JPS61130303A - Hydrogenation of conjugated diene polymer - Google Patents
Hydrogenation of conjugated diene polymerInfo
- Publication number
- JPS61130303A JPS61130303A JP59252148A JP25214884A JPS61130303A JP S61130303 A JPS61130303 A JP S61130303A JP 59252148 A JP59252148 A JP 59252148A JP 25214884 A JP25214884 A JP 25214884A JP S61130303 A JPS61130303 A JP S61130303A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- supported
- carrier
- conjugated diene
- hydrogenation
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 20
- 150000001993 dienes Chemical class 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 230000000737 periodic effect Effects 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 35
- 229910052763 palladium Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000003426 co-catalyst Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000004581 coalescence Methods 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 3
- 150000007942 carboxylates Chemical class 0.000 abstract description 2
- 150000002823 nitrates Chemical class 0.000 abstract description 2
- 125000005595 acetylacetonate group Chemical group 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- -1 organic acid salts Chemical class 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000002560 nitrile group Chemical group 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical class [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003599 detergent Substances 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
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium 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
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical class [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 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
- 239000011733 molybdenum Chemical class 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000011414 polymer cement Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-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
- 238000004073 vulcanization Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は共役ジエン系重合体の炭素−炭素二重結合を水
素化する方法に関するものでらる。更に詳しくは、担体
担持パラジウム触媒と反応溶媒に溶解した特定な元素を
含む化合物助触媒として併用することを特徴とする高活
性、高選択性を有する共役ジエン系重合体の水素化方法
に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for hydrogenating carbon-carbon double bonds in a conjugated diene polymer. More specifically, it relates to a method for hydrogenating a conjugated diene polymer having high activity and high selectivity, which is characterized by using a carrier-supported palladium catalyst and a compound containing a specific element dissolved in a reaction solvent as a co-catalyst.
（従来の技術）
一般に共役ジエン系（４）重合体は弾性体として広（工
業的に利用されている。しかし、これらの重合体は重合
体鎖中および／ｉたは側鎖に共役ジエンに帰因する炭素
−炭素二重結合を有し、これは加硫等に有効に利用され
る反面、耐候性、耐酸化性、耐熱性等に劣る欠点ともな
っている。これらの欠点は、重合体鎖中の炭素−炭素二
重結合を水素化して不飽和二重結合をなくすことによっ
て大幅に改良される。(Prior art) In general, conjugated diene-based (4) polymers are widely used as elastic bodies (industrially).However, these polymers contain conjugated diene in the polymer chain and /i or side chain. It has carbon-carbon double bonds, which can be used effectively for vulcanization, etc., but it also has drawbacks such as poor weather resistance, oxidation resistance, heat resistance, etc. These drawbacks are A significant improvement is achieved by hydrogenating the carbon-carbon double bonds in the chain to eliminate unsaturated double bonds.
かかる目的で不飽和二重結合を水素化する方法は数多（
提案されておシ、これらの反応に用いられる触媒として
は（１）ニッケル、コバルト、鉄、チタニウム、ロジウ
ム等の有機酸塩おるいはアセチルアセトン塩と有機アル
ミニウム、亜鉛、リチウム等の還元剤を溶媒中で反応し
て得られるいわゆるチーグラー型の均一系触媒あるいは
（２）ニッケル。There are many methods for hydrogenating unsaturated double bonds for this purpose (
The catalysts used in these reactions are (1) organic acid salts such as nickel, cobalt, iron, titanium, rhodium, etc. or acetylacetone salts and reducing agents such as organic aluminum, zinc, lithium, etc. in a solvent; The so-called Ziegler-type homogeneous catalyst or (2) nickel obtained by reacting inside.
白金、パラジウム、ロジウム、ルテニウム等ノ金属をカ
ーボン、７リカ、アルミナ、クリ力アルミナ等の多孔性
担体に担持された担体担持触媒とが一般に知られている
。A carrier-supported catalyst in which metals such as platinum, palladium, rhodium, and ruthenium are supported on a porous carrier such as carbon, hexachloride, alumina, and alumina is generally known.
（発明が解決しようとする問題点）
前者のチーグラー型触媒は一般に、水素化活性を発現さ
せるために混合した触媒成分をあらかじめ還元する必要
があり、更に還元された触媒自体が酸素や水分く対して
安定性を欠き、取扱い方が困難であり、再現性にも問題
がある。(Problems to be Solved by the Invention) Generally speaking, the former Ziegler type catalyst needs to reduce the mixed catalyst components in advance in order to develop hydrogenation activity, and furthermore, the reduced catalyst itself has a high resistance to oxygen and moisture. They lack stability, are difficult to handle, and have problems with reproducibility.
一方後者の担体担持触媒は一般に高温高圧での水素によ
る還元および反応が必要であり、一般に選択性に劣る◇
これらを改善する手段として担体上に触媒金属と同時に
助触媒金属を担持して活性を上げ、選択性を向上させる
方法が提案されている（特開昭５４−７７６８９．特開
昭５６−８１３０５． 特開昭５６−８１５０６等）
。On the other hand, the latter carrier-supported catalyst generally requires reduction and reaction with hydrogen at high temperature and high pressure, and is generally inferior in selectivity ◇ As a means to improve this, a co-catalyst metal is supported on the carrier at the same time as the catalyst metal to increase the activity. A method for improving the selectivity has been proposed (JP-A-54-77689, JP-A-56-81305, JP-A-56-81506, etc.).
.
ところで、担体担持触媒を調製する方法として一般に■
含浸法と■イオン交換法がある。前者は担体に５〜１０
重量−程度までは触媒金属を担持可能と言われているが
、前述の助触媒金属を触媒金属と所望の割合で担持させ
るに娘含浸速度、沈降速度等の条件が厳しくコントロー
ルされていなければならず、再現性が劣る０特に少スケ
ールで見い出した条件を大スケールへスケールアップす
る際に多大の困難を伴うのが一般である０一方後者のイ
オン交換法では、担体側にイオン交換できる基を有する
担体に限定される（シリカ。By the way, as a method for preparing a catalyst supported on a carrier, generally
There are two methods: impregnation method and ■ion exchange method. The former is 5 to 10 on the carrier.
Although it is said that it is possible to support the catalyst metal up to a certain weight, conditions such as daughter impregnation rate and sedimentation rate must be strictly controlled in order to support the above-mentioned co-catalyst metal in the desired ratio with the catalyst metal. In general, it is very difficult to scale up conditions found on a small scale to a large scale.On the other hand, in the latter ion exchange method, a group capable of ion exchange is added to the support side. (silica).
アルミナ＠ｔＱ、）と共に、一般に含浸法と比較して担
持される触媒金属量は少ない０また助触媒金属を併用す
る際、担持工程に訃いてイオン状態になっていないと使
用できず、使用できる金属塩が限定される。Along with alumina @tQ,), the amount of catalyst metals supported is generally smaller than in the impregnation method.0Also, when using co-catalyst metals, they cannot be used unless they are in an ionic state due to the support process, and cannot be used. Metal salts are limited.
以上のように、重合体中の炭素−炭素二重結合を水素化
する触媒としてチーグラー型触媒にしても担体担持触媒
にしても解決すべき問題は多い。As described above, there are many problems to be solved whether a Ziegler type catalyst or a supported catalyst is used as a catalyst for hydrogenating carbon-carbon double bonds in a polymer.
（問題点を解決するための手段）
本発明者等は先に共役ジエン系に）重合体の水素化触媒
としてパラジウムと共に助触として特定の元素を同一の
担体に担持させた触媒が高活性。(Means for Solving the Problems) The present inventors first discovered that a catalyst for hydrogenating a polymer (conjugated diene system) in which palladium and a specific element as a co-catalyst were supported on the same carrier had high activity.
高選択性を有することを見い出した（特開昭５６−８１
５０５、特開昭５６−８１５０６）。discovered that it has high selectivity (Japanese Unexamined Patent Publication No. 56-81
505, Japanese Unexamined Patent Publication No. 56-81506).
しかしながら、この担持触媒についても前記の触媒調製
上の問題点が存在する◎
本発明者等は前記の問題点を改善すべ（鋭意検討した結
果、パラジウム担体担持触媒と特定の元素を含む均一系
助触媒とを併用した触媒は高活性。However, this supported catalyst also has the above-mentioned problems in catalyst preparation. The inventors of the present invention have found that the above-mentioned problems should be improved (as a result of intensive study, a palladium-supported catalyst and a homogeneous support containing a specific element were found. Catalysts used in combination with catalysts are highly active.
高選択性を有すると共に再現性よ（触媒調製できること
を見い出し本発明を完成するに到った。It was discovered that the catalyst can be prepared with high selectivity and reproducibility, and the present invention has been completed.
従って、本発明の目的は共役ジエン系重合体の水素化に
おいて、高活性を有すると同時に重合体鎖中あるいは側
鎖中の炭素−炭素二重結合を選択的に水素化し得るｐａ
系触媒を提供することにある。Therefore, an object of the present invention is to provide a PA that has high activity and can selectively hydrogenate carbon-carbon double bonds in polymer chains or side chains in the hydrogenation of conjugated diene polymers.
The objective is to provide a system catalyst.
本発明のこの目的は共役ジエン系重合体の炭素−炭素二
重結合を溶媒中で水素化するに際し、パラジウムを多孔
性担体に担持させた担体担持触媒と、周期律表１Ａ、
ＩＩＡ、 ＩＶＡ、 ＶＡ、 ”ｉＩＡ、 ＨＡ 及び
■族ならびに銅、アルミニウム、ホウ素、錫。This object of the present invention is to provide a carrier-supported catalyst in which palladium is supported on a porous carrier, and a carrier-supported catalyst in which palladium is supported on a porous carrier when hydrogenating a carbon-carbon double bond of a conjugated diene polymer in a solvent.
Groups IIA, IVA, VA, IIA, HA and ■ as well as copper, aluminum, boron, tin.
セリウム及びランタンから選択される少な（とも１種の
元素を含む化合物を助触媒として溶媒に溶解１．ｆ停田
子／、？″ｋにｔｈ遣ぜられふ。A compound containing a small amount of an element selected from cerium and lanthanum is dissolved in a solvent as a cocatalyst and sent to 1.f.
このような溶媒可溶性の特定の元素を含む化合物を助触
媒に用いることは、助触媒／触媒のモル比を正確に、再
現性よ（所望の値に設定でき、活性を再現するのに効果
が大きい０
本発明のパラジウム担持触媒は通常の担体担持触媒の調
製法に従えば良く、特に制限されない０例えばパラジウ
ム元素あるいはパラジウムのノ・ロゲン化物、酸化物、
水酸化物、酸塩化物、硫酸化物、炭酸化物等の塩の水溶
液等に活性炭、シリカ等の通常水素化反応に使用される
担体を浸漬することによって担持させることができる。Using a compound containing such a specific solvent-soluble element as a cocatalyst makes it possible to accurately and reproducibly set the cocatalyst/catalyst molar ratio to a desired value, which is effective in reproducing activity. Large 0 The palladium-supported catalyst of the present invention may be prepared by a conventional method for preparing a catalyst supported on a carrier, and is not particularly limited.
It can be supported by immersing a carrier commonly used in hydrogenation reactions, such as activated carbon or silica, in an aqueous solution of salts such as hydroxides, acid chlorides, sulfates, and carbonates.
担体へのパラジウムの担持量は担体当シ１１．００１〜
３０重量％であシ、好ましくはａ、ｏｉ〜１０重量％で
ある。担持されるパラジウムが余りにも少なすぎると反
応時使用する担体担持触媒量が多すぎて系内の攪拌が困
難になり、触媒の分散が悪くなり触媒が有効に使われな
（なる〇一方担持量が多 ：すぎると担体上の
パラジウムの分散が悪くなり、またパラジウム粒子径も
大きくなり、触媒活性が低下する。The amount of palladium supported on the carrier is 11.001~
It is 30% by weight, preferably a, oi to 10% by weight. If the amount of supported palladium is too small, the amount of catalyst supported on the carrier used during the reaction will be too large, making it difficult to stir the system, resulting in poor dispersion of the catalyst and the catalyst not being used effectively. Too much amount: If the amount is too large, the dispersion of palladium on the carrier will be poor, the palladium particle size will also become large, and the catalytic activity will decrease.
本発明で使用する助触媒は周期律表１Ａ、ＩＩＡ、ＭＡ
、ＶＡ、ＭＡ、■Ａ、■族ならびに銅、アルミニウム、
ホウ素、錫、セリウム及びランタンから選択される少な
（とも１種の元素を含み、かつ水素化反応に使用する溶
媒に可溶な化合物である。The co-catalyst used in the present invention is 1A, IIA, MA of the periodic table.
, VA, MA, ■A, ■ group as well as copper, aluminum,
It is a compound that contains at least one element selected from boron, tin, cerium, and lanthanum, and is soluble in the solvent used in the hydrogenation reaction.
このような化合物としては、該元素のカルボン酸塩、ア
セチルアセトン塩、硝酸塩、炭酸塩、オルト酸（ホウ酸
、タングステン酸、モリブデン酸などの）、などが代表
的化合物として例示されるが、水素化反応に使用する溶
媒に可溶な化合物であれば上記の化合物に限定されない
。Representative examples of such compounds include carboxylates, acetylacetone salts, nitrates, carbonates, and ortho acids (boric acid, tungstic acid, molybdic acid, etc.) of the element, but hydrogenated The compound is not limited to the above compounds as long as it is soluble in the solvent used in the reaction.
助触媒として使用される元素のパラジウムに対する原子
比はｏ、ｏｏｉ〜１の範囲にあり、好ましくはｏ、ｏｏ
ｓ〜［ｌＬ５である。担体担持触媒の使用量はパラジウ
ム量で重合体当り５〜２０００ ＰＰ！！１の範囲にあ
り、好ましくは１０〜１０００ ｐｐｍである。The atomic ratio of the element used as cocatalyst to palladium is in the range o,ooi to 1, preferably o,ooi
s ~ [lL5. The amount of palladium used for the catalyst supported on the carrier is 5 to 2000 PP per polymer! ! 1, preferably 10 to 1000 ppm.
２０００ ｐｐｍ以上使用することはできるが経済的で
ない。Although it is possible to use more than 2000 ppm, it is not economical.
本発明で使用される共役ジエン系重合体は共役ジエンモ
ノマーが、１．ｓ−フタジエン、２．５−ジメチルブタ
ジェン、インプレン、１．５−ペンタジェン等から選ば
れた１種またはそれ以上のモノマーで、全モノマー中０
〜１００重量％、および／またはエチレン性不飽和モノ
マーが、不飽和ニトリル、たとえばアクリロニトリル、
メタクリロニトリルなど、モノビニリデン芳香族炭化水
素たとｊ＝ハ、スｆレン、アルキルスチレン（ｏ−、ｍ
＋。The conjugated diene polymer used in the present invention has a conjugated diene monomer that contains 1. One or more monomers selected from s-phtadiene, 2,5-dimethylbutadiene, imprene, 1,5-pentadiene, etc., with 0% of all monomers
~100% by weight and/or the ethylenically unsaturated monomer is an unsaturated nitrile, e.g. acrylonitrile,
Monovinylidene aromatic hydrocarbons such as methacrylonitrile, j=ha, sfrene, alkylstyrene (o-, m
+.
ｐ−メチルスチレン、エチルスチレンナト）、ジメチル
アミノスチレン、スチレンスルホン酸など、不飽和カル
ボン酸またはそのエステル、たとえばアクリル酸、メタ
アクリル酸、クロトン酸、イタコン酸、マレイン酸また
はアクリル酸メチル、アクリル酸エチル、アクリル酸ブ
チル、アクリル酸２−エチルヘキシル、メタアクリル酸
メチルなど、ビニルピリジンおよびビニルエステルたと
えば酢酸ビニルなどから選ばれた１種またはそれ以上の
モノマーで全モノマー中０〜９０重量％で構成された共
役ジエン重合体および／または共役ジエン共重合体であ
る。unsaturated carboxylic acids or their esters, such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid or methyl acrylate, acrylic acid One or more monomers selected from vinyl pyridine and vinyl esters such as vinyl acetate, such as ethyl, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate, and are composed of 0 to 90% by weight of the total monomers. conjugated diene polymer and/or conjugated diene copolymer.
これらの働重合体は乳化重合、溶液重合、塊状重合など
いずれの重合方式で製造されたものであっても良く、具
体的にはポリイソプレン、ポリブタジェン、ステレンー
ブメジエン（ランダムアルいはブロック）共重合体、ア
クリロニトリル−ブタジェン（ランダムあるいは交互）
共重合体等が挙げられる。These working polymers may be produced by any polymerization method such as emulsion polymerization, solution polymerization, or bulk polymerization. ) copolymer, acrylonitrile-butadiene (random or alternating)
Examples include copolymers.
水素化反応はこれらの重合体を溶媒に溶解して溶液状態
で行う。重合体の濃度は１〜７０重ｉｓ、好ましくは１
〜４０重量％である。溶媒としては触媒に悪影響を与え
ず、水素化される重合体を溶解するものであれば特に制
限はされないが、ベンゼン、トルエン、キシレン、ヘキ
サン、７クロヘキサン、テトラヒドロフラン、アセトン
、メチルエチルケトン、７クロヘキサノン、酢酸エチル
等が一般に使用される。溶液重合で製造された重合体は
重合体セメントのま＼で水素化することもできる。The hydrogenation reaction is carried out in a solution state by dissolving these polymers in a solvent. The concentration of the polymer is between 1 and 70 polymers, preferably 1
~40% by weight. The solvent is not particularly limited as long as it does not adversely affect the catalyst and dissolves the polymer to be hydrogenated, but examples include benzene, toluene, xylene, hexane, 7-chlorohexane, tetrahydrofuran, acetone, methyl ethyl ketone, 7-chlorohexanone. , ethyl acetate, etc. are commonly used. Polymers produced by solution polymerization can also be hydrogenated in the polymer cement.
水素化反応はオートクレーブ中で実施され、反応温度は
０〜３００°Ｃ１好ましくは２０〜１５０°Ｃである。The hydrogenation reaction is carried out in an autoclave, and the reaction temperature is 0-300°C, preferably 20-150°C.
選択的水素化反応が進行し、望ましくない副反応を抑え
るためには１５０°Ｃ以下の温度が好ましい。A temperature of 150° C. or lower is preferred in order to allow the selective hydrogenation reaction to proceed and to suppress undesirable side reactions.
水素圧は特に限定されるものではないが、通常大気圧〜
３００ ｋｇ／ｅｘ”の範囲で行なわれ、好ましくは５
〜２００ ｋｌ／（がである。５００ ｋｆ／菌１以上
は設備上、操作上から実用的でない〇
水素化された重合体は耐候性、耐オゾン性、耐熱性、耐
寒性等に憬れ、広い分野での使用が可能である〇
以下実施例により本発明を具体的に説明する。Hydrogen pressure is not particularly limited, but is usually between atmospheric pressure and
300 kg/ex”, preferably 5
~200 kl/(is. 500 kf/bacteria 1 or more is not practical from the equipment and operational standpoint. Hydrogenated polymers have poor weather resistance, ozone resistance, heat resistance, cold resistance, etc., and are widely used. The present invention will be explained in detail with reference to Examples below.
重合体の水素化率はヨウ素価法によシ求めた。以下の実
施例では触媒量とは担体と触媒の合計量を意味している
。The hydrogenation rate of the polymer was determined by the iodine value method. In the following examples, the amount of catalyst means the total amount of carrier and catalyst.
実施例１
シリカ（メルク社製品ＭｅｒｃｋｏｇｅＩＳ工２０（Ｉ
Ａを使用）を担体としてｐａを担持させた担体担持触媒
単独および担体担持触媒と同時に第１表に記載の元素の
各酢酸塩を助触媒に用いてアクリロニトリル−ブタジェ
ン共重合体（以下ＮＢＲと略す）の水素化を行った。供
用系の場合は各元素とＰ（Ｌとの原子比を０．０５：１
で行った０担体担持触媒は塩化パラジウム（ｐａｃ４）
のアンモニア水溶液中に７リカを浸漬し、充分含浸させ
念ものを使用した。なお、いずれの場合にも担体当りの
ｐａ担持量は２重液チである。Example 1 Silica (Merckoge IS 20 (I)
Acrylonitrile-butadiene copolymer (hereinafter abbreviated as NBR) was prepared by using a carrier-supported catalyst alone and simultaneously with a carrier-supported catalyst using each acetate of the elements listed in Table 1 as a co-catalyst. ) was hydrogenated. In the case of a commercial system, the atomic ratio of each element and P (L) is 0.05:1.
The catalyst supported on the 0 carrier was palladium chloride (pac4).
7.7 Lika was immersed in an aqueous ammonia solution to thoroughly impregnate it and then used as a detergent. In any case, the amount of pa supported per carrier is double liquid.
（水素化方法）
容量１００ｄのオートクレーブにテトラヒドロフラン４
５？にＮＢＲ（結合アクリロニトリル量３４．０重量％
、ＭＬ１＋４ １００℃−４９）５７を溶解した溶液に
助触媒として用いる各種酢酸塩を溶解しＰ改担持触媒を
α０６２５７（ポリマー１００重量部当９担持触媒１２
５重量部に相当する〕仕込んだ。系内全窒素置換後水素
にて５０ｋｆ／ｃ１１ｔ に加圧し、５５°Ｃで４時間
水素化反応を行った。結果を第１表に示す◇いずれの場
合にもニトリル基の還元は認められなかった。(Hydrogenation method) Add 4 liters of tetrahydrofuran to an autoclave with a capacity of 100 d.
5? and NBR (bound acrylonitrile amount 34.0% by weight)
, ML1+4 100℃-49) 57 was dissolved in various acetate salts used as co-catalysts, and the P-supported catalyst was prepared using α06257 (9 supported catalysts 12 per 100 parts by weight of polymer).
5 parts by weight]. After purging the entire system with nitrogen, the pressure was increased to 50 kf/c11t with hydrogen, and a hydrogenation reaction was carried out at 55°C for 4 hours. The results are shown in Table 1.◇Reduction of the nitrile group was not observed in any case.
第１表
（ただしＡ４Ｚｒに関しては酸化物の酢酸塩を使用。）
実施例２
助触媒としてＣｓ Ｃ３０ｓ 、ＨＢ Ｏｓ 、−Ｍ２
Ｏ３゜Ｈ，ＷＯ２，＞よびに、 Ｈ，Ｓ ｂ、 ｏ、を
使用する以外は実施例′１と同様にしてＮＢＨの水素化
を行った〇結果を第２表に示す。いずれの触媒を用いて
も＝ｉトリル基の還元は認められなかった。Table 1 (However, for A4Zr, the oxide acetate is used.) Example 2 Cs C30s, HB Os, -M2 as promoters
Table 2 shows the hydrogenation of NBH in the same manner as in Example '1 except that O3°H, WO2, > and H, S b, o were used. No reduction of the =i tolyl group was observed using any of the catalysts.
第２堀
実施例３
助触媒としてそれぞれニッケル、コバルト、鉄の硝酸塩
、銅のナフテン酸およびステアリン酸塩を各元素とパラ
ジウムとの原子比が０．０５：１になるよ、うに使用し
た。Second Moat Example 3 Nitrate of nickel, cobalt, and iron, and naphthenic acid and stearate of copper were used as cocatalysts so that the atomic ratio of each element to palladium was 0.05:1.
これらの触媒の活性を調べる為に容量１００ｄのオート
クレーブにテトラハイドロフラン３７％に３？のポリブ
タジェン（シス−１４含［９８％。To examine the activity of these catalysts, 37% tetrahydrofuran and 3% tetrahydrofuran were placed in an autoclave with a capacity of 100 d. of polybutadiene (containing cis-14 [98%.
ｖｂ１＋４ｉ ｏａＣ−４０）を溶解した溶液に上記助
眩媒として用いる金属塩を浴解しｐａ触媒Ｑ、０５２５
ン（シリカにＰｄを２重量％担持、ポリマー１００砿量
部当り担持触媒ｔ ７５］ｉ量部に相当する）を士込ん
だ。系内を窒素置換後水素にて５０ ｋｇ／ｃｓ”で加
圧し、８０℃で５時間水素化反応を行った。The metal salt used as the anti-glare medium was dissolved in a solution of OA C-40) to prepare pa catalyst Q, 0525.
(2% by weight of Pd supported on silica, corresponding to 75]i parts of supported catalyst per 100 parts of polymer) was added. After replacing the inside of the system with nitrogen, the system was pressurized with hydrogen at 50 kg/cs'' and a hydrogenation reaction was carried out at 80° C. for 5 hours.
古来を第３表に示す。The ancient history is shown in Table 3.
第３表
実施例４
助触媒としてそれぞれ銅、モリブデン、マンガン、バナ
ジウム、チタン、ニッケル、コバルト及び鉄のアセチル
アセトン塩を各元素とパラジウムとの原子比が０．０５
：１になるように使用した。Table 3 Example 4 Acetylacetone salts of copper, molybdenum, manganese, vanadium, titanium, nickel, cobalt, and iron were used as promoters, respectively, and the atomic ratio of each element to palladium was 0.05.
:1.
これらの触媒の活性を調べる為に容量１００−のオート
クレーブにアセトン４５？１ＣＮＢｕ（結合アクリロニ
トリル４Ｑ、９％、 Ｍ Ｌ １＋４１０ ＱＣ埋５
１）５ｙ−を溶解した溶液に上記アセチルアセトン塩を
溶解し、ｐａ触媒ｔ−ｃｉ、０６２５ｆ仕込んだ（シリ
ヵに２重量％ Ｐａを担持、ポリマー１００重量部当り
担持触媒ｔ２５重量部に相当する）０系内を窒素置換後
、水素にて５０ ｋｔｉ／ａｘ”に加圧し、５５°Ｃで
４時間水素化反応を行った０結果を第４表に示す。いず
れの場合にもニトリル基の還元は認められなかった。To investigate the activity of these catalysts, acetone 45?1CNBu (bonded acrylonitrile 4Q, 9%, M L 1 + 410 QC buried 5
1) The above acetylacetone salt was dissolved in a solution of 5y-, and a pa catalyst t-ci, 0625f was charged (2% by weight of Pa supported on silica, corresponding to 25 parts by weight of supported catalyst t per 100 parts by weight of polymer)0 After purging the system with nitrogen, the pressure was increased to 50 kti/ax" with hydrogen, and the hydrogenation reaction was carried out at 55°C for 4 hours. The results are shown in Table 4. In either case, the reduction of the nitrile group was I was not able to admit.
第４表
（ただしＭｏ、 Ｖ、 Ｔｉはそれぞれ酸化物のアセチ
ルアセトン塩を使用）
実施例５
助触媒としてそれぞれ銅、コバルト及びニッケルのアセ
チルアセトン塩を使用する際、各元素とパラジウムとの
原子比をＱ、０１． ＣｌＯ２，０，１，０，２と変化
させた。Table 4 (For Mo, V, and Ti, each uses an oxide acetylacetone salt.) Example 5 When using acetylacetone salts of copper, cobalt, and nickel as cocatalysts, the atomic ratio of each element to palladium is Q. , 01. It was changed to ClO2, 0, 1, 0, 2.
これらの触媒の活性を調べる為に実施例４と同様にして
ＮＢＲの水素化反応を行った。結果を第５表に示す。い
ずれの触媒を用いてもニトリル基の還元は認められなか
った。In order to examine the activity of these catalysts, a hydrogenation reaction of NBR was carried out in the same manner as in Example 4. The results are shown in Table 5. No reduction of nitrile groups was observed using any of the catalysts.
第５表
実施例６
活性炭（太田薬品社製 白鷺Ａ）を担体に用いたｐａ担
持触媒（ｐａｃ／、の水溶液中に活性炭を浸漬し、活性
炭中へ十分含浸させた後、ホルマリン−力性ソーダで還
元して担体担持触媒として使用。担体当りのＰ（Ｌの担
持量は１重量％）？、用い、助触媒としてそれぞれセリ
ウム、鉄及び銅の硝酸塩を用いた０各元素とｐａとの原
子比は０．１：１である。Table 5 Example 6 Activated carbon (Shirasagi A manufactured by Ota Pharmaceutical Co., Ltd.) was immersed in an aqueous solution of a PA-supported catalyst (PAC/, manufactured by Ota Pharmaceutical Co., Ltd.), and after sufficiently impregnating it into the activated carbon, formalin-hydrolytic soda was added. and used as a catalyst supported on a carrier.The amount of P per carrier (the amount of L supported is 1% by weight) was used, and the atoms of each element and pa using cerium, iron, and copper nitrates as cocatalysts, respectively. The ratio is 0.1:1.
これらの触媒の活性を調べる為に、テトラハイドロフラ
ン３７ンに３１のポリイソグレン（クスｔ４含量９７チ
ＭＬ１＋４１００℃−８０，工Ｒと略記）、およびス
チレン−ブタジェンランダム共重合体（結合スチレン量
２３．５重量％、ＭＬｊ＋４１００℃−５０，ＳＢＲと
略記する）をそれぞれ溶解し、容量１００１Ｌｊのオー
トクレーブに上記Ｐ４触媒０．１０５１を助触媒と共に
仕込んだ。系内を窒素で置換後水素で５０ ｋｐ／ａｘ
”に加圧後９０℃で５時間水素化反応を行った。この反
応をそれぞれ各３回行った。In order to investigate the activity of these catalysts, we added 31 polyisogrene (Kust4 content: 97%, ML1+4100℃-80, abbreviated as Engineering R) and styrene-butadiene random copolymer (combined styrene content: 23%) to 37% of tetrahydrofuran. 0.5% by weight, MLj+4100°C-50, abbreviated as SBR) were respectively dissolved, and 0.1051% of the above P4 catalyst was charged together with a promoter into an autoclave having a capacity of 1001Lj. After replacing the system with nitrogen, 50 kp/ax with hydrogen
After pressurizing to 90°C, hydrogenation reaction was carried out for 5 hours at 90°C. This reaction was carried out three times each.
結果を第６表に示す。いずれの触媒でもＳＢＲ中の結合
スチレンのベンゼン核は還元されなかった。The results are shown in Table 6. None of the catalysts reduced the benzene nucleus of bound styrene in SBR.
比較例
比較の為に助触媒をｐａと同時担持した系の活性と再現
性を工ＲとＳＢＨの水素化により調べた。Comparative Example For comparison, the activity and reproducibility of a system in which a co-catalyst was co-supported with PA was investigated by hydrogenation of R and SBH.
活性炭を担体として、これにパラジウム単独およびＰａ
と同時にセリウム、鉄及び銅のそれぞれを担持させた。Using activated carbon as a carrier, palladium alone and Pa
At the same time, cerium, iron, and copper were each supported.
各元素源としてそれぞれの塩化物を用い、これらの水溶
液に活性炭を浸漬し、活性炭中に十分含浸させ、ホルマ
リン−力性ソーダで還元して担体担持触媒として使用し
た。併用系の場合は各元素とパラジウムとの原子比を０
．１：１で行った。またいずれの場合にも担体当りのｐ
ａは１重量％である。Each chloride was used as a source of each element, and activated carbon was immersed in these aqueous solutions to be sufficiently impregnated into the activated carbon, which was then reduced with formalin-hydrohydric soda and used as a carrier-supported catalyst. In the case of a combination system, the atomic ratio of each element and palladium should be 0.
．． It was 1:1. In both cases, p per carrier
a is 1% by weight.
これらの同時担持触媒を用いそれぞれ３回づつ実施例６
と同様にして水素化反応を行ない触媒活性及び再現性を
調べた。結果を第６表に示す０実施例６の触媒は再現性
は良好であるが、同時担持触媒については再現性が悪（
、銅化合物を助触媒に使用した場合には触媒活性も低下
することがわかった。Example 6 using these co-supported catalysts three times each
A hydrogenation reaction was carried out in the same manner as above, and the catalytic activity and reproducibility were investigated. The results are shown in Table 6. The catalyst of Example 6 has good reproducibility, but the reproducibility of the co-supported catalyst is poor (
It was found that the catalytic activity also decreased when a copper compound was used as a co-catalyst.
Claims (1)
素化するに際し、パラジウムを多孔性担体に担持させた
担体担持触媒と、周期律表 I Ａ、IIＡ、IVＡ、ＶＡ、
VIＡ、VIIＡ及びVIII族ならびに銅、アルミニウム、ホ
ウ素、錫、セリウム、ランタンから選択される少なくと
も１種の元素を含む化合物を溶媒に溶解し、助触媒とし
て使用することを特徴とする共役ジエン系重合体の水素
化方法。When hydrogenating the carbon-carbon double bond of a conjugated diene polymer in a solvent, a carrier-supported catalyst in which palladium is supported on a porous carrier, and periodic table IA, IIA, IVA, VA,
A conjugated diene-based polymer characterized in that a compound containing Group VIA, VIIA and VIII and at least one element selected from copper, aluminum, boron, tin, cerium and lanthanum is dissolved in a solvent and used as a co-catalyst. Hydrogenation method of coalescence.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59252148A JPS61130303A (en) | 1984-11-29 | 1984-11-29 | Hydrogenation of conjugated diene polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59252148A JPS61130303A (en) | 1984-11-29 | 1984-11-29 | Hydrogenation of conjugated diene polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61130303A true JPS61130303A (en) | 1986-06-18 |
| JPH0578562B2 JPH0578562B2 (en) | 1993-10-29 |
Family
ID=17233145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59252148A Granted JPS61130303A (en) | 1984-11-29 | 1984-11-29 | Hydrogenation of conjugated diene polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61130303A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0368381A2 (en) * | 1988-11-09 | 1990-05-16 | Shell Internationale Researchmaatschappij B.V. | Hydrogenation process |
| JP2004506787A (en) * | 2000-08-25 | 2004-03-04 | クレイトン・ポリマーズ・リサーチ・ベー・ベー | Method for making selectively hydrogenated block copolymer of vinyl aromatic hydrocarbon and conjugated diene |
-
1984
- 1984-11-29 JP JP59252148A patent/JPS61130303A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0368381A2 (en) * | 1988-11-09 | 1990-05-16 | Shell Internationale Researchmaatschappij B.V. | Hydrogenation process |
| JP2004506787A (en) * | 2000-08-25 | 2004-03-04 | クレイトン・ポリマーズ・リサーチ・ベー・ベー | Method for making selectively hydrogenated block copolymer of vinyl aromatic hydrocarbon and conjugated diene |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0578562B2 (en) | 1993-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1130265C (en) | Catalyst capable of using on carrier in organic compound conversion reaction | |
| US6627578B2 (en) | Catalyst for selective hydrogenation | |
| WO2017201644A1 (en) | Palladium-based supported hydrogenation catalyst and preparation method therefor and application thereof | |
| US6248924B1 (en) | Process for reacting an organic compound in the presence of a supported ruthenium catalyst | |
| JPS59161415A (en) | Hydrogenation of carbon-carbon double bond in unsaturated polymer | |
| TW200906487A (en) | Alumina having a complex pore structure, and catalyst and process for selective hydrogenation of cracking gasoline | |
| JPH0474141A (en) | Production of cycloolefin | |
| WO2024008171A1 (en) | Transition-metal-based dehydrogenation catalyst for low-carbon alkane, and preparation method therefor and use thereof | |
| JP6345267B2 (en) | Process for preparing polymers having amino groups using heterogeneous iron catalysts | |
| JPS61130303A (en) | Hydrogenation of conjugated diene polymer | |
| CN1110472C (en) | Improved process for hydrogenation of maleic acid to 1,4-butanediol | |
| US2917466A (en) | Platinum metal catalysts | |
| CN115259985A (en) | Method for catalyzing selective hydrogenation of acetylene by using monatomic catalyst | |
| JPS615036A (en) | Production of alcohol | |
| JPS6335642B2 (en) | ||
| JPS6335641B2 (en) | ||
| CN1344585A (en) | Noble metal catalyst method of resisting CO poisoning | |
| EP2329879A1 (en) | Catalyst for selective hydrogenation of acetylene compounds in 1,3-butadiene, method for producing the same and method of using the same | |
| EP3437737A1 (en) | Method for preparing dispersion of metal-containing particles and method for producing hydrogenated conjugated diene polymer | |
| JPS59228937A (en) | Catalyst for selectively hydrogenating poly-unsaturated organic compound. | |
| JPH0655077A (en) | Catalyst for isomerization of hydrocarbon and method for isomerizing hydrocarbon with the same | |
| US5750457A (en) | Solid acid catalyst for paraffin conversion and process for paraffin conversion using the same | |
| CN117466698A (en) | Alkyne selective hydrogenation method | |
| JP3422062B2 (en) | Method for producing diacetoxybutene | |
| Auer et al. | The Synthesis of Amines by Catalytic Hydrogenation of Nitro Compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |