAOYSA-M [NH4+].[Fe+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Fe+].[O-]S([O-])(=O)=O ZLXPLDLEBORRPT-UHFFFAOYSA-M 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 125000005340 bisphosphate group Chemical group 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding 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
- 239000011111 cardboard Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 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
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000011953 free-radical catalyst Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 229940116335 lauramide Drugs 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- KCTMTGOHHMRJHZ-UHFFFAOYSA-N n-(2-methylpropoxymethyl)prop-2-enamide Chemical compound CC(C)COCNC(=O)C=C KCTMTGOHHMRJHZ-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 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
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- KJHVQUXINXTRMC-UHFFFAOYSA-N sulfanediol zinc Chemical compound [Zn].S(O)O KJHVQUXINXTRMC-UHFFFAOYSA-N 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 235000019263 trisodium citrate Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000009941 weaving Methods 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
- 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
- C08F18/00—Homopolymers and 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
- C08F18/02—Esters of monocarboxylic acids
- C08F18/04—Vinyl esters
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08J3/18—Plasticising macromolecular compounds
-
- 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
- C09D131/04—Homopolymers or copolymers of vinyl acetate
-
- 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
- C09J131/04—Homopolymers or copolymers of vinyl acetate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Biological Depolymerization Polymers (AREA)
- Medicinal Preparation (AREA)
Abstract
本发明提供可生物降解的乙烯酯聚合物水分散
液，该分散液的固体含量为20至70％(重量，以分散
液的总重量为基准)，且是采用乳化聚合法借助自由
基聚合作用制得，其中，在有10至50％(重量，以单
体相为基准)的可生物降解的增塑剂及0.5至15.0％
(重量，以单体相为基准)的可生物降解的乳化剂和/
或可生物降解的保护胶体的存在下，使一单体相实施
聚合作用。
Description
本发明涉及可降解的乙烯酯聚合物水分散液、其制法及其用途。
聚醋酸乙烯酯仅可缓慢地生物降解是已公开的事实（Huang S.J.，Biodegradable Polymers in：Encyclopedia of Polymer Sciences，Vol ume 2，Pages 220-243）。M. Buday（C.A.101（4）：24316n）曾揭示：即使在活性污泥中，聚醋酸乙烯酯及丙烯酸丁酯/醋酸乙烯酯共聚物分散液亦仅能相当缓慢地降解，且降解速率与粒子大小及其比表面积有关。覆膜材料，一经形成，例如当在涂覆部分使用了醋酸乙烯酯分散液后，仍不易降解。实际上，这些物质的生物降解须耗时数年。经交联的产品，则依交联程度的不同，降解速率愈加缓慢。
用作粘合剂或涂覆剂的乙烯酯共聚物，其增塑共聚单体，例如：乙烯、丙烯酸丁酯或丙烯酸2-乙基己酯，可进一步延缓生物降解。该项作用，由这些共聚单体可延缓乙酸乙烯酯单元水解成可生物降解的乙烯醇单元的事实而获得说明（Huang S.J.，Biodegradable Polymers in：Encyclopedia of Polymer Sciences，Volume 2，Pages 220-243）。
尤其由于环保意识提高，日益迫切需要容易生物降解的塑料。所以，纺织及造纸工业要求涂覆及粘合组合物内所用的粘结剂，必须是可生物降解、任意交联的塑料水分散液。
WO-A 91/02025及EP-A 400532曾述及若干可生物降解的共聚物组合物，其中包括乙烯/乙酸乙烯酯共聚物、淀粉及增塑剂。这些组合物是将组合物的固体成分加以混合及共挤出而制得的。
本发明的目的是提供几种乙烯酯聚合物水分散液，这些水分散液可生物降解，且适用作涂覆剂及粘合剂。
本发明涉及可生物降解的乙烯酯聚合物水分散液，该分散液的固体含量为20至70%重量比（以分散液的总重量为基准），且是采用乳化聚合法借助自由基聚合作用制得，其中，在有10至50%（重量，以单体相为基准）的可生物降解的增塑剂及0.5至15.0%（重量，以单体相为基准）的可生物降解的乳化剂和/或可生物降解的保护胶体的存在下，使一单体相聚合，该单体相包括：
a）50至100重量份的一种或多种乙烯酯，所述乙烯酯选自一组包括由具有1至15个碳原子的分枝或不分枝烷基羧酸所形成的乙烯酯;
b）0至30重量份的乙烯和/或由（甲基）丙烯酸或乙烯型不饱和二羧酸与具有1至10个碳原子的醇所形成的酯;及
c）0至20重量份的其他单-或聚-乙烯型不饱和化合物。
优选的乙烯酯是：乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、十二烷酸乙烯酯、乙酸1-甲基乙烯酯、三甲基乙酸乙烯酯及具有9或10个碳原子、α-支链的单羧酸的乙烯酯，例如：VeoVa9R或VeoVa10R。
甲基丙烯酸、丙烯酸或乙烯型不饱和二羧酸的酯，其优选的是：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-乙基己酯及反丁烯二酸和/或顺丁烯二酸的酯或半酯，例如：反丁烯二酸二异丙酯。
适当的共聚单体c）是官能共聚单体，例如：丙烯酰胺、顺丁烯二酸-酰胺、磺酸乙烯酯、N-乙烯吡咯烷酮及N-乙烯内酯。其他亦适当的共聚单体是可交联的共聚单体，例如：乙酰乙酸乙烯酯、或其他可共聚合的乙酰乙酸酯;可共聚合的烷氧基硅烷化合物，例如：乙烯基三乙氧基硅烷;可共聚合的环氧化物，例如：缩水甘油醇的乙烯基或烯丙基化合物;N-羟甲基化合物，例如：N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺及N-羟甲基烯丙基氨基甲酸酯;及乙烯型不饱和羧酸的N-烷氧基烷酰胺，例如：N-（异丁氧基甲基）-丙烯酰胺。更适当的共聚单体是聚乙烯型不饱和共聚单体，例如：乙二醇的二乙烯基及二烯丙基醚;饱和二羧酸的二乙烯基及二烯丙基酯;聚羧酸的聚乙烯基及聚烯丙基酯，例如：邻苯二甲酸二烯丙基酯及顺丁烯二酸二烯丙基酯;二-及聚羟基化合物与（甲基）丙烯酸的二-及聚酯;（甲基）丙烯酸或巴豆酸、顺丁烯二酸或反丁烯二酸的乙烯基及烯丙基酯;及二乙烯基苯及三聚氰酸三烯丙基酯。
假若适当，以0.1至10重量份的官能性和/或可交联的共聚单体c），优选的是：仅乙酸乙烯酯实施聚合作用。单体相的其他优选组成物是：
75至95重量份的乙酸乙烯酯，5至25重量份的乙烯及（假若适当）0.1至10重量份的官能性和/或可交联的共聚单体c）;
65至95重量份的乙酸乙烯酯，5至35重量份的十二烷酸乙烯酯、乙酸1-甲基乙烯酯、三甲基乙酸乙烯酯、VeoVa9或VeoVa10及（假若适当）0.1至10重量份的官能性的和/或可交联的共聚单体c）;
50至70重量份的乙酸乙烯酯，5至30重量份的VeoVa9或VeoVa10，5至25重量份的乙烯及（假若适当）0.1至10重量份的官能性和/或可交联的共聚单体c）;
50至70重量份的乙酸乙烯酯，5至25重量份的乙烯，0.5至20重量份的（甲基）丙烯酸酯及（假若适当）5至30重量份的VeoVa9或VeoVa10和/或0.1至10重量份的官能性和/或可交联的共聚单体c）。
可生物降解的增塑剂，其较为适当的是：C4至C12-α，ω-链烷二羧酸的烷基酯，其中，这些酯的烷基可含有2至18个碳原子。可举的实例是：癸二酸酯，例如：癸二酸二丁酯;1，2-亚乙基二醇（ethyleme glycot）衍生物、丙三醇衍生物及山梨糖醇衍生物的十二烷酸酯，及柠檬酸酯，例如：柠檬酸三丁酯。聚合物增塑剂，例如：优选为分子量为800至5000（最好为1500至3000）的乙二醇己二酸聚酯、聚乙二醇，聚丙二醇。前述的聚合物增塑剂，其具有酯、酰胺或胺基甲酸乙酯等终端基的尤为优选。前述的增塑剂亦可以混合物形式而使用。
非离子乳化剂或可生物降解的非离子及阴离子乳化剂的混合物，亦可用作可生物降解的乳化剂。但非离子乳化剂较为优选。
适当的非离子乳化剂的实例是：聚氧乙烯缩合生成物，例如：聚氧乙烯十二烷基醚，聚氧乙烯十八烯基（oleyl）醚及聚氧乙烯氢化枞酸基（hydroabietyl）醚。其他的实例是：高级脂肪酸的聚氧乙烯酯，例如：聚氧乙烯十二酸酯、聚氧乙烯油酸酯及环氧乙烷与树脂酸及高油酸的缩合生成物，聚氧乙烯酰胺与胺的缩合生成物，例如：N-聚乙烯-十二酰胺及N-十二烷基-N-聚氧乙烯胺，聚氧乙烯硫醚，例如：聚氧乙烯正-十二烷基硫醚、环氧乙烷/环氧丙烷共聚物及由脂肪醇所形成的带有环氧乙烷单元的聚乙二醇醚。不用前述的聚氧乙烯化合物，亦可采用相对应的聚-N-甲酰-或聚-N-乙酰胺乙烯。
依照本发明可使用的非离子乳化剂，亦包含许多称作“Pluronics”的表面活性剂，其通用化学式为：HO（C2H4O）a（C3H6O）b（C2H4O）cH，其中，a、b及c为1或更大的整数。若a及c保持大致恒定不变，b增加，此类化合物变得更难溶于水及更易溶于油，所以更加疏水。
合适的阴离子乳化剂的实例是：脂肪酸的碱金属或铵盐，硫酸烷基酯及烷基磺酸，例如：十二酸盐、硫酸十二烷基酯或磺酸十二烷基酯。其他实例是：磺基琥珀酸与一元脂肪醇所形成的半酯。
乳化剂总量所占的浓度为0.5至15%（重量，以单体相为基准）。单独一种乳化剂或前述乳化剂的混合物均可使用。若所用的为乳化剂的混合物，以采用较疏水的乳化剂与较亲水的乳化剂相搭配较为有利。较疏水的乳化剂，于88℃以下的1%浓度水溶液中具有一浊度点，较亲水的乳化剂，于88℃或以上的1%浓度水溶液中具有一浊度点。
除乳化剂外，本发明的分散液亦可包括保护胶体或只包括保护胶体，以产生稳定作用。可生物降解的保护胶体，其较为适当且值得一提的是：
淀粉;氰烷化、羟烷化和/或羧甲烷化的淀粉;糊精、明胶及酪蛋白，及甲基-、羟乙基-、羟丙基-及乙酰基纤维素;以及聚乙烯醇、聚乙烯己内酰胺、聚乙烯吡咯烷酮及前述最后三类化合物的水溶性共聚物。
这些保护胶体可以使用的量，与粘度及稳定作用所需的量有关。举例说来，若使用已经稳定的淀粉，则1%（重量，以单体相为基准）的量即已足够。但若其粘度较高，使用量不超过8%（重量，以单体相为基准）也属适当。对比之下，低分子量的糊精，使用量亦高达100%（重量，以单体相为基准）以上。若使用普通聚乙烯醇，且不需另外添加乳化剂，通常需要3%（重量，以单体相为基准）以上的量。
本发明的乳化聚合是在0至100℃的温度下进行的，优选为35至80℃。乙烯实施共聚合作用的优选压力可高达100巴（1×107Pa）。若无乙烯参与共聚合作用，在特定聚合作用温度下，聚合作用至少是在单体自生的压力下进行的。
实施乳化聚合作用，优选采用氧化还原催化剂***。在此步骤中，还原剂及氧化剂可依照反应需要计量加入，或先将氧化剂全部加入反应器内，再陆续将还原剂计量加入，以控制聚合作用。以单体相为基准，所需氧化剂是0.01至1.5%（重量），优选0.03至0.8%（重量）。以单体相为基准，还原剂的优选使用量是0.01至1.0%（重量）。催化剂氧化部分的实例是：过硫酸铵或钾、过氧化氢、叔丁基氢过氧化物，过氧二磷酸盐，例如：过氧二磷酸钾、钠及铵，及过氧二硫酸盐，例如：过氧二硫酸铵。还原剂部分的实例是：亚硫酸钠、亚硫酸氢钠、甲醛化次硫酸锌（Zinc formaldehyde-sulfoxylate）或甲醛化次硫酸钠（Sodium formaldehyde-sulfoxylate）。H2/贵金属催化剂，同时使用少量重金属盐作为活化剂，也同样适合。“Fundamental Principles of Polymerization”（G.F.Alelio，J.Wiley and SonsInc.，New York，1952）第333页以后诸页，曾述及适当的氧化还原催化剂***。
原则上，在无还原剂存在的情况下，也可能使用自由基催化剂，如氢过氧化物、过硫酸盐、过氧二磷酸盐。在本***中或上述的各***中，也可能使用例如微量铁盐作为加速剂。
共聚合作用进行时，pH值以2.5至7较为优选。开始时，可用少量酸或碱达到该pH值。为防止聚合作用过程中pH值急剧下降，可加入若干缓冲物质。这类物质的实例是：碳酸钠或碳酸铵、硼砂、乙酸钠及柠檬酸钠及第一级和第二级碱金属磷酸盐的混合物。
实施本发明的乳化聚合作用，优选以采用计量法。在此作用中，优选的方式是：除共聚单体c）之外，首先将5至30%（重量）的乙烯酯a）及其他共聚单体加入反应器内，单体相的其余部分则计量加入。若有乙烯参加共聚合作用，开始时可一次将其全部加入或部分地计量加入。优选的是，于聚合作用开始前，先建立乙烯的压力，聚合作用进行期间，假若适当，陆续送入乙烯，以保持乙烯的压力恒定不变。举例言之，为制备不同组成的聚合物，于聚合反应过程中，乙烯的压力当然亦可改变。
乳化剂及（假若适当）保护胶体系于开始时加入反应器或采用全部或部分计量加入。部分乳化剂或保护胶体，需用计量加入的，其添加工作，至迟须于分散液的固体含量已达35%（重量）较为优选。本发明的分散液，其固体含量介于20至70%（重量）。即使固体含量甚高时，这类分散液的粘度亦相当低。
本发明的可生物降解的分散液，可适作纸张、织物、玻璃纤维、木材及卡纸板的涂覆剂及粘合剂。
分散液的生物降解作用，因含有可生物降解的增塑剂、乳化剂及（假若适当）可生物降解的保护胶体而得以加速，因微生物的降解作用最初主要是由这些物质本身开始，亦即乙烯酯聚合物的表面积及其降解速率因而增加。经覆膜及交联的标本得以快速衰变，单体/增塑剂混合物的聚合性的大幅改善是惊人的。
以下实施例，可对本发明作进一步的说明：
分散液的制备
制备分散液所使用的装置，是一附有锚型搅拌器的双壁式2升反应器。单体及辅助剂是经由精密计量器具加入。两种催化剂（过硫酸铵（APS）/Brüggolit）分别以4%及2%浓度的溶液，以软管泵计量加入。温度借助恒温器及内部温度调节器保持在45℃。
初始混合物的组成为：
40 克（8%重量）表1所示单体及增塑剂的混合物
220 克水
0.59 克Aerosol A102（磺基琥珀酸与具有10至12个碳原子的一元脂肪醇所形成的半酯）的30%浓度溶液
1.07 克Genapol PF40（环氧乙烷/环氧丙烷共聚物）的97%浓度溶液
0.2 克硫酸铵铁
用甲酸将初始混合物的pH值调至3.4。
将计量液1及2加入初始混合物内：
计量液1 （计量加入时间约6小时）：
2.92 克过氧二硫酸铵溶于70毫升水中
计量液2 （计量加入时间约6小时）：
1.48 克Brüggolit溶解于72.5毫升水中
聚合作用开始后，计量液3及4开始加入：
计量液3 （计量加入时间约3.5小时）：
460 克（92%重量）表1所示单体及增塑剂与3毫升Vanisol溶液的混合物
计量液4 （计量加入时间约3.5小时）：
6.16 克丙烯酸
42.5 克N-羟甲基丙烯酰胺（48%浓度水溶液）
48.0 克Genapol OX130（具有13个环氧乙烷基的脂肪醇所形成的聚乙二醇醚）的25%浓度溶液
24.0 克水
如此制备的分散液，其固体含量、残余单体含量、粘度、K值及粒子大小均具特征。其湿渣及分散液稳定度亦经鉴定。所得结果详见表1。
为鉴定各实施例中所制分散液的薄膜性能，将分散液倾倒入一模具内并予以烘干，则形成约1毫米厚的薄膜。该薄膜的强度、粘合性、渗出、外观及硬度均借助目视加以鉴定。所得结果如表1所示。
为鉴定生物降解性能，借助上述方法制得0.2毫米厚的薄膜，依照ISO846方法B，对这种薄膜作真菌试验。于14日后测定真菌繁殖及麻点。测定结果亦如表1所示。
Claims (7)
1、一种可生物降解的乙烯酯聚合物水分散液，该分散液的固体含量为20至70%(重量，以分散液的总重量为基准)，且是采用乳化聚合法借助自由基聚合作用制得，其中，在有10至50%(重量，以单体相为基准)的可生物降解的增塑剂及0.5至15.0%(重量，以单体相为基准)的可生物降解的乳化剂和/或可生物降解的保护胶体的存在下，使一单体相实施聚合作用，该单体相包括：
a)50至100重量份的一种或多种乙烯酯，所述乙烯酯选自具有1至15个碳原子的不分枝或分枝烷基羧酸所形成的乙烯酯，
b)0至30重量份的乙烯和/或由(甲基)丙烯酸或乙烯型不饱和二羧酸与具有1至10个碳原子的醇所形成的酯，及
c)0至20重量份的其他单-或聚-乙烯型不饱和化合物。
2、如权利要求1所述的可生物降解的水分散液，所述分散液包括可生物降解的增塑剂，C4至C12-α，ω-烷二羧酸的烷基酯，其中，所述酯的烷基可含有2至18个碳原子，分子量为800至5000的乙二醇己二酸聚酯、聚乙二醇或聚丙二醇。
3、如权利要求1或2所述的水分散液，所述分散液包括可生物降解的乳化剂，聚氧乙烯缩合生成物、高级脂肪酸的聚氧乙烯酯、聚氧乙烯酰胺、聚氧乙烯硫醚、环氧乙烷/环氧丙烷共聚物或由脂肪醇所形成的带有环氧乙烷单元的聚乙二醇醚。
4、如权利要求1至3之一所述的水分散液，所述分散液包括可生物降解的保护胶体，淀粉，氰烷化、羟烷化、和/或羧甲烷化的淀粉，糊精、明胶、酪蛋白、甲基-、羟乙基-、羟丙基-及乙酰基纤维素，聚乙烯醇、聚乙烯己内酰胺或聚乙烯吡咯烷酮。
5、如权利要求1至4之一所述的水分散液，其中，所述的共聚单体相的组成物是：乙酸乙烯酯及（假若适当）0.1至10重量份的官能性和/或可交联的共聚单体c）;或
75至95重量份的乙酸乙烯酯，5至25重量份的乙烯及（假若适当）0.1至10重量份的官能性和/或可交联的共聚单体c）;或
65至95重量份的乙酸乙烯酯，5至35重量份的十二烷酸乙烯酯、乙酸1-甲基乙烯酯、三甲基乙酸乙烯酯、VeoVa9或VeoVa10，及（假若适当）0.1至10重量份的官能性和/或可交联的共聚单体c）;或
50至70重量份的乙酸乙烯酯，5至30重量份的VeoVa9或VeoVa10，5至25重量份的乙烯，及（假若适当）0.1至10重量份的官能性和/或可交联的共聚单体c）;或
50至70重量份的乙酸乙烯酯，5至25重量份的乙烯，0.5至20重量份的（甲基）丙烯酸酯，及（假若适当）5至30重量份的VeoVa9或VeoVa10和/或0.1至10重量份的官能性和/或可交联的共聚单体c）。
6、一种制备如权利要求1至5之一所述的可生物降解的水分散液的方法，该方法包括：在温度0至100℃、并有氧化还原催化剂***存在的情况下进行乳化聚合作用，其中，最初先将所用的5至30%（重量）的乙烯酯a）及除共聚单体c）外的其他共聚单体加入反应器内，其余部分则计量加入，乳化剂和/或保护胶体可于开始时加入反应器或全部或部分计量地加入。
7、一种将权利要求1至5之一所述的可生物降解的水分散液用作涂覆剂或粘合剂的方法。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4242781A DE4242781A1 (de) | 1992-12-17 | 1992-12-17 | Biologisch abbaubare, wäßrige Dispersionen |
| DEP4242781.9 | 1992-12-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1088940A true CN1088940A (zh) | 1994-07-06 |
Family
ID=6475653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93120849A Pending CN1088940A (zh) | 1992-12-17 | 1993-12-17 | 可生物降解的水分散液 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5750617A (zh) |
| EP (1) | EP0603746B1 (zh) |
| JP (1) | JP2645637B2 (zh) |
| KR (1) | KR0133969B1 (zh) |
| CN (1) | CN1088940A (zh) |
| DE (2) | DE4242781A1 (zh) |
| ES (1) | ES2077463T3 (zh) |
| TW (1) | TW267177B (zh) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103732711A (zh) * | 2011-08-05 | 2014-04-16 | 塞拉尼斯乳液有限公司 | 用于在粘合剂中使用的低甲醛乙烯基酯/乙烯共聚物分散体 |
| CN105189563A (zh) * | 2013-04-10 | 2015-12-23 | 盛禧奥欧洲有限公司 | 使用多级降解法生产高固体份淀粉分散液的工艺 |
| CN105722866A (zh) * | 2013-11-14 | 2016-06-29 | 瓦克化学股份公司 | 包含乙酸乙烯酯-乙烯共聚物的地面铺层粘合剂组合物 |
| CN107118624A (zh) * | 2017-04-28 | 2017-09-01 | 青岛高智高新科技有限公司 | 一种环境美化用易降解粉刷颜料 |
| CN111117529A (zh) * | 2019-12-30 | 2020-05-08 | 广东银洋环保新材料有限公司 | 一种可自然降解的胶粘剂及其制备方法和胶粘带 |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19526759A1 (de) * | 1995-07-21 | 1997-01-23 | Wacker Chemie Gmbh | Redispergierbare, vernetzbare Dispersionspulver |
| US6162850A (en) * | 1997-09-24 | 2000-12-19 | Cook Composites And Polymers Co. | Heat resistant emulsion resins |
| SK281409B6 (sk) * | 1998-02-19 | 2001-03-12 | Duslo, A. S. | Spôsob prípravy kopolymérovej vodnej disperzie na báze vinylesteru versatikovej kyseliny, vinylacetátu a akrylátových esterov |
| DE10027016A1 (de) * | 2000-05-31 | 2001-12-20 | Cht R Beitlich Gmbh | Polymerdispersion mit verbesserter biologischer Abbaubarkeit |
| JP2001354841A (ja) * | 2000-06-16 | 2001-12-25 | Showa Highpolymer Co Ltd | 生分解性ポリエステルの水系分散液 |
| JP2002003607A (ja) * | 2000-07-13 | 2002-01-09 | Showa Highpolymer Co Ltd | 生分解性ポリエステルの水系分散液の製造方法 |
| DE10065058A1 (de) * | 2000-12-27 | 2002-07-11 | Sasol Germany Gmbh | Alkoxylierte Alkohole als Weichmacher für Polyvinylacetat-Kuststoffe |
| DE102005057645A1 (de) * | 2005-12-01 | 2007-06-06 | Celanese Emulsions Gmbh | Polyvinylesterdispersionen mit niedriger Filmbildtemperatur und hoher Wasserbeständigkeit sowie deren Verwendung |
| DE102006030557A1 (de) * | 2006-07-03 | 2008-01-10 | Celanese Emulsions Gmbh | Verfahren zur Herstellung wässriger Vinylester-Dispersionen |
| DE102007004298A1 (de) * | 2007-01-23 | 2008-07-24 | Eukalin Spezial-Klebstoff Fabrik Gmbh | Dispersionsklebstoff mit verringerter Migrationsneigung |
| 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 |
| AT506168B1 (de) * | 2007-11-23 | 2012-02-15 | Univ Wien Tech | Verwendung von zusammensetzungen zur herstellung biologisch abbaubarer, bioverträglicher, vernetzter polymere auf basis von polyvinylalkohol |
| US10329393B2 (en) | 2012-12-12 | 2019-06-25 | Eastman Chemical Company | Copolysters plasticized with polymeric plasticizer for shrink film applications |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE542476A (zh) * | 1954-11-01 | |||
| GB854191A (en) * | 1958-02-05 | 1960-11-16 | British Celanese | Improvements in or relating to the production of resinous compositions |
| GB901379A (en) * | 1960-02-17 | 1962-07-18 | Ici Ltd | Plasticisers |
| US3769151A (en) * | 1972-02-14 | 1973-10-30 | Union Oil Co | Adhesive composition and method of preparation |
-
1992
- 1992-12-17 DE DE4242781A patent/DE4242781A1/de not_active Withdrawn
-
1993
- 1993-09-23 TW TW082107822A patent/TW267177B/zh active
- 1993-12-09 KR KR1019930027112A patent/KR0133969B1/ko not_active IP Right Cessation
- 1993-12-16 ES ES93120310T patent/ES2077463T3/es not_active Expired - Lifetime
- 1993-12-16 EP EP93120310A patent/EP0603746B1/de not_active Expired - Lifetime
- 1993-12-16 DE DE59300631T patent/DE59300631D1/de not_active Expired - Fee Related
- 1993-12-17 JP JP5343232A patent/JP2645637B2/ja not_active Expired - Lifetime
- 1993-12-17 CN CN93120849A patent/CN1088940A/zh active Pending
-
1996
- 1996-08-05 US US08/689,092 patent/US5750617A/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103732711A (zh) * | 2011-08-05 | 2014-04-16 | 塞拉尼斯乳液有限公司 | 用于在粘合剂中使用的低甲醛乙烯基酯/乙烯共聚物分散体 |
| CN103732711B (zh) * | 2011-08-05 | 2016-04-06 | 塞拉尼斯乳液有限公司 | 用于在粘合剂中使用的低甲醛乙烯基酯/乙烯共聚物分散体 |
| CN105189563A (zh) * | 2013-04-10 | 2015-12-23 | 盛禧奥欧洲有限公司 | 使用多级降解法生产高固体份淀粉分散液的工艺 |
| CN105189563B (zh) * | 2013-04-10 | 2018-09-11 | 盛禧奥欧洲有限公司 | 使用多级降解法生产高固体份淀粉分散液的工艺 |
| CN105722866A (zh) * | 2013-11-14 | 2016-06-29 | 瓦克化学股份公司 | 包含乙酸乙烯酯-乙烯共聚物的地面铺层粘合剂组合物 |
| CN105722866B (zh) * | 2013-11-14 | 2019-02-22 | 瓦克化学股份公司 | 包含乙酸乙烯酯-乙烯共聚物的地面铺层粘合剂组合物 |
| CN107118624A (zh) * | 2017-04-28 | 2017-09-01 | 青岛高智高新科技有限公司 | 一种环境美化用易降解粉刷颜料 |
| CN111117529A (zh) * | 2019-12-30 | 2020-05-08 | 广东银洋环保新材料有限公司 | 一种可自然降解的胶粘剂及其制备方法和胶粘带 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0603746B1 (de) | 1995-09-20 |
| KR0133969B1 (ko) | 1998-04-20 |
| ES2077463T3 (es) | 1995-11-16 |
| TW267177B (zh) | 1996-01-01 |
| JP2645637B2 (ja) | 1997-08-25 |
| EP0603746A1 (de) | 1994-06-29 |
| DE4242781A1 (de) | 1994-06-23 |
| DE59300631D1 (de) | 1995-10-26 |
| US5750617A (en) | 1998-05-12 |
| JPH06211910A (ja) | 1994-08-02 |
| KR940014465A (ko) | 1994-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1088940A (zh) | 可生物降解的水分散液 | |
| CA1225791A (en) | Crotonate-containing copolymers, processes for their preparation and their use as thickeners in aqueous systems and as sizing agents | |
| DE602004001109T2 (de) | Polyvinylalkohol Copolymere und daraus formbare wasserlösliche Filme und Behälter | |
| EP0299787B1 (en) | Cloth-softening liquid composition | |
| US5292800A (en) | Water-in-oil polymer emulsions | |
| CN1124286C (zh) | 基于醋酸乙烯酯树脂的乳液的制备方法,以及含水粘合剂 | |
| EP1957188B2 (en) | A method of drying an absorbent polymer with a surfactant | |
| EP0153728A2 (en) | A method for preparing a vinyl acetate/ethylene emulsion using two polyvinyl alcohols as a stabilising system and an adhesive composition comprising the emulsion | |
| CN1243131A (zh) | 聚合物分散体 | |
| CA1282294C (en) | Toilet soap containing polymeric thickener | |
| EP1209198B1 (en) | Carboxylated polymer composition | |
| EP0072317B1 (fr) | Latex de copolymères acétate de vinyle-oléfine et procédé de préparation | |
| EP0072735B1 (fr) | Latex de polymères d'acétate de vinyle et procédé de préparation | |
| CN1151991A (zh) | 使用特定的烯不饱和可聚合水溶性非离子表面活性剂的改进的乳液聚合方法 | |
| EP1012196B1 (de) | Verfahren zur herstellung lösemittelfreier polivinylester-dispersionen mit erhöhter wasserresistenz | |
| US3778399A (en) | Novel emulsion adhesive compositions of vinyl acetate polymers | |
| EP0072734A1 (fr) | Procédé de préparation de latex de copolymères acétate de vinyle-oléfine | |
| EP3390606A1 (en) | Concentrated liquid detergents including antiredeposition polymers | |
| US3324064A (en) | Aqueous dispersions of vinylidene chloride-acrylate-vinylsulfonic acid copolymers | |
| CN1756778A (zh) | 环氧改性的氯乙烯－乙烯基酯共聚物固态树脂 | |
| JPH09209294A (ja) | 紙にまたは厚紙に撥油性および撥水性を付与する処理方法 | |
| EP0438949B1 (fr) | Agent de stabilisation non toxique des suspensions aqueuses de silico-aluminates de sodium | |
| JP3294910B2 (ja) | ポリクロロプレンラテックス組成物 | |
| US5478884A (en) | Oxyalkylene group-containing polyvinyl alcohol resin composition and process for the production of shaped articles from said composition | |
| US4748202A (en) | Novel aqueous dispersions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |