CN108778502B - 金属担载型催化剂、以及氢化共轭二烯系聚合物的制造方法 - Google Patents
金属担载型催化剂、以及氢化共轭二烯系聚合物的制造方法 Download PDFInfo
- Publication number
- CN108778502B CN108778502B CN201780017148.8A CN201780017148A CN108778502B CN 108778502 B CN108778502 B CN 108778502B CN 201780017148 A CN201780017148 A CN 201780017148A CN 108778502 B CN108778502 B CN 108778502B
- Authority
- CN
- China
- Prior art keywords
- metal
- supported catalyst
- conjugated diene
- catalyst
- diene polymer
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 229920000642 polymer Polymers 0.000 title claims description 46
- 150000001993 dienes Chemical class 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 50
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 50
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 50
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 230000001186 cumulative effect Effects 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 47
- 238000005984 hydrogenation reaction Methods 0.000 description 39
- 229920001577 copolymer Polymers 0.000 description 30
- 238000000034 method Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000000178 monomer Substances 0.000 description 15
- 229910052763 palladium Inorganic materials 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 239000004816 latex Substances 0.000 description 9
- 229920000126 latex Polymers 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 7
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 150000002941 palladium compounds Chemical class 0.000 description 7
- 229910052682 stishovite Inorganic materials 0.000 description 7
- 229910052905 tridymite Inorganic materials 0.000 description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010556 emulsion polymerization method Methods 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- -1 vinyl aromatic compounds Chemical class 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FPFVPEGEWVRCGK-UHFFFAOYSA-N 1-ethenoxy-2-fluoroethane Chemical compound FCCOC=C FPFVPEGEWVRCGK-UHFFFAOYSA-N 0.000 description 1
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-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
- GFDLMAQAFYECMB-UHFFFAOYSA-N 4-(2-hydroxypropoxy)but-2-yn-1-ol Chemical compound CC(O)COCC#CCO GFDLMAQAFYECMB-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- NTDQECXVEKMBFD-UHFFFAOYSA-K [Rh+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O Chemical compound [Rh+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O NTDQECXVEKMBFD-UHFFFAOYSA-K 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical group C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- LTMGJWZFKVPEBX-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile;prop-2-enoic acid Chemical compound C=CC=C.C=CC#N.OC(=O)C=C LTMGJWZFKVPEBX-UHFFFAOYSA-N 0.000 description 1
- VVDUCPQZFYLJDA-UHFFFAOYSA-K butanoate;rhodium(3+) Chemical compound [Rh+3].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O VVDUCPQZFYLJDA-UHFFFAOYSA-K 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- NKKMVIVFRUYPLQ-NSCUHMNNSA-N crotononitrile Chemical compound C\C=C\C#N NKKMVIVFRUYPLQ-NSCUHMNNSA-N 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 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
- IYDMNMSJMUMQBP-UHFFFAOYSA-N dipotassium;palladium(2+);tetracyanide Chemical compound [K+].[K+].[Pd+2].N#[C-].N#[C-].N#[C-].N#[C-] IYDMNMSJMUMQBP-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 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
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 239000011976 maleic acid Substances 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
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- BHZSLLSDZFAPFH-UHFFFAOYSA-L palladium(2+);difluoride Chemical compound F[Pd]F BHZSLLSDZFAPFH-UHFFFAOYSA-L 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- OZVHAYAOFBRGQV-UHFFFAOYSA-K pentanoate;rhodium(3+) Chemical compound [Rh+3].CCCCC([O-])=O.CCCCC([O-])=O.CCCCC([O-])=O OZVHAYAOFBRGQV-UHFFFAOYSA-K 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- MMRXYMKDBFSWJR-UHFFFAOYSA-K rhodium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Rh+3] MMRXYMKDBFSWJR-UHFFFAOYSA-K 0.000 description 1
- QRRFFHBDASQYFJ-UHFFFAOYSA-K rhodium(3+);triformate Chemical compound [Rh+3].[O-]C=O.[O-]C=O.[O-]C=O QRRFFHBDASQYFJ-UHFFFAOYSA-K 0.000 description 1
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/02—Hydrogenation
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
-
- 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Catalysts (AREA)
Abstract
本发明提供一种金属担载型催化剂,其是使金属和/或金属化合物担载于载体而成的,在2.3重量%的聚乙烯吡咯烷酮水溶液中,在氢气氛下,以温度50℃、36rpm的条件振动1小时之际,上述金属担载型催化剂中所包含的金属和/或金属化合物的减少率为20重量%以上。
Description
技术领域
本发明涉及一种金属担载型催化剂、以及氢化共轭二烯系聚合物的制造方法,更详细而言,涉及能够实现高加氢率的金属担载型催化剂以及使用这样的金属担载型催化剂的氢化共轭二烯系聚合物的制造方法。
背景技术
在制造医药农药、石油化学产品、聚合物等的化学工业中,广泛进行着将各种化合物所包含的碳-碳不饱和键、碳-氮不饱和键进行氢化而转换为对应的饱和键的氢化反应。
例如,在聚合物制造领域中,作为共轭二烯系聚合物的有用的改性手段,公知将共轭二烯系聚合物的碳-碳双键选择性地或部分地氢化的方法,氢化丙烯腈-丁二烯共聚物等氢化共轭二烯系聚合物正以工业规模生产。
这样的氢化共轭二烯系聚合物通过例如下述的制造工艺来制造。即,将包含共轭二烯的单体乳液聚合,将通过乳液聚合得到的胶乳凝固、干燥,接下来,将通过凝固、干燥得到的原料聚合物溶解于有机溶剂(氢化反应溶剂),由此得到原料聚合物的溶液,向其中添加含有铂族元素等金属的催化剂,进行氢化而制造。
作为上述工艺所使用的含有金属的催化剂,可举出例如金属元素、金属元素的化合物等。这样的金属元素、金属元素的化合物通过例如使其担载于载体而被用作金属担载型催化剂(参考例如专利文献1)。
现有技术文献
专利文献
专利文献1:日本特开昭58-17103号公报。
发明内容
发明要解决的问题
另一方面,上述的金属担载型催化剂通常含有铂族元素等稀有金属,因此,对于这样的金属担载型催化剂,要求即使为少量的使用量也可得到充分的加氢率。
本发明是鉴于这样的实际情况而完成的,其目的在于提供能够实现高加氢率的金属担载型催化剂。
用于解决问题的方案
本发明人等对使用使金属和/或金属化合物担载于载体而成的金属担载型催化剂的情况下的加氢率的提高进行了深入研究,结果发现,在聚乙烯吡咯烷酮水溶液中以规定的条件振动时的金属和/或金属化合物的减少率为20重量%以上的金属担载型催化剂的催化剂活性优异,因而能够实现高加氢率,以至完成了本发明。
即,根据本发明,可提供一种金属担载型催化剂,是使金属和/或金属化合物担载于载体而成的,在2.3重量%的聚乙烯吡咯烷酮水溶液中,在氢气氛下,以温度50℃、36rpm的条件振动1小时之际,上述金属担载型催化剂中所包含的金属和/或金属化合物的减少率为20重量%以上。
本发明的金属担载型催化剂优选是使铂族元素和/或含铂族元素化合物作为上述金属和/或金属化合物担载于载体而成的。
在本发明的金属担载型催化剂中,优选上述聚乙烯吡咯烷酮水溶液所包含的聚乙烯吡咯烷酮的以聚苯乙烯换算的重均分子量为8000~12000。
本发明的金属担载型催化剂优选以体积基准求出的粒径分布中的50%累积径超过0μm且为100μm以下。
本发明的金属担载型催化剂优选以个数基准求出的粒径分布中的50%累积径超过0μm且为2μm以下。
此外,在本发明中,可提供一种氢化共轭二烯系聚合物的制造方法,在溶剂中,在上述的金属担载型催化剂的存在下,将共轭二烯系聚合物氢化。
发明效果
根据本发明,可提供能够实现高加氢率的金属担载型催化剂、以及使用这样的金属担载型催化剂的氢化共轭二烯系聚合物的制造方法。
具体实施方式
金属担载型催化剂
本发明的金属担载型催化剂是使金属和/或金属化合物担载于载体而成的,
在2.3重量%的聚乙烯吡咯烷酮水溶液中,在氢气氛下,以温度50℃、36rpm的条件振动1小时之际,金属担载型催化剂中所包含的金属和/或金属化合物的减少率为20重量%以上。
作为构成金属担载型催化剂的金属和/或金属化合物,只要为可用作共轭二烯系聚合物的氢化反应的催化剂的金属或金属化合物即可,没有特别限定,从催化剂活性的观点出发,优选使用铂族元素和/或含铂族元素化合物,即,钌、铑、钯、锇、铱或铂、或者含有它们的化合物。在这些之中,优选钯、铑或它们的化合物,更优选钯或钯化合物。此外,也可以并用2种以上的铂族元素、含铂族元素化合物,在这种情况下也优选将钯、钯化合物作为主要的催化剂成分。
钯化合物通常使用II价或IV价的钯化合物,其形态为盐、络盐。
作为钯化合物,可举出例如醋酸钯、氰化钯、氟化钯、氯化钯、溴化钯、碘化钯、硝酸钯、硫酸钯、氧化钯、氢氧化钯、(环辛二烯)二氯化钯、(降冰片二烯)二氯化钯、双(三苯基膦)二氯化钯、四氯钯酸钠、六铝钯酸铵、四氰基钯酸钾等。
在这些钯化合物中,优选醋酸钯、硝酸钯、硫酸钯、氯化钯、四氯钯酸钠、六氯钯酸铵,更优选醋酸钯、硝酸钯以及氯化钯。
作为铑化合物,可举出例如氯化铑、溴化铑、碘化铑、硝酸铑、硫酸铑、醋酸铑、蚁酸铑、丙酸铑、丁酸铑、戊酸铑、环烷酸铑、乙酰丙酮铑、氧化铑、三氢氧化铑等。
作为用于形成金属担载型催化剂的载体,只要为通常可用作金属催化剂的载体的载体即可,具体而言,优选:通常作为吸附剂使用的活性炭;含有硅、铝、镁等的无机化合物。
作为这样的载体,优选从活性炭、活性白土、滑石、黏土、氧化铝凝胶、二氧化硅、硅藻土、合成沸石等公知的催化剂用载体中适宜选择,此外,作为将作为催化剂成分的金属或金属化合物担载于载体的方法,可举出例如含浸法、涂覆法、喷雾法、沉淀法等。金属或金属化合物的担载量以作为催化剂成分的金属或金属化合物相对于金属或金属化合物和载体的合计量的比例计,优选为0.1~20重量%,更优选为0.1~10重量%,进一步优选为0.1~5重量%。
此外,就本发明的金属担载型催化剂而言,在2.3重量%的聚乙烯吡咯烷酮(PVP)水溶液中,在氢气氛下,以温度50℃、36rpm的条件振动1小时之际,金属担载型催化剂中所包含的金属和/或金属化合物的减少率(以下适当地称为“PVP分散时金属减少率”)为20重量%以上,优选为25重量%以上,更优选为30重量%以上。此外,上限没有特别限定,通常为70重量%以下。根据本发明,通过将PVP分散时金属减少率设为上述范围,从而能够使金属担载型催化剂的催化剂活性提高,由此,在用作氢化反应的催化剂的情况下,能够实现高加氢率。另外,在本发明中,PVP分散时金属减少率能够通过下述式(1)算出,PVP分散时金属减少率越高,意味着分散后的金属担载型催化剂中的金属和/或金属化合物的量越少。
PVP分散时金属减少率(重量%)=100-(“在PVP水溶液中振动后的金属担载型催化剂中所包含的金属和/或金属化合物的重量(g)”÷“在PVP水溶液中振动前的金属担载型催化剂中所包含的金属和/或金属化合物的重量(g)”)×100···(1)
特别地,本发明人等以即使为少量的使用量也得到充分的加氢率为目的,对使金属和/或金属化合物担载于载体而成的金属担载型催化剂与使用其的情况下的加氢率的关系进行了深入研究。然后,进行了深入研究的结果发现,当PVP分散时金属减少率变高时,催化剂活性特别是在用作氢化反应的催化剂的情况下的加氢率也变高,以至完成了本发明。
另外,通过将PVP分散时金属减少率设为上述范围从而能够提高催化剂活性特别是在用作氢化反应的催化剂的情况下的加氢率的原因尚不明确,但可认为例如以下的原因。即,PVP分散时金属减少率高会导致在聚乙烯吡咯烷酮水溶液中振动时,金属担载型催化剂所包含的作为催化剂成分的金属和/或金属化合物之中,溶出到聚乙烯吡咯烷酮水溶液中的量多。即,能够认为能够与聚乙烯吡咯烷酮接触的金属和/或金属化合物的量也多。因此,可以预想到,当PVP分散时金属减少率高时,实际进行共轭二烯系聚合物的氢化反应时,金属担载型催化剂所包含的作为催化剂成分的金属和/或金属化合物之中,能够与供于氢化反应的共轭二烯系聚合物接触的量变多,由此能够实现高加氢率。
此外,测定PVP分散时金属减少率时,在2.3重量%的PVP水溶液中,在氢气氛下,以温度50℃、36rpm的条件,使金属担载型催化剂振动1小时即可,该情况下的金属担载型催化剂与PVP水溶液的比例以“金属担载型催化剂∶PVP水溶液”的重量比计设为0.75∶100即可,此外,此时的体系中的压力设为1MPa(表压)即可。此外,作为构成PVP水溶液的聚乙烯吡咯烷酮,使用以聚苯乙烯换算的重均分子量处在8000~12000的范围的聚乙烯吡咯烷酮即可。
另外,作为使PVP分散时金属减少率为20重量%以上的方法,没有特别限定,可举出例如对通过含浸法、涂覆法、喷雾法、沉淀法等得到的金属担载型催化剂进行粉碎的方法等。在该情况下,优选以体积基准求出的粒径分布中的50%累积径优选超过0μm且为100μm以下、更优选超过0μm且为50μm以下的方式进行粉碎。或者,优选以个数基准求出的粒径分布中的50%累积径优选超过0μm且为2μm以下、更优选超过0μm且为1μm以下的方式进行粉碎。另外,作为使PVP分散时金属减少率为20重量%以上的方法,除了进行粉碎的方法以外,也能够使用例如使用粒径小的载体的方法、使用高比表面积的载体的方法等。
氢化共轭二烯系聚合物的制造方法
本发明的氢化共轭二烯系聚合物的制造方法具有在溶剂中、在上述的本发明的金属担载型催化剂的存在下、将共轭二烯系聚合物氢化的工序。
在本发明的制造方法中,氢化为将共轭二烯系聚合物所包含的碳-碳双键的至少一部分加氢而转换为饱和键的反应。本发明中所使用的共轭二烯系聚合物为将共轭二烯单体单独、或者将能够与共轭二烯单体共聚的单体与该共轭二烯单体组合,通过现有公知的乳液聚合法或溶液聚合法、优选使用乳液聚合法而制造的聚合物。
作为用于形成共轭二烯系聚合物的共轭二烯单体,只要为具有共轭二烯结构的聚合性单体就没有特别限定,可举出例如1,3-丁二烯、2-甲基-1,3-丁二烯(异戊二烯)、2,3-二甲基-1,3-丁二烯、2-氯-1,3-丁二烯、1,3-戊二烯等。在这些之中,优选1,3-丁二烯、2-甲基-1,3丁二烯,更优选1,3丁二烯。
作为能够与共轭二烯单体共聚的单体,可举出例如:丙烯腈、甲基丙烯腈、巴豆腈等α,β-烯属不饱和腈单体;丙烯酸、甲基丙烯酸、巴豆酸、富马酸、马来酸、衣康酸等α,β-烯属不饱和羧酸;丙烯酸甲酯、丙烯酸正丁酯、丙烯酸2-乙基己酯、丙烯酸三氟乙酯、甲基丙烯酸甲酯等α,β-烯属不饱和羧酸酯;丙烯酰胺、甲基丙烯酰胺等α,β-烯属不饱和羧酸酰胺;苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、二乙烯基苯等乙烯基芳香族化合物;醋酸乙烯酯、丙酸乙烯酯等羧酸的乙烯酯;氟乙基乙烯基醚等乙烯基醚化合物等。
作为本发明中使用的共轭二烯系聚合物的具体例子,可举出丁二烯聚合物、异戊二烯聚合物、丁二烯-苯乙烯共聚物、丙烯腈-丁二烯共聚物、丙烯腈-异戊二烯共聚物、丙烯腈-丁二烯-异戊二烯共聚物、甲基丙烯腈-丁二烯共聚物、甲基丙烯腈-异戊二烯共聚物、甲基丙烯腈-丁二烯-异戊二烯共聚物、丙烯腈-甲基丙烯腈-丁二烯共聚物、丙烯腈-丁二烯-丙烯酸甲酯共聚物、丙烯腈-丁二烯-丙烯酸共聚物、丙烯腈-丁二烯-丙烯酸酯共聚物等。
在上述共轭二烯系聚合物中,从作为氢化共轭二烯系聚合物的制造原料的实用性、通用性的观点出发,优选丙烯腈-丁二烯共聚物、甲基丙烯腈-丁二烯共聚物、丙烯腈-丁二烯-丙烯酸酯共聚物,更优选丙烯腈-丁二烯共聚物。
构成共轭二烯系聚合物的单体单元的组成比没有特别限定,优选共轭二烯单体单元为5~100重量%、能够与其共聚的单体的单元为95~0重量%,更优选共轭二烯单体单元为10~90重量%、能够与其共聚的单体的单元为90~10重量%。此外,共轭二烯系聚合物的重均分子量(凝胶渗透色谱法,标准聚苯乙烯换算)也没有特别限定,通常为5000~500000。
作为共轭二烯系聚合物的优选的制备方法的乳液聚合法,通常使用自由基聚合引发剂在水系介质中进行聚合,在乳液聚合法中,聚合引发剂、分子量调节剂使用公知的这些即可。聚合反应可以用间歇式、半间歇式、连续式中的任一者,聚合温度、压力也没有特别限定。使用的乳化剂也没有特别限定,能够使用阴离子性表面活性剂、阳离子性表面活性剂、两性表面活性剂、非离子性表面活性剂等,优选阴离子性表面活性剂。这些乳化剂可以分别单独使用,也可以并用2种以上。其使用量没有特别限定。
通过乳液聚合而得到的共轭二烯系聚合物胶乳的固体成分浓度没有特别限定,通常为2~70重量%,优选为5~60重量%。其固体成分浓度能够通过混合法、稀释法、浓缩法等公知的方法适宜地调节。
共轭二烯系聚合物的氢化反应可以对通过乳液聚合而得到的胶乳直接以胶乳的状态进行,从催化剂活性等观点出发,优选将通过乳液聚合而得到的胶乳进行凝固、干燥而得到共轭二烯系聚合物橡胶,将该共轭二烯系聚合物橡胶溶解于适当的溶剂中,以聚合物溶液的状态进行。
胶乳的凝固、干燥通过公知的方法进行即可,优选设置使进行凝固而得到的团粒与碱性水溶液接触的处理工序,从而改性至得到的共轭二烯系聚合物橡胶溶解于四氢呋喃(THF)而测定的聚合物溶液的pH超过7。溶解于THF而测定的聚合物溶液的pH优选为7.2~12的范围,更优选为7.5~11.5的范围,最优选为8~11的范围。通过该团粒与碱性水溶液的接触处理,从而能够使溶液体系氢化迅速进行。
聚合物溶液中的共轭二烯系聚合物的溶液浓度优选为1~70重量%,更优选为2~40重量%。作为有机溶剂,可举出例如:正己烷、环己烷、正庚烷等脂肪族烃;苯、甲苯、二甲苯、氯苯等芳香族烃;丙酮、甲基乙基酮、二乙基酮、甲基异丙基酮、2-戊酮、3-戊酮、环戊酮、环己酮等酮类;二乙醚、四氢呋喃、二氧杂环己烷、苯甲醚等醚类;醋酸乙酯等酯类等。在这些有机溶剂中,优选使用酮类,特别优选使用丙酮。
氢化反应的温度通常为0~200℃,优选为5~150℃,更优选为10~100℃。通过将氢化反应的温度设为上述范围,从而能够抑制副反应并使反应速度充分。
进行氢化反应时的氢压以表压计通常为0.1~20MPa,优选为0.1~15MPa,更优选为0.1~10MPa。反应时间没有特别限定,通常为30分钟~50小时。另外,氢气优选首先用氮等非活性气体置换反应体系,进而用氢置换后进行加压。
根据本发明的氢化共轭二烯系聚合物的制造方法,由于使用上述的本发明的金属担载型催化剂,因此即使在金属担载型催化剂的使用量比较少的情况下也能够实现高加氢率。而且,作为其结果,能够提高生产效率。
实施例
以下,基于详细的实施例对本发明进行进一步说明,但是本发明并不限定于这些实施例。另外,以下中,只要没有特别限定,“份”为重量基准。此外,试验和评价如下所述。
PVP分散时金属减少率
在100ml的不锈钢制加压容器中,加入0.15g的Pd/SiO2催化剂和20g的聚乙烯吡咯烷酮(PVP)水溶液(PVP:Ashland制造,PVP-K15,以聚苯乙烯换算的重均分子量为10000)(PVP的含量:2.3重量%)。接下来,将该不锈钢制加压容器内的气体置换为H2后,升压至1MPa(表压)。接下来,将该不锈钢制加压容器固定在设置于温度50℃的恒温槽内的旋转器具,以转速:36rpm振动1小时。
然后,对于在PVP溶液中振动前和振动后的Pd/SiO2催化剂,称量Pd/SiO2催化剂,通过硝酸、氢氟酸和硫酸加热分解后进行定容。对于该溶液,使用原子吸光装置(商品名“SPS-5000”,Seiko Instruments公司制造)进行原子吸光测定,从而求出Pd的含量(g),按照下述式,算出PVP分散时金属减少率。
PVP分散时金属减少率(重量%)=100-(在PVP水溶液中振动后的Pd/Si O2催化剂中的Pd的含量(g)÷在PVP水溶液中振动前的Pd/SiO2催化剂中的Pd的含量(g))×100
加氢率
加氢率是测定加氢前的丙烯腈-丁二烯共聚物的碘值和加氢后的丙烯腈-丁二烯共聚物的碘值、根据它们的比例求出的。另外,碘值按照JIS K 6235测定。
制造例1
将5质量份的作为钯化合物的氯化钯溶解于85质量份的作为溶剂的盐酸水中,将10质量份的平均粒径为1000μm的二氧化硅含浸。接下来,使溶剂挥发后,进行烧结,从而得到钯担载于二氧化硅而成的未粉碎Pd/SiO2催化剂。得到的未粉碎Pd/SiO2催化剂的以个数基准求出的粒径分布中的50%累积径为1000μm、以体积基准求出的粒径分布中的50%累积径为1000μm。此外,对于得到的未粉碎Pd/SiO2催化剂,按照上述的方法测定PVP分散时金属减少率,结果为18重量%。
制造例2
取出上述中得到的未粉碎Pd/SiO2催化剂中的一部分,使用小型超高速粉碎机(商品名“Wonder Blender WB-1”,OSAKA CHEMICAL CO.,Lt d.制造)作为粉碎装置,进行粉碎,从而得到粉碎Pd/SiO2催化剂。得到的粉碎Pd/SiO2催化剂的以个数基准求出的粒径分布中的50%累积径为0.4μm、以体积基准求出的粒径分布中的50%累积径为25μm。此外,对于得到的粉碎Pd/SiO2催化剂,按照上述的方法测定PVP分散时金属减少率,结果为35重量%。
实施例1
在反应器中依次加入2份的油酸钾、180份的离子交换水、37份的丙烯腈及0.5份的叔十二烷基硫醇。接下来,将反应器内部用氮置换后,添加63份的丁二烯,将反应器冷却至10℃,添加0.01份的氢过氧化枯烯和0.01份的硫酸亚铁。接下来,以反应器保持在10℃的状态搅拌内容物16小时。之后,向反应器内添加10重量%的对苯二酚水溶液而使聚合反应终止后,从聚合反应液去除未反应的单体,从而得到丙烯腈-丁二烯共聚物的胶乳。聚合转化率为90%。
接下来,在与上述不同的反应器中,加入300份的溶解了3份氯化钙(凝固剂)的水,一边在50℃对其进行搅拌,一边将上述中得到的胶乳向凝固水中滴下。然后,向其中加入氢氧化钾水溶液而将pH值保持在11.5并使聚合物团粒析出后,从凝固水中分离取得聚合物团粒,进行水洗后,在50℃减压干燥。接下来,将得到的聚合物团粒溶解于丙酮,从而制备聚合物含量为15重量%的丙酮溶液。
然后,将制造例2中得到的粉碎Pd/SiO2催化剂加入到得到的丙烯腈-丁二烯共聚物的丙酮溶液以使得钯量相对于丙烯腈-丁二烯共聚物为110重量ppm,将其投入到带有搅拌机的高压釜中,流通氮气10分钟而除去溶解氧。接下来,将体系内用氢气置换2次后,加压5MPa的氢,将内容物加热至50℃,搅拌6小时,从而进行氢化反应,接下来,进行干燥,由此得到氢化丙烯腈-丁二烯共聚物。对于得到的氢化丙烯腈-丁二烯共聚物,按照上述方法测定加氢率,结果为90.1%。
实施例2
将制造例2中得到的粉碎Pd/SiO2催化剂的使用量变更为钯量相对于丙烯腈-丁二烯共聚物为150重量ppm的量,除此以外,与实施例1同样地进行,得到氢化丙烯腈-丁二烯共聚物。对于得到的氢化丙烯腈-丁二烯共聚物,按照上述方法测定加氢率,结果为93.8%。
实施例3
将制造例2中得到的粉碎Pd/SiO2催化剂的使用量变更为钯量相对于丙烯腈-丁二烯共聚物为180重量ppm的量,除此以外,与实施例1同样地进行,得到氢化丙烯腈-丁二烯共聚物。对于得到的氢化丙烯腈-丁二烯共聚物,按照上述方法测定加氢率,结果为95.4%。
比较例1
代替制造例2中得到的粉碎Pd/SiO2催化剂而使用制造例1中得到的未粉碎Pd/SiO2催化剂,并且将未粉碎Pd/SiO2催化剂的使用量变更为钯量相对于丙烯腈-丁二烯共聚物为180重量ppm的量,除此以外,与实施例1同样地进行,得到氢化丙烯腈-丁二烯共聚物。对于得到的氢化丙烯腈-丁二烯共聚物,按照上述方法测定加氢率,结果为88.2%。
[表1]
表1
通过比较实施例1~3和比较例1的结果可知,使用了PVP分散时金属减少率为35重量%的粉碎Pd/SiO2催化剂的实施例1~3与使用了PVP分散时金属减少率为18重量%的未粉碎Pd/SiO2催化剂的比较例1相比较,不论其使用量与比较例1相同或更少,均得到了加氢率优异的结果。
Claims (4)
1.一种金属担载型催化剂,是使金属和/或金属化合物担载于载体而成的,其特征在于,
在2.3重量%的聚乙烯吡咯烷酮水溶液中,在氢气氛下,以温度50℃、36rpm的条件振动1小时之际,所述金属担载型催化剂中所包含的金属和/或金属化合物的减少率为20重量%以上,
所述金属担载型催化剂的以体积基准求出的粒径分布中的50%累积径超过0μm且为100μm以下、或者以个数基准求出的粒径分布中的50%累积径超过0μm且为2μm以下。
2.根据权利要求1所述的金属担载型催化剂,其是使铂族元素和/或含铂族元素化合物作为所述金属和/或金属化合物担载于载体而成的。
3.根据权利要求1或2所述的金属担载型催化剂,其中,所述聚乙烯吡咯烷酮水溶液中所包含的聚乙烯吡咯烷酮的以聚苯乙烯换算的重均分子量为8000~12000。
4.一种氢化共轭二烯系聚合物的制造方法,在溶剂中,在权利要求1~3中任一项所述的金属担载型催化剂的存在下,将共轭二烯系聚合物氢化。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016072665 | 2016-03-31 | ||
JP2016-072665 | 2016-03-31 | ||
JP2016-164711 | 2016-08-25 | ||
JP2016164711 | 2016-08-25 | ||
PCT/JP2017/012716 WO2017170585A1 (ja) | 2016-03-31 | 2017-03-28 | 金属担持型触媒および水素化共役ジエン系重合体の製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108778502A CN108778502A (zh) | 2018-11-09 |
CN108778502B true CN108778502B (zh) | 2022-01-04 |
Family
ID=59965737
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201780017148.8A Active CN108778502B (zh) | 2016-03-31 | 2017-03-28 | 金属担载型催化剂、以及氢化共轭二烯系聚合物的制造方法 |
Country Status (5)
Country | Link |
---|---|
US (2) | US20190083959A1 (zh) |
EP (1) | EP3437738A4 (zh) |
JP (1) | JP6795029B2 (zh) |
CN (1) | CN108778502B (zh) |
WO (1) | WO2017170585A1 (zh) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS585304A (ja) * | 1981-07-01 | 1983-01-12 | Asahi Chem Ind Co Ltd | 水添重合体の製造方法 |
CN1409730A (zh) * | 1999-12-08 | 2003-04-09 | 陶氏环球技术公司 | 氢化芳族聚合物的方法 |
CN101003011A (zh) * | 2006-01-18 | 2007-07-25 | 中国科学院大连化学物理研究所 | 用于水/有机加氢反应的微反应器及其制备方法和应用 |
CN101463102A (zh) * | 2007-12-17 | 2009-06-24 | 朗盛公司 | 基于二烯烃的聚合物的氢化 |
CN101780406A (zh) * | 2009-01-19 | 2010-07-21 | 中国科学院化学研究所 | 一种纳米金属催化剂及其制备方法与应用 |
CN103347903A (zh) * | 2010-07-28 | 2013-10-09 | 朗盛德国有限责任公司 | 基于二烯的聚合物的氢化 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6058242B2 (ja) * | 1981-06-10 | 1985-12-19 | 日本ゼオン株式会社 | 水素化共役ジエン系重合体の製造方法 |
JPS5817103A (ja) * | 1981-07-24 | 1983-02-01 | Nippon Zeon Co Ltd | 共役ジエン系重合体の水素化方法 |
US5128297A (en) * | 1990-03-30 | 1992-07-07 | Nippon Zeon Co., Ltd. | Method for hydrogenating conjugated diene polymer |
JP4123852B2 (ja) * | 2002-07-18 | 2008-07-23 | 日本ゼオン株式会社 | 水素化触媒安定化剤、水素化触媒溶液及びその調製方法、水素化反応方法 |
US7919431B2 (en) * | 2003-09-03 | 2011-04-05 | Synfuels International, Inc. | Catalyst formulation for hydrogenation |
JP5556501B2 (ja) * | 2010-08-19 | 2014-07-23 | マツダ株式会社 | 排気ガス浄化用触媒及び排気ガス浄化用触媒の製造方法 |
JP5895600B2 (ja) * | 2012-03-01 | 2016-03-30 | 日産自動車株式会社 | 排ガス浄化触媒及びその製造方法 |
JP2015163387A (ja) * | 2014-01-30 | 2015-09-10 | 積水化学工業株式会社 | 合成用の触媒及びその製造方法、酸素化物の製造装置ならびに酸素化物の製造方法 |
JP6031562B2 (ja) * | 2015-06-29 | 2016-11-24 | 旭化成株式会社 | シリカ系材料及びその製造方法、並びに貴金属担持物及びそれを触媒として用いるカルボン酸類の製造方法 |
-
2017
- 2017-03-28 EP EP17775122.9A patent/EP3437738A4/en active Pending
- 2017-03-28 US US16/087,710 patent/US20190083959A1/en not_active Abandoned
- 2017-03-28 JP JP2018508094A patent/JP6795029B2/ja active Active
- 2017-03-28 CN CN201780017148.8A patent/CN108778502B/zh active Active
- 2017-03-28 WO PCT/JP2017/012716 patent/WO2017170585A1/ja active Application Filing
-
2021
- 2021-10-08 US US17/497,488 patent/US20220023840A1/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS585304A (ja) * | 1981-07-01 | 1983-01-12 | Asahi Chem Ind Co Ltd | 水添重合体の製造方法 |
CN1409730A (zh) * | 1999-12-08 | 2003-04-09 | 陶氏环球技术公司 | 氢化芳族聚合物的方法 |
CN101003011A (zh) * | 2006-01-18 | 2007-07-25 | 中国科学院大连化学物理研究所 | 用于水/有机加氢反应的微反应器及其制备方法和应用 |
CN101463102A (zh) * | 2007-12-17 | 2009-06-24 | 朗盛公司 | 基于二烯烃的聚合物的氢化 |
CN101780406A (zh) * | 2009-01-19 | 2010-07-21 | 中国科学院化学研究所 | 一种纳米金属催化剂及其制备方法与应用 |
CN103347903A (zh) * | 2010-07-28 | 2013-10-09 | 朗盛德国有限责任公司 | 基于二烯的聚合物的氢化 |
Also Published As
Publication number | Publication date |
---|---|
JP6795029B2 (ja) | 2020-12-02 |
US20220023840A1 (en) | 2022-01-27 |
US20190083959A1 (en) | 2019-03-21 |
JPWO2017170585A1 (ja) | 2019-02-14 |
EP3437738A1 (en) | 2019-02-06 |
EP3437738A4 (en) | 2019-11-27 |
WO2017170585A1 (ja) | 2017-10-05 |
CN108778502A (zh) | 2018-11-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7385010B2 (en) | Hydrogenation of diene-based polymer latex | |
EP1705194B1 (en) | Hydrogenation of diene-based polymer latex | |
CN107708860B (zh) | 催化剂回收方法 | |
KR100910255B1 (ko) | 수소화된 공역디엔계 중합체의 제조방법 | |
CA2806424A1 (en) | Hydrogenation of diene-based polymers | |
CN108778502B (zh) | 金属担载型催化剂、以及氢化共轭二烯系聚合物的制造方法 | |
CA2501199A1 (en) | Organic solvent-free hydrogenation of diene-based polymers | |
EP1203777B1 (en) | Process for removal of catalyst residues | |
US11266978B2 (en) | Method for preparing dispersion of metal-containing particles and method for producing hydrogenated conjugated diene polymer | |
EP3116916B1 (en) | Process for the reduction of nitrile groups of hydrogenated nitrile rubber | |
TWI432469B (zh) | 以二烯為基礎之聚合物的氫化作用 | |
JP2004002768A (ja) | 水素化反応混合物から触媒を回収する方法および水素化共役ジエン系重合体の製造方法 | |
JP4110267B2 (ja) | 触媒回収方法 | |
JP2004141694A (ja) | 水素化触媒回収方法 | |
JP4123852B2 (ja) | 水素化触媒安定化剤、水素化触媒溶液及びその調製方法、水素化反応方法 | |
JPS6335642B2 (zh) | ||
JPS6335641B2 (zh) | ||
JP2770463B2 (ja) | 水素化共役ジエン系重合体の製造方法 | |
JP4239490B2 (ja) | 水素化重合体の製造方法 | |
JPH0578562B2 (zh) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |