CN106145078B - Method for synthesizing neodymium phosphate solution and synthesized neodymium phosphate solution - Google Patents
Method for synthesizing neodymium phosphate solution and synthesized neodymium phosphate solution Download PDFInfo
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- CN106145078B CN106145078B CN201510142593.XA CN201510142593A CN106145078B CN 106145078 B CN106145078 B CN 106145078B CN 201510142593 A CN201510142593 A CN 201510142593A CN 106145078 B CN106145078 B CN 106145078B
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- metal halide
- neodymium
- phosphoric acid
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- DZNFWGVDYGAMJB-UHFFFAOYSA-K neodymium(3+);phosphate Chemical compound [Nd+3].[O-]P([O-])([O-])=O DZNFWGVDYGAMJB-UHFFFAOYSA-K 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 67
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 96
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 40
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 35
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- -1 phosphate ester Chemical class 0.000 claims abstract description 31
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 29
- 239000010452 phosphate Substances 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 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 17
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000002808 molecular sieve Substances 0.000 claims abstract description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 48
- 239000003054 catalyst Substances 0.000 claims description 45
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 41
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 40
- 235000021317 phosphate Nutrition 0.000 claims description 35
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 28
- 150000002910 rare earth metals Chemical class 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 12
- 150000005309 metal halides Chemical class 0.000 claims description 12
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- 150000001924 cycloalkanes Chemical class 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 230000026030 halogenation Effects 0.000 claims description 4
- 238000005658 halogenation reaction Methods 0.000 claims description 4
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 2
- 238000004064 recycling Methods 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 16
- 229920003051 synthetic elastomer Polymers 0.000 abstract description 14
- 239000005061 synthetic rubber Substances 0.000 abstract description 14
- 229920001971 elastomer Polymers 0.000 abstract description 11
- 239000005060 rubber Substances 0.000 abstract description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000003292 glue Substances 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract 2
- 239000000047 product Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 description 8
- KWKDMHWAAVTQSZ-UHFFFAOYSA-N neodymium phosphoric acid Chemical compound [Nd].P(O)(O)(O)=O KWKDMHWAAVTQSZ-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 108010010803 Gelatin Proteins 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 229920000159 gelatin Polymers 0.000 description 7
- 239000008273 gelatin Substances 0.000 description 7
- 235000019322 gelatine Nutrition 0.000 description 7
- 235000011852 gelatine desserts Nutrition 0.000 description 7
- 235000011007 phosphoric acid Nutrition 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 5
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 229910000159 nickel phosphate Inorganic materials 0.000 description 5
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 5
- 230000037048 polymerization activity Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000003483 aging Methods 0.000 description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- DBLHYLDWZSNRBI-UHFFFAOYSA-N N=NC=NN.N=NC=NN.P(=O)(O)(O)O Chemical compound N=NC=NN.N=NC=NN.P(=O)(O)(O)O DBLHYLDWZSNRBI-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 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
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A method for synthesizing a neodymium phosphate solution and the synthesized neodymium phosphate solution, the method comprises the following steps: preparing a metal halide salt into a saturated metal halide salt aqueous solution; mixing acidic phosphate with an organic solvent to obtain a phosphate solution, wherein the volume ratio of the acidic phosphate to the organic solvent is 1: 2-1: 20; adding neodymium oxide solid powder into a phosphate solution, stirring to obtain a turbid solution, and heating to 20-50 ℃; adding the saturated metal halide salt aqueous solution into the turbid solution, heating and stirring, adding a molecular sieve, reacting for 20-90 minutes at 20-70 ℃, standing and layering after the reaction is finished, separating to obtain an oil phase which is a neodymium phosphate solution, wherein the molar ratio of the metal halide salt to the acidic phosphate ester is controlled to be 1: 5-1: 50. the neodymium phosphate solution contains a small amount of phosphoric acid non-rare earth metal salt, so that the viscosity of the glue solution can be reduced in the polymerization catalysis process of the synthetic rubber, and the production loss is reduced; the molecular weight distribution of the synthetic rubber is widened, and the processability of the rubber is improved.
Description
Technical field
The present invention relates to a kind of synthetic method of neodymium phosphate solution, more particularly to it is a kind of using saturation metal halide solution as
The method of the synthesis neodymium phosphate solution of catalyst, belongs to compound synthesis technical field.
Background technology
Phosphoric acid neodymium catalyst is differently combined with other components, is aged, and can be used as olefin polymerization catalysis.Neodymium phosphate
Research work for olefin polymerization catalysis is in eighties of last century the seventies it has been reported that phosphoric acid neodymium catalyst used is solid
Phosphoric acid neodymium catalyst.
《Rare earth catalyst synthetic rubber collected works》In " different coordinating group rare earth compound urging in isoprene polymerization
Change activity " neodymium phosphate has been sketched in (Science Press, 1980, Changchun the 4th research department of applied chemistry of the Chinese Academy of Sciences) has urged
The preparation method of agent, its product are solid phosphoric acid neodymium catalyst.The solid catalyst is insoluble in alkane, aromatic solvent, and it is made
Preparation Method is：Make neodymia and hydrochloric acid reaction, prepare the neodymium chloride aqueous solution；Phosphate is mixed with ethanol, adds ammoniacal liquor soap
Change；The neodymium chloride aqueous solution is added into sodium phosphate saponification liquor, product is neodymium phosphate (powdered or floccule) after reaction, sedimentation,
Separate, be filtrated to get solid phosphoric acid neodymium；Solid phosphoric acid neodymium is washed with ethanol, is settled, separates, is filtered, in triplicate or more；Institute
Obtain solid phosphoric acid neodymium to dry, ethanol is volatilized completely.Phosphoric acid neodymium catalyst prepared by this method is solid, and neodymium phosphate is dried
Journey is cumbersome, and production process produces substantial amounts of ethanol aqueous waste solution, can not be used repeatedly, and product is insoluble in alkane solvent, aromatic hydrocarbons,
Alkane solvent is dissolved in after adding alkyl aluminum, but multicomponent catalyst ageing process can be by larger limitation.
A kind of preparation side of neodymium phosphate is each provided in United States Patent (USP) US6838534, US7157533, US7056998
Method, it is essentially identical with above-mentioned method, is to prepare neodymium chloride solution with hydrochloric acid reaction using neodymia, is then respectively adopted
Di-(2-ethylhexyl)phosphoric acid ester and acetone, di-(2-ethylhexyl)phosphoric acid ester and acetone, di-(2-ethylhexyl)phosphoric acid ester and
Acetone reacts, and neodymium phosphate solid catalyst is prepared.
The experimental method of prior art (publication number CN101778853A) is the disclosed skill of French Rhodia invention
Art, but refer in CN101778853A the preparation method of the solution of rare-earth organophosphate in organic solvent, rush used
Enter agent i.e. catalyst and be selected from water, nitric acid, hydrochloric acid, acetic acid, formic acid and propionic acid and these sour rare-earth salts.Patent
Catalyst in CN101778853A used in embodiment 5 is the neodymium chloride aqueous solution, is rare earth metal halide salt.
Specific inventory and reaction temperature and the time of its method are disclosed in patent CN101778853A.And patent
Influence of the water content to reaction system is not mentioned in CN101778853A.Neodymium phosphate solution viscosity made from this method compared with
Height, residual solid content and residual acid comparision contents are high, and the neodymium phosphate solution of gained also needs to filter, washes multiple, distillation etc.
Step can be only used for rubber polymerization and use.
The content of the invention
It is an object of the invention to provide a kind of preparation method of neodymium phosphate solution and obtained neodymium phosphate solution, with solution
Neodymium phosphate solution composition certainly prepared by art methods is single, can not have during polymerization catalyzed as synthetic rubber
Effect reduces the defects of gelatin viscosity.
To achieve the above object, the present invention proposes a kind of method for synthesizing neodymium phosphate solution, comprises the following steps：
Step 1：Saturation metal halide saline solution is made in metal halide salt, with the saturation metal halide saline solution
For catalyst；
Step 2：Acid phosphoric acid ester and organic solvent are mixed to get phosphate ester solution, the acid phosphoric acid ester with it is organic molten
The volume ratio of agent is 1：2-1：20, the organic solvent is linear paraffin or cycloalkane or aromatic hydrocarbons；
Step 3：Neodymia solid powder is added to stirring in phosphate ester solution and obtains turbid solution, and is heated to 20-50
DEG C, the mol ratio of the neodymia and the acid phosphoric acid ester is 1:6；
Step 4：The saturation metal halide saline solution is added in the turbid solution, heating stirring, adds molecule
Sieve, reacted at 20-70 DEG C 20-90 minutes, reaction terminates rear static layering, isolated oil phase, and the oil phase is neodymium phosphate
Solution, the metal halide salt and the mol ratio control of the acid phosphoric acid ester are 1：5-1：50.
Wherein, the metal halide salt is non-rare earth metal halide salt, the non-rare earth metal halide salt be selected from nickel chloride,
Iron chloride, cobalt chloride or titanium chloride, the metallic element have catalytic action to alkene or alkadienes.
Wherein, a small amount of nickel, iron, cobalt, titanium can generate organic phosphate and be present in neodymium phosphate solution, the nickel, iron, cobalt,
The organic phosphate of titanium plays a part of activated centre in the course of the polymerization process, improves the processed and applied performance of product.
Wherein, it is described to be heated to the 20-50 DEG C of preheating temperature for turbid solution before catalyst addition in step 3, it can make anti-
It should accelerate and make reaction more complete.
Wherein, the water that the molecular sieve removes dereaction generation is added in step 4, catalyst system and catalyzing is met that kinetics will
Ask.
Wherein, the acid phosphoric acid ester is acid organo phosphates, it is preferred that the acid organo phosphates are (RO)2POOH, R (RO) POOH or R2POOH, the R are the alkyl or its isomers of 2-13 carbon, more preferably, the acidic organo phosphorus
Acid esters is one in di-(2-ethylhexyl)phosphoric acid ester, 2- ethylhexyl phosphoric acid 2- ethylhexyls and methyl acid phosphate diformazan fat in heptan
Kind is several.
Wherein, the organic solvent is the one or more in hexane, heptane, the oil of carbon six.
Wherein, in the step 1, it is by 0-6 crystallization of band that metal halide salt is made into saturation metal halide saline solution
Saturation nickel chloride aqueous solution is made in the nickel chloride of water, and the saturation nickel chloride aqueous solution is that 20-50 DEG C of saturation nickel chloride is water-soluble
Liquid.
It is preferred that also include step 5：Reaction terminates rear static layering, and lower floor is aqueous metal halogenation saline solution, recovery
Use again.
Moreover, to achieve the above object, the present invention also proposes a kind of neodymium phosphate solution, is synthesized by above-mentioned method, described
The chemical formula of neodymium phosphate is NdD3, D represents acid phosphoric acid ester, and the acid phosphoric acid ester is acid organo phosphates.The neodymium phosphate
Solution contains a small amount of Metal organophosphates, and the chemical formula of the Metal organophosphates is MDn, M represents metal, and D represents acid
Property phosphate, n represents the quantity of organophosphorus ester contained, and the acid phosphoric acid ester is acid organo phosphates.
Invention effect：
For the method for the present invention during neodymium phosphate solution is synthesized, catalyst choice is non-rare earth metal halide salt
Saturated solution, a small amount of non-rare earth metal halide salt of saturation can react with acid phosphoric acid ester, the non-rare earth gold of a small amount of phosphoric acid of generation
Belong to salt, and the non-rare earth metal salt of phosphoric acid equally has polymerization activity, contains in the neodymium phosphate solution of method of the invention synthesis few
The non-rare earth metal salt of phosphoric acid is measured, has it specifically to act on during polymerization catalyzed as synthetic rubber, is in particular in：
During polymerization, gelatin viscosity is reduced, reduces energy loss；The molecular weight distribution of synthetic rubber is set to broaden, it is original possessing
Outside the premium properties of rare-earth rubber, the processing characteristics of rubber is improved.
Especially the present invention selection saturation nickel chloride aqueous solution, a small amount of saturation nickel chloride aqueous solution can and acid phosphoric acid ester
Reaction, a small amount of nickel phosphate of generation equally have polymerization activity, contained in the neodymium phosphate solution of method of the invention synthesis a small amount of
Nickel phosphate, during polymerization catalyzed as synthetic rubber, gelatin viscosity can be reduced, reduces energy loss；Make synthetic rubber
Molecular weight distribution broaden, outside the premium properties for possessing original rare-earth rubber, improve the processing characteristics of rubber.
Water content in reaction system directly affects the progress of this reaction, makes reaction slack-off or terminates, and makes in the present invention
While ensureing catalytic action with saturation nickel chloride aqueous solution, the water content in reaction system is controlled, a small amount of chlorination can be made in addition
Nickel reacts with phosphate, meets the requirement of its reaction power.Using saturation nickel chloride aqueous solution as catalyst, there is its special work
With and meaning.
Using the method for the present invention, dehydrating agent (such as molecular sieve, silica gel) is added during the course of the reaction, except dereaction is given birth to
Into water, its object is to control water content in course of reaction, make catalyst system and catalyzing meet kinetics requirement, reaction generation production
Thing is the neodymium phosphate solution containing a small amount of nickel phosphate, is new bimetallic catalyst, is synthesized available for rubber；In addition, reaction system
Water content is fewer, and the reaction speed of the reaction is faster, reacts the more thorough of progress；Finally, the water content of reaction system is controlled
The viscosity of reaction product neodymium phosphate solution can be made reduce, and can directly be utilized.
Neodymium phosphate solution prepared by the method for the present invention can be as the rare-earth catalysis system for triggering alkene, diene polymerization
In major catalyst, can effectively reduce gelatin viscosity during polymerization catalyzed as synthetic rubber, polymerize with product
Active height, simple production process, production cost are low.Moreover, the aqueous phase obtained in delaminating process can pacify after processing
Full discharge, and Reusability.Non-pollutant discharge in this method course of reaction, environmental pollution will not be caused.
The product of method provided by the present invention is neodymium phosphate solution, can be as the rare earth for triggering alkene, diene polymerization
Major catalyst in catalyst system and catalyzing；The product can dissolve each other with alkane, aromatic hydrocarbons equal solvent arbitrary proportion, be aged in multicomponent catalyst
During more and more free aging may be selected.
Metal halide salt of the present invention is non-rare earth metal halide salt, and the non-rare earth metal halide salt is selected from chlorination
Nickel, iron chloride, cobalt chloride, titanium chloride, the metallic element have catalytic action, a small amount of nickel, iron, cobalt, titanium to alkene or alkadienes
Organic phosphate can be generated to be present in neodymium phosphate solution, the nickel, iron, cobalt, the organic phosphate of titanium play in the course of the polymerization process
The effect in activated centre, improve the processed and applied performance of product.
Brief description of the drawings
Fig. 1 be embodiment 1 used by process units structural representation.
Wherein, reference：
1- first charging apertures
2- nickel chloride solution kettles
3- second charging apertures
4- reactors
5- drain holes
The charging apertures of 6- the 3rd
The charging apertures of 7- the 4th
Embodiment
The present invention is by the way that using neodymia as raw material, using non-rare earth metal halide salt as catalyst, it is molten that synthesis obtains neodymium phosphate
Liquid.
Present invention firstly provides a kind of method for synthesizing neodymium phosphate solution, it comprises the following steps：
Step 1：Saturation metal halide saline solution is made in metal halide salt, with the saturation metal halide saline solution
For catalyst；
Step 2：Acid phosphoric acid ester and organic solvent are mixed to get phosphate ester solution, the acid phosphoric acid ester with it is organic molten
The volume ratio of agent is 1：2-1：20, the organic solvent is linear paraffin or cycloalkane or aromatic hydrocarbons；
Step 3：Neodymia solid powder is added to stirring in phosphate ester solution and obtains turbid solution, and is heated to 20-50
DEG C, the mol ratio of the neodymia and the acid phosphoric acid ester is 1:6；
Step 4：The saturation metal halide saline solution is added in the turbid solution, heating stirring, adds molecule
Sieve, reacted at 20-70 DEG C 20-90 minutes, reaction terminates rear static layering, isolated oil phase, and the oil phase is neodymium phosphate
Solution, the metal halide salt and the mol ratio control of the acid phosphoric acid ester are 1：5-1：50.
It is preferred that also include step 5：Reaction terminates rear static layering, and lower floor is aqueous metal halogenation saline solution, recovery
Use again.
Wherein, the metal halide salt is non-rare earth metal halide salt, the non-rare earth metal halide salt be selected from nickel chloride,
Iron chloride, cobalt chloride or titanium chloride, the metallic element have catalytic action to alkene or alkadienes.
Wherein, a small amount of nickel, iron, cobalt, titanium can generate organic phosphate and be present in neodymium phosphate solution, the nickel, iron, cobalt,
The organic phosphate of titanium plays a part of activated centre in the course of the polymerization process, improves the processed and applied performance of product.
Wherein, it is described to be heated to the 20-50 DEG C of preheating temperature for turbid solution before catalyst addition in step 3, it can make anti-
It should accelerate and make reaction more complete.
Wherein, the water that the molecular sieve removes dereaction generation is added in step 4, catalyst system and catalyzing is met that kinetics will
Ask.
Wherein, in the step 1, it is by 0-6 crystallization of band that metal halide salt is made into saturation metal halide saline solution
Saturation nickel chloride aqueous solution is made in the nickel chloride of water, and the saturation nickel chloride aqueous solution is that 20-50 DEG C of saturation nickel chloride is water-soluble
Liquid.
In the above-mentioned methods, used acid phosphoric acid ester can be acid organo phosphates；Preferably, the acidity is organic
Phosphate is (RO)2POOH, R (RO) POOH or R2POOH etc., wherein, R is the alkyl or its isomers of 2-13 carbon.More preferably
Ground, acid organo phosphates are di-(2-ethylhexyl)phosphoric acid ester, 2- ethylhexyl phosphoric acid 2- ethylhexyls and methyl acid phosphate
One or more in diformazan fat in heptan etc..
In the above-mentioned methods, used organic solvent can be alkane or cycloalkane or aromatic hydrocarbons etc., preferably straight chain alkane
Hydrocarbon or cycloalkane etc.；It is highly preferred that above-mentioned organic solvent is the one or more in hexane, heptane, the oil of carbon six etc..
The neodymium phosphate solution obtained by the above method, it can be dissolved each other with alkane, aromatic hydrocarbons equal solvent with arbitrary proportion, more
More, more free agings may be selected in component catalyst ageing process.Obtained by during isolated oil phase
Aqueous phase be nickel chloride the aqueous solution, may be reused, avoid environmental pollution.
Present invention also offers a kind of neodymium phosphate solution, and it is synthesized by above-mentioned method, the chemical formula of the neodymium phosphate
For NdD3, wherein D represents acid phosphoric acid ester, such as acid organo phosphates, and the neodymium phosphate solution contains a small amount of metal organophosphor
Hydrochlorate, the chemical formula of the Metal organophosphates is MDn, M represents metal, and D represents acid phosphoric acid ester, and n represents having of containing
The quantity of machine phosphate, the acid phosphoric acid ester are acid organo phosphates.
In order to which technical characteristic, purpose and the beneficial effect of the present invention is more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
Embodiment 1
A kind of method for synthesizing neodymium phosphate solution is present embodiments provided, it is carried out using the process units shown in Fig. 1
, this method comprises the following steps：
1st, six water nickel chlorides are configured to saturation nickel chloride aqueous solution in nickel chloride solution kettle 2；
2nd, six oily 840kg of carbon is added into reactor 4 by first charging aperture 1, then adds 2- ethylhexyl phosphoric acids 2-
Ethylhexyl 150kg, molecular sieve 5kg, heating stirring 5min；
3rd, neodymia solid powder 25kg is added into reactor 4 by the 3rd charging aperture 6, stirs 5min；
4th, the saturation nickel chloride aqueous solution in nickel chloride solution kettle 2 is added in reactor 4 by second charging aperture 3
Row reaction, the addition of saturation nickel chloride aqueous solution is 5L, and reaction temperature control is 35-50 DEG C, and reaction time control is
90min；
5th, after the completion of reacting, stop the stirring in reactor 4, stand 30min, treat material layering in kettle, pass through drain hole 5
Lower floor's aqueous phase is exported, is added to through the 4th charging aperture 7 in nickel chloride solution kettle 2, stay in reactor 4 for oil phase, the oil
It is mutually neodymium phosphate solution, can be exported by drain hole 5, the neodymium phosphate solution under nitrogen protection can be long-term in products pot
Preserve.
Conclusion：Saturation nickel chloride solution plays a part of catalyst in the reaction of synthesis neodymium phosphate solution.
Embodiment 2
The present embodiment verifies its catalytic action in embodiment 1 synthesizes neodymium phosphate solution methods of saturation nickel chloride solution, should
Checking test comprises the following steps：
1st, six oily 840kg of carbon is added into reactor 4 by first charging aperture 1, then adds 2- ethylhexyl phosphoric acids 2-
Ethylhexyl 150kg, add molecular sieve 5kg, heating stirring 5min；
2nd, neodymia solid powder 25kg is added into reactor 4 by the 3rd charging aperture 6, stirs 5min；It will mix molten
Liquid temperature control is 50-55 DEG C, stirs 60min, and any reaction does not occur for neodymia；
3rd, six water nickel chlorides are configured to saturation nickel chloride aqueous solution in nickel chloride solution kettle 2；
4th, the saturation nickel chloride aqueous solution in nickel chloride solution kettle 2 is added in reactor 4 by second charging aperture 3
Row reaction, the addition of saturation nickel chloride aqueous solution is 5L, and reaction temperature control is 50-55 DEG C, and reaction time control is
60min, neodymia start to react, and reaction solution is light blue purple；
5th, after the completion of reacting, stop the stirring in reactor 4, stand 30min, treat material layering in kettle, pass through drain hole 5
Lower floor's aqueous phase is exported, is added to through the 4th charging aperture 7 in nickel chloride solution kettle 2, stay in reactor 4 for oil phase, the oil
It is mutually neodymium phosphate solution, can be exported by drain hole 5.
Conclusion：Saturation nickel chloride solution plays a part of catalyst in the reaction of synthesis neodymium phosphate solution.
Embodiment 3
A kind of method for synthesizing neodymium phosphate solution is present embodiments provided, it is carried out using the process units shown in Fig. 1
, this method comprises the following steps：
1st, six water titanium chlorides are configured to saturation titanium chloride aqueous solution in titanium chloride solution kettle 2；
2nd, six oily 840kg of carbon is added into reactor 4 by first charging aperture 1, then adds 2- ethylhexyl phosphoric acids 2-
Ethylhexyl 150kg, molecular sieve 5kg, heating stirring 5min；
3rd, neodymia solid powder 25kg is added into reactor 4 by the 3rd charging aperture 6, stirs 5min, will mix molten
Liquid temperature control is 20-50 DEG C, stirs 60min, and any reaction does not occur for neodymia；
4th, the saturation titanium chloride aqueous solution in titanium chloride solution kettle 2 is added in reactor 4 by second charging aperture 3
Row reaction, the addition of saturation titanium chloride aqueous solution is 5L, and reaction temperature control is 20-70 DEG C, and reaction time control is
20min；
5th, after the completion of reacting, stop the stirring in reactor 4, stand 30min, treat material layering in kettle, pass through drain hole 5
Lower floor's aqueous phase is exported, is added to through the 4th charging aperture 7 in titanium chloride solution kettle 2, stay in reactor 4 for oil phase, the oil
It is mutually neodymium phosphate solution, can be exported by drain hole 5, the neodymium phosphate solution under nitrogen protection can be long-term in products pot
Preserve.
Conclusion：Saturation titanium chloride solution plays a part of catalyst in the reaction of synthesis neodymium phosphate solution.
In addition, iron chloride, cobalt chloride can be applied equally in above-described embodiment 1-3.
Embodiment 4
Activity rating is carried out to neodymium phosphate solution prepared by embodiment 1, wherein, catalyst is that the rare earth in embodiment 1 is urged
Agent.
Activity rating method：Evaluated using batch solution polymerization technique synthesizing rare-earth butadiene rubber, specific method is：
The oil of 2100mL carbon six is added into polymeric kettle, then 5.74mol butadiene is added into polymeric kettle, is stirred, and make polymeric kettle
Interior temperature of charge is maintained at 35-50 DEG C, pressure≤0.4MPa in kettle, and the oil of carbon six, the requirement of butadiene adition process use N2Protection,
Avoid contact with air, oxygen gas and water etc.；2.87 × 10 are added into catalyst addition tube-4mol NdD3/5.74×10- 3molDIBAL-H/1.0×10-3molEASC；The catalyst in catalyst addition tube is pressed into reactor using N2, will be anti-
Kettle pressure N2 ftercompctions are answered to 0.45-0.50MPa；It is 60-80 DEG C to control jacket of polymerization coolant-temperature gage, and reaction is discharged after 4 hours
Material；Material boils 40 minutes in boiling water in kettle, takes out material and is pressed dry in mill (mill temperature control is 120 DEG C)
Afterwards, rare earth polybutadiene rubber is obtained, is weighed.Obtain dry glue 290g.
Catalyst：The catalyst system and catalyzing includes NdD3, tri- kinds of components of DIBAL-H and EASC, wherein NdD3There is provided for embodiment 1
Catalyst.
Polymerization technique is polymerize using batch solution, and reactor uses 5L polymerization reaction kettles, and agitating mode is stirred using anchor formula,
Agitation revolution is 100r/min, and fourth oil concentration is 12g/100mL, polymerization reaction time 3.5-4.5h, and polymeric reaction temperature is
60-120 DEG C, polymerization pressure 0.3-0.8MPa.
Activity evaluation shows that polymerization reaction monomer conversion ratio reaches 94%, and product Mooney is 44.2.
Evaluate and test conclusion：Using NdD3For major catalyst, with DIBAL-H and EASC composition ternary RE catalyst system and catalyzings, can draw
Send out polymerizing butadiene, synthesizing rare-earth butadiene rubber, the results showed that, the neodymium phosphate solution prepared using the present invention is major catalyst,
Activity is good, and monomer conversion reaches more than 90%.
The effect of the present invention：
For the method for the present invention during neodymium phosphate solution is synthesized, catalyst choice is non-rare earth metal halide salt
Saturated solution, a small amount of non-rare earth metal halide salt of saturation can react with acid phosphoric acid ester, the non-rare earth gold of a small amount of phosphoric acid of generation
Belong to salt, and the non-rare earth metal salt of phosphoric acid equally has polymerization activity, contains in the neodymium phosphate solution of method of the invention synthesis few
The non-rare earth metal salt of phosphoric acid is measured, has it specifically to act on during polymerization catalyzed as synthetic rubber, is in particular in：Again
During polymerization, gelatin viscosity is reduced, reduces production loss；The molecular weight distribution of synthetic rubber is set to broaden, it is original possessing
Outside the premium properties of rare-earth rubber, the processing characteristics of rubber is improved.
Especially the present invention selection saturation nickel chloride aqueous solution, a small amount of saturation nickel chloride aqueous solution can and acid phosphoric acid ester
Reaction, a small amount of nickel phosphate of generation equally have polymerization activity, contained in the neodymium phosphate solution of method of the invention synthesis a small amount of
Nickel phosphate, during polymerization catalyzed as synthetic rubber, gelatin viscosity can be reduced, reduce production loss；Make synthetic rubber
Molecular weight distribution broaden, outside the premium properties for possessing original rare-earth rubber, improve the processing characteristics of rubber.
Water content in reaction system directly affects the progress of this reaction, makes reaction slack-off or terminates, and makes in the present invention
While ensureing catalytic action with saturation nickel chloride aqueous solution, the water content in reaction system is controlled, a small amount of chlorination can be made in addition
Nickel reacts with phosphate, meets the requirement of its reaction power.Using saturation nickel chloride aqueous solution as catalyst, there is its special work
With and meaning.
Using the method for the present invention, dehydrating agent (such as molecular sieve, silica gel) is added during the course of the reaction, except dereaction is given birth to
Into water, its object is to control water content in course of reaction, make catalyst system and catalyzing meet kinetics requirement.
Neodymium phosphate solution prepared by the method for the present invention can effectively drop during polymerization catalyzed as synthetic rubber
Low gelatin viscosity, have the characteristics that product polymerization activity height, simple production process, production cost are low, environment friendly and pollution-free.
Compared with prior art, the method for synthesis neodymium phosphate solution provided by the present invention has advantages below：Existing skill
Phosphoric acid neodymium catalyst synthesized by preparation method in art is solid, and reaction is that generation neodymium phosphate sinks under ethanol or acetone effect
Form sediment, the precipitation is insoluble in alkane, aromatic solvent；And the product of method provided by the present invention is neodymium phosphate solution, and this hair
Product obtained by bright method can dissolve each other with alkane, aromatic hydrocarbons equal solvent arbitrary proportion, in multicomponent catalyst ageing process
More and more free aging may be selected；
In addition, method provided by the present invention will not produce the acetone or alcohol aqueous solution in preparation process, production it is not related to
Product are repeatedly washed, dried, and production technology is substantially simple, and production cost is low, moreover, the nickel chloride obtained in delaminating process is water-soluble
It liquid, may be reused, environmental pollution will not be caused.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (14)
- A kind of 1. method for synthesizing neodymium phosphate solution, it is characterised in that comprise the following steps：Step 1：Saturation metal halide saline solution is made in metal halide salt, using the saturation metal halide saline solution to urge Agent；Step 2：Acid phosphoric acid ester and organic solvent are mixed to get phosphate ester solution, the acid phosphoric acid ester and organic solvent Volume ratio is 1：2-1：20, the organic solvent is linear paraffin or cycloalkane or aromatic hydrocarbons；Step 3：Neodymia solid powder is added to stirring in phosphate ester solution and obtains turbid solution, and is heated to 20-50 DEG C, institute The mol ratio for stating neodymia and the acid phosphoric acid ester is 1:6；Step 4：The saturation metal halide saline solution is added in the turbid solution, heating stirring, adds molecular sieve, To be reacted at 20-70 DEG C 20-90 minutes, reaction terminates rear static layering, isolated oil phase, and the oil phase is neodymium phosphate solution, The metal halide salt and the mol ratio control of the acid phosphoric acid ester are 1：5-1：50.
- 2. according to the method for claim 1, it is characterised in that the metal halide salt is non-rare earth metal halide salt.
- 3. according to the method for claim 2, it is characterised in that the non-rare earth metal halide salt is selected from nickel chloride, chlorination Iron, cobalt chloride or titanium chloride.
- 4. according to the method for claim 3, it is characterised in that a small amount of nickel, iron, cobalt, titanium generation organic phosphate are present In neodymium phosphate solution, the nickel, iron, cobalt, the organic phosphate of titanium play a part of activated centre in the course of the polymerization process, improve production The processed and applied performance of thing.
- 5. according to the method for claim 1, it is characterised in that described to be heated to 20-50 DEG C and exist for turbid solution in step 3 Preheating temperature before catalyst addition.
- 6. according to the method for claim 1, it is characterised in that the molecular sieve is added in step 4 except dereaction generation Water.
- 7. according to the method for claim 1, it is characterised in that the acid phosphoric acid ester is acid organo phosphates.
- 8. according to the method for claim 7, it is characterised in that the acid organo phosphates are (RO)2POOH、R(RO) POOH or R2POOH, the R are the alkyl or its isomers of 2-13 carbon.
- 9. according to the method for claim 8, it is characterised in that the acid organo phosphates are two (2- ethylhexyls) phosphorus One or more in acid esters, 2- ethylhexyl phosphoric acid 2- ethylhexyls and methyl acid phosphate diformazan heptyl ester.
- 10. according to the method for claim 1, it is characterised in that the organic solvent is in hexane, heptane, the oil of carbon six It is one or more of.
- 11. according to the method for claim 1, it is characterised in that in the step 1, saturation gold is made in metal halide salt It is that the nickel chloride with the 0-6 crystallization water is made into saturation nickel chloride aqueous solution to belong to halogenation saline solution.
- 12. according to the method for claim 11, it is characterised in that the saturation nickel chloride aqueous solution is 20-50 DEG C full And nickel chloride aqueous solution.
- 13. according to the method for claim 1, it is characterised in that also including step 5：Reaction terminates rear static layering, lower floor For aqueous metal halogenation saline solution, recycling.
- 14. a kind of neodymium phosphate solution, it is characterised in that synthesized by the method any one of claim 1-13, the phosphorus The chemical formula of sour neodymium is NdD3, D represents acid phosphoric acid ester, and the acid phosphoric acid ester is acid organo phosphates, and the neodymium phosphate is molten Liquid contains a small amount of Metal organophosphates, and the chemical formula of the Metal organophosphates is MDn, M represents metal, and D represents acidity Phosphate, n represent the quantity of the organophosphorus ester contained, and the acid phosphoric acid ester is acid organo phosphates.
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| WO2008090141A1 (en) * | 2007-01-23 | 2008-07-31 | Rhodia Operations | Method for preparing a solution of a rare earth organophosphate |
| WO2010133608A1 (en) * | 2009-05-19 | 2010-11-25 | Societe De Technologie Michelin | Method for synthesising a rare earth organophosphate and use thereof to prepare a "preformed" catalytic system |
| CN103224517A (en) * | 2013-04-17 | 2013-07-31 | 中国石油天然气股份有限公司 | Method for synthesizing solution type neodymium phosphate complex |
| CN103694386A (en) * | 2013-12-19 | 2014-04-02 | 山东玉皇化工有限公司 | Preparation method of organic neodymium phosphate catalyst system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2008090141A1 (en) * | 2007-01-23 | 2008-07-31 | Rhodia Operations | Method for preparing a solution of a rare earth organophosphate |
| WO2010133608A1 (en) * | 2009-05-19 | 2010-11-25 | Societe De Technologie Michelin | Method for synthesising a rare earth organophosphate and use thereof to prepare a "preformed" catalytic system |
| CN103224517A (en) * | 2013-04-17 | 2013-07-31 | 中国石油天然气股份有限公司 | Method for synthesizing solution type neodymium phosphate complex |
| CN103694386A (en) * | 2013-12-19 | 2014-04-02 | 山东玉皇化工有限公司 | Preparation method of organic neodymium phosphate catalyst system |
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