WO2023025396A1 - Verfahren zur rückgewinnung von restmonomeren bei der herstellung von vinylester-ethylen-mischpolymerisaten - Google Patents
Verfahren zur rückgewinnung von restmonomeren bei der herstellung von vinylester-ethylen-mischpolymerisaten Download PDFInfo
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- WO2023025396A1 WO2023025396A1 PCT/EP2021/073747 EP2021073747W WO2023025396A1 WO 2023025396 A1 WO2023025396 A1 WO 2023025396A1 EP 2021073747 W EP2021073747 W EP 2021073747W WO 2023025396 A1 WO2023025396 A1 WO 2023025396A1
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- WIPO (PCT)
- Prior art keywords
- stage
- ethylene
- vinyl ester
- vinyl
- polymerization
- Prior art date
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 84
- 239000000178 monomer Substances 0.000 title claims abstract description 53
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229920001038 ethylene copolymer Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000005977 Ethylene Substances 0.000 claims abstract description 88
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 79
- 239000012071 phase Substances 0.000 claims abstract description 47
- 239000008346 aqueous phase Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012736 aqueous medium Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 64
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 50
- 239000004815 dispersion polymer Substances 0.000 description 18
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 11
- 238000002156 mixing Methods 0.000 description 9
- 239000003999 initiator Substances 0.000 description 8
- -1 Vinyl halides Chemical class 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical class OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920000945 Amylopectin Polymers 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical class C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical class [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 229940071162 caseinate Drugs 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical class CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical class OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QWVBGCWRHHXMRM-UHFFFAOYSA-N hexadecoxycarbonyloxy hexadecyl carbonate Chemical compound CCCCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCCCC QWVBGCWRHHXMRM-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- SNWKNPMDQONHKK-UHFFFAOYSA-N methyl 2-sulfanylpropanoate Chemical compound COC(=O)C(C)S SNWKNPMDQONHKK-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical class [H]C([H])([H])* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical class OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 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
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical class CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/001—Removal of residual monomers by physical means
- C08F6/003—Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
Definitions
- the invention relates to processes for preparing vinyl ester-ethylene copolymers by means of free-radically initiated polymerization of vinyl esters, ethylene and optionally other ethylenically unsaturated monomers in an aqueous medium at a pressure of from 5 to 120 bar abs. with recovery of unreacted monomers.
- Polymers based on vinyl esters, ethylene and optionally other monomers such as vinyl chloride or (meth)acrylic acid esters are used in many applications, particularly in the form of aqueous dispersions or water-redispersible polymer powders, for example in coating materials or adhesives for a wide variety of substrates.
- Such polymers are generally stabilized by protective colloids, such as polyvinyl alcohols, or low molecular weight, surface-active compounds.
- monomers which are liquid under polymerization conditions such as vinyl acetate or vinyl chloride
- ethylene is between 5 and 120 bar abs. partly in the form of a gas, so that generally not such high ethylene conversion rates can be achieved under the industrially customary polymerization conditions.
- ethylene polymerizes more slowly than, for example, vinyl acetate, and on the other hand, a large fraction of ethylene is present in the gas phase and cannot take part in the polymerization there under the usual conditions of emulsion or suspension polymerization, since in such polymerization processes the polymerization reaction only takes place in the liquid phase takes place with the participation of the ethylene fraction, which is dissolved in water, monomer and particles. For economic reasons, the large-scale polymerization should be completed in the shortest possible time, but this inevitably means that the ethylene used cannot be polymerized completely.
- the polymerization is usually carried out with an ethylene residual gas content of ⁇ 10% by weight. -%, preferably ⁇ 5 wt.
- the depressurization process usually includes the transfer of the reaction mixture (polymer dispersion+residual gas) from a pressure reactor to a pressureless reactor, with the remaining ethylene being separated off.
- the latex obtained can then be further demonomerized in a known manner.
- the excess ethylene is disposed of, generally incinerated.
- the object of the present invention was to provide processes for the preparation of vinyl ester-ethylene copolymers which make it possible to reuse the largest possible proportion of the residual gas produced economically for the free-radically initiated polymerization of vinyl esters and ethylene and preferably to increase the space-time yield increase .
- the invention relates to processes for preparing vinyl ester-ethylene copolymers by means of free-radically initiated polymerization of vinyl esters, ethylene and, if appropriate, other ethylenically unsaturated monomers in an aqueous medium at a pressure of from 5 to 120 bar abs. , characterized in that a ) the polymerization mixture is pressurized to a pressure of from 1 to 15 bar abs .
- the polymerization mixture from stage a) is generally an aqueous dispersion which is obtained by free-radically initiated polymerization of vinyl esters, ethylene and optionally other ethylenically unsaturated monomers in an aqueous medium at a pressure of from 5 to 120 bar abs. is obtained .
- the conversion of the monomers, in particular the monomers which are liquid under the polymerization conditions is preferably from 85 to 99% by weight, more preferably from 87 to 98% by weight and particularly preferably from 90 to 96% by weight.
- the conversion of the monomers is generally the quotient of the weight of the vinyl ester-ethylene copolymers present in the polymerization mixture of stage a) and the total weight of the vinyl ester-ethylene copolymers and monomers present in the polymerization mixture of stage a).
- the polymerization mixture is pressurized to a pressure of from 1 to 15 bar abs. , preferably 2 to 10 bar abs. and particularly preferably 2 to 5 bar abs. relaxed.
- the polymerization mixture is generally transferred into a phase separation apparatus or low-pressure vessel which is under the appropriate pressure.
- a gas phase containing ethylene and an aqueous phase containing vinyl ester and vinyl ester-ethylene copolymers are generally formed.
- the ethylene-containing gas phase of stage a) contains preferably >75% by weight, more preferably >85% by weight and most preferably >95% by weight of ethylene, based on the total weight of that contained in the polymerization mixture of stage a). Ethylene, or based on the total weight of the ethylene contained in the gas phase and the aqueous phase of stage a).
- the ethylene-containing gas phase of stage a) contains preferably 50 to 95% by weight, more preferably 70 to 90% by weight and most preferably 75 to 90% by weight of ethylene, based on the total weight of the ethylene-containing gas phase stage a) .
- the ethylene-containing gas phase can also contain other components, such as vinyl esters, other monomers, water or inerts, for example nitrogen, argon or saturated hydrocarbons such as ethane.
- the share of the other Constituents is preferably 5 to 50% by weight, particularly preferably 10 to 30% by weight and most preferably 10 to 25% by weight, based on the total weight of the ethylene-comprising gas phase of stage a).
- the gas phase of stage a) preferably contains ⁇ 20% by weight, particularly preferably ⁇ 10% by weight, of vinyl ester, based on the total weight of vinyl ester in the gas phase and the aqueous phase of stage a).
- the gas phase of stage a) preferably contains d 2% by weight, particularly preferably d 1% by weight, of water, based on the total weight of water in the gas phase and the aqueous phase of stage a).
- the aqueous phase of stage a) preferably contains from 35 to 65% by weight, particularly preferably from 40 to 60% by weight, of vinyl ester-ethylene copolymers.
- the aqueous phase of stage a) preferably contains 0.5 to 5% by weight, particularly preferably 1 to 3% by weight, of monomers, in particular vinyl esters such as vinyl acetate.
- the aqueous phase of stage a) preferably contains 34.5 to 64.5% by weight, particularly preferably 39 to 59% by weight, of water. The percentages by weight are based on the total weight of the aqueous phase of stage a).
- the relaxation in stage a) is preferably carried out adiabatically.
- the temperature of the polymerization mixture is preferably from 75.degree. C. to 120.degree. C., particularly preferably from 80.degree. C. to 110.degree.
- the temperature of the polymerization mixture is preferably from 75.degree. C. to 120.degree. C., particularly preferably from 80.degree. C. to 110.degree.
- stage b) the ethylene-containing gas phase and the aqueous phase of stage a) containing vinyl esters and vinyl ester-ethylene copolymers can be separated in a conventional manner, for example using a phase separator.
- the ethylene-containing gas phase b) is generally divided into vinyl ester, ie generally a starting material for the polymerization recorded .
- This can take place, for example, in mixing devices, for example static mixers, agitators, mixing tubes or, in particular, absorption systems.
- Preferred absorption systems are in the form of columns, in particular packed columns or structured columns.
- Inert materials such as nitrogen, argon or saturated hydrocarbons are preferably separated off from the mixing device, in particular at the top of the mixing device, for example via a pressure maintenance system, and discharged from the process.
- the vinyl esters are preferably brought to a temperature of 5° C. to 20° C. before they enter the mixing device.
- the vinyl esters are fed into the mixing device in countercurrent to the ethylene-containing gas phase b); the ethylene-comprising gas phase b) is taken up in vinyl ester.
- Any other substances present in the ethylene-containing gas phase b), in particular vinyl esters passed into the ethylene-containing gas phase in stage a), are preferably condensed in the mixing device and preferably exit the mixing device together with the ethylene absorbed in vinyl ester.
- the mixture obtained in this way is generally fed into the reactor for the free-radically initiated polymerization of vinyl esters, ethylene and, if appropriate, other ethylenically unsaturated monomers.
- the mixture can be compressed to the reactor pressure, for example by means of a pump, preferably after leaving the mixing device and/or before being introduced into the reactor.
- the mixture obtained in stage b) preferably contains 0.5 to 5% by weight. -% ethylene, based on the amount of vinyl ester.
- This can be beneficial in increasing ethylene recovery rates.
- a compression ratio of preferably 1.5 to 3 is selected.
- the compression ratio is the ratio of compressor outlet pressure to compressor inlet pressure. Compression of the ethylene-comprising gas phase from stage a) is particularly preferably dispensed with.
- the aqueous phase from stage a) is pressurized to a pressure of from 0.1 to 0.5 bar abs. , preferably 0.15 to 0.4 bar abs. , particularly preferably from 0.2 to 0.3 bar abs., expanded, forming a gas phase containing vinyl ester and water and an aqueous phase containing vinyl ester-ethylene copolymers.
- the gas phase comprising vinyl esters and water from stage c) is generally separated off, then condensed and then used in the free-radically initiated polymerization of vinyl esters, ethylene and, if appropriate, other ethylenically unsaturated monomers.
- any ethylene remaining in the aqueous phase in stage a) is in stage c), preferably almost completely, converted into the gas phase of stage c) and preferably completely or largely dissolved in the condensate of stage c) and preferably used in the free-radically initiated polymerization.
- Any ethylene not condensed in stage c) or not dissolved in the condensate from stage c) is preferably removed via a vacuum pump, in particular together with non-condensed water and vinyl ester and, if appropriate, inerts.
- the relaxation in stage c) is preferably carried out adiabatically.
- the aqueous phase has a temperature of preferably 75.degree. C. to 120.degree. C., particularly preferably 80.degree. C. to 110.degree. C., before the expansion in stage c) is carried out. Cooling by preferably 20° C. to 50° C., in particular 20° C. to 40° C., takes place in the course of the depressurization in stage c).
- the gas phase which forms in stage c) and contains vinyl ester and water has a temperature of preferably 50.degree. C. to less than 80.degree. C., in particular less than 75.degree.
- the expansion in stage c) can take place, for example, in a conventional phase separator. Alternatively, heat can also be supplied in stage c), for example by heating or preferably by means of steam. Steam and the aqueous phase are particularly preferably passed countercurrently through a separating apparatus, for example a packed column or structured column.
- the condensation in stage c) is preferably carried out at a temperature of from 0.degree. C. to 15.degree. C., particularly preferably from 5.degree. C. to 10.degree.
- the condensation in stage c) is carried out in two stages.
- the first stage is preferably carried out at a temperature of 15°C to 40°C, more preferably 20°C to 35°C.
- the second stage preferably takes place at a temperature of 0°C to 15°C, more preferably 5°C to 10°C.
- water and vinyl ester can be condensed out one after the other.
- This procedure is characterized by particular energy efficiency.
- the two-stage condensation has the advantage that mainly water is obtained in the first stage and mainly vinyl ester as condensate in the second stage. This enables separate processing.
- the recirculation can be carried out only partially in order to remove water-soluble or vinyl ester-soluble impurities.
- the condensate is preferably completely recycled into the free-radically initiated polymerization.
- the condensers are preferably connected to the phase separator of stage c) on the gas side.
- the condensate from stage c) preferably contains from 25 to 75% by weight, particularly preferably from 40 to 60% by weight, of vinyl ester.
- the condensate from stage c) preferably contains from 25 to 75% by weight, particularly preferably from 40 to 60% by weight, of water. These figures in % by weight are based in each case on the total weight of the condensate from stage c).
- the condensate from stage c) preferably contains 25 to 75% by weight, particularly preferably 35 to 65% by weight, of vinyl esters, based on the total weight of the vinyl esters, which are contained in the aqueous phase of stage a containing vinyl esters and vinyl ester-ethylene copolymers ) were included.
- the condensate preferably contains 50 to 100% by weight, particularly preferably 90 to 100% by weight, of vinyl esters, based on the total weight of the vinyl esters were contained in the aqueous phase of stage a) containing vinyl esters and vinyl ester-ethylene copolymers.
- Stage c) condensate is reused in the free radical initiated polymerization of vinyl esters and ethylene.
- the condensate is preferably introduced directly or immediately, optionally after temperature control, into the reactor for the free-radically initiated polymerization of vinyl esters and ethylene, for example using a pump.
- stage c after the gas phase comprising vinyl ester and water has been separated off, there generally remains an aqueous phase comprising vinyl ester-ethylene copolymers (aqueous phase from stage c)).
- This aqueous phase preferably contains ⁇ 2% by weight, particularly preferably 0 to 1% by weight, of vinyl ester, based on the total weight of this aqueous phase containing vinyl ester-ethylene copolymers.
- This aqueous phase formed in stage c) preferably contains ⁇ 10 ppm, particularly preferably 0 to 5 ppm, ethylene.
- the residual monomer content of the polymer dispersion remaining after stage c) is preferably 1 to 10,000 ppm, particularly preferably 500 to 5000 ppm. If additional energy is supplied to stage c), for example in the form of heat output or steam, the residual monomer content is preferably 1 to 1000 ppm, particularly preferably 10 to 100 ppm.
- the vinyl ester content of the polymer dispersion after stage c) is, for example, 50 to 80% by weight lower than at the reactor exit. If additional energy is supplied to stage c), for example in the form of heat output or steam, the vinyl ester content is >99% by weight lower than at the reactor outlet.
- the aqueous phase formed in stage c) has a temperature of preferably 50°C to less than 80°C.
- the aqueous phase from stage c) can be post-polymerized for further residual monomer removal using known methods, generally by post-polymerization initiated with a redox catalyst.
- Volatile residual monomers can also be removed (stripping) by means of distillation, preferably under reduced pressure, and optionally with passing through or overflowing of inert entraining gases such as air, nitrogen or steam.
- the aqueous phase from step a) can be subjected to post-polymerization or stripping.
- the two-stage decompression in steps a) and c) can be combined with a two-stage post-polymerization by post-polymerizing both the aqueous phase from stage a) (first post-polymerization) and the aqueous phase from stage c) (second post-polymerization).
- the first post-polymerization polymerizes preferably from 25 to 90% by weight, particularly preferably from 50 to 75% by weight, of the vinyl esters present in the aqueous phase of stage a).
- the vinyl esters remaining after the first post-polymerization preferably 25 to 75% by weight, particularly preferably 50 to 75% by weight, are converted into the gas phase in stage c).
- the vinyl esters then still remaining in the aqueous phase from stage c) can be polymerized to completion in a second post-polymerization.
- This process variant makes it particularly advantageous to achieve low residual monomer contents, preferably ⁇ 100 ppm, particularly preferably ⁇ 50 ppm.
- Post-polymerization and stripping can be dispensed with in the process according to the invention, or post-polymerization or stripping can be carried out in a shorter period of time than in conventional processes, since the residual monomer content has already been reduced by steps a) to c) of the process according to the invention.
- the process according to the invention is generally suitable for batch or semi-batch processes and is particularly advantageous for continuous processes.
- the aqueous polymer dispersions obtainable therewith have a solids content of 30 to 75% by weight. -%, preferably from 50 to 60 wt. -% .
- Suitable vinyl esters are those of carboxylic acids having 1 to 18 carbon atoms. Preference is given to vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methyl vinyl acetate, vinyl pivalate and vinyl esters of a-branched monocarboxylic acids having 9 to 13 carbon atoms, for example VeoVa ⁇ or VeoVal fl (trade names from Shell). Vinyl acetate is particularly preferred.
- suitable monomers which can be copolymerized with vinyl esters and ethylene are acrylic esters or methacrylic esters of unbranched or branched alcohols having 1 to 18 carbon atoms.
- Preferred methacrylic acid esters or acrylic acid esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate.
- Methyl acrylate, methyl methacrylate, n-butyl acrylate, t-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.
- Vinyl halides such as vinyl chloride are also suitable.
- auxiliary monomers are copolymerized. 0.1 to 15% by weight are preferred.
- auxiliary monomers are ethylenically unsaturated mono- and dicarboxylic acids; ethylenically unsaturated carboxylic acid amides and carboxylic acid nitriles; ethylenically unsaturated sulfonic acids or their salts.
- pre-crosslinking comonomers such as polyethylenically unsaturated comonomers, or post-crosslinking comonomers, for example N-methylolacrylamide (NMA).
- NMA N-methylolacrylamide
- epoxy functional comonomers such as glycidyl methacrylate and silicon functional comonomers.
- Mixtures of vinyl acetate and ethylene are preferably used; and mixtures of vinyl acetate and other vinyl esters such as vinyl laurate or vinyl esters of a-branched monocarboxylic acids having 9 to 13 carbon atoms and ethylene; and mixtures of vinyl chloride, ethylene and vinyl esters, for example vinyl laurate.
- the selection of monomers or the selection of the proportions by weight of the comonomers is carried out in such a way that a glass transition temperature Tg of ⁇ 50° C. to +50° C., preferably ⁇ 20° C. to +20° C., generally results.
- the glass transition temperature Tg of the polymers can be determined in a known manner by means of differential scanning calorimetry (DSC).
- Tg n the glass transition temperature in Kelvin of the homopolymer of monomer n. Tg values for homopolymers are listed in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975).
- the preparation of the polymers by means of free-radically initiated polymerization in an aqueous medium is preferably carried out by the suspension polymerization process and in particular by the emulsion polymerization process, preferably in the presence of protective colloids and/or emulsifiers. Such methods are known per se.
- the polymerization temperature is generally from 40°C to 100°C, preferably from 60°C to 90°C
- the polymerization is generally carried out at a pressure of from 5 to 120 bar abs. worked.
- the polymerization is generally initiated using the water-soluble or monomer-soluble initiators or redox initiator combinations customary for emulsion polymerization or suspension polymerization.
- water-soluble initiators are the sodium, potassium and ammonium salts of peroxodisulfuric acid, hydrogen peroxide, t-butyl peroxide, t-butyl hydroperoxide, potassium peroxodiphosphate, t-butyl peroxopivalate, cumene hydroperoxide, isopropylbenzene monohydroperoxide, azobisisobutyronitrile.
- Examples of monomer-soluble initiators are dicetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide.
- the initiators mentioned are generally used in an amount of from 0.01 to 0.5% by weight, based on the total weight of the monomers.
- Combinations of the initiators mentioned in combination with reducing agents are generally used as redox initiators.
- Suitable reducing agents are, for example, the sulfites or bisulfites of alkali metals and of ammonium, for example sodium sulfite, the derivatives of sulfoxylic acid such as zinc or alkali metal formaldehyde sulfoxylates, for example sodium hydroxymethanesulfite, and ascorbic acid.
- the amount of reducing agent is preferably from 0.01 to 0.5% by weight, based on the total weight of the monomers.
- Substances that regulate the molecular weight can be used during the polymerization to control the molecular weight. If regulators are used, they are usually used in amounts of between 0.01 and 5.0% by weight, based on the monomers to be polymerized. Regulators can generally be metered in separately or else premixed with reaction components. Examples of such substances are n-dodecyl mercaptan, tert. -Dodecyl mercaptan, mercaptopropionic acid, mercaptopropionic acid methyl ester, isopropanol and acetaldehyde. Preferably no controlling substances are used.
- Suitable protective colloids are partially hydrolyzed polyvinyl alcohols; polyvinylpyrrolidones; polyvinyl acetals; Polysaccharides in water-soluble form such as starches (amylose and amylopectin), celluloses and their carboxymethyl, methyl, hydroxyethyl, hydroxypropyl derivatives; Proteins such as casein or caseinate, soya protein, gelatin; lignosulfonates; synthetic polymers such as poly(meth)acrylic acid, copolymers of (meth)acrylates with carboxyl-functional comonomer units, poly(meth)acrylamide, polyvinylsulfonic acids and their water-soluble copolymers; Melamine formaldehyde sulfonates, naphthalene formaldehyde sulfonates, styrene maleic acid and vinyl ether maleic acid copolymers. Partially hydrolyzed or fully hydrolyzed polyvinyl alcohols
- the protective colloids are generally used in a total amount of 1 to 20% by weight. -%, based on the total weight of the monomers, added during the polymerization.
- the protective colloid fraction can, for example, be completely initially introduced or partially initially introduced and partially metered in.
- Anionic, cationic or also nonionic emulsifiers are suitable for the polymerization of emulsifiers.
- anionic surfactants are alkyl sulfates with a chain length of 8 to 18 carbon atoms, alkyl or alkylaryl ether sulfates with 8 to 18 carbon atoms in the hydrophobic radical and up to 40 ethylene or propylene oxide units, alkyl or alkylaryl sulfonates with 8 to 18 carbon atoms, esters and semi-esters of sulfosuccinic acid with monohydric alcohols or alkylphenols.
- nonionic surfactants are alkyl polyglycol ethers or alkylaryl polyglycol ethers with 8 to 40 ethylene oxide units.
- the emulsifiers are used in an amount of 0.1 to 5% by weight. -% based on the amount of monomer used.
- polymer dispersions with low residual monomer contents can be obtained in an advantageous manner. This is also of particular importance if the polymer dispersions are subsequently dried to a powder in a spray dryer, since this is from the dryer exhaust air Residual monomers must be laboriously removed in order to comply with emission limits.
- residual vinyl ester and ethylene monomers can be separated off in a technically simple, efficient, energy-saving and therefore economical manner and reused in the polymerization.
- Recompression steps with compressors, in particular with multi-stage compressors, or temperature control of vinyl esters and ethylene can be dispensed with here. Further steps for cleaning the residual gas can be omitted.
- the residual vinyl ester and ethylene monomers can be almost completely recycled for the polymerization, so that the disposal of residual gas is significantly simplified.
- the polymer dispersions are generally concentrated, for example by 1 to 20% by weight. -%, in particular 2 to 8 wt. -% .
- the polymerization can be carried out at lower solids content. This reduces fouling during the polymerization and accelerates the removal of heat from the polymerization reactor, which allows an increase in the space-time yield and reduces reactor downtimes for removing fouling.
- the mass flow of the polymer dispersion was reduced to a pressure of 1.0 bar absolute with the aid of a control valve.
- the polymer dispersion was then post-polymerized for 1 hour with the addition of initiator.
- the polymer dispersion thus obtained contained 100 ppm vinyl acetate and 35 ppm ethylene.
- the mass flow of the polymer dispersion was reduced to a pressure of 0.2 bar absolute with the aid of a control valve.
- the polymer dispersion was then post-polymerized for 1 hour with the addition of the same amount of initiator as in Comparative Example 1a.
- the polymer dispersion thus obtained contained 30 ppm of vinyl acetate and 1 ppm of ethylene.
- Example 1c Two-stage decompression of the polymer dispersion at 3 bar and 0.2 bar:
- the mass flow of the polymer dispersion was initially reduced to a pressure of 3 bar absolute with the aid of a control valve.
- 0.22 wt. -% ethylene in the gas phase and 700 ppm ethylene remained in the dispersion.
- the ethylene stripped off in this way was dissolved in the vinyl acetate feed without further compression, which was then introduced into the polymerization reactor.
- the polymer dispersion was then post-polymerized for 1 hour with the addition of the same amount of initiator as in Comparative Example 1a.
- the polymer dispersion obtained in this way contained 30 ppm of vinyl acetate and 1 ppm of ethylene.
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US18/267,792 US20240084059A1 (en) | 2021-08-27 | 2021-08-27 | Method for recovering residual monomers in the preparation of vinyl ester-ethylene copolymers |
PCT/EP2021/073747 WO2023025396A1 (de) | 2021-08-27 | 2021-08-27 | Verfahren zur rückgewinnung von restmonomeren bei der herstellung von vinylester-ethylen-mischpolymerisaten |
CN202180079598.6A CN116568712A (zh) | 2021-08-27 | 2021-08-27 | 回收乙烯基酯-乙烯共聚物的制备中的残余单体的方法 |
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DE10253043A1 (de) | 2002-11-14 | 2004-06-03 | Wacker Polymer Systems Gmbh & Co. Kg | Verfahren zur Rückgewinnung von Restethylen bei der Herstellung von Vinylester-Ethylen-Mischpolymerisaten |
WO2007074075A1 (de) | 2005-12-22 | 2007-07-05 | Wacker Chemie Ag | Rückgewinnung von ethylen und vinylacetat aus dem restgasstrom der vinylester-ethylen-mischpolymerisatherstellung |
CN204607899U (zh) * | 2015-04-17 | 2015-09-02 | 中国石油化工集团公司 | 一种evoh生产过程中的乙烯回收系统 |
EP3321292A1 (de) | 2016-09-19 | 2018-05-16 | LG Chem, Ltd. | Verfahren zur rückgewinnung von ethylen und vinylbasiertem comonomer |
WO2021013354A1 (de) * | 2019-07-25 | 2021-01-28 | Wacker Chemie Ag | Verfahren zur herstellung einer wässrigen polymerisatdispersion |
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DE10253043A1 (de) | 2002-11-14 | 2004-06-03 | Wacker Polymer Systems Gmbh & Co. Kg | Verfahren zur Rückgewinnung von Restethylen bei der Herstellung von Vinylester-Ethylen-Mischpolymerisaten |
WO2007074075A1 (de) | 2005-12-22 | 2007-07-05 | Wacker Chemie Ag | Rückgewinnung von ethylen und vinylacetat aus dem restgasstrom der vinylester-ethylen-mischpolymerisatherstellung |
CN204607899U (zh) * | 2015-04-17 | 2015-09-02 | 中国石油化工集团公司 | 一种evoh生产过程中的乙烯回收系统 |
EP3321292A1 (de) | 2016-09-19 | 2018-05-16 | LG Chem, Ltd. | Verfahren zur rückgewinnung von ethylen und vinylbasiertem comonomer |
WO2021013354A1 (de) * | 2019-07-25 | 2021-01-28 | Wacker Chemie Ag | Verfahren zur herstellung einer wässrigen polymerisatdispersion |
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