CN1422879A - 不溶性高交联米花状聚合物作为助滤剂和/或稳定剂的应用 - Google Patents
不溶性高交联米花状聚合物作为助滤剂和/或稳定剂的应用 Download PDFInfo
- Publication number
- CN1422879A CN1422879A CN02155366A CN02155366A CN1422879A CN 1422879 A CN1422879 A CN 1422879A CN 02155366 A CN02155366 A CN 02155366A CN 02155366 A CN02155366 A CN 02155366A CN 1422879 A CN1422879 A CN 1422879A
- Authority
- CN
- China
- Prior art keywords
- vinyl
- huazhuanjuhewu
- weight
- gram
- aqueous liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title abstract description 17
- 239000003381 stabilizer Substances 0.000 title abstract 2
- 241000574138 Ozothamnus diosmifolius Species 0.000 title 1
- 238000001914 filtration Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims description 32
- 230000003311 flocculating effect Effects 0.000 claims description 25
- 235000013405 beer Nutrition 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- -1 N-caprolactam Chemical compound 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 13
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000004971 Cross linker Substances 0.000 claims description 4
- 230000001588 bifunctional effect Effects 0.000 claims description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- MMFCEMSIUPCRLD-UHFFFAOYSA-N 1-ethenyl-4-methylimidazole Chemical compound CC1=CN(C=C)C=N1 MMFCEMSIUPCRLD-UHFFFAOYSA-N 0.000 claims description 2
- PBGPBHYPCGDFEZ-UHFFFAOYSA-N 1-ethenylpiperidin-2-one Chemical compound C=CN1CCCCC1=O PBGPBHYPCGDFEZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003440 styrenes Chemical class 0.000 claims description 2
- 235000019985 fermented beverage Nutrition 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 abstract description 10
- 238000011105 stabilization Methods 0.000 abstract description 10
- 239000004793 Polystyrene Substances 0.000 abstract description 3
- 229920002223 polystyrene Polymers 0.000 abstract description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 abstract 2
- 241000482268 Zea mays subsp. mays Species 0.000 abstract 2
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 241001249696 Senna alexandrina Species 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 235000018553 tannin Nutrition 0.000 description 8
- 239000001648 tannin Substances 0.000 description 8
- 229920001864 tannin Polymers 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002609 medium Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 235000013361 beverage Nutrition 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000008442 polyphenolic compounds Chemical class 0.000 description 5
- 235000013824 polyphenols Nutrition 0.000 description 5
- 229920000523 polyvinylpolypyrrolidone Polymers 0.000 description 5
- 235000013809 polyvinylpolypyrrolidone Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 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 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001256 steam distillation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 244000144992 flock Species 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 description 2
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 description 2
- 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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- IYRHBDVSMINOTQ-UHFFFAOYSA-N aniline;ethene Chemical compound C=C.NC1=CC=CC=C1 IYRHBDVSMINOTQ-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 description 2
- 235000005487 catechin Nutrition 0.000 description 2
- 229950001002 cianidanol Drugs 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- UACSZOWTRIJIFU-UHFFFAOYSA-N hydroxymethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCO UACSZOWTRIJIFU-UHFFFAOYSA-N 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012673 precipitation polymerization Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- 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
- QMMOXUPEWRXHJS-HWKANZROSA-N (e)-pent-2-ene Chemical compound CC\C=C\C QMMOXUPEWRXHJS-HWKANZROSA-N 0.000 description 1
- KFUSEUYYWQURPO-UHFFFAOYSA-N 1,2-dichloroethene Chemical compound ClC=CCl KFUSEUYYWQURPO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ATBDZSAENDYQDW-UHFFFAOYSA-N 3-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(C=C)=C1 ATBDZSAENDYQDW-UHFFFAOYSA-N 0.000 description 1
- JSDZSLGMRRSAHD-UHFFFAOYSA-N 3-methylbutan-2-ylcyclopropane Chemical compound CC(C)C(C)C1CC1 JSDZSLGMRRSAHD-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 description 1
- 240000003259 Brassica oleracea var. botrytis Species 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- WLYGSPLCNKYESI-RSUQVHIMSA-N Carthamin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1[C@@]1(O)C(O)=C(C(=O)\C=C\C=2C=CC(O)=CC=2)C(=O)C(\C=C\2C([C@](O)([C@H]3[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O3)O)C(O)=C(C(=O)\C=C\C=3C=CC(O)=CC=3)C/2=O)=O)=C1O WLYGSPLCNKYESI-RSUQVHIMSA-N 0.000 description 1
- DYQVDISPPLTLLR-HJQYTNQXSA-N Carthamin Natural products CC[C@H]1O[C@H]([C@H](O)[C@@H](O)[C@@H]1O)[C@]2(O)C(=C(C=C/3C(=O)C(=C(O)[C@](O)([C@@H]4O[C@H](CO)[C@@H](O)[C@H](O)[C@H]4O)C3=O)C(=O)C=Cc5ccc(O)cc5)C(=O)C(=C2O)C(=O)C=Cc6ccc(O)cc6)O DYQVDISPPLTLLR-HJQYTNQXSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000004890 malting Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- XXQBGBUZLWZPKT-UHFFFAOYSA-N n-prop-2-enoylbuta-2,3-dienamide Chemical compound C=CC(=O)NC(=O)C=C=C XXQBGBUZLWZPKT-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- CCEKAJIANROZEO-UHFFFAOYSA-N sulfluramid Chemical group CCNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CCEKAJIANROZEO-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000013311 vegetables Nutrition 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
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12H—PASTEURISATION, STERILISATION, PRESERVATION, PURIFICATION, CLARIFICATION OR AGEING OF ALCOHOLIC BEVERAGES; METHODS FOR ALTERING THE ALCOHOL CONTENT OF FERMENTED SOLUTIONS OR ALCOHOLIC BEVERAGES
- C12H1/00—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages
- C12H1/02—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material
- C12H1/04—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material
- C12H1/0416—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material with the aid of organic added material
- C12H1/0424—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material with the aid of organic added material with the aid of a polymer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/02—Loose filtering material, e.g. loose fibres
- B01D39/04—Organic material, e.g. cellulose, cotton
-
- 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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
-
- 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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- General Engineering & Computer Science (AREA)
- Genetics & Genomics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Non-Alcoholic Beverages (AREA)
- Distillation Of Fermentation Liquor, Processing Of Alcohols, Vinegar And Beer (AREA)
- Filtration Of Liquid (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Removal Of Specific Substances (AREA)
Abstract
本文描述了使用含聚苯乙烯的米花状聚合物作为助滤剂和/或稳定剂以过滤或稳定水成液、一种过滤和/或稳定化作用的方法和仅轻微溶胀的新型米花状聚合物。
Description
本发明涉及将含聚苯乙烯的米花状聚合物用作过滤或稳定水成液的助滤剂和/或稳定剂、一种过滤和/或稳定化作用的方法以及仅轻微溶胀的新型米花状聚合物。
在许多饮料生产方法中,通过沉淀或过滤分离可结合配合物的多酚或蛋白质是一个重要的处理步骤,因为除去这些物质可导致更长的保质期。
通常,首先通过过滤将导致浊雾的物质如多酚或蛋白质分离出来进行稳定化处理。可通过结合缩短保质期的物质或将其沉淀出来以实现稳定化。例如,硅胶结合或沉淀蛋白质,聚乙烯基吡咯烷酮结合多酚。
长期以来,助滤剂和/或稳定剂一直分开使用或一起使用。当它们各自单独使用时,设备昂贵,而当一起使用时,后处理通常是一个问题。
术语“助滤剂”意指在过滤中作为预涂材料以本体形式、粉、颗粒或纤维等形式使用的各种产品。
为了得到更松软的滤饼积累,在开始过滤前可将助滤剂施用于过滤介质上作为助滤剂层(预涂过滤剂),或将助滤剂连续地加入至预滤物中。
已知的过滤添加剂是,例如,硅藻土,源自煅烧硅藻土的天然产品。主要成分是无定形改性SiO2,伴有铝、铁和其它元素的氧化物及其硅酸盐化合物。珍珠岩是来源于火山经灼烧过的并经研磨选择过的膨胀粘土(流纹岩)。其结构是层状的,可在化学上描述为硅酸钠、硅酸钾、铝硅酸盐。膨润土是具有高膨胀性和高吸收能力的粘土矿。
助滤剂在过滤过程中应形成多孔环境,吸收要除去的杂质并便利于液相的流出。
添加剂应有增加的孔率,在压力的影响下也不应该变形。此外,这些物质应该在化学上是惰性的,并且容易回收。
对于过滤啤酒而言,目前使用的主要是硅藻土预涂过滤器和片过滤器。在预涂过滤中,在过滤开始前,将硅藻土预备层预涂在载体表面(滤网)上。在预涂此预备层后,将粗细硅藻土的混合物加入要过滤的啤酒中(预滤)。在生产啤酒的过程中,所希望的硅藻土消耗量必须是150至200克/百升啤酒。硅藻土特别是因为其孔体积大、堆积密度低、吸收能力较高和比表面积高而被证明适于预涂过滤。
使用硅藻土的一个缺点是在一定数量的操作小时后由于保留的固体物质,硅藻土失去效能,它必须从过滤载体表面除去并进行更换。
由于有相关的法律规定,填埋用过的硅藻土是可能的,但难度大并且花费很大。企图再生不能作为过滤材料使用的硅藻土在实践上一直未能实现。此外,因为可能的致癌作用,硅藻土已经被讨论了一段时间。
WO 98/40149描述了使用细颗粒植物纤维作为助滤剂。这些助滤剂包括木质颗粒、木质纤维和木质粉碎残渣。在使用前,颗粒必须以稀酸和/或碱金属氢氧化物溶液进行处理。
WO 96/35497公开了过滤水性介质特别是啤酒的可再生助滤剂,包括聚酰胺、聚氯乙烯、聚丙烯、聚苯乙烯或聚己内酰胺。
EP 483 099描述了使用由粒径在5至50微米的球状粒子组成的助滤剂过滤啤酒的方法。
EP 351 361描述了作为稳定剂和助滤剂的高交联聚乙烯基吡咯烷酮(PVPP)。
WO 00/68286公开了含苯乙烯的米花状聚合物,其苯乙烯含量大于50重量%。
除去饮料中导致浊雾或影响稳定性的组分,例如从啤酒中除去多酚,与口味质量紧密相连。但是,使用先有技术中的助滤剂或稳定剂,对多酚的吸收根据目标进行调整仅仅是可能的,不过难度很大。
因此,本发明的一个目的是提供一种用于饮料生产中的助滤剂和/或稳定剂,它首先再生简单,并可能按所希望的方式影响对导致浊雾的物质或妨碍稳定性的物质的吸收。
我们发现通过发明的米花状聚合物可惊人地达到此目标。
本发明涉及不溶的仅轻微溶胀的米花状聚合物,它包含:
a)0.1至99重量%的N-乙烯基内酰胺或N-乙烯基胺
b)0至10重量%的双官能交联剂组分
c)0.1至50重量%的至少一种可通过自由基进行聚合的其它单体
在此,各组分重量百分数以米花状聚合物的总量为基础,总和为100%。
米花状聚合物的名称指具有花菜式结构的发泡硬质聚合物颗粒。因为其通常的高交联结构,米花状聚合物一般不溶并且事实上不溶胀。
米花状聚合物例如用于从饮料中吸收单宁并用作离子交换剂。含羰基的米花状聚合物也可通过皂化含丙烯酸酯和丙烯酰胺单元的聚合物得到。
Ullmanns工业化学百科全书第四版第19卷385页(1980)(UllmannsEncyklopdia der Tech.Chemie,4th Edition,Volume 19,page 385(1980))中开示了当N-乙烯基吡咯烷酮与碱金属和碱土金属的氢氧化物和醇盐一起加热时,在自发反应中形成在水中仅轻微溶胀的不溶聚合物。在缺氧情况下当N-乙烯基吡咯烷酮与二乙烯基化合物一起加热时也形成这样的称为米花状聚合物的物质。
亲水组分a)一般意指N-乙烯基内酰胺或N-乙烯基胺。在此优选的亲水组分是下列可聚合的共聚单体:N-乙烯基内酰胺和N-乙烯基胺,特别是N-乙烯基吡咯烷酮、N-乙烯基哌啶酮、N-乙烯基己内酰胺、N-乙烯基咪唑、N-乙烯基-2-甲基咪唑、N-乙烯基-4-甲基咪唑和N-乙烯基甲酰胺。
优选的亲水组分是N-乙烯基吡咯烷酮、N-乙烯基咪唑和N-乙烯基己内酰胺,特别优选N-乙烯基吡咯烷酮。
在本发明的上下文中,以聚合物的总量计,单体a)的用量为0.1至99重量%、优选大于50重量%。
单体b)一般意指在分子中包含至少两个烯键式不饱和非共轭双键的化合物,因此它们在聚合中作为双官能交联剂。单体b)的优选代表是,例如,亚烷基二丙烯酰胺如亚甲基二丙烯酰胺和N,N’-丙烯酰乙二胺、N,N’-二乙烯基亚乙基脲、N,N’-二乙烯基亚丙基脲、亚乙基-双-3-(N-乙烯基吡咯烷酮)、N,N’-二乙烯基二咪唑基-(2,2’)丁烷和1,1’-双-(3,3’-乙烯基苯并咪唑基-2-酮)-(1,4)-丁烷。其它合适的交联剂是,例如,二(甲基)丙烯酸烷撑二醇酯如二丙烯酸乙二酯、二异丁烯酸乙二酯、丙烯酸四甘醇酯、二异丁烯酸四甘醇酯、丙烯酸二甘醇酯、异丁烯酸二甘醇酯、芳香二乙烯基化合物如二乙烯基苯和二乙烯基甲苯以及丙烯酸乙烯酯、丙烯酸烯丙酯、异丁烯酸烯丙酯、二乙烯基二噁烷、季戊四醇三烯丙醚和这些交联剂的混合物。
特别优选的交联剂是N,N’-二乙烯基亚乙基脲和二乙烯基苯。
以聚合物的总量计,交联剂的用量宜为0至10重量%、优选0.2至8重量%、特别优选0.2至5重量%。
单体c)一般意指能进行自由基聚合的化合物。单体c)的优选代表是,例如,单烯烃或二烯烃如丙烯、乙烯、异丁烯、甲基丁-1-烯、甲基戊-1-烯、异戊二烯、丁二烯、己二烯、二环戊二烯、亚乙基降冰片烯、苯乙烯或不饱和苯乙烯衍生物例如含砜苯乙烯,例如苯乙烯-3-磺酸或苯乙烯-3-磺酸钠、苯乙烯-4-磺酸或苯乙烯-4-磺酸钠和含氨基苯乙烯。含氨基苯乙烯是,例如,在3位置上具有下列取代基的苯乙烯:-CH2N+(CH3)3Cl-、-CH2N+(CH3)2CH2CH2OHCl-、-CH2N(CH3)2、CH2NHCH3、CH2NH2。其它单体是卤化乙烯单体,例如氯乙烯、氟乙烯、氯丁二烯或1,2-二氯乙烯。单体c)还包括α,β-不饱和酸单体衍生物如丙烯酸酯、甲基丙烯酸酯、如丙烯酰胺和丙烯腈。这些酯的例子具体是丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸异丙酯、甲基丙烯酸异丙酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、丙烯酸十八酯、甲基丙烯酸十八酯和衍生于异构丁醇的丙烯酸酯和甲基丙烯酸酯和丙烯酸羟乙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟甲酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟丁酯。其它合适的单体是,例如,不饱和醇和胺及其衍生物、例如乙烯醇、醋酸乙烯酯、丙酸乙烯酯、硬脂酸乙烯酯、苯甲酸乙烯酯、马来酸乙烯酯、丁酸乙烯酯、邻苯二甲酸烯丙酯、烯丙基三聚氰胺;α,β-不饱和酸如丙烯酸和甲基丙烯酸可被中和或不被中和。单体c)还包括α,β-不饱和酸的单体衍生物如丙烯酸酯、甲基丙烯酸酯、丙烯酰胺、丙烯腈。这些酯的具体例子是丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸异丙酯、甲基丙烯酸异丙酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、丙烯酸十八酯、甲基丙烯酸十八酯和衍生于异构丁醇的丙烯酸酯和甲基丙烯酸酯以及丙烯酸羟乙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟甲酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟丁酯。其它单体是丙烯酰胺和甲基丙烯酰胺。优选使用苯乙烯、丙烯酸、甲基丙烯酸,特别优选使用苯乙烯。
在本发明的上下文中,以聚合物的总量计,单体c)的用量为0.1至50重量%、优选20至50重量%。
使用已知的方法例如沉淀聚合或通过本体聚合进行端聚合作用。优选如EP-A-0 177 812中所述的方法进行,其中在无氧气和聚合引发剂的存在下通过将99.6至99.8重量%的N-乙烯基吡咯烷酮与0.4至1.2重量%的含有至少两个烯键式不饱和双键的作为交联剂的化合物的混合物加热至60至150℃的温度来启动端聚合作用。聚合特别是通过少量氢氧化钠溶液或氢氧化钾溶液的存在来引发的。在短时间内便形成了可聚合米花状聚合物,并且在加入剩余单体混合物即特别是单体苯乙烯和剩余量的单体c)时,启动这些单体的端聚合而无任何诱导期。此外,也可以将可聚合米花状聚合物转移至装有单体和交联剂的容器中,或先加入到容器中,再将单体和交联剂加入此容器中。
端聚合也可在没有溶剂的情况下进行。在此情况下,通过引入氮气使a)、b)和c)的单体混合物成为惰性的,然后将其加热至20至200℃、优选100至200℃、特别优选150至180℃的温度范围。甚至在聚合过程中,连续将温和的氮气流通过单体是有利的。
在釜内低于大气压的压力下的聚合不含氧气,在此压力下单体沸腾。取决于所用单体的类型和所选择的温度,混合物在1至20小时内聚合。例如,在150℃和310mbar下使用强力搅拌器进行搅拌由N-乙烯基酰胺与2%的N,N’-二乙烯基亚乙基脲进行聚合,在2.5小时后开始形成聚合物颗粒。聚合物颗粒量慢慢增加直到聚合时间约10小时后,反应混合物由粉末组成。由此得到的米花状聚合物收率大于90%,呈粉末状,平均颗粒尺寸在约10微米至5毫米之间、优选在10微米至500微米之间。
就制备米花状聚合物而言,优选水中进行的沉淀聚合。在此方便地选择单体的浓度以便能在整个反应时间容易地对反应混合物进行搅拌。如果水中单体的浓度太高,例如95%,聚合物颗粒通常变得粘稠,使搅拌比在无水时更为困难。为了在传统搅拌罐中进行反应,以水混合物为基础,选择单体的浓度在约5至30重量%之间、优选在10至20重量%之间。如果有更强劲的搅拌器,水溶液中的单体浓度可增至50重量%,如果合适,甚至高于50重量%。
通过将待聚合的混合物加热至沸腾可最好地排斥氧气,如果合适,还可以另外通过将例如氮气通过反应混合物来产生惰性气体气氛。聚合温度可在很宽的范围例如在约20至200℃、优选50至150℃内变化。
在一些情况下,加入少量的以单体计0.1至1重量%的还原剂如亚硫酸钠、焦亚硫酸钠、连二亚硫酸钠、抗坏血酸或还原剂的混合物对于完全除去溶解的氧气也可以是有利的。
在一个特别优选的聚合实施方案中,将单体c)、一部分交联剂、水和如果合适,缓冲液以及还原剂在温和的氮气流中加热直至开始出现聚合物颗粒。然后,在0.2至10小时的过程中向其中加入已通过对其吹氮气成为惰性(特别是)苯乙烯或丙烯酸混合物(带有或不带有交联剂、带有或不带有作为稀释剂的水)。也可将苯乙烯或丙烯酸和交联剂溶于与水互溶的溶剂中。这可以是,例如,较低的醇如甲醇、乙醇、异丙醇、正丙醇或叔丁醇。此方法的优点是端聚合作用仅花费较短的时间。可将米花状聚合物从水溶液中离析出来并进行提纯。
米花状聚合物的收率通常在约70至大于99%的理论收率之间。它们也可通过过滤或离心方法从水悬浮液中分离出来,随后以水洗涤并以传统干燥器如循环空气箱或真空干燥箱、桨式干燥器或气流干燥器。米花状聚合物实际上不溶于水和所有的溶剂,在其中也仅轻微溶胀。
本发明进一步涉及过滤水成液和/或使水成液稳定的方法,它包括使用一种作为助滤剂或稳定剂的聚合物,该聚合物包含
a)0.1至99重量%的N-乙烯基内酰胺或N-乙烯基胺
b)0至10重量%的双官能交联剂组分
c)0.1至50重量%的至少一种可通过自由基进行聚合的其它单体
在此,各组分的重量百分数以米花状聚合物的总量为基础,总和为100%。
实施此方法的方式可以分别是仅进行水溶液介质的过滤或者稳定化处理,或除了过滤外,同时也进行稳定化处理。
在过滤中,优选使用预涂过滤技术。
本发明也涉及使用本发明的聚合物作为助滤剂和/或稳定剂。
术语“过滤”意指由不连续相(被分散的物质)、和连续相(分散介质)组成的悬浮液(预滤物)流动通过多孔的过滤介质。在此过程中,固体颗粒沉积在过滤介质上,被过滤的液体(滤液)以澄清的状态离开过滤介质。在此情况下用于克服流动阻力的外力是施用的压力差。
在过滤操作中,原则上可采用不同的固体沉积方式。大体上,这包括表面过滤或饼过滤、片过滤和网过滤。通常涉及至少两种操作的组合。
在表面过滤或饼过滤的情况下,将不同设计的被称作是预涂过滤的过滤用于饮料的过滤(见Kunze,Wolfgang,酿造和制麦工艺学(TechnologieBrauer und Malzer,7th Edition,1994,p.372)。所有预涂体系共有的事实是存在于待过滤的液体中的固体和有意加入的固体(助滤剂)被过滤介质截留,形成滤饼。在过滤过程中,必须通过滤饼流动,对于过滤介质是这种情况。这类过滤也被称作预涂过滤。
待过滤和/或稳定化处理的液体包括果汁或发酵的饮料如酒或啤酒。本发明方法特别适用于过滤和/或稳定啤酒。
创造性制备的助滤剂或稳定剂呈现出良好的对水润湿性和稳定的流速同时具有良好的过滤性能。
下列实施例意在更具体地描述而不是本发明。
实施例
实施例1 (VP∶Sty)(50∶50)
将1800克蒸馏水、148克N-乙烯基吡咯烷酮(VP)、1.8克N,N’-二乙烯基亚乙基脲和0.125克氢氧化钠在引入温和氮气流的搅拌设备中加热至60℃。然后加入0.272克连二亚硫酸钠。将此混合物加热至75℃并保持在此温度。30分钟后形成白色片状物。然后,在4小时的过程中均匀地加入2克二乙烯基苯溶于148克苯乙烯(Sty)中形成的溶液。白色片状物转变成聚合物悬浮物,它慢慢变得很粘。在4小时的过程中,将此批产品用0.2克连二亚硫酸钠溶于1250毫升蒸馏水中形成的溶液进行稀释。再将此批产品进一步在80℃加热1小时,然后冷却。此实验以水蒸汽蒸馏进行提纯,再将粘滞的悬浮物滤出,以水洗涤以除去诸如可溶的聚合物和单体之类的杂质。产品的重量为285克,收率为95%。
实施例2(VP∶Sty)(90∶10)
将1800克蒸馏水、267克N-乙烯基吡咯烷酮、3克N,N’-二乙烯基亚乙基脲和0.125克氢氧化钠在引入温和氮气流的搅拌设备中加热至60℃。然后加入0.272克连二亚硫酸钠。将此混合物加热至75℃并保持在此温度。30分钟后形成白色片状物。然后,在4小时的过程中均匀地加入0.5克二乙烯基苯溶于29.5克苯乙烯中形成的溶液。白色片状物转变成聚合物悬浮物,它慢慢变得很粘。在4小时的过程中,将此批产品用0.2克连二亚硫酸钠溶于1250毫升蒸馏水中形成的溶液稀释。再将此批产品进一步在80℃加热1小时,然后冷却。此实验以水蒸汽蒸馏进行提纯,再将粘滞的悬浮物滤出,以水洗涤以除去诸如可溶的聚合物和单体之类的杂质。产品的重量为267克,收率为89%。
实施例3(VP∶Sty∶AA)(5∶35∶60)(对比实施例)
将1800克蒸馏水、15克N-乙烯基吡咯烷酮、0.3克N,N’-二乙烯基亚乙基脲和0.125克氢氧化钠在引入温和氮气流的搅拌设备中加热至60℃。然后加入0.272克连二亚硫酸钠。将此混合物加热至75℃并保持在此温度。30分钟后形成白色片状物。然后,在4小时的过程中均匀地加入两种溶液:i)3克二乙烯基苯溶于102克苯乙烯中形成的溶液;ii)180克丙烯酸(AA)。白色片状物转变成聚合物悬浮物,它慢慢变得很粘。在4小时的过程中,将此批产品用0.2克连二亚硫酸钠溶于1250毫升蒸馏水中形成的溶液稀释。再将此批产品进一步在80℃加热1小时,然后冷却。此实验以水蒸汽蒸馏进行提纯,再将粘滞的悬浮物滤出,以水洗涤以除去诸如可溶的聚合物和单体之类的杂质。产品的重量为267克,收率为89%。
实施例4(VP∶Sty∶AA)(5∶25∶70)(对比实施例)
将1800克蒸馏水、15克N-乙烯基吡咯烷酮、0.3克N,N’-二乙烯基亚乙基脲和0.125克氢氧化钠在引入温和氮气流的搅拌设备中加热至60℃。然后加入0.272克连二亚硫酸钠。将此混合物加热至75℃并保持在此温度。30分钟后形成白色片状物。然后,在4小时的过程中均匀地加入两种溶液:i)2克二乙烯基苯溶于73克苯乙烯中形成的溶液;ii)210克丙烯酸。白色片状物转变成聚合物悬浮物,它慢慢变得很粘。在4小时的过程中,将此批产品用0.2克连二亚硫酸钠溶于1250毫升蒸馏水中形成的溶液稀释。再将此批产品进一步在80℃加热1小时,然后冷却。此实验以水蒸汽蒸馏进行提纯,再将粘滞的悬浮物滤出,以水洗涤以除去诸如可溶的聚合物和单体之类的杂质。产品的重量为255克,收率为85%。
对比实施例Divergan F(BASF,德国),不溶的高交联乙烯基吡咯烷酮基聚合物。单宁的吸收
儿茶素减少
样品稳定化接触时间5分钟 | 量 | 单宁PVP/毫克/升 |
未处理啤酒 | 50克/百升 | 50.87 |
实施例3 | 50克/百升 | 41.14 |
实施例5 | 50克/百升 | 34.50 |
实施例6 | 50克/百升 | 54.50 |
Divergan F | 50克/百升 | 9.50 |
样品稳定化接触时间5分钟 | 量 | 儿茶素减少% |
实施例1 | 50克/百升 | 3.69 |
实施例2 | 50克/百升 | 6.52 |
实施例3(对比) | 50克/百升 | 13.60 |
实施例4(对比) | 50克/百升 | 20.46 |
下述稳定化实验在选择的实施例上进行。为此,具体采用下列手段:
在分析前,通过搅拌将啤酒脱气(啤酒脱碳酸气)。必须选择磁搅拌器的速度以便没有大气氧溶入啤酒中。
PVPP的吸收能力
称出20至100毫克PVPP(以干物质计)
加入200毫升脱碳酸气的啤酒
在搅拌过程中的接触时间正好5分钟
通过玻璃料滤出
对滤液进行单宁或花色素原测定
不加入PVPP的上述空白啤酒(空白值)
分析规程
花色素原的测定方法
G.Harris,R.W.Ricketts的“非生物浊雾的研究”(“Studies onnon-biological haze...”),J.Inst.Brew.,Vol.65,331-333(1959),MEBAK,Brautechn。分析方法(Analysenmethoden)[酿酒的分析方法]([Analyticalmethods for brewingl),Volume II,3rd Edition,171-172(1993),对按照1999年4月22日的MEBAK决定的方法的修正。
通过热盐酸经转换成红花色素对花色素原进行光度测定。
单宁的测定方法
鞣液比重计,自Pfeuffer(浊雾滴定)
聚乙烯基吡咯烷酮决定了啤酒的单宁含量。类蛋白质化合物通过H键积累单宁。配合的结果是形成浊雾。在鞣液比重计中,浊雾作为加入的PVP量的函数进行测量。结果给出的是以毫克PVP/升啤酒计的单宁含量。
从单宁值计算PVPP的吸收能力(%)。
标准浊雾溶液的过滤
通过澄清标准浊雾溶液测定过滤活动,这即是确定浊雾的福尔马阱悬浮液。这些溶液已为表征饮料工业中助滤剂的本领域普通技术人员所知。此实验作为预涂过滤进行实施。为此目的,在4.4巴的预涂压力下按照EBC实验方法以发明的助滤剂对福尔马阱悬浮液进行过滤。在每种情况下5升流动后,根据EBC方法测定浊雾。当EBC值小于1时,滤液被认为是澄清的。此外,测量流速和过滤体的压降(过滤体上流和下流的压力差)。发明的聚合物具有低压降和高过滤速度的特点。在整个实验中,预涂压力和过滤速度保持不变,这证实所发明助滤剂的有利性质(长使用寿命)。过滤实验
聚合物 | 流量升/小时 | 15升后压力降Δp(巴) | EBC-浊雾(开始) | EBC-浊雾(5升后) | EBC-浊雾(10升后) | EBC-浊雾(15升后) |
实施例1 | 30 | 0.2 | 15.3 | 0.2 | 0.2 | 0.1 |
实施例2 | 30 | 0.2 | 20 | 0.8 | 0.4 | 0.2 |
Claims (11)
1.一种不溶的仅轻微溶胀的米花状聚合物,该米花状聚合物包含:
a)0.1至99重量%的N-乙烯基内酰胺或N-乙烯基胺
b)0至10重量%的双官能交联剂组分
c)0.1至50重量%的至少一种可通过自由基进行聚合的其它单体
在此,各组分重量百分数以米花状聚合物的总量为基础,总和为100%。
2.根据权利要求1中的米花状聚合物,其中在(c)中提出的聚合物选自苯乙烯和/或至少一种单不饱和苯乙烯衍生物和/或丙烯酸以及其酯和酰胺。
3.根据权利要求1或2中任一项所要求的米花状聚合物,其中在(a)中提出的N-乙烯基内酰胺或N-乙烯基胺选自N-乙烯基吡咯烷酮、N-乙烯基哌啶酮、N-乙烯基己内酰胺、N-乙烯基咪唑、N-乙烯基-2-甲基咪唑、N-乙烯基-4-甲基咪唑和N-乙烯基甲酰胺。
4.根据权利要求1至3中任一项所要求的米花状聚合物的用途,用作助滤剂和/或稳定剂以过滤或稳定水成液。
5.根据权利要求4的用途,其中使用米花状聚合物,除了过滤,同时稳定水成液。
6.一种过滤和/或稳定水成液的方法,该方法包括使用权利要求1至3中任一项所要求的聚合物。
7.根据权利要求6的方法,其中在过滤中使用预涂过滤。
8.根据权利要求6和7中任一项所要求的方法,其中所述的水成液选自果汁饮料或发酵饮料的一种液体。
9.根据权利要求6至8中任一项所要求的方法,其中所述的水成液是啤酒。
10.一种助滤剂,该助滤剂含有在权利要求1至3中任一项所要求的聚合物。
11.一种稳定剂,该稳定剂含有在权利要求1至3中任一项所要求的聚合物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10160140A DE10160140A1 (de) | 2001-12-07 | 2001-12-07 | Verwendung unlöslicher hochvernetzter Popcorn-Polymerisate als Filterhilfs- und/oder Stabilisierungsmittel |
DE10160140.9 | 2001-12-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1422879A true CN1422879A (zh) | 2003-06-11 |
Family
ID=7708363
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN02155366A Pending CN1422879A (zh) | 2001-12-07 | 2002-12-09 | 不溶性高交联米花状聚合物作为助滤剂和/或稳定剂的应用 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20030124233A1 (zh) |
EP (1) | EP1318159A3 (zh) |
JP (1) | JP2003238633A (zh) |
CN (1) | CN1422879A (zh) |
DE (1) | DE10160140A1 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101137709B (zh) * | 2005-03-16 | 2011-05-11 | 巴斯福股份公司 | 具有降低的苯乙烯残余单体含量的由聚苯乙烯和交联聚乙烯吡咯烷酮组成的共混物的制备方法 |
CN101516923B (zh) * | 2006-09-12 | 2011-06-15 | 巴斯夫欧洲公司 | 制备由聚苯乙烯和交联聚乙烯基吡咯烷酮组成的且具有降低的残余苯乙烯单体含量的共挤出物的方法 |
CN101918526B (zh) * | 2007-06-06 | 2016-04-13 | 巴斯夫欧洲公司 | N-乙烯基咪唑聚合物在改进生物发酵溶液规定值性能中的用途 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10051266A1 (de) * | 2000-10-16 | 2002-04-25 | Basf Ag | Verfahren zur Filtration einer Flüssigkeit, mit einem Filterhilfsmittel und Verfahren zu deren Herstellung |
DE10215147A1 (de) * | 2002-04-05 | 2003-10-16 | Basf Ag | Verwendung von Polymerisation, enthaltend thermoplastische Polymere als Filterhilfs- und/oder Stabilisierungsmittel |
JP2007268351A (ja) * | 2006-03-30 | 2007-10-18 | Kitakyushu Foundation For The Advancement Of Industry Science & Technology | フェノール類・カルボン酸類捕捉材及びそれを用いた分離具並びにそれを用いたフェノール類・カルボン酸類の分離方法 |
GB2487762B (en) | 2011-02-03 | 2015-09-09 | Porvair Filtration Group Ltd | Composite material |
US8883239B2 (en) | 2013-02-26 | 2014-11-11 | Universidad De Talca | Clarification and selective binding of phenolic compounds from liquid foodstuff or beverages using smart polymers |
EP3074106B1 (en) * | 2013-11-28 | 2021-07-28 | Cytiva BioProcess R&D AB | Stabilization of fermented beverages |
EP3377549A4 (en) * | 2015-11-20 | 2019-07-03 | ISP Investments LLC | PROLIFERATIVE POLYMERS WITH LACTINE UNITS |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US70161A (en) * | 1867-10-29 | Improved bkush | ||
US4344846A (en) * | 1973-03-16 | 1982-08-17 | Max Klein | Filtration using expanded styrene-polymer and polyolefin micro-bits |
DE3209224A1 (de) * | 1982-03-13 | 1983-09-15 | Basf Ag | Verfahren zur herstellung von unloeslichen, nur wenig quellbaren polymerisaten von basischen vinylheterocyclen und deren verwendung |
DE3434137A1 (de) * | 1984-09-18 | 1986-03-20 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von unloeslichen, nur wenig quellbaren pulverfoermigen polymeren |
US4792400A (en) * | 1987-03-09 | 1988-12-20 | Gaf Corporation | Insoluble vinyl lactam clarifiers |
DE4000978A1 (de) * | 1990-01-16 | 1991-07-18 | Basf Ag | Verfahren zur entfernung von schwermetallionen aus wein und weinaehnlichen getraenken |
DE4237439A1 (de) * | 1992-11-06 | 1994-05-11 | Basf Ag | Unlösliche, nur wenig quellbare Polymerisate mit Aminogruppen, Verfahren zu ihrer Herstellung und ihre Verwendung |
FR2733922B1 (fr) * | 1995-05-12 | 1997-07-25 | Interbrew Sa | Nouveaux adjuvants de filtration, nouveaux supports de filtration, procede de filtration les utilisant et procede de regeneration desdits adjuvants |
DE19920944A1 (de) * | 1999-05-07 | 2000-11-09 | Basf Ag | Styrol-haltige Popcorn-Polymerisate, Verfahren zu deren Herstellung und Verwendung |
-
2001
- 2001-12-07 DE DE10160140A patent/DE10160140A1/de not_active Withdrawn
-
2002
- 2002-12-03 EP EP02027072A patent/EP1318159A3/de not_active Withdrawn
- 2002-12-04 US US10/309,057 patent/US20030124233A1/en not_active Abandoned
- 2002-12-04 JP JP2002352814A patent/JP2003238633A/ja active Pending
- 2002-12-09 CN CN02155366A patent/CN1422879A/zh active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101137709B (zh) * | 2005-03-16 | 2011-05-11 | 巴斯福股份公司 | 具有降低的苯乙烯残余单体含量的由聚苯乙烯和交联聚乙烯吡咯烷酮组成的共混物的制备方法 |
CN101516923B (zh) * | 2006-09-12 | 2011-06-15 | 巴斯夫欧洲公司 | 制备由聚苯乙烯和交联聚乙烯基吡咯烷酮组成的且具有降低的残余苯乙烯单体含量的共挤出物的方法 |
CN101918526B (zh) * | 2007-06-06 | 2016-04-13 | 巴斯夫欧洲公司 | N-乙烯基咪唑聚合物在改进生物发酵溶液规定值性能中的用途 |
Also Published As
Publication number | Publication date |
---|---|
JP2003238633A (ja) | 2003-08-27 |
EP1318159A2 (de) | 2003-06-11 |
EP1318159A3 (de) | 2003-12-03 |
DE10160140A1 (de) | 2003-06-12 |
US20030124233A1 (en) | 2003-07-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5094867A (en) | Removal of heavy metal ions from wine and wine-like beverages | |
US5539071A (en) | Crosslinked methacrylic anhydride copolymers | |
US3941718A (en) | Insoluble crosslinked homopolymers and copolymers, polymerized on an inert substrate | |
CN1422879A (zh) | 不溶性高交联米花状聚合物作为助滤剂和/或稳定剂的应用 | |
US4658002A (en) | Preparation of insoluble polymer powders which are only slightly swellable | |
EP2240415A1 (en) | Composite polymeric filtration media | |
US20160318001A1 (en) | Water absorbent polymers and a process for their preparation | |
CN1371925A (zh) | 用作助滤剂的粒状聚合物 | |
JP4189149B2 (ja) | 水性液のための濾過助剤としての粒子状ポリマーの使用 | |
US20030162853A1 (en) | Use of adsorbent polymer particles in DNA separation | |
JPH07179504A (ja) | 微粒子ポリマーおよびその製造方法 | |
JP2006509066A (ja) | 不溶性で、高度に架橋した、スチレン4−スルホン酸塩を含むポップコーンポリマー、その製造、及び使用 | |
CA2128950A1 (en) | The removal of aluminum ions from beverages | |
US8420737B2 (en) | Method for the production of co-extrudates composed of polystyrene and of a crosslinked polyvinylpyrrolidone with reduced residual styrene monomer content | |
AU596509B2 (en) | Improved insoluble vinyl lactam clarifiers | |
JP3459502B2 (ja) | ポリフェノール吸着剤 | |
US4758633A (en) | Insoluble vinyl lactam clarifiers | |
GB2075479A (en) | Recovery of cerium from polymer dispersions | |
CN115672054A (zh) | 含羧基聚醚砜/聚乙烯醇复合超滤膜及其制备方法 | |
KR20160102208A (ko) | 물흡수제 중합체와 이들의 제조를 위한 공정 | |
JPS608382A (ja) | 螢光性粒子の製造法 | |
JPH02304051A (ja) | 水容性の良好なる高分子量重合体の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |