CN1022107C - Method for preparing polymer from carboxylic acid monomer - Google Patents
Method for preparing polymer from carboxylic acid monomer Download PDFInfo
- Publication number
- CN1022107C CN1022107C CN 88102702 CN88102702A CN1022107C CN 1022107 C CN1022107 C CN 1022107C CN 88102702 CN88102702 CN 88102702 CN 88102702 A CN88102702 A CN 88102702A CN 1022107 C CN1022107 C CN 1022107C
- Authority
- CN
- China
- Prior art keywords
- monomer
- weight
- solvent
- salt
- mixture
- 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.)
- Expired - Lifetime
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 71
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 14
- 229920000642 polymer Polymers 0.000 title abstract description 14
- -1 alkyl acetates Chemical class 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 229920000570 polyether Polymers 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 25
- 239000003999 initiator Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229940086737 allyl sucrose Drugs 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- LZDXRPVSAKWYDH-UHFFFAOYSA-N 2-ethyl-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)COCC=C LZDXRPVSAKWYDH-UHFFFAOYSA-N 0.000 claims description 2
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical group C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims 1
- 229940022682 acetone Drugs 0.000 claims 1
- 229940043232 butyl acetate Drugs 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 229940093499 ethyl acetate Drugs 0.000 claims 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims 1
- 229940011051 isopropyl acetate Drugs 0.000 claims 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 229940090181 propyl acetate Drugs 0.000 claims 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 abstract description 3
- 125000002843 carboxylic acid group Chemical group 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract 2
- 150000005846 sugar alcohols Polymers 0.000 abstract 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 150000002978 peroxides Chemical class 0.000 abstract 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229940059574 pentaerithrityl Drugs 0.000 description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920005601 base polymer Polymers 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 235000015320 potassium carbonate Nutrition 0.000 description 5
- 230000008719 thickening Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 210000003097 mucus Anatomy 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229940048053 acrylate Drugs 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000001261 hydroxy acids Chemical group 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002002 slurry 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
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-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
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 244000287680 Garcinia dulcis 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005587 bubbling 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical group [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 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
- 238000005502 peroxidation Methods 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- AMLFJZRZIOZGPW-UHFFFAOYSA-N prop-1-en-1-amine Chemical compound CC=CN AMLFJZRZIOZGPW-UHFFFAOYSA-N 0.000 description 1
- MRXVCTWDXRBVLW-UHFFFAOYSA-N prop-2-enoylsulfamic acid Chemical compound OS(=O)(=O)NC(=O)C=C MRXVCTWDXRBVLW-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
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-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
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
Abstract
A polymer of an ethylenically unsaturated carboxylic acid containing from 3 to 5 carbon atoms is prepared in a solvent selected from acetone and lower alkyl acetates and in the presence of not more than 5% of a cross-linking agent selected from the group consisting of peroxides and peroxydicarbonates, the polymer containing less than 0.2% by weight of unreacted monomer, the cross-linking agent being selected from the group consisting of polyalkenyl polyethers of polyhydric alcohols containing more than one alkenyl group per molecule, the polyhydric alcohols containing at least 4 carbon atoms and at least 3 hydroxyl groups. The polymerization temperature is from 40 to 85 ℃, the viscosity of the mixture after completion of the polymerization is less than 1000 centipoise, and the carboxylic acid groups of the polymer are about 1% to 10% neutralized.
Description
The polymkeric substance of unsaturated carboxylic acid and its esters comes out for many years.This base polymer comprises homopolymer and contains 10%(weight) multipolymer of following other copolymerisable monomer.Typical unsaturated carboxylic acid monomer has vinylformic acid, methacrylic acid, toxilic acid or its acid anhydrides, methylene-succinic acid etc.For example United States Patent (USP) 2,798, and 053 has introduced the multipolymer of vinylformic acid and a small amount of polyalkenyl polyether linking agent, and this multipolymer is gel, and it can absorb big water gaging or solvent and its volume is obviously increased, and is especially all the more so in the form that is in salt.United States Patent (USP) 3,940,351 and 4,062,817 have introduced unsaturated carboxylic acid and at least a its alkyl contains the acrylate of 1 to 20 carbon atom or the polymkeric substance of methacrylic ester.Even this base polymer is effective thickening material under the situation that quite a large amount of inorganic salt are arranged equally.United States Patent (USP) 3,915,921 and 4,066,583 have introduced the method for the same or similar polymkeric substance of preparation in similar system.
United States Patent (USP) 4,267,103 have introduced unsaturated carboxylic acid or the polymkeric substance of its esters in some solvent, wherein 1%(weight) above carboxyl is neutralized.The molecular weight of this base polymer is greater than 500, is up to millions ofly, but generally is in 10,000 to 100 ten thousand scope.This base polymer also is effective thickening material.
Summary of the invention:
In acetone or acetic acid low alkyl group ester solvent, under 40 ℃ to 85 ℃ conditions, make one or more be added with 0.1% to 1%(weight) monomer polymerization of initiator, preparation contains the single unsaturated carboxylic acid monomer of 3 to 5 carbon atoms and the polymkeric substance of salt thereof, its contained responseless unsaturated monomer amount is lower than 0.2%(weight), polymerization reaction mixture is lower than 30%(weight in contained amount of monomer of polyreaction initial stage), when finishing polyreaction, material Brooker Fil moral viscosity is determined as under 22 ℃ of 60 rev/mins of conditions and is lower than about 1000 centipoises in the reactor.
Detailed description of the invention:
At some application facet such as makeup and pharmaceutical preparations, the toxicity of each composition needs close inspection, has only the component that satisfies strict demand just to be used.This class thickening material mentioned in this article then must make monomer transform fully basically, makes wherein residual unsaturated monomer content be lower than about 0.2%(weight), and to be lower than about 0.1%(weight) for good.Weight percent to be converted to then 0.1%(weight of ppm) be equivalent to 1000ppm, vice versa.
According to known systems, production will make residual monomer content be lower than about 0.2%(weight such as polymkeric substance such as polyacrylic acid in vinyl acetic monomer) be impossible.But can reduce residual or unreacted monomer content by adding aftertreatments such as initiator and elevated temperature.This aftertreatment to polymkeric substance is disadvantageous, because this need increase initiator amount and time expand, has improved cost thus, and can cause polymer degradation.Make monomer polymerization by method of the present invention, can be without above-mentioned last handling process, just can produce to contain be less than 0.2%(weight) this base polymer of lower concentration unreacted monomer.
United States Patent (USP) 4,267,103rd, the example of prior art, polymkeric substance wherein contains a large amount of unreacted monomers.Introduced in this patent working example 1 70 ℃ and be added with allyl group tetramethylolmethane linking agent and the condition of lauroyl peroxide initiator under the polyreaction of vinylformic acid in vinyl acetic monomer.With sodium hydroxide the concentration of the hydroxy-acid group in the polymkeric substance is neutralized to 7.83% degree.The transformation efficiency of polyreaction is only seen the row head of the 8th row for 90%().
Press United States Patent (USP) 4,267 in 2 liters of band stirred reactors, the same program of regulation is made revision test with identical component consumption among 103 embodiment 1.The polymkeric substance that repeats embodiment 1 gained contains 1.03%(weight) unreacted vinylformic acid, this content is too high, is not suitable for purposes of the present invention.
Repeat other experiments of 4,267,103 li of United States Patent (USP)s, but the polymkeric substance that the ownership system gets all contains a large amount of unreacted vinylformic acid.And, then can obtain only to contain the polymkeric substance of the vinylformic acid of a small amount of unreacted monomer with other comonomer by method of the present invention, unreacted monomer content is lower than 0.2%(weight), and to be lower than 0.1%(weight) for good.
Polymkeric substance of the present invention comprises homopolymer and multipolymer.Principal monomer accounts for the 90%(weight of monomer mixture at least) preferably account for 95%(weight at least), it can be selected from monounsaturated monocarboxylic acid and di-carboxylic acid and its esters as first monomer.Second monomer (comonomer just) accounts for 10% of monomer mixture weight at most, to account for 5% at most for good.
The molecular weight of this base polymer is greater than about 500, and mostly is millions of most, and weight-average molecular weight is preferably about 10,000 to about 100 ten thousand.
Principal monomer is selected from olefinic unsaturated monocarboxylic acid and di-carboxylic acid and its esters that contains 3 to 5 carbon atoms, preferably is selected from monocarboxylic acid and its esters and acid anhydrides.Wherein the monomer of Shi Yonging comprises vinylformic acid, methacrylic acid, its vinylformic acid of second, α-Lv Daibingxisuan, alpha-cyanoacrylate, methylene-succinic acid, toxilic acid and maleic anhydride.In this class monomer, be good to select vinylformic acid, methacrylic acid, toxilic acid and maleic anhydride for use, because their general costs are lower, be easy to buy, can also make good polymkeric substance.In these monomers, select vinylformic acid the best for use.
Second monomer or title comonomer are selected from and contain a CH at least
2The monomer of=C end group or vinylidene.This class comonomer comprises the esters of acrylic acid of representing with following formula:
R is the alkyl that contains 1 to 30 carbon atom in the formula.This group comonomer comprises the acrylate that has aliphatic group, and wherein R contains 1 to 30 carbon atom, and is good to contain 2 to 20 carbon atoms.In these comonomers, R ' is hydrogen or low alkyl group, preferably hydrogen or methyl.The example of aliphatic acrylate comprises propylene ester ester in the last of the ten Heavenly stems, propylene ester isodecyl ester, vinylformic acid dodecane ester, vinylformic acid octadecane ester, vinylformic acid docosane ester, vinylformic acid triacontane ester, methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, Octyl acrylate, EHA and corresponding methyl acrylic ester.
Also can use other suitable monomer as second comonomer.They comprise acrylamido sulfonic acid; Propenyl nitrile such as vinyl cyanide; Propenyl amide such as acrylamide; N-hydroxyalkyl amide class such as N hydroxymethyl acrylamide; The alpha-olefines such as ethene and the propylene that contain 2 to 12 carbon atoms; Dienes such as divinyl and 1,3-pentadiene; Ethylidene norbornene and Dicyclopentadiene (DCPD); Vinyl ester such as vinyl acetate and vinyl benzoate; The vinyl aromatic same clan such as vinylbenzene; Vinyl and allyl ethers and ketone such as vinyl methyl ether and vinyl ketone; The vinyl nitrile; The Qing Wanji esters of acrylic acid; Vinyl halides and vinylidene halides such as vinylchlorid and vinylidene chloride; And other comonomer of introducing in the 4th row of United States Patent (USP) 4,267,103 and the 5th row.
This polymkeric substance can be with containing two CH at least
2Any multifunctional vinylidene monomer of=C end group gives crosslinked, and its example comprises divinyl, isoprene, Vinylstyrene, divinyl naphthalene, allyl acrylate etc.If used certain cross-linking monomer, the useful especially linking agent that then is used to prepare multipolymer is that per molecule is at least with the polyalkenyl polyether of two alkenyl ethers.And with the olefinic double bonds and the methylene radical end group CH of wherein alkenyl
2It is the most useful that=C joins.The usefulness of polyether linking agent increases with the number of potential polymerisable group on the molecule.Preferably use per molecule on average to contain the polyether of two or more alkenyl ether groups.It is the diallyl ethers, 1 of 50 to 1000 polyether glycol that typical linking agent has allyl group tetramethylolmethane, allyl sucrose, trimethylolpropane allyl ether, molecular weight, 6-hexanediyl ester, Viscoat 295, pentaerythritol triacrylate, tetramethylene diacrylate, diacrylate ethyl, triethylene glycol dimethacrylate etc.Improved the swelling behavior of multipolymer behind the crosslinked polymer.
If be added with cross-linking monomer, then add other monomeric gross weight by the carboxylic acid monomer.Polymeric blends contains 5% the cross-linking monomer of having an appointment at most, preferably contains 0.2% to 2.0%.
The solvent that is liquid when room temperature is 22 ℃ is applicable to the present invention, and The suitable solvent is selected from the low alkyl group acetic ester that contains 1 to 6 carbon atom (is good to contain 2 to 4 carbon atoms) in acetone and the alkyl.The object lesson of these acetic esters comprises vinyl acetic monomer, Iso Butyl Acetate, n-butyl acetate etc.The consumption of solvent should make that monomer solid content is lower than about 30%(weight in the system), and be 10% to 20% for good with solid content.
Water content in the solvent should reduce as far as possible, and about 3% because if the water content in the solvent surpasses, reaction mass can become deleterious solid rubber shape material.Can make the bed body of the material of solvent dehydration that solvent is constantly dewatered through distillation column or through siccative or other solvent, can obtain satisfied result.But because polyreaction can produce water byproduct and make this problem complicated.But, can remove water in the reaction mass as stated above and the water content of solvent can be controlled at be lower than 3% concentration, and to be controlled at 0.05% to 1% for good.
Monomeric polyreaction generally is to carry out in the presence of radical initiator in solvent medium, and this reaction can be carried out in closed container under inert atmosphere and spontaneous pressure or artificial induction's pressure condition.Or under barometric point and reflux conditions, in open containers, carry out.According to the type of selected initiator, polymeric reaction temperature can be in about 40 ℃ to 85 ℃ changes, and is better with 45 ℃ to 55 ℃ or 70 ℃ to 80 ℃.The radical initiator that is suitable for is that those can be the initiator of polymkeric substance with all conversion of monomers under temperature of reaction substantially.The example of this class initiator comprises two (2-ethylhexyl) peroxy dicarbonate, two (sec-butyl) peroxy dicarbonates, two (sec.-propyl) peroxidation, two carbon carboxylic esters, dicyclohexyl peroxy dicarbonate, double hexadecyl peroxy dicarbonate, two (n-propyl) peroxy dicarbonate, lauroyl peroxide and other similar superoxide and peroxy dicarbonate.Two (2-ethylhexyl) peroxy dicarbonate is that effectively lauroyl peroxide then is only under 70 ℃ to 80 ℃ temperature of reaction condition effectively under 45 ℃ to 55 ℃ temperature of reaction.By the charging monomer weight, the consumption of initiator generally is lower than 2%, and is good with 0.4% to 1.0%.
In order to prevent polymer gel, should adopt the metallic compound (as oxyhydroxide, oxide compound or carbonate etc.) of first main group to make to have at least partly that hydroxy-acid group is neutralized.Its example comprises lithium, sodium, potassium, caesium etc.; And employing and ammonia and some amine method of reacting, ammonia and amine comprise morpholine,, two and trolamine, monopropylene glycol amine and other amine, wherein, partial polymer salt is seldom dissolving in reaction medium.
Hydroxy-acid group on monomer or the polymkeric substance preferably has 1%(weight) more than be neutralized or form the salt of above-mentioned substance.Have more than 2% until about 10%(weight) the carboxylic acid group just to be neutralized or to be converted into suitable salt before carrying out polymerization then better.Usually the polarity and the medium polar solvent that easily form hydrogen bond are not suitable for doing the not solvent of salifiable carbonyl bearing polymer, because this solvent can make the polymers swell that contains free acid become deleterious colloid.
The size that also will consider reactor emphatically can influence polymerization results.In among a small circle as to carry out polyreaction in pop bottle or 1 liter, 2 liters reactors be the same thing, and on a large scale as to carry out polyreaction at 30 gal reactor or bigger reactor be a different matter.Some that has disclosed with prior art polyreactions among a small circle are opposite, and the present invention is illustrated and what propose claim is large-scale polyreaction.
Embodiment 1
This experiment is the repetition to prior art embodiment, and product wherein contains a large amount of unreacted monomers.This embodiment is not the summary of the invention that this paper introduced and proposed claim.
By same program and use vinyl acetic monomer solvent, Acrylic Acid Monomer, the 50% causticity allyl group tetramethylolmethane linking agent and the lauroyl peroxide initiator of same amount, repeat the embodiment 1 in the United States Patent (USP) 4,267,603.Use 2 liters of stirred reactors.Detect after 1 hour 45 minutes, mixture becomes solid in the reactor, stops to detect, and carries out reaction in 1 hour 15 minutes again.From reactor, dig out under the polymer blocks made and in 95 to 105 ℃ and the 27 inches vacuum conditions dried overnight in the Roto-Vap vacuum drier.Get some dry polymers of making soluble in water make 1%, 0.5% and 0.2%(weight) solution, and to be neutralized to the pH value with sodium hydroxide be 7.3 to 7.8 scope.The BrooKfield viscosity number of solution (20 rev/mins) is respectively 74000 centipoises, 46000 centipoises and 610 centipoises.Dry polymer contains 1.03% unreacted acrylic acid.
Embodiment 2
This embodiment is the pro rata amplification to an embodiment of prior art, and the polymkeric substance of producing thus also is unacceptable, because the contained residue unit of polymkeric substance, just unreacted monomer is too many.This embodiment is not the summary of the invention that this paper introduced and proposed claim.
With United States Patent (USP) 4,267,103 embodiment 2 is amplified to 2 upgrading reactors in proportion in this example.With 50% sodium hydroxide 300 gram vinylformic acid are neutralized to 7% degree of neutralization thus, the vinyl acetic monomers that subsequently this mixture 1200 grams together contained 0.05% water and 1.5 gram allyl group tetramethylolmethanes add together to be with in 2 liters of jacketed reactors that stir.Removed oxygen in 30 minutes to the logical nitrogen bubble of mixture, add 0.15 gram lauroyl peroxide then and be heated to 77.2 ℃ of reflux temperatures.Sustained reaction 6 hours, then in Roto Vap vacuum drier under in 95 to 105 ℃ with the mixture dried overnight in the reactor.The contained residual acrylic acid of the polymkeric substance of making is 1.77%.The pH value is that 7.3 to 7.8. 0.2%, 0.5% and 1.0% mucous viscosity is respectively 11400 centipoises, 46000 centipoises and 56000 centipoises.The viscosity that polyreaction is finished rear slurry is about 500 centipoises.
Embodiment 3
This embodiment is the amplification in proportion to prior art embodiment, and the polymkeric substance that is generated is because contain too much residual monomer unreacted monomer just, so also be unacceptable.This embodiment is not the summary of the invention that this paper introduced and proposed claim.
With United States Patent (USP) 4,267,103 embodiment 3 is amplified to 2 upgrading reactors in proportion, and adding 195 grams, to be neutralized to 4% vinylformic acid, 1305 gram water-contents with salt of wormwood be 0.05% vinyl acetic monomer, 2.145 gram allyl sucroses and the 0.78 gram lauroyl peroxide as initiator.Under 62 ℃, reacted 6 hours.The polymkeric substance of making contains 1.22% residual acrylic acid, and mucus viscosity is as follows:
Mucus viscosity under 20 rev/mins and 25 ℃ of conditions:
0.2% 2,850 centipoises
0.5% 46,000 centipoise
1.0% 90,000 centipoise
Slurry viscosity after polyreaction is finished is about 400 centipoises.
Embodiment 4
This embodiment is the explanation to the summary of the invention of this paper introduction and proposition claim.
Make the neutralization of 24 pounds of (10.9 kilograms) acrylate moieties with 0.69 pound of (0.313 kilogram) Anhydrous potassium carbonate in the reactor of 30 gallons (850 liters), this is equivalent to 3% carboxylic acid and is neutralized.Adding 176 pounds of (79.9 kilograms) water content to reactor again is 0.05% vinyl acetic monomer and 0.2758 pound of (0.125 kilogram) allyl group tetramethylolmethane and with nitrogen bubbling 30 minutes under room temperature.Add 54.5 gram two (2-ethylhexyl) peroxy dicarbonates this moment, and reactor is heated to 50 ℃ adds the initiator afterreactions and carried out altogether 7 hours.Reaction mixture is entered one 5 cubic feet (141 liters) rotary drum driers, and under vacuum condition dry 12 hours.The content of the contained residual acrylic acid of making of polymkeric substance is 199ppm, and mucus viscosity is as follows:
Mucus viscosity in 20 rev/mins and 25 ℃ conditions:
0.2% 9,600 centipoises
0.5% 41,500 centipoises
1.0% 66,000 centipoise
Embodiment 5
By in 30 gallons of (850 liters) reactors, carrying out a series of polyreactions with above embodiment 4 described identical programs.Below table 1 polymer performance having listed its prescription and made.(table is seen the literary composition back)
In last table, " GAA " expression ice shape vinylformic acid." K
2CO
3" be salt of wormwood; " AS " expression allyl sucrose linking agent; " APE " expression allyl group tetramethylolmethane linking agent, " EHP " represents two (2-ethylhexyl) peroxy dicarbonate initiator, consumption is by per used umbers of 100 parts by weight of acrylic acid monomers (phm).
Can see that residual vinylformic acid is in 0.2%(weight) below, or being less than 2000ppm, the contained residual monomer contents of polymkeric substance of preceding two tests are lower than 0.1% or 1000ppm.
Embodiment 6
This embodiment shows that water is to the influence of polyreaction in the solvent.
The feed proportioning amount of giving by table 2 in 2 liters of reactors is carried out a series of polymerization reaction tests.At first with salt of wormwood acrylate moiety is neutralized, the vinyl acetic monomer and the allyl group tetramethylolmethane of confluent add in the reactor with being furnished with then.Fed nitrogen bubble 30 minutes to reactor then, then add i.e. two (2-ethylhexyl) peroxy dicarbonate of initiator, and temperature of reaction is heated to 50 ℃.The reaction carried out 6 hours, then in 95 to 105 ℃ in the Roto-Vap vacuum drier with the reaction mixture dried overnight.Mensuration polymkeric substance concentration in water is (the pH value being neutralized to 7.3 to 7.8 with sodium hydroxide) mucous viscosity of 0.2%, 0.5% and 1.0%.The results are shown in table 2, shown the disadvantageous effect of water.(table is seen the literary composition back)
In the last table, " GAA " expression ice shape vinylformic acid (gram number), " K
2CO
3" expression salt of wormwood (gram number), " EHP " represents ethylhexyl peroxy dicarbonate initiator (phm): APE " expression allyl group tetramethylolmethane linking agent (phm).Water content is a 3.25%(weight in the solvent) time, test 6 is interrupted.
Present embodiment shows, water-content in the solvent should be controlled at and be no more than about 2% degree, is preferably lower than 1% of weight of solvent.
Embodiment 7
Present embodiment shows the application of multipolymer as thickening material.
In 2 liters of reactors, carry out a series of polyreactions by embodiment 6 described programs.In these reactions, contain comonomer in the raw material monomer.Used comonomer comprises methacrylic acid octadecane ester (SMA), 2-ethylhexyl acrylate (EHA), N tert butyl acrylamide (N-t-BuAm) and 2-acrylamido-2-methyl propane sulfonic acid (AMPS).These comonomers are carried out copolymerization with vinylformic acid and sodium acrylate in vinyl acetic monomer.Its prescription, temperature of reaction and the polymer performance of making are listed in table 3.(table is seen the literary composition back)
In last table, " RX.Temp. ℃ " expression temperature of reaction ℃; " K
2CO
3" expression salt of wormwood gram number; Used initiator comprises lauroyl peroxide (Lpo) and two (2-ethylhexyl) peroxy dicarbonate (EHP); Used linking agent comprises allyl group season tetrol (APE) and allyl sucrose (AS).
Show that according to result shown in the above table 3 this multipolymer also can play effective thickening material.
Claims (7)
1, a kind ofly be lower than under 1% condition in the water yield by the carboxylic acid monomer, prepare contained unreacted monomer and be lower than 0.2%, and the carboxyl of the acid monomer that is neutralized greater than 1% less than the method for 10% polymkeric substance, this method be included in a kind of described carboxylic acid monomer or its salt solvable and the insoluble solvent of polymkeric substance exists down and account for the linking agent of raw material monomer weight 0.2-2% and the existence of the lauroyl peroxide of 0.4-1.0% under make at least 90% ethylenically unsaturated carboxylic acids monomer that contains 3 to 5 carbon atoms, the raw material monomer polymerization of its part neutral salt and their mixture, wherein said solvent is selected from acetone, alkyl contains the alkyl acetate of 1-6 carbon atom and their mixture, and its temperature of reaction is 70-80 ℃; Or accounting for being selected from of raw material monomer 2% (weight) when mainly being the initiator of peroxy dicarbonate with being less than, temperature of reaction is 45-55 ℃, carries out above-mentioned polyreaction.
2, the process of claim 1 wherein that the amount of described solvent should make the content of raw material monomer described in this solvent be less than 30%(weight); Under 60 rev/mins and 22 ℃ of conditions, record the Brookfield viscosity of described polymkeric substance in this solution after polyreaction is finished and be lower than 1000 centipoises; The consumption of described peroxy dicarbonate initiator is a 0.4-1.0%(weight).
3, the process of claim 1 wherein that described raw material monomer contains 95%(weight at least) described carboxylic acid monomer or its salt; Described solvent is selected from acetone, ethyl acetate, isopropyl acetate, propyl acetate, butylacetate and their mixture; Wherein said initiator is selected from lauroyl peroxide, two (2-ethylhexyl) peroxy dicarbonate, two (sec-butyl) peroxy dicarbonate, two (sec.-propyl) peroxy dicarbonate, dicyclohexyl peroxy dicarbonate, double hexadecyl peroxy dicarbonate, two (n-propyl) peroxy dicarbonate and their mixture.
4, the method for claim 1, it is 10-20%(weight that the consumption of wherein said solvent should make the content of raw material monomer described in this solvent), after polyreaction is finished, under 60 rev/mins and 22 ℃ of conditions, record the Brookfield viscosity of described polymkeric substance in this solvent and be lower than 1000 centipoises.
5, the process of claim 1 wherein that described carboxylic acid monomer is selected from vinylformic acid or its salt, methacrylic acid or its salt, toxilic acid or its salt, maleic anhydride or its salt, methylene-succinic acid or its salt and their mixture; Described raw material monomer contains 95%(weight at least) described carboxylic acid or its salt, all the other are selected from the alkyl acrylate that contains 1-30 carbon atom in the alkyl.
6, the method for claim 5, wherein said raw material monomer contains 10%(weight) the following alkyl acrylate that contains 2-20 carbon atom in the alkyl or the comonomer of its mixture of being selected from.
7, the method for claim 6, the contained unreacted unit of wherein said polymkeric substance is less than 0.1%(weight); Described solvent is an ethyl acetate; Described linking agent is selected from diallyl ether, allyl group isoamyl tetrol and their mixture that allyl sucrose, trimethylolpropane allyl ether, molecular weight are 50 to 1000 polyether glycol; Described polyreaction is implemented in 30 gallons or bigger reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88102702 CN1022107C (en) | 1987-02-24 | 1988-05-10 | Method for preparing polymer from carboxylic acid monomer |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/017,966 US4758641A (en) | 1987-02-24 | 1987-02-24 | Polycarboxylic acids with small amount of residual monomer |
| CN 88102702 CN1022107C (en) | 1987-02-24 | 1988-05-10 | Method for preparing polymer from carboxylic acid monomer |
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| Publication Number | Publication Date |
|---|---|
| CN1037521A CN1037521A (en) | 1989-11-29 |
| CN1022107C true CN1022107C (en) | 1993-09-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 88102702 Expired - Lifetime CN1022107C (en) | 1987-02-24 | 1988-05-10 | Method for preparing polymer from carboxylic acid monomer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049583C (en) * | 1993-10-22 | 2000-02-23 | 杜军强 | Chinese medicine contrast agent for stomach B-ultrasonic and its preparation |
-
1988
- 1988-05-10 CN CN 88102702 patent/CN1022107C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049583C (en) * | 1993-10-22 | 2000-02-23 | 杜军强 | Chinese medicine contrast agent for stomach B-ultrasonic and its preparation |
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| CN1037521A (en) | 1989-11-29 |
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