CN1066461C - 制备橡胶模塑材料的方法 - Google Patents
制备橡胶模塑材料的方法 Download PDFInfo
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- CN1066461C CN1066461C CN95196770A CN95196770A CN1066461C CN 1066461 C CN1066461 C CN 1066461C CN 95196770 A CN95196770 A CN 95196770A CN 95196770 A CN95196770 A CN 95196770A CN 1066461 C CN1066461 C CN 1066461C
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- rubber
- monomer
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- polymerization
- moulding
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- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000010068 moulding (rubber) Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title description 2
- 229920001971 elastomer Polymers 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 230000008961 swelling Effects 0.000 claims abstract description 4
- -1 bicyclic pentadiene esters Chemical class 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 13
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- 230000009466 transformation Effects 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- DNPFOADIPJWGQH-UHFFFAOYSA-N octan-3-yl prop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C=C DNPFOADIPJWGQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 2
- 238000001149 thermolysis Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract 1
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- 239000000126 substance Substances 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000001177 diphosphate Substances 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- HOWGUJZVBDQJKV-UHFFFAOYSA-N docosane Chemical compound CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical class CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- QHMGJGNTMQDRQA-UHFFFAOYSA-N dotriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC QHMGJGNTMQDRQA-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- HMSWAIKSFDFLKN-UHFFFAOYSA-N hexacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC HMSWAIKSFDFLKN-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- POOSGDOYLQNASK-UHFFFAOYSA-N tetracosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC POOSGDOYLQNASK-UHFFFAOYSA-N 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002819 montanyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 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 compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000003643 water by type 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
一种制备橡胶改性模塑材料的方法,其中
在第一阶段,将含有至少一种通式(Ⅰ)的丙烯酸或甲基丙烯酸烷基酯(a)、具有两个或多个双键的第一种单体(b)和若需要含量达60wt%的第二种单体(c)或多种单体的第一种混合物(A)优选进行游离基聚合得到丙烯酸酯单体单元含量至少为30wt%的橡胶(B),所述通式(Ⅰ)为:
其中R1为氢或甲基,R2为1至32个碳原子的烷基,
在第二阶段,将所得橡胶(B)在加或不加溶剂情况下溶解或溶胀于第三种单体(d)或多种单体中,形成第二种混合物(C),及
在第三阶段,将溶解或溶胀后形成的第二种混合物(C)在0℃至200℃的温度进行聚合得到橡胶改性模塑材料(D),所述橡胶改性材料(D)含有1-60wt%的橡胶(B)并在所述材料(D)中,接枝形式的橡胶(B)以直径为0.1-20μm的粒子存在。
Description
本发明涉及制备处于溶解或溶胀状态的橡胶改性模塑材料,尤其是丙烯腈/苯乙烯/丙烯酸酯模塑材料的方法和由此方法制备的橡胶改性模塑材料。
橡胶改性模塑材料是其中弹性体(如橡胶)微区埋入热塑性材料基体中的材料。目前对具有表面光泽、冲击强度和拉伸强度的橡胶改性模塑材料的需求相当大。所需力学性能正是基于这种特定的微区结构。
橡胶改性模塑材料的多相特性和随之而来的微区结构基于的事实是,该材料包括相互不溶混或仅部分溶混的不同聚合物组分。材料的冲击强度来自于在变形至断裂过程中增加的能量吸收。消耗的能量被用于形成微空穴或用于引发基体聚合物链的滑动过程。因此多相特性是获得高冲击强度的必须条件。
下列特点也是有利的:1.两种化学上不同的聚合物组分形成限定颗粒尺寸的稳定分散体,该分散体既在热塑性熔体(加工)中不出现相分离,又在高温下形成高分子溶液中不趋向于均化。2.在弹性体颗粒和基体之间必须存在偶联,即在相边界必须能够传输应力。
在弹性体颗粒边界处的最有效相偶联通过接枝共聚实现。例如,在制备丙烯腈/苯乙烯/丙烯酸酯(ASA)模塑材料中,一般采取的方法是首先形成丙烯酸酯橡胶,然后通过与包括苯乙烯和丙烯腈的混合物聚合,将基于后两种单体的共聚物接枝到丙烯酸酯橡胶上。
乳液聚合制备ASA模塑材料的方法公开于(例如)DE 32 06 136、3149 046、31 49 358、32 27 555、31 29 378、31 29 472、29 40 804、28 26 925和19 11 882中。该橡胶在乳液中由丙烯酸正丁酯和少量含两个双键的单体制备。该方法的缺点是,由于乳液聚合以及由于聚合物分散体沉淀生成了大量的水,它必须被除去。此外,通过该方法制备的模塑材料对于所有用途不具有足够的冲击强度和拉伸强度。同时由其生产的模制体的光泽不能在宽范围内变化。
由于这些原因,在溶液中制备模塑材料是最有利的,这些方法公开于EP 0 095 919和DE 11 82 811中。
根据EP 0 095 919,在橡胶上不发生共聚单体的接枝,即在边界处无有效的偶联。根据DE 11 82 811,橡胶由丙烯酸正丁酯和0.5至10wt%的具有两个可游离基聚合的双键的共聚单体制备。苯乙烯/丙烯腈(SAN)单体混合物的聚合在橡胶转化率为10至80%时开始。结果,橡胶的接枝部分与聚合物基体的组成不同,导致模塑材料较差的力学性能。同时,橡胶单元在接枝壳(即接枝支链)中的聚合导致产品的维卡软化温度降低。
本发明目的在于提供一种具有改进的冲击强度、拉伸强度和断裂伸长的橡胶改性模塑材料的制备方法。
我们发现本发明目的通过该新方法实现,其中在第一阶段,将含有至少一种通式(Ⅰ)的丙烯酸或甲基丙烯酸烷基酯(a)、具有两个或多个双键的第一种单体(b)和(若需要)含量达60wt%第二种单体(c)或多种单体的第一种混合物(A)优选进行游离基聚合得到丙烯酸酯单体单元含量至少为30wt%的橡胶(B),所述通式(Ⅰ)为:其中R1为氢或甲基R2为1至32个碳原子的烷基,
在第二阶段,将所得橡胶(B)在加或不加溶剂情况下溶解或溶胀于第三种单体(d)或多种单体中,形成第二种混合物(C),及
在第三阶段,将溶解或溶胀后形成的第二种混合物(C)在0℃至200℃的温度聚合得到橡胶改性模塑材料(D),所述橡胶改性材料(D)含有1-60wt%的橡胶(B)并在所述橡胶改性材料(D)中,接枝形式的橡胶以直径为0.1-20μm的粒子存在。
接枝共聚在第三阶段进行,所得接枝共聚物的骨架由橡胶(B)形成并且这些接枝链由第三种单体(d)形成。由于不能进行100%接枝,因此一些橡段将丙烯酸酯或甲基丙烯酸酯与一种具有两个或多个双键的单体共聚。现在我们假设,模塑材料性能的改进特别是基于下列事实:
1.第一阶段共聚后残留的第一种单体(b)的双键用作为第三种单体(d)的增长链的接枝点,
2.含有引入的第一种单体(b)的聚丙烯酸或甲基丙烯酸烷基酯的分子量与无引入第一种单体(b)的相比得以提高,
3.使用具有两个或多个双键的第一种单体(b)减少了橡胶的低分子量部分。这导致改进了其机械性能。
1至32个碳原子的烷基R2的例子是甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基、正庚基、正辛基、乙基己基、正壬基、正癸基、正十二烷基、正十四烷基、正十六烷基、正十八烷基、正二十烷基、正二十二烷基、正二十四烷基、正二十六烷基、正二十八烷基、正三十烷基、正三十一烷基和正三十二烷基。
在本发明优选的实施方案中,R2是具有1至18个碳原子的烷基。
在本发明另一优选的实施方案中,混合物(A)具有如下组成:30至99.9 wt%的丙烯酸或甲基丙烯酸烷基酯(a),0.1至10wt%的第一种单体(b)和0至60wt%的第二种单体(c),
优选范围是:36至99.9wt%的(a),0.1至4wt%的(b)和0至60wt%的(c),所有数值都按混合物(A)的总重量以wt%计。
橡胶(B)的玻璃化温度优选低于0℃,更优选低于-10℃,其中玻璃化温度按照ASTM 3418借助DSC测定。因此橡胶具有所需的柔软度。玻璃化温度可通过用丙烯酸酯或甲基丙烯酸酯(其聚合物具有所需玻璃化温度)或通过用丙烯酸酯和甲基丙烯酸酯(它们具有不同的侧链(通式Ⅰ中的R2)长度)的混合物调整。这种调节玻璃化温度基于的事实是丙烯酸酯和甲基丙烯酸酯的玻璃化温度随侧链长度增加开始降低,然后经过最小值,最后再次增加。最小值出现在约7个碳原子的侧链时(对于聚丙烯酸酯)和在10个碳原子的侧链时(对于聚甲基丙烯酸酯)。因此,此侧链R2的一般长度范围是优选的。
制备的橡胶改性模塑材料(D)含有1至60,优选5至40wt%的橡胶(B)。此上限由模塑材料必须具有足够强度(尽管埋有橡胶微区)的事实确定。下限基本上由在形变过程中必须吸收足够的能量确定。
在本发明进一步优选的实施方案中,将丙烯酸正丁酯或丙烯酸乙基己基酯或其混合物用作丙烯酸或甲基丙烯酸烷基酯。
第一种单体(b)的例子有:甲基丙烯酸烯丙酯,二丙烯酸丁二醇酯,二乙烯基苯、三聚氰酸三烯丙酯和丙烯酸二氢双环戊二烯基酯,其中优选最后一个。
第二种单体(c)的例子有:苯乙烯,丙烯腈,丙烯酸,甲基丙烯酸,最后两种单体的衍生物如丙烯酰胺,甲基丙烯酰胺,丙烯酸缩水甘油酯,甲基丙烯酸缩水甘油酯,马来酸酐,马来酰亚胺和乙烯。其它例子是含有热分解时形成游离基的基团如过氧基、偶氮基和不稳定C-C-键的单体,例如叔丁基-3-异丙烯基-枯基过氧化物或过氧巴豆酸叔丁酯。混合物(A)含有达60wt%,优选40wt%的这种单体。
单体(d)的例子是已对(c)所说明并不含提供游离基的基团的那些,优选是下式的苯乙烯:(其中R7和R8可以是相同或不同的,各自为氢或1至8个碳原子的烷基,n为0至4),和丙烯腈。因此按本发明方法特别是制备ASA模塑材料。
在本发明方法的第三阶段中,聚合可按溶液或本体聚合方式连续进行,或在转化率至少15%后按悬浮聚合方式继续进行。
橡胶中丙烯酸酯单体单元的含量是至少30wt%,优选至少60wt%;特别优选至少90wt%。
聚合在0至200℃,优选50至160℃下进行,所有常规聚合方法都可以使用,但游离基聚合是优选的。
混合物可含有添加剂如润滑剂、抗氧剂、着色剂、玻璃纤维和/或填料。
下面本发明将参考具体优选的实施方案详细描述。
在模塑材料中,接枝形式的橡胶以粒径0.1至20μm,优选0.1至10μm的颗粒形式存在于聚合物基体中,双态或三态分布是优选的。橡胶颗粒为胶囊、棒、小滴、迷宫、小室(cell)、球团、壳、棒束或滴束形式。然而,还观察到由多个球形颗粒组成的颗粒。小室或最后提及的形式是优选的。所述颗粒形式描述于A.Echte,化学分期连载进展(Advances inChemical Serials),222(1989),p29中。
实施例
在实施例中,使用如下化合物:
环己烷、丙烯酸丁酯、丙烯酸二氢双环戊二烯基酯、丙烯腈和苯乙烯,它们是购自BASF的产品并在不再纯化下使用。
LuviskolK 90也是购自BASF的产品,它是K值为90(在25℃下浓度1%的水溶液中测定)的聚乙烯基吡咯烷酮。K值的测量方法描述于纤维素化学,13(1932),p.358-364中。
二磷酸四钠购自Merck,偶氮二异丁腈购自Akzo Chemical。
使用的稳定剂为3-(3,5-二叔丁基-4-羟苯基)丙酸十八烷基酯,它是Ciba Geigy以Irganox1076出售的酚类抗氧剂。
Ertivinol是Ercros公司的一种聚乙烯醇。
RongalitC是羟基甲磺酸的钠盐。实验1(比较例)
a.制备橡胶
将750g环己烷加入烧瓶中并在氮气下在搅拌下加热至75℃,然后加入125g丙烯酸正丁酯和545mg偶氮二异丁腈。在此后的4小时内连续计量加入375g丙烯酸正丁酯然后将反应再持续进行3.5小时。转化率为94wt%,然后用1g Irganox 1076加以稳定。
b.制备终产物
在旋转蒸发器中在减压下除去环己烷并用苯乙烯代替,然后加入丙烯腈得到69.2wt%苯乙烯、23wt%丙烯腈和7.8wt%橡胶的混合物。将1923g这种溶液与2.3lg Irganox1076和1.35g叔十二烷硫醇一起加入一5升的铁釜中并在氮气下在搅拌下加热至130℃。转化率39wt%时,加入1.9g过氧化二枯基、1900g水、20g Luviskol K90、1.0g二磷酸四钠和59.8g的Ertivinol的10%水溶液。按如下完成物料聚合:
110℃下3小时
130℃下3小时
140℃下6小时
然后将混合物冷却,将聚合物过滤出来并干燥。实验2(根据本发明):
重复实验1,但4.0wt%的丙烯酸正丁酯被丙烯酸二氢双环戊二烯基酯代替。橡胶制备时的转化率为98wt%。
实施例3(比较例)
将下列起始物质在氮气和搅拌下加入一玻璃烧瓶中。在30℃经3小时计量加下列原料1和2并使物料继续聚合2小时。聚合反应反应转化率为98wt%。起始物质:
525.5g 水
4.8g C12-18石蜡磺酸的40%的水溶液
1.36g 氢过氧化叔丁基
0.088g 硫酸亚铁原料1:
450g 丙烯酸正丁酯原料2:
188.0g 水
14.4g C12-18石蜡磺酸钾的40%溶液
0.58g 雕白粉C
分散体用硫酸镁溶液沉淀并干燥。然后将橡胶溶于苯乙烯/丙烯腈单体混合物中并如下聚合单体:
a.在一铁釜中于搅拌和氮气氛下制备下列溶液:
69.2重量份苯乙烯
23.0重量份丙烯腈
7.8重量份乳液中制备的橡胶
0.1重量份Irganox1076
0.2重量份叔十二烷硫醇
溶液加热至80℃并加入0.04重量份过新戊酸正丁酯。
b.在转化率为28wt%时加入以下物质:
0.1重量份过氧化二枯基
100重量份水
1重量份LuviskolK90
0.1重量份二磷酸四钠
3.0重量份Ertivinol 10%的水溶液。按如下完成物料的聚合:
110℃下3小时
130℃下3小时
140℃下6小时
然后冷却,滤出聚合物并干燥。实验4(本发明)
重复实施例3,但用丙烯酸二氢双环戊二烯基酯代替4wt%的丙烯酸正丁酯。
结果
冲击强度 拉伸强度 断裂伸长
KJ/m2 N/mm2 %
<----------23℃---------->
1.(比较例) 11 59 2,3
2.(本发明) 26 73 4,4
3.(比较例) 17 n.g. n.g.
4.(本发明) 41 n.g. n.g.
n.g.:未测量
可以看出,按本发明在橡胶中使用共聚单体(b)与不含单体(b)的橡胶模塑材料相比可大大改进其机械性能。
Claims (10)
1.一种制备橡胶改性模塑材料的方法,其中
在第一阶段,将含有30-99.9wt%至少一种通式(Ⅰ)的丙烯酸或甲基丙烯酸烷基酯(a)、0.1-10wt%具有两个或多个双键的第一种单体(b)和0-60t%的第二种单体(c)或多种单体的第一种混合物(A)进行聚合得到丙烯酸酯单体单元含量至少为30wt%的橡胶(B),所述通式(Ⅰ)为:
其中R1为氢或甲基,R2为1至32个碳原子的烷基,
在第二阶段,将所得橡胶(B)在加或不加溶剂情况下溶解或溶胀于第三种单体(d)或多种单体中,形成第二种混合物(C),及
在第三阶段,将溶解或溶胀后形成的第二种混合物(C)在0℃至200℃的温度进行聚合得到橡胶改性模塑材料(D),所述橡胶改性材料(D)含有1-60wt%的橡胶(B)并在所述橡胶改性材料(D)中,接枝形式的橡胶(B)以直径为0.1至20μm的粒子存在。
2.如权利要求1的方法,其中R2为1至18个碳原子的烷基。
3.如权利要求1的方法,其中混合物(A)进行游离基聚合得到橡胶(B)。
4.如权利要求1的方法,其中制备含有5至40wt%橡胶(B)的橡胶改性模塑材料(D),按橡胶模改性塑材料(D)的总重量计。
5.如权利要求1的方法,其中使用丙烯酸正丁酯或丙烯酸乙基己基酯作为丙烯酸或甲基丙烯酸烷基酯(a)。
6.如权利要求1的方法,其中使用的第一种单体(b)是丙烯酸二氢双环戊二烯基酯。
7.如权利要求1的方法,其中将苯乙烯和丙烯腈用作第三种单体(d)。
8.如权利要求1的方法,其中第二种单体(c)含有热分解时形成游离基的基团。
9.如权利要求1的方法,其中第三阶段在转化率达到至少15%后聚合以悬浮聚合方式继续进行。
10.按照方法权利要求1的方法制备的橡胶模塑材料。
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US4426499A (en) * | 1981-02-06 | 1984-01-17 | Bayer Aktiengesellschaft | Process for the production of graft polymers |
EP0306806A2 (de) * | 1987-09-09 | 1989-03-15 | Bayer Ag | Verfahren zur Herstellung von Pfropfpolymerisaten |
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WO1996015167A1 (de) | 1996-05-23 |
DE59503547D1 (de) | 1998-10-15 |
EP0792299B1 (de) | 1998-09-09 |
JPH10508652A (ja) | 1998-08-25 |
DE4440676A1 (de) | 1996-05-15 |
CN1169741A (zh) | 1998-01-07 |
EP0792299A1 (de) | 1997-09-03 |
ES2124596T3 (es) | 1999-02-01 |
KR970707188A (ko) | 1997-12-01 |
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