CN103694386B - A kind of preparation method of organic neodymium phosphate catalyst system - Google Patents
A kind of preparation method of organic neodymium phosphate catalyst system Download PDFInfo
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- CN103694386B CN103694386B CN201310702157.4A CN201310702157A CN103694386B CN 103694386 B CN103694386 B CN 103694386B CN 201310702157 A CN201310702157 A CN 201310702157A CN 103694386 B CN103694386 B CN 103694386B
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- phosphoric acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- DZNFWGVDYGAMJB-UHFFFAOYSA-K neodymium(3+);phosphate Chemical compound [Nd+3].[O-]P([O-])([O-])=O DZNFWGVDYGAMJB-UHFFFAOYSA-K 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 89
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 51
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims abstract description 43
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000007127 saponification reaction Methods 0.000 claims abstract description 34
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000032683 aging Effects 0.000 claims abstract description 26
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 11
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000012670 alkaline solution Substances 0.000 claims abstract description 6
- 239000006166 lysate Substances 0.000 claims abstract description 3
- ZPLUZNXSYCCJOE-UHFFFAOYSA-N phosphoric acid;propan-2-one Chemical compound CC(C)=O.OP(O)(O)=O ZPLUZNXSYCCJOE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010092 rubber production Methods 0.000 claims abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 75
- 238000006243 chemical reaction Methods 0.000 claims description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 46
- -1 organo phosphates Chemical class 0.000 claims description 46
- 239000007787 solid Substances 0.000 claims description 29
- KWKDMHWAAVTQSZ-UHFFFAOYSA-N neodymium phosphoric acid Chemical compound [Nd].P(O)(O)(O)=O KWKDMHWAAVTQSZ-UHFFFAOYSA-N 0.000 claims description 28
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 26
- 238000004090 dissolution Methods 0.000 claims description 18
- 229910052779 Neodymium Inorganic materials 0.000 claims description 17
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 17
- 238000013019 agitation Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 230000006837 decompression Effects 0.000 claims description 13
- 238000000967 suction filtration Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 claims description 11
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 11
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 150000001993 dienes Chemical class 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 235000021317 phosphate Nutrition 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910000091 aluminium hydride Inorganic materials 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- OSPSWZSRKYCQPF-UHFFFAOYSA-N dibutoxy(oxo)phosphanium Chemical compound CCCCO[P+](=O)OCCCC OSPSWZSRKYCQPF-UHFFFAOYSA-N 0.000 claims description 3
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 3
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 claims description 2
- QWUGXIXRFGEYBD-UHFFFAOYSA-M ethylmercuric chloride Chemical compound CC[Hg]Cl QWUGXIXRFGEYBD-UHFFFAOYSA-M 0.000 claims description 2
- GWUWXYLXFDAAOO-UHFFFAOYSA-N heptyl dimethyl phosphate Chemical compound CCCCCCCOP(=O)(OC)OC GWUWXYLXFDAAOO-UHFFFAOYSA-N 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 230000001737 promoting effect Effects 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 8
- 239000005060 rubber Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 239000012153 distilled water Substances 0.000 description 33
- 238000003756 stirring Methods 0.000 description 24
- 239000007788 liquid Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 235000011121 sodium hydroxide Nutrition 0.000 description 17
- 230000000694 effects Effects 0.000 description 13
- 239000002244 precipitate Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 230000037048 polymerization activity Effects 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 229920003049 isoprene rubber Polymers 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229940005605 valeric acid Drugs 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 150000001206 Neodymium Chemical class 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerization Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation method of organic neodymium phosphate catalyst system.The method, comprises the following steps：The aqueous solution of neodymium trichloride is prepared using neodymium oxide and hydrochloric acid；Organic phosphoric acid and acetone are mixed to get organic phosphoric acid solution；Alkaline solution is added in organic phosphoric acid acetone soln to carry out saponification and obtains saponification liquor；The viscosity of lysate is adjusted after dissolving completely with viscosity-controlling agent；Binary ageing and ternary ageing are carried out respectively, you can must directly apply to the rare-earth catalysis system of rubber production.Technology provided by the present invention is when rare-earth rubber catalyst system is prepared, by adding certain viscosity-controlling agent so that organic phosphoric acid neodymium salt is more conducive to be dissolved in organic solvent, and the viscosity of catalyst solution can be adjusted as desired by the addition for controlling viscosity-controlling agent, substantially increase its mobility.The skill upgrading industrial production operability of organic neodymium phosphate catalyst system, indirectly reduces production cost.
Description
（One）Technical field
The present invention relates to a kind of catalyst system and catalyzing, specifically one kind are applied to isoprene or butadiene solution polymerization life
Produce the preparation method of the organic neodymium phosphate catalyst system of rare-earth isoprene rubber, rare earth polybutadiene rubber or fourth isoprene rubber.
（Two）Background technology
The development for developing all its corresponding catalyst always of rubber industry is inseparable, and Ziegler-Natta is catalyzed
The appearing as of agent synthesizes butadiene rubber and isoprene rubber and brings revolutionary breakthrough, is that modern rubber industry is laid a good foundation.
The appearance of the catalyst such as lithium system, iron system, titanium system, cobalt system, nickel system is greatly facilitated the development further of rubber industry.Eighties of last century
From the sixties, China begins one's study Rare Earth rubber catalyst, and achieves important breakthrough.Compared with traditional rubber catalyst,
Rare earth catalyst is had the characteristics that in rubber polymerisation：With saturated hydrocarbons as solvent, beneficial to environmental protection；Monomer conversion is high；No
Reaction is easily crosslinked, generates gel；Dimer generating rate is low, it is possible to reduce dimer pollution on the environment；Temperature
Structure and performance impact to polymerizate is little.
With the active highest of Nd-based catalyst in rare earth series catalysts, urged using the ternary ageing of organic acid neodymium mostly now
Change system.Changchun should be changed place and have studied within 1975 the neodymium series such as P204, P507, P229 catalyst system and catalyzing to isoprene polymerization catalysis
The research of activity（Science Press in 1980《Rare earth catalyst synthetic rubber collected works》）, they are shown than other carboxylic acid neodymium
（Such as aphthenic acids, neodecanoic acid, isooctyl acid etc.）Higher activity.Again there are a lot of people to study afterwards to do conjugated diene with neodymium phosphate and gather
The catalyst of conjunction, such as Laubry（01820350.7 and 01820478.3）Et al. report and prepare three-element catalytic body with neodymium phosphate
System has synthesized the isoprene rubber with high 1,4- cis-structure.
In the past with research of the organic phosphoric acid neodymium as catalyst, the SOLID ORGANIC phosphoric acid neodymium catalyst for synthesizing is having
When machine solvent dissolves, dissolubility is poor, takes long enough to dissolve, and the solution viscosity after dissolving is larger, and mobility is relatively
Difference, is unfavorable for transport and serialization industrial production.For this kind of shortcoming, the present invention proposes a kind of effective solution.
（Three）Content of the invention
It is an object of the invention to provide a kind of method of the preparation of organic neodymium phosphate catalyst system, in the inventive technique
In propose a kind of dissolving in organic solvent of organic phosphoric acid neodymium for solving to occur during in the past production organic phosphoric acid neodymium catalyst
Property poor, dissolving elapsed time length, larger, poor fluidity the new technology of solution viscosity after dissolving.The technology is being prepared
Organic phosphoric acid neodymium salt adds certain viscosity-controlling agent hydrotropy when being dissolved in organic solvent, and by controlling the addition of viscosity-controlling agent
Adjust the viscosity of solution.
The present invention is achieved through the following technical solutions：
A kind of preparation method of organic neodymium phosphate catalyst system, which is characterized in that：Comprise the following steps：
（1）Prepare the aqueous solution of neodymium trichloride：The aqueous solution of neodymium trichloride is prepared using neodymium oxide and hydrochloric acid；
（2）Prepare organic phosphoric acid solution：Organic phosphoric acid and acetone are mixed to get organic phosphoric acid solution；
（3）Prepare saponification liquor：Alkaline solution is added in organic phosphoric acid acetone soln to carry out saponification and obtains saponification
Liquid, at 20-70 DEG C, time control is in 20-50 min, and should carry out under agitation for the temperature control of the saponification；
（4）Prepare organic phosphoric acid neodymium：The saponification liquor of gained is added under agitation in neodymium trichloride solution, in 20-70
20-60 min is reacted at DEG C, obtain SOLID ORGANIC neodymium phosphate, after the completion of reaction by the way of decompression suction filtration then at 60 DEG C
Drying solid obtains organic phosphoric acid neodymium；
（5）Dissolving, tune viscosity：The organic solvent of organic phosphoric acid neodymium solid after drying dissolves, and adds viscosity to adjust
Agent hydrotropy, adjusts the viscosity of lysate with viscosity-controlling agent after dissolving completely；
（6）It is aged, prepares product：The catalyst for reconciling good appropriate viscosity is sequentially added conjugated diene monomer, alkyl
Aluminum compound solution, chloride solution, carry out binary ageing and ternary ageing, you can must directly apply to rubber production respectively
Rare-earth catalysis system.
In the alkaline solution, with the mol ratio of organic phosphoric acid for being slightly less than 1, specific requirement is 0.99 to solute.
The preparation method of the organic neodymium phosphate catalyst system of the present invention, step（1）In, the aqueous solution of neodymium trichloride dense
Spend for 0.5-2.5 mol/L.
The preparation method of the organic neodymium phosphate catalyst system of the present invention, step（2）In, organic phosphoric acid solution, its concentration
For 0.3-2.0 mol/L, neodymium trichloride is controlled to 1 with the mol ratio of organic phosphoric acid:3.
The preparation method of the organic neodymium phosphate catalyst system of the present invention, organic phosphoric acid are acid organo phosphates, specifically
For（RO）2POOH、R(RO)POOH、R2POOH, wherein R for carbon number for 2-13 alkyl；More specifically, acid organo phosphates are
Two（2- ethylhexyl）Phosphate, 2- ethylhexyl phosphoric acid 2- ethylhexyl, two（2- ethylhexyl）Phosphoric acid or methyl acid phosphate
One kind in dimethyl heptyl ester.
The preparation method of the organic neodymium phosphate catalyst system of the present invention, step（3）In, alkaline solution is that NaOH is molten
One kind in liquid, potassium hydroxide solution or ammonia spirit.
The preparation method of the organic neodymium phosphate catalyst system of the present invention, step（5）In, molten for preparing organic neodymium phosphate
Liquid and dilution organic solvent be pentane, hexane, heptane and six oil of carbon in one or more, specifically, for prepare and dilute
The organic solvent that releases is hexane, promote catalyst dissolution and adjust catalyst viscosity viscosity-controlling agent be organic acid, organic
Acid esters, Organic Alcohol, can be specifically formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, capric acid, dodecyl
Benzene sulfonic acid, two（2- ethylhexyl）Phosphate, 2- ethylhexyl phosphoric acid 2- ethylhexyl, two（2- ethylhexyl）Phosphoric acid, first
Base di(2-ethylhexyl)phosphate meptyl ester, tributyl phosphate, triphenyl phosphate, phosphorous acid dibutyl ester, diethyl phosphite, phosphorous acid hexichol
Ester, repefral, diethyl phthalate, dioctyl phthalate, methyl alcohol, ethanol, propyl alcohol, butanol, penta
One or more in alcohol, hexanol, enanthol, octanol, isodecanol etc., adjust the addition root of the viscosity-controlling agent of catalyst viscosity
Determine, specifically, the addition of viscosity-controlling agent and organic phosphoric acid according to the viscosity of organic phosphoric acid neodymium and/or the k value of requirement
In neodymium, the mol ratio of neodymium is 0.25 3:1.
The preparation method of the organic neodymium phosphate catalyst system of the present invention, step（6）In, the conjugated diene monomer of addition
For the one kind in isoprene, pentadiene and butadiene, the alkyl aluminum compound of addition is triisobutyl aluminium, two isobutyls of hydrogenation
One kind in base aluminium and diethyl aluminium hydride, the chloride of addition is di-isobutyl aluminum chloride, diethylaluminum chloride and sesquialter second
One kind in base aluminium chloride.
Beneficial effects of the present invention：Technology provided by the present invention prepare rare-earth rubber catalyst system when, by plus
Enter certain viscosity-controlling agent so that organic phosphoric acid neodymium salt is more conducive to be dissolved in organic solvent, its dissolution time is substantially reduced, and
And the viscosity of catalyst solution can be adjusted as desired by the addition for controlling viscosity-controlling agent, substantially increase its flowing
Property.The skill upgrading industrial production operability of organic neodymium phosphate catalyst system, indirectly reduces production cost.
（Four）Specific embodiment
Embodiment 1：
Using neodymium oxide and the neodymium trichloride aqueous solution that hydrochloric acid compound concentration is 1.14 mol/L；Prepared with acetone dense
Spend the P507 solution for 0.35 mol/L；With the sodium hydrate aqueous solution that distilled water compound concentration is 4.97 mol/L.
2 L P507 acetone solns are taken in 10 L containers, 0.5 L distilled water is added, then adds 140 mL under agitation
Sodium hydroxide solution, 30 min of stirring reaction at 50 DEG C, you can saponification liquor.205 mL neodymium trichloride solution are measured, then
1.5 L distilled water and 0.5 L acetone is added to be diluted in 10 L containers.Saponification liquor is slowly added dropwise and is diluted into above-mentioned neodymium trichloride
In liquid, quick 30 min of stirring reaction under normal temperature.A large amount of white precipitates are generated in course of reaction, using decompression after the completion of reaction
The mode of suction filtration obtains SOLID ORGANIC neodymium phosphate, then 72 h of drying solid at 60 DEG C.
Weigh 53 g of organophosphor neodymium of four parts of preparations respectively, be dissolved in 1 L hexane, wherein, first part is not added with viscosity regulation
Agent, second part is separately added into mol ratio to the 4th part（A/Nd）For 0.5,1.0,1.5 viscosity-controlling agent organic acid A, during dissolving
Between as shown in table 1 with solution rotating viscosity.
Solute effect of 1 viscosity-controlling agent of table to organic phosphoric acid neodymium
| A/Nd | 0 | 0.5 | 1.0 | 1.5 |
| Dissolution time/h | 72 | 19 | 10 | 5 |
| Viscosity/mPa s | >10000 | 225 | 168 | 55 |
Embodiment 2：
Using neodymium oxide and the neodymium trichloride aqueous solution that hydrochloric acid compound concentration is 1.14 mol/L；Prepared with acetone dense
Spend the P204 solution for 0.35 mol/L；With the sodium hydrate aqueous solution that distilled water compound concentration is 4.97 mol/L.
2 L P204 acetone solns are taken in 10 L containers, 0.5 L distilled water is added, then adds 140 mL under agitation
Sodium hydroxide solution, 30 min of stirring reaction at 50 DEG C, you can saponification liquor.205 mL neodymium trichloride solution are measured, then
1.5 L distilled water and 0.5 L acetone is added to be diluted in 10 L containers.Saponification liquor is slowly added dropwise and is diluted into above-mentioned neodymium trichloride
In liquid, quick 30 min of stirring reaction under normal temperature.A large amount of white precipitates are generated in course of reaction, using decompression after the completion of reaction
The mode of suction filtration obtains SOLID ORGANIC neodymium phosphate, then 72 h of drying solid at 60 DEG C.
Weigh 55 g of organophosphor neodymium of four parts of preparations respectively, be dissolved in 1 L hexane, wherein, first part is not added with viscosity regulation
Agent, second part is separately added into mol ratio to the 4th part（A/Nd）For 0.5,1.0,1.5 viscosity-controlling agent organic acid A, during dissolving
Between as shown in table 2 with solution rotating viscosity.
Solute effect of 2 viscosity-controlling agent of table to organic phosphoric acid neodymium
| A/Nd | 0 | 0.5 | 1.0 | 1.5 |
| Dissolution time/h | 72 | 20 | 11 | 5 |
| Viscosity/mPa s | >10000 | 240 | 155 | 62 |
Embodiment 3：
Using neodymium oxide and the neodymium trichloride aqueous solution that hydrochloric acid compound concentration is 1.14 mol/L；Prepared with acetone dense
Spend the P507 solution for 0.35 mol/L；With the sodium hydrate aqueous solution that distilled water compound concentration is 4.97 mol/L.
2 L P507 acetone solns are taken in 10 L containers, 0.5 L distilled water is added, then adds 140 mL under agitation
Sodium hydroxide solution, 30 min of stirring reaction at 50 DEG C, you can saponification liquor.205 mL neodymium trichloride solution are measured, then
1.5 L distilled water and 0.5 L acetone is added to be diluted in 10 L containers.Saponification liquor is slowly added dropwise and is diluted into above-mentioned neodymium trichloride
In liquid, quick 30 min of stirring reaction under normal temperature.A large amount of white precipitates are generated in course of reaction, using decompression after the completion of reaction
The mode of suction filtration obtains SOLID ORGANIC neodymium phosphate, then 72 h of drying solid at 60 DEG C.
Weigh 53 g of organophosphor neodymium of four parts of preparations respectively, be dissolved in 1 L hexane, wherein, first part is not added with viscosity regulation
Agent, second part is separately added into mol ratio to the 4th part（B/Nd）For 0.5,1.0,1.5 viscosity-controlling agent organic acid esters B, dissolve
Time is as shown in table 3 with solution rotating viscosity.
Solute effect of 3 viscosity-controlling agent of table to organic phosphoric acid neodymium
| B/Nd | 0 | 0.5 | 1.0 | 1.5 |
| Dissolution time/h | 72 | 24 | 13 | 7 |
| Viscosity/mPa s | >10000 | 265 | 175 | 75 |
Embodiment 4：
Using neodymium oxide and the neodymium trichloride aqueous solution that hydrochloric acid compound concentration is 1.14 mol/L；Prepared with acetone dense
Spend the P204 solution for 0.35 mol/L；With the sodium hydrate aqueous solution that distilled water compound concentration is 4.97 mol/L.
2 L P204 acetone solns are taken in 10 L containers, 0.5 L distilled water is added, then adds 140 mL under agitation
Sodium hydroxide solution, 30 min of stirring reaction at 50 DEG C, you can saponification liquor.205 mL neodymium trichloride solution are measured, then
1.5 L distilled water and 0.5 L acetone is added to be diluted in 10 L containers.Saponification liquor is slowly added dropwise and is diluted into above-mentioned neodymium trichloride
In liquid, quick 30 min of stirring reaction under normal temperature.A large amount of white precipitates are generated in course of reaction, using decompression after the completion of reaction
The mode of suction filtration obtains SOLID ORGANIC neodymium phosphate, then 72 h of drying solid at 60 DEG C.
Weigh 55 g of organophosphor neodymium of four parts of preparations respectively, be dissolved in 1 L hexane, wherein, first part is not added with viscosity regulation
Agent, second part is separately added into mol ratio to the 4th part（B/Nd）For 0.5,1.0,1.5 viscosity-controlling agent organic acid esters B, dissolve
Time is as shown in table 4 with solution rotating viscosity.
Solute effect of 4 viscosity-controlling agent of table to organic phosphoric acid neodymium
| B/Nd | 0 | 0.5 | 1.0 | 1.5 |
| Dissolution time/h | 72 | 24 | 13 | 7 |
| Viscosity/mPa s | >10000 | 266 | 178 | 77 |
Embodiment 5：
Using neodymium oxide and the neodymium trichloride aqueous solution that hydrochloric acid compound concentration is 1.14 mol/L；Prepared with acetone dense
Spend the P507 solution for 0.35 mol/L；With the sodium hydrate aqueous solution that distilled water compound concentration is 4.97 mol/L.
2 L P507 acetone solns are taken in 10 L containers, 0.5 L distilled water is added, then adds 140 mL under agitation
Sodium hydroxide solution, 30 min of stirring reaction at 50 DEG C, you can saponification liquor.205 mL neodymium trichloride solution are measured, then
1.5 L distilled water and 0.5 L acetone is added to be diluted in 10 L containers.Saponification liquor is slowly added dropwise and is diluted into above-mentioned neodymium trichloride
In liquid, quick 30 min of stirring reaction under normal temperature.A large amount of white precipitates are generated in course of reaction, using decompression after the completion of reaction
The mode of suction filtration obtains SOLID ORGANIC neodymium phosphate, then 72 h of drying solid at 60 DEG C.
Weigh 53 g of organophosphor neodymium of four parts of preparations respectively, be dissolved in 1 L hexane, wherein, first part is not added with viscosity regulation
Agent, second part is separately added into mol ratio to the 4th part（C/Nd）For 0.5,1.0,1.5 viscosity-controlling agent Organic Alcohol C, during dissolving
Between as shown in table 5 with solution rotating viscosity.
Solute effect of 5 viscosity-controlling agent of table to organic phosphoric acid neodymium
| C/Nd | 0 | 0.5 | 1.0 | 1.5 |
| Dissolution time/h | 72 | 28 | 15 | 8 |
| Viscosity/mPa s | >10000 | 423 | 215 | 86 |
Embodiment 6：
Using neodymium oxide and the neodymium trichloride aqueous solution that hydrochloric acid compound concentration is 1.14 mol/L；Prepared with acetone dense
Spend the P204 solution for 0.35 mol/L；With the sodium hydrate aqueous solution that distilled water compound concentration is 4.97 mol/L.
2 L P204 acetone solns are taken in 10 L containers, 0.5 L distilled water is added, then adds 140 mL under agitation
Sodium hydroxide solution, 30 min of stirring reaction at 50 DEG C, you can saponification liquor.205 mL neodymium trichloride solution are measured, then
1.5 L distilled water and 0.5 L acetone is added to be diluted in 10 L containers.Saponification liquor is slowly added dropwise and is diluted into above-mentioned neodymium trichloride
In liquid, quick 30 min of stirring reaction under normal temperature.A large amount of white precipitates are generated in course of reaction, using decompression after the completion of reaction
The mode of suction filtration obtains SOLID ORGANIC neodymium phosphate, then 72 h of drying solid at 60 DEG C.
Weigh 55 g of organophosphor neodymium of four parts of preparations respectively, be dissolved in 1 L hexane, wherein, first part is not added with viscosity regulation
Agent, second part is separately added into mol ratio to the 4th part（C/Nd）For 0.5,1.0,1.5 viscosity-controlling agent Organic Alcohol C, during dissolving
Between as shown in table 6 with solution rotating viscosity.
Solute effect of 6 viscosity-controlling agent of table to organic phosphoric acid neodymium
| C/Nd | 0 | 0.5 | 1.0 | 1.5 |
| Dissolution time/h | 72 | 28 | 16 | 7 |
| Viscosity/mPa s | >10000 | 435 | 221 | 90 |
Embodiment 7：
Using neodymium oxide and the neodymium trichloride aqueous solution that hydrochloric acid compound concentration is 1.14 mol/L；Prepared with acetone dense
Spend the P507 solution for 0.35 mol/L；With the sodium hydrate aqueous solution that distilled water compound concentration is 4.97 mol/L.
2 L P507 acetone solns are taken in 10 L containers, 0.5 L distilled water is added, then adds 140 mL under agitation
Sodium hydroxide solution, 30 min of stirring reaction at 50 DEG C, you can saponification liquor.205 mL neodymium trichloride solution are measured, then
1.5 L distilled water and 0.5 L acetone is added to be diluted in 10 L containers.Saponification liquor is slowly added dropwise and is diluted into above-mentioned neodymium trichloride
In liquid, quick 30 min of stirring reaction under normal temperature.A large amount of white precipitates are generated in course of reaction, using decompression after the completion of reaction
The mode of suction filtration obtains SOLID ORGANIC neodymium phosphate, then 72 h of drying solid at 60 DEG C.
Weigh 53 g of organophosphor neodymium of four parts of preparations respectively, be dissolved in 1 L hexane, wherein, first part is not added with viscosity regulation
Agent, second part is separately added into mol ratio to the 4th part（(A+B)/Nd）Viscosity-controlling agent organic acid A for 0.5,1.0,1.5 and have
Machine acid esters B (1：1), dissolution time is as shown in table 7 with solution rotating viscosity.
Solute effect of 7 viscosity-controlling agent of table to organic phosphoric acid neodymium
| (A+B)/Nd | 0 | 0.5 | 1.0 | 1.5 |
| Dissolution time/h | 72 | 22 | 12 | 6 |
| Viscosity/mPa s | >10000 | 236 | 136 | 62 |
Embodiment 8：
Using neodymium oxide and the neodymium trichloride aqueous solution that hydrochloric acid compound concentration is 1.14 mol/L；Prepared with acetone dense
Spend the P204 solution for 0.35 mol/L；With the sodium hydrate aqueous solution that distilled water compound concentration is 4.97 mol/L.
2 L P204 acetone solns are taken in 10 L containers, 0.5 L distilled water is added, then adds 140 mL under agitation
Sodium hydroxide solution, 30 min of stirring reaction at 50 DEG C, you can saponification liquor.205 mL neodymium trichloride solution are measured, then
1.5 L distilled water and 0.5 L acetone is added to be diluted in 10 L containers.Saponification liquor is slowly added dropwise and is diluted into above-mentioned neodymium trichloride
In liquid, quick 30 min of stirring reaction under normal temperature.A large amount of white precipitates are generated in course of reaction, using decompression after the completion of reaction
The mode of suction filtration obtains SOLID ORGANIC neodymium phosphate, then 72 h of drying solid at 60 DEG C.
Weigh 55 g of organophosphor neodymium of four parts of preparations respectively, be dissolved in 1 L hexane, wherein under normal temperature, stirring, first part
Viscosity-controlling agent is not added with, second part is separately added into mol ratio to the 4th part（(A+B）/Nd）Viscosity for 0.5,1.0,1.5 is adjusted
Agent organic acid A and organic acid esters B (1：1), dissolution time is as shown in table 8 with solution rotating viscosity.
Solute effect of 8 viscosity-controlling agent of table to organic phosphoric acid neodymium
| (A+B)/Nd | 0 | 0.5 | 1.0 | 1.5 |
| Dissolution time/h | 72 | 23 | 12 | 6 |
| Viscosity/mPa s | >10000 | 239 | 136 | 65 |
Embodiment 9：
Using neodymium oxide and the neodymium trichloride aqueous solution that hydrochloric acid compound concentration is 0.5 mol/L；Prepared with acetone dense
Spend (the C for 1.0 mol/L13H27)2POOH solution；Water-soluble with potassium hydroxide solution that distilled water compound concentration is 4.97 mol/L
Liquid.
Take 0.7 L (C13H27)2POOH acetone soln adds 2.8 L distilled water in 10 L containers, then adds under agitation
Enter 140 mL potassium hydroxide aqueous solutions, 50 min of stirring reaction at 20 DEG C, you can saponification liquor.Measure 467 mL neodymium trichlorides
Solution, is subsequently adding 3.4 L distilled water and 1.1 L acetone are diluted in 10 L containers.Saponification liquor is slowly added dropwise into above-mentioned three
In neodymium chloride dilution, quick 60 min of stirring reaction at 50 DEG C.A large amount of white precipitates are generated in course of reaction, and reaction is completed
SOLID ORGANIC neodymium phosphate is obtained afterwards by the way of decompression suction filtration, then 75 h of drying solid at 50 DEG C.
Weigh 55 g of organophosphor neodymium of four parts of preparations respectively, be dissolved in 1 L pentane, wherein, first part is not added with viscosity regulation
Agent, second part is separately added into mol ratio to the 4th part（A/Nd）For 0.5,1.0,1.5 viscosity-controlling agent organic acid A, during dissolving
Between as shown in table 2 with solution rotating viscosity.
Solute effect of 2 viscosity-controlling agent of table to organic phosphoric acid neodymium
| A/Nd | 0 | 0.5 | 1.0 | 1.5 |
| Dissolution time/h | 72 | 20 | 11 | 5 |
| Viscosity/mPa s | >10000 | 240 | 155 | 62 |
Embodiment 10：
Using neodymium oxide and the neodymium trichloride aqueous solution that hydrochloric acid compound concentration is 2.5 mol/L；Prepared with acetone dense
Spend (the C for 2.0 mol/L2H4O)2POOH solution；With the ammonia spirit that distilled water compound concentration is 4.97 mol/L.
Take 0.35 L (C2H4O)2POOH acetone soln adds 1.4 L distilled water, then under agitation in 10 L containers
Add 140 mL ammonia spirits, 20 min of stirring reaction at 70 DEG C, you can saponification liquor.Measure 93.4 mL neodymium trichlorides molten
Liquid, is subsequently adding 0.68L distilled water and 0.2 L acetone is diluted in 10 L containers.Saponification liquor is slowly added dropwise into above-mentioned trichlorine
Change in neodymium dilution, quick 20 min of stirring reaction at 70 DEG C.A large amount of white precipitates are generated in course of reaction, after the completion of reaction
SOLID ORGANIC neodymium phosphate is obtained by the way of decompression suction filtration, then 80 h of drying solid at 40 DEG C.
Weigh 55 g of organophosphor neodymium of four parts of preparations respectively, be dissolved in 1 L pentane and heptane mixture, wherein, first part
Viscosity-controlling agent is not added with, second part is separately added into mol ratio to the 4th part（A/Nd）Have for 0.5,1.0,1.5 viscosity-controlling agent
Machine acid A, dissolution time are as shown in table 2 with solution rotating viscosity.
Solute effect of 2 viscosity-controlling agent of table to organic phosphoric acid neodymium
| A/Nd | 0 | 0.5 | 1.0 | 1.5 |
| Dissolution time/h | 72 | 20 | 11 | 5 |
| Viscosity/mPa s | >10000 | 240 | 155 | 62 |
Embodiment 11：
Using neodymium oxide and the neodymium trichloride aqueous solution that hydrochloric acid compound concentration is 0.5 mol/L；Prepared with acetone dense
Spend the C for 1.0 mol/L10H20(C10H20O) POOH solution；With the potassium hydroxide that distilled water compound concentration is 4.97 mol/L
The solution aqueous solution.
Take 0.7 LC10H20(C10H20O) POOH acetone soln adds 2.8 L distilled water, Ran Hou in 10 L containers
Stirring is lower to add 140 mL potassium hydroxide aqueous solutions, 50 min of stirring reaction at 20 DEG C, you can saponification liquor.Measure 467 mL
Neodymium trichloride solution, is subsequently adding 3.4 L distilled water and 1.1 L acetone are diluted in 10 L containers.Saponification liquor is slowly added dropwise
Enter in above-mentioned neodymium trichloride dilution, quick 60 min of stirring reaction at 50 DEG C.A large amount of white precipitates are generated in course of reaction,
SOLID ORGANIC neodymium phosphate is obtained by the way of decompression suction filtration after the completion of reaction, then 75 h of drying solid at 50 DEG C.
Weigh 55 g of organophosphor neodymium of four parts of preparations respectively, be dissolved in 1 L carbon, six oil, wherein, first part is not added with viscosity tune
Section agent, second part is separately added into mol ratio to the 4th part（A/Nd）For 0.5,1.0,1.5 viscosity-controlling agent organic acid A, dissolve
Time is as shown in table 2 with solution rotating viscosity.
Solute effect of 2 viscosity-controlling agent of table to organic phosphoric acid neodymium
| A/Nd | 0 | 0.5 | 1.0 | 1.5 |
| Dissolution time/h | 72 | 20 | 11 | 5 |
| Viscosity/mPa s | >10000 | 240 | 155 | 62 |
Embodiment 12：
The di-isobutyl aluminum chloride of the diisobutylaluminium hydride solution of 1.0 mol/Ls, 0.3 mol/L is prepared with hexane respectively
Solution and concentration are the butadiene hexane solution of 13.5 g/100mL.
Using the organic phosphoric acid neodymium catalyst prepared in embodiment 1（A/Nd=0.5）, respectively take 50 mL and be placed in 100 mL ageing
In bottle, 12 mL butadiene hexane solutions are separately added into, then according to Al/Nd（Mol ratio, similarly hereinafter）It is separately added into for 5,7,10
7.5th, the diisobutylaluminium hydride solution of 10.5,13.5,15 mL, being placed in 30 DEG C of water-baths carries out binary 30 min of ageing.Finally
According to the di-isobutyl aluminum chloride solution that Cl/Nd is 2.5 addition, 25 mL, being placed in 60 DEG C of water-baths carries out ternary 2 h of ageing.Old
After the completion of change, 12 h under normal temperature, are stood.Ageing liquid is homogeneous yellowish-brown transparent liquid.Polymerization activity evaluation result is as shown in table 1：
9 different aluminum of table is than the polymerization result under different catalysts consumption
Embodiment 13：
The di-isobutyl aluminum chloride of the diisobutylaluminium hydride solution of 1.0 mol/Ls, 0.3 mol/L is prepared with hexane respectively
Solution and concentration are the butadiene hexane polymer fluid of 13.5 g/100mL.
Using the organic phosphoric acid neodymium catalyst prepared in embodiment 1（A/Nd=1.0）, respectively take 50 mL and be placed in 100 mL ageing
In bottle, 12 mL butadiene hexane solutions are separately added into, then according to Al/Nd（Mol ratio, similarly hereinafter）It is separately added into for 5,7,10
7.5th, the diisobutylaluminium hydride solution of 10.5,13.5,15 mL, being placed in 30 DEG C of water-baths carries out binary 30 min of ageing.Finally
According to the di-isobutyl aluminum chloride solution that Cl/Nd is 2.5 addition, 25 mL, being placed in 60 DEG C of water-baths carries out ternary 2 h of ageing.Old
After the completion of change, 12 h under normal temperature, are stood.Ageing liquid is homogeneous yellowish-brown transparent liquid.Polymerization activity evaluation result is as shown in table 1：
10 different aluminum of table is than the polymerization result under different catalysts consumption
Embodiment 14：
The di-isobutyl aluminum chloride of the diisobutylaluminium hydride solution of 1.0 mol/Ls, 0.3 mol/L is prepared with hexane respectively
Solution and concentration are the butadiene hexane polymer fluid of 13.5 g/100mL.
Using the organic phosphoric acid neodymium catalyst prepared in embodiment 3（B/Nd=1.0）, respectively take 50 mL and be placed in 100 mL ageing
In bottle, 12 mL butadiene hexane solutions are separately added into, then according to Al/Nd（Mol ratio, similarly hereinafter）It is separately added into for 5,7,10
7.5th, the diisobutylaluminium hydride solution of 10.5,13.5,15 mL, being placed in 30 DEG C of water-baths carries out binary 30 min of ageing.Finally
According to the di-isobutyl aluminum chloride solution that Cl/Nd is 2.5 addition, 25 mL, being placed in 60 DEG C of water-baths carries out ternary 2 h of ageing.Old
After the completion of change, 12 h under normal temperature, are stood.Ageing liquid is homogeneous yellowish-brown transparent liquid.Polymerization activity evaluation result is as shown in table 1：
11 different aluminum of table is than the polymerization result under different catalysts consumption
Embodiment 15：
The di-isobutyl aluminum chloride of the diisobutylaluminium hydride solution of 1.0 mol/Ls, 0.3 mol/L is prepared with hexane respectively
Solution and concentration are the butadiene hexane polymer fluid of 13.5 g/100mL.
Using the organic phosphoric acid neodymium catalyst prepared in embodiment 5（C/Nd=1.0）, respectively take 50 mL and be placed in 100 mL ageing
In bottle, 12 mL butadiene hexane solutions are separately added into, then according to Al/Nd（Mol ratio, similarly hereinafter）It is separately added into for 5,7,10
7.5th, the diisobutylaluminium hydride solution of 10.5,13.5,15 mL, being placed in 30 DEG C of water-baths carries out binary 30 min of ageing.Finally
According to the di-isobutyl aluminum chloride solution that Cl/Nd is 2.5 addition, 25 mL, being placed in 60 DEG C of water-baths carries out ternary 2 h of ageing.Old
After the completion of change, 12 h under normal temperature, are stood.Ageing liquid is homogeneous yellowish-brown transparent liquid.Polymerization activity evaluation result is as shown in table 1：
12 different aluminum of table is than the polymerization result under different catalysts consumption
Embodiment 16：
The chlorination diisobutyl of the diisobutylaluminium hydride solution of 1.0 mol/Ls, 0.3 mol/L is not prepared with six oil of carbon
Aluminum solutions and concentration are the butadiene hexane polymer fluid of 13.5 g/100mL.
Using the organic phosphoric acid neodymium catalyst prepared in embodiment 11（B/Nd=1.0）, respectively taking 50 mL, to be placed in 100 mL old
Change in bottle, 12 mL pentadiene solution are separately added into, then according to Al/Nd（Mol ratio, similarly hereinafter）It is separately added into for 5,7,10
7.5th, the triisobutyl aluminum solutions of 10.5,13.5,15 mL, being placed in 30 DEG C of water-baths carries out binary 30 min of ageing.Last according to
Cl/Nd is the sesquialter ethylmercury chloride aluminum solutions of 2.5 addition, 25 mL, and being placed in 60 DEG C of water-baths carries out ternary 2 h of ageing.It has been aged
Cheng Hou, stands 12 h under normal temperature.Ageing liquid is homogeneous yellowish-brown transparent liquid.Polymerization activity evaluation result is as shown in table 1：
11 different aluminum of table is than the polymerization result under different catalysts consumption
In above-described embodiment, for prepare organic neodymium phosphate solution and dilution organic solvent be pentane, hexane, heptane and
One or more in six oil of carbon, promote catalyst dissolution and adjust catalyst viscosity viscosity-controlling agent be formic acid, acetic acid, third
Acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, capric acid, DBSA, two（2- ethylhexyl）Phosphate, 2- ethyl hexyl
Base phosphoric acid 2- ethylhexyl, two（2- ethylhexyl）Phosphoric acid, methyl acid phosphate dimethyl heptyl ester, tributyl phosphate, phosphoric acid triphen
Ester, phosphorous acid dibutyl ester, diethyl phosphite, diphenyl phosphite, repefral, diethyl phthalate,
One kind or several in dioctyl phthalate, methyl alcohol, ethanol, propyl alcohol, butanol, amylalcohol, hexanol, enanthol, octanol, isodecanol etc.
Kind.The conjugated diene monomer of addition is the one kind in isoprene, pentadiene and butadiene, the alkyl aluminum compound of addition
For the one kind in triisobutyl aluminium, diisobutylaluminium hydride and diethyl aluminium hydride, the chloride of addition is chlorination diisobutyl
One kind in aluminium, diethylaluminum chloride and sesquialter ethylmercury chloride aluminium.
Claims (1)
1. a kind of preparation method of organic neodymium phosphate catalyst system, it is characterised in that：Comprise the following steps：
（1）Prepare the aqueous solution of neodymium trichloride：The aqueous solution of neodymium trichloride, neodymium trichloride is prepared using neodymium oxide and hydrochloric acid
The aqueous solution concentration be 0.5-2.5 mol/L；
（2）Prepare organic phosphoric acid solution：Organic phosphoric acid and acetone are mixed to get organic phosphoric acid solution, its concentration is 0.3-2.0
Mol/L, neodymium trichloride are controlled to 1 with the mol ratio of organic phosphoric acid:3, organic phosphoric acid is acid organo phosphates, is（RO）2POOH、R(RO)POOH、R2POOH, wherein R for carbon number for 2-13 alkyl；
（3）Prepare saponification liquor：Alkaline solution is added in organic phosphoric acid acetone soln to carry out saponification and obtains saponification liquor, institute
The temperature control of saponification is stated at 20-70 DEG C, time control is in 20-50 min, and should carry out under agitation, and alkaline solution is
One kind in sodium hydroxide solution, potassium hydroxide solution or ammonia spirit；
（4）Prepare organic phosphoric acid neodymium：The saponification liquor of gained is added in neodymium trichloride solution under agitation, at 20-70 DEG C
Reaction 20-60 min, obtains SOLID ORGANIC neodymium phosphate by the way of decompression suction filtration after the completion of reaction, then dries at 60 DEG C
Solid obtains organic phosphoric acid neodymium；
（5）Dissolving, tune viscosity：The organic solvent of organic phosphoric acid neodymium solid after drying dissolves, and adds viscosity-controlling agent to help
Molten, the viscosity of lysate is adjusted after dissolving completely with viscosity-controlling agent, organic with dilution for preparing organic neodymium phosphate solution
Solvent is hexane, and the viscosity-controlling agent for promoting catalyst dissolution and adjusting catalyst viscosity is organic acid esters, in particular two（2-
Ethylhexyl）Phosphate, 2- ethylhexyl phosphoric acid -2- ethylhexyl, methyl acid phosphate dimethyl heptyl ester, tributyl phosphate, phosphorus
Triphenyl phosphate ester, phosphorous acid dibutyl ester, diethyl phosphite, diphenyl phosphite, repefral, phthalic acid two
Ethyl ester, dioctyl phthalate, the addition of viscosity-controlling agent are 0.25 3 with the mol ratio of neodymium in organic phosphoric acid neodymium:1；
（6）It is aged, prepares product：The catalyst for reconciling good appropriate viscosity is sequentially added conjugated diene monomer, alkyl calorize
Polymer solution, chloride solution, carry out binary ageing and ternary ageing, you can must directly apply to the rare earth of rubber production respectively
Catalyst system and catalyzing, the conjugated diene monomer of addition are the one kind in isoprene, pentadiene and butadiene, the alkyl aluminum of addition
Compound is the one kind in triisobutyl aluminium, diisobutylaluminium hydride and diethyl aluminium hydride, and the chloride of addition is chlorination two
One kind in aluminium isobutyl, diethylaluminum chloride and sesquialter ethylmercury chloride aluminium.
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| CN106145078B (en) * | 2015-03-27 | 2018-03-13 | 中国石油天然气股份有限公司 | A kind of method for synthesizing neodymium phosphate solution and synthesized neodymium phosphate solution |
| CN106905458A (en) * | 2015-12-22 | 2017-06-30 | 中国石油天然气股份有限公司 | Rare earth catalyst containing mixed ligand and its preparation method and application |
| CN107522807B (en) * | 2016-06-21 | 2019-12-10 | 中国石油天然气股份有限公司 | Preparation method of catalyst for preparing rare earth butadiene rubber |
| CN107522806B (en) * | 2016-06-21 | 2020-03-10 | 中国石油天然气股份有限公司 | Continuous polymerization method for preparing rare earth butadiene rubber |
| CN110294822B (en) * | 2018-03-21 | 2021-12-31 | 中国石油化工股份有限公司 | Butadiene-isoprene copolymer and preparation method thereof |
| CN110294823B (en) * | 2018-03-21 | 2022-01-04 | 中国石油化工股份有限公司 | Butadiene-isoprene copolymer and preparation method thereof |
| CN112442151B (en) * | 2019-09-03 | 2023-07-21 | 中国石油化工股份有限公司 | Catalytic copolymerization for preparing poly (butadiene-isoprene) |
| CN116023533A (en) * | 2021-10-25 | 2023-04-28 | 中国石油化工股份有限公司 | Neodymium phosphonate solution and preparation method and application thereof |
| CN115433294B (en) * | 2022-08-17 | 2023-09-12 | 中国科学院大连化学物理研究所 | Preparation method of solution type phosphate rare earth catalyst and application of solution type phosphate rare earth catalyst in preparation of butadiene-isoprene rubber |
| CN117106115B (en) * | 2023-10-24 | 2024-02-13 | 传化智联股份有限公司 | Butadiene polymerization pre-catalyst and preparation method thereof, catalyst and preparation method of polybutadiene |
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| CN1649919A (en) * | 2002-05-16 | 2005-08-03 | 米其林技术公司 | Catalytic system for the preparation of polybutadienes and preparation process |
| CN101589051A (en) * | 2007-01-23 | 2009-11-25 | 罗地亚管理公司 | Method for preparing a solution of a rare earth organophosphate |
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| CN101589051A (en) * | 2007-01-23 | 2009-11-25 | 罗地亚管理公司 | Method for preparing a solution of a rare earth organophosphate |
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