CN116023533B - Neodymium phosphonate solution and preparation method and application thereof - Google Patents
Neodymium phosphonate solution and preparation method and application thereof Download PDFInfo
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- VMLVLKLHQLWCOB-UHFFFAOYSA-H [Nd+3].[Nd+3].[O-]P([O-])=O.[O-]P([O-])=O.[O-]P([O-])=O Chemical compound [Nd+3].[Nd+3].[O-]P([O-])=O.[O-]P([O-])=O.[O-]P([O-])=O VMLVLKLHQLWCOB-UHFFFAOYSA-H 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims description 155
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 50
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 31
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 25
- -1 2-ethylhexyloxy Chemical group 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000008346 aqueous phase Substances 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 150000007514 bases Chemical class 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 8
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 8
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000002685 polymerization catalyst Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 14
- 238000009776 industrial production Methods 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000012071 phase Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical group [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 14
- 229910052779 Neodymium Inorganic materials 0.000 description 9
- ZLMKQJQJURXYLC-UHFFFAOYSA-N bis(2-ethylhexoxy)-oxophosphanium Chemical compound CCCCC(CC)CO[P+](=O)OCC(CC)CCCC ZLMKQJQJURXYLC-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003926 complexometric titration Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- PQAOATBZHSOOHQ-UHFFFAOYSA-N 1-hexoxyphosphonoyloxyhexane Chemical compound CCCCCCOP(=O)OCCCCCC PQAOATBZHSOOHQ-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- HZIUHEQKVCPTAJ-UHFFFAOYSA-N 3-(2-ethylhexoxyphosphonoyloxymethyl)heptane Chemical compound CCCCC(CC)COP(=O)OCC(CC)CCCC HZIUHEQKVCPTAJ-UHFFFAOYSA-N 0.000 description 1
- RPAHVZMBEOTVNE-UHFFFAOYSA-N CCCCC(CC)CO[PH2]=O Chemical compound CCCCC(CC)CO[PH2]=O RPAHVZMBEOTVNE-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 150000001206 Neodymium Chemical class 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 241000863480 Vinca Species 0.000 description 1
- CDOMXXVCZQOOMT-UHFFFAOYSA-N [phenoxy(phenyl)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(C=1C=CC=CC=1)(=O)OC1=CC=CC=C1 CDOMXXVCZQOOMT-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 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 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000032798 delamination Effects 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
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- PLSFNSJUKGEOSL-UHFFFAOYSA-N dioctoxy(oxo)phosphanium Chemical compound CCCCCCCCO[P+](=O)OCCCCCCCC PLSFNSJUKGEOSL-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 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
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000007966 viscous suspension Substances 0.000 description 1
Abstract
The invention relates to the field of preparation of neodymium phosphonate, and discloses a neodymium phosphonate solution, a preparation method and application thereof. The neodymium phosphonate solution is characterized in that the solution viscosity of the neodymium phosphonate solution is lower than 200 mPa.s when measured at the concentration of 0.1mol/L at 25 ℃, and the chloride ion content in the neodymium phosphonate solution is not higher than 10ug/g when the concentration of the neodymium phosphonate is 0.1 mol/L. The neodymium phosphonate solution has the advantages of low viscosity and low impurity content, can be conveniently applied to industrial production, and is particularly favorable for conveying and accurate metering.
Description
Technical Field
The invention relates to the field of preparation of neodymium phosphonate, in particular to a neodymium phosphonate solution and a preparation method and application thereof.
Background
Phosphonates have been used as extractants for extracting metallic elements from rare earths, after which it has been found by accident that neodymium phosphonates have activity for catalyzing the polymerization of conjugated dienes. Both the national science vinca institute and michelin corporation have conducted studies based on phosphonate neodymium catalytic conjugated dienes to give products with high cis-1, 4-structure content (> 97%), and found that phosphonate neodymium is catalytically active at very low alkylating reagent levels ([ Al ]/[ Nd ] = 5), while other neodymium salt systems are catalytically inactive at such low aluminium levels. This feature makes the catalyst relatively low cost, creating advantages for industrial applications.
Currently, there are two methods of preparation of neodymium phosphonate. One is a solid process, for example, CN1479753a describes that the solid neodymium phosphonate obtained by this process cannot be completely dissolved in solvents commonly used in industry (alkane, toluene, etc.), the obtained catalyst is in a viscous suspension, and this heterogeneous catalyst may lead to a low utilization efficiency of neodymium atoms, and on the other hand may cause difficult transportation and inaccurate metering, which makes industrial production difficult. The second is a solution method, but the solution viscosity is large due to the characteristic of neodymium phosphonate, and is usually 10000mpa·s or more. This makes it difficult to delaminate the oil and water phases during the synthesis process, and water in the oil phase is difficult to remove, thereby causing the neodymium phosphonate to contain a large amount of impurities, further affecting the subsequent use. In addition, the high viscosity also makes the neodymium phosphonate have particularly poor fluidity and jelly shape, so that the neodymium phosphonate is difficult to accurately measure in application and cannot be used in industrial production.
In order to solve the problem of high viscosity, CN103694378A adds a viscosity regulator, such as one or more of di (2-ethylhexyl) phosphonate, 2-ethylhexyl phosphonate-2-ethylhexyl ester, methyl phosphonate dimethyl heptyl, tributyl phosphonate, triphenyl phosphonate, dioctyl phosphonate, diethyl phosphonate, diphenyl phosphonate, dimethyl phthalate, diethyl phthalate and dioctyl phthalate, into the phosphonate neodymium solution after the synthesis reaction is finished, wherein the molar ratio of the addition of the viscosity regulator to neodymium in the organic phosphonate neodymium is 0.25-3:1. The addition of the viscosity modifier can significantly reduce the viscosity of the final product, but cannot solve the problem of high impurity content caused by difficult delamination in the synthesis process.
CN103224517a adds butadiene and/or isoprene and alcohols such as ethanol, propanol, butanol, hexanol, etc. to the oil phase, and although the solution viscosity is improved, the introduced alcohols are also an impurity for the subsequent use in rare earth catalysts.
Disclosure of Invention
The invention aims to provide a neodymium phosphonate solution and a preparation method and application thereof, the neodymium phosphonate solution has the advantages of low viscosity and low impurity content.
In a first aspect of the invention, there is provided a neodymium phosphonate solution, wherein the neodymium phosphonate solution has a solution viscosity of less than 200 mPa-s as measured at a concentration of 0.1mol/L at 25 ℃ and the chloride ion content of the neodymium phosphonate solution is not higher than 10ug/g at a neodymium phosphonate concentration of 0.1 mol/L.
Preferably, the neodymium phosphonate solution has a solution viscosity of less than 100 mPa-s measured at a concentration of 0.1mol/L at 25 ℃.
Preferably, the chloride ion content of the neodymium phosphonate solution is not higher than 7ug/g when the concentration of neodymium phosphonate is 0.1 mol/L.
Preferably, the neodymium ion concentration of the phosphonate neodymium solution is 0.04-0.5mol/L, preferably 0.1-0.2mol/L.
Preferably, the solvent of the neodymium phosphonate solution is n-hexane.
According to a second aspect of the present invention, there is provided a method for preparing the above neodymium phosphonate solution, wherein the method comprises the step of contacting a neodymium chloride aqueous solution, an organic phosphonate, an organic solvent and an alkaline compound, wherein the molar ratio of the organic phosphonate to the neodymium chloride in the neodymium chloride aqueous solution is 4-6:1, and the alkaline compound is used in an amount such that the pH value of the aqueous phase is 5 or less.
Preferably, the contacting comprises contacting the aqueous neodymium chloride solution with the organic phosphonate and the organic solvent first and then contacting the first contact product with the basic compound second.
Preferably, the content of neodymium chloride in the neodymium chloride aqueous solution is 0.1-0.5 mol/L.
Preferably, the molar ratio of the organic phosphonate to the neodymium chloride in the neodymium chloride aqueous solution is 4-5:1.
Preferably, the organophosphonate is of the structure shown in formula (1), wherein R d1、Rd2 and R d3 are each independently hydrogen, hydroxy, C 1-C20 alkyl or C 1-C20 alkoxy, and at least one of R d1、Rd2 and R d3 is C 1-C20 alkyl or C 1-C20 alkoxy,
Preferably, in formula (1), R d1 is hydroxy and R d2 and R d3 are both 2-ethylhexyloxy.
Preferably, in formula (1), R d1 is hydroxy and R d2 and R d3 are both 2-ethylhexyl.
Preferably, in formula (1), R d1 is hydroxy, R d2 is 2-ethylhexyl and R d3 is 2-ethylhexyloxy.
Preferably, the organic solvent is one or more of C 5-C10 alkane, C 5-C10 cycloalkane and C 6-C12 arene, more preferably, the organic solvent is one or more of hexane, cyclohexane, heptane, pentane, isopentane, octane, methylcyclohexane, benzene, toluene, xylene and cumene.
Preferably, the organic solvent is used in an amount such that the volume of the organic phase and the volume of the aqueous phase are 0.3-2:1.
Preferably, the alkaline compound is used in an amount such that the pH of the aqueous phase is 4-5.
Preferably, the alkaline compound is used in the form of an aqueous solution, the content of the alkaline compound in the aqueous solution of the alkaline compound is 0.1-5.0 mol/L, more preferably, the aqueous solution of the alkaline compound is dropwise added into the first contact product to carry out the second contact, and even more preferably, the dropwise adding speed is 2.0-20.0 mL/min.
Preferably, the basic compound is one or more of hydroxide and ammonia.
Preferably, the second contact temperature is 30-80 ℃.
According to a third aspect of the invention, there is provided a neodymium phosphonate solution prepared by the preparation method of the invention.
Preferably, the neodymium phosphonate solution has a solution viscosity of less than 200 mPa-s, measured at a concentration of 0.1mol/L at 25 ℃, and the chloride ion content of the neodymium phosphonate solution is not higher than 10ug/g at a neodymium phosphonate concentration of 0.1 mol/L.
Preferably, the neodymium phosphonate solution has a solution viscosity of less than 100 mPa-s measured at a concentration of 0.1mol/L at 25 ℃.
Preferably, the chloride ion content of the neodymium phosphonate solution is not higher than 7ug/g when the concentration of neodymium phosphonate is 0.1 mol/L.
Preferably, the concentration of the neodymium phosphonate solution is 0.04-0.5mol/L, preferably 0.1-0.2mol/L.
Preferably, the solvent of the neodymium phosphonate solution is n-hexane.
According to a fourth aspect of the present invention, there is provided the use of a neodymium phosphonate solution of the present invention or a neodymium phosphonate solution prepared by a method of preparing a neodymium phosphonate solution of the present invention in the preparation of an olefin polymerization catalyst.
The neodymium phosphonate solution has the advantages of low viscosity and low impurity content, can be conveniently applied to industrial production, and is particularly favorable for conveying and accurate metering.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect of the invention, there is provided a neodymium phosphonate solution having a solution viscosity of less than 200 mPa-s as measured at a concentration of 0.1mol/L at 25 ℃ and a chloride ion content of not more than 10ug/g at a neodymium phosphonate concentration of 0.1 mol/L.
According to the present invention, it is preferable that the solution viscosity of the neodymium phosphonate solution is lower than 100 mPa.s when measured at 25 ℃ at a concentration of 0.1mol/L, more preferable that the solution viscosity of the neodymium phosphonate solution is lower than 90 mPa.s when measured at 25 ℃ at a concentration of 0.1mol/L, still more preferable that the solution viscosity of the neodymium phosphonate solution is 40-90 mPa.s when measured at 25 ℃ at a concentration of 0.1 mol/L.
Specific values of the solution viscosity of the neodymium phosphonate solution measured at 25℃and a concentration of 0.1mol/L include ：5mPa·s、10mPa·s、20mPa·s、30mPa·s、40mPa·s、42mPa·s、50mPa·s、60mPa·s、65mPa·s、70mPa·s、80mPa·s、87mPa·s、90mPa·s、100mPa·s、112mPa·s、130mPa·s、150mPa·s、173mPa·s and 190 mPas, for example.
According to the present invention, it is preferable that the chloride ion content in the neodymium phosphonate solution is not higher than 10ug/g at a neodymium phosphonate concentration of 0.1mol/L, more preferable that the chloride ion content is not higher than 9ug/g at a neodymium phosphonate concentration of 0.1mol/L, still more preferable that the chloride ion content is not higher than 8ug/g at a neodymium phosphonate concentration of 0.1mol/L, still more preferable that the chloride ion content is not higher than 7ug/g at a neodymium phosphonate concentration of 0.1mol/L, still more preferable that the chloride ion content is 5 to 7ug/g at a neodymium phosphonate concentration of 0.1 mol/L.
Specific values of the chloride ion content include, for example, 1ug/g, 2ug/g, 3ug/g, 4ug/g, 5ug/g, 6ug/g, 7ug/g, 8ug/g, 9ug/g, or 10ug/g.
Preferably, the neodymium ion concentration of the phosphonate neodymium solution is 0.04-0.5mol/L, preferably 0.1-0.4mol/L, more preferably 0.1-0.3mol/L, more preferably 0.1-0.2mol/L, and even more preferably 0.1-0.16mol/L.
In the present invention, as described later, the solution viscosity was measured at 25℃by a rotary viscometer, the chloride ion content was measured by the molar method of GB/T15453-2008, and the concentration of the neodymium phosphonate solution was measured by a complexometric titration method. These methods are described in the publications and will not be described in detail.
According to the invention, the solvent in the neodymium phosphonate solution is preferably a preparation solvent, for example, one or more of C 5-C10 alkane, C 5-C10 cycloalkane and C 6-C12 arene, preferably one or more of hexane, cyclohexane, heptane, pentane, isopentane, octane, methylcyclohexane, benzene, toluene, xylene and cumene, and particularly preferably n-hexane.
According to a second aspect of the present invention, there is provided a method for preparing the above neodymium phosphonate solution, wherein the method comprises the step of contacting a neodymium chloride aqueous solution, an organic phosphonate, an organic solvent and an alkaline compound, wherein the molar ratio of the organic phosphonate to the neodymium chloride in the neodymium chloride aqueous solution is 4-6:1, and the alkaline compound is used in an amount such that the pH value of the aqueous phase is 5 or less.
According to the invention, the aqueous solution of neodymium chloride can be obtained by reacting neodymium oxide with hydrochloric acid, or can be obtained by adopting a mode of dissolving anhydrous neodymium chloride or neodymium chloride containing crystal water in water. The concentration of neodymium chloride is not particularly limited as long as the neodymium chloride is ensured to be completely dissolved. For example, the concentration of the aqueous solution of neodymium chloride may be 0.1 to 0.5mol/L. In actual operation, since neodymium oxide, anhydrous neodymium chloride or neodymium chloride containing crystallization water of some manufacturers contains a very small amount of substances insoluble in water, in order to ensure the quality of subsequent products, when the conditions are met, filter paper or stainless steel mesh is preferably adopted to filter the neodymium chloride aqueous solution for reuse.
According to the invention, preferably, the molar ratio of the organic phosphonate to neodymium chloride in the neodymium chloride aqueous solution is 4-5:1. By making the molar ratio of the organophosphonate to neodymium chloride in the neodymium chloride aqueous solution within the above-described range, the activity for the catalyst can be further improved.
According to the present invention, preferably, the organic phosphonate is of the structure shown in formula (1), wherein R d1、Rd2 and R d3 are each independently hydrogen, hydroxy, C 1-C20 alkyl or C 1-C20 alkoxy, and at least one of R d1、Rd2 and R d3 is C 1-C20 alkyl or C 1-C20 alkoxy, preferably R d1、Rd2 and R d3 are each independently hydroxy, C 4-C12 alkyl or C 4-C12 alkoxy, and at least one of R d1、Rd2 and R d3 is C 4-C12 alkyl or C 4-C12 alkoxy, more preferably R d1 is hydroxy, at least one of R d2 and R d3 is alkyl or alkoxy, and R d2 and R d3 are each independently selected from n-butyl, Isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-methylpentyl, 2-ethylpentyl, n-hexyl, 2-methylhexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 2-methylpentoxy, 2-ethylpentoxy, n-hexyloxy, 2-methylhexyloxy, 2-ethylhexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy or n-dodecyloxy.
Specific examples of the organic phosphonate may be selected from, for example, one or more of the compounds shown in the following formulas:
in the formula (1), R d1 is hydroxyl, R d2 and R d3 are both 2-ethylhexyl oxy (namely di (2-ethylhexyl) phosphonate);
In the formula (1), R d1 is hydroxyl, R d2 and R d3 are both 2-ethylhexyl (namely di (2-ethylhexyl) phosphinate);
In formula (1), R d1 is hydroxy, R d2 is 2-ethylhexyl, and R d3 is 2-ethylhexyloxy (i.e., mono-2-ethylhexyl (2-ethylhexyl) phosphate).
The organic phosphonate compound according to the present invention may be obtained in a conventional manner in the art, for example, may be commercially available, or may be prepared by a conventional method in the art, and the present invention is not particularly limited thereto.
According to the invention, the organic solvent is a compound capable of dissolving neodymium organophosphonate, for example, one or more of C 5-C10 alkane, C 5-C10 cycloalkane and C 6-C12 arene, preferably one or more of hexane, cyclohexane, heptane, pentane, isopentane, octane, methylcyclohexane, benzene, toluene, xylene and cumene.
The amount of the above-mentioned organic solvent is not particularly limited, and it is preferable that the amount of the organic solvent is such that the concentration of the final product is not higher than 0.5mol/L. In addition, the organic solvent is preferably used in an amount such that the volume of the organic phase and the volume of the aqueous phase are 0.3 to 2:1, more preferably 0.5 to 1:1.
According to the present invention, the above-mentioned contact may be performed by mixing an aqueous neodymium chloride solution, an organic phosphonate, an organic solvent and a basic compound together, or by mixing two or more kinds of the above-mentioned components and then mixing the above-mentioned components with each other. In order to provide a neodymium phosphonate solution having a lower viscosity and a lower impurity content, preferably, the contacting comprises a first contacting of an aqueous neodymium chloride solution with an organic phosphonate and an organic solvent followed by a second contacting of the first contacted product with a basic compound.
In the present invention, the first contact is for sufficiently dissolving the reaction raw material, and preferably, the temperature of the first contact may be, for example, 5 to 80 ℃, and from the viewpoint of energy saving, the first contact is preferably performed at 10 to 50 ℃. The time for the first contact is not particularly limited, and may be, for example, 1 minute or more, preferably 1 to 5 minutes, as long as the reaction raw materials can be dissolved well.
According to the present invention, preferably, the alkaline compound is used in an amount such that the PH of the aqueous phase is 4 to 5.
According to the present invention, the alkaline compound is a substance having a pH of more than 7 by itself or after being formulated into an aqueous solution, preferably one or more of hydroxide and aqueous ammonia, more preferably one or more of sodium hydroxide, potassium hydroxide and aqueous ammonia. For the basic compound in solid form, it is usually formulated into an aqueous solution. The concentration of the aqueous solution is not particularly limited as long as sufficient dissolution is ensured, and may be, for example, 0.1 to 5.0mol/L.
Preferably, the aqueous alkaline substance solution is added dropwise, and the dropping speed can be 2.0-20.0 mL/min, preferably 5.0-10.0 mL/min, relative to 350mL of the dropped material. And if the dropping speed is too low, the production efficiency is too low, the dropping speed is too high, the product generation rate is high, and the layering and impurity separation of the final oil-water phase are not facilitated.
In the invention, the term "the drop acceleration can be 2.0-20.0 mL/min relative to 350mL of the dropped material" means that the drop acceleration can be 2.0-20.0 mL/min when the dropped material is 350mL, and can be 4.0-40.0 mL/min when the dropped material is 700mL, so as to determine the drop acceleration of the dropped material with different volumes.
According to the present invention, preferably, the second contact temperature is 30 to 80 ℃, more preferably 30 to 55 ℃, still more preferably 45 to 55 ℃, particularly preferably 50 ℃, and the reaction rate and energy saving can be both achieved by performing at 50 ℃.
The time for the second contact may be, for example, 1 hour or more, preferably 1 to 6 hours, and more preferably 1 to 2 hours, as long as the reaction is sufficiently performed.
According to a third aspect of the invention, there is provided a neodymium phosphonate solution prepared by the preparation method of the invention.
The solution viscosity of the neodymium phosphonate solution prepared by the preparation method is lower than 200 mPa.s at 25 ℃ when the concentration is 0.1mol/L, and the chloride ion content in the neodymium phosphonate solution is not higher than 10ug/g when the concentration of the neodymium phosphonate is 0.1 mol/L.
Preferably, the neodymium phosphonate solution has a solution viscosity of less than 100 mPa.s measured at 25 ℃ at a concentration of 0.1mol/L, more preferably the neodymium phosphonate solution has a solution viscosity of less than 90 mPa.s measured at 25 ℃ at a concentration of 0.1mol/L, still more preferably the neodymium phosphonate solution has a solution viscosity of 40-90 mPa.s measured at 25 ℃ at a concentration of 0.1 mol/L.
Preferably, the chloride ion content in the neodymium phosphonate solution is not higher than 10ug/g when the neodymium phosphonate concentration is 0.1mol/L, more preferably not higher than 9ug/g when the neodymium phosphonate concentration is 0.1mol/L, still more preferably not higher than 8ug/g when the neodymium phosphonate concentration is 0.1mol/L, more preferably not higher than 7ug/g when the neodymium phosphonate concentration is 0.1mol/L, and still more preferably 5-7ug/g when the neodymium phosphonate concentration is 0.1 mol/L.
Preferably, the neodymium ion concentration of the phosphonate neodymium solution is 0.04-0.5mol/L, preferably 0.1-0.4mol/L, more preferably 0.1-0.3mol/L, more preferably 0.1-0.2mol/L, and even more preferably 0.1-0.16mol/L.
Preferably, the solvent of the neodymium phosphonate solution is n-hexane.
According to a fourth aspect of the present invention, there is provided the use of a neodymium phosphonate solution of the present invention or a neodymium phosphonate solution prepared by a method of preparing a neodymium phosphonate solution of the present invention in the preparation of an olefin polymerization catalyst.
The present invention will be described in detail by way of examples, but the present invention is not limited to the following examples.
In the following examples and comparative examples, the solution viscosity was measured at 25℃using a rotary viscometer, the chloride ion content was measured according to the molar method in GB/T15453-2008, and the neodymium ion concentration of the neodymium phosphonate solution was measured using a complexometric titration method.
Example 1
Into a 1000mL three-necked flask, 120mL of an aqueous solution of neodymium chloride having a concentration of 0.25mol/L, 200mL of n-hexane and 56g of di (2-ethylhexyl) phosphonate were charged, and heated to 50℃in a water bath. Stirring was started, then an aqueous sodium hydroxide solution (0.50 mol/L) was added dropwise to the flask via a constant pressure funnel, and after 170ml was added dropwise (30 minutes elapsed), the reaction was continued for 30 minutes, and the pH of the aqueous phase was measured to be 4.0. Wherein the molar ratio of phosphonate to neodymium is 5.8. After the reaction is finished, standing and layering are carried out, oil-water phase layering is good, and the interface is free of turbid impurities. The oil phase was separated and the solution viscosity at 25℃was found to be 81 mPas, the chloride ion content in the solution was found to be 5.1ug/g and the concentration was found to be 0.148mol/L. When the concentration was 0.1mol/L, the chloride ion content in the solution was 3.4ug/g.
The obtained neodymium phosphonate solution was diluted to 0.1mol/L with n-hexane, and the solution viscosity measured at 25℃was 42 mPas.
Example 2
Into a 1000mL three-necked flask, 120mL of an aqueous solution of neodymium chloride having a concentration of 0.25mol/L, 200mL of n-hexane and 48g of di (2-ethylhexyl) phosphonate were charged, and heated to 50℃in a water bath. Stirring was started, then an aqueous sodium hydroxide solution of 0.50mol/L was added dropwise to the flask via a constant pressure funnel, and the reaction was continued for 30 minutes after 180ml was added dropwise (time-consuming 30 minutes), and the pH of the aqueous phase was measured to be 4.5. Wherein the molar ratio of phosphonate to neodymium is 5.0. After the reaction is finished, standing and layering are carried out, oil-water phase layering is good, and the interface is free of turbid impurities. The oil phase was separated and the solution viscosity at 25℃was found to be 131 mPas, the chloride ion content in the solution was found to be 6.4ug/g and the concentration was found to be 0.155mol/L. When the concentration was 0.1mol/L, the chloride ion content in the solution was 4.1ug/g.
The obtained neodymium phosphonate solution was diluted to 0.1mol/L with n-hexane, and the solution viscosity measured at 25℃was 65 mPas.
Example 3
Into a 1000mL three-necked flask, 120mL of an aqueous solution of neodymium chloride having a concentration of 0.25mol/L, 250mL of n-hexane and 40g of di (2-ethylhexyl) phosphonate were charged, and heated to 50℃in a water bath. Stirring was started, then, dropwise adding a sodium hydroxide aqueous solution having a concentration of 0.50mol/L to the flask via a constant pressure funnel was started, 190ml was added dropwise (40 minutes elapsed), the reaction was continued for 30 minutes, and the pH of the aqueous phase was measured to be 5.0. Wherein the molar ratio of phosphonate to neodymium is 4.1. After the reaction is finished, standing and layering are carried out, oil-water phase layering is good, and the interface is free of turbid impurities. The oil phase was separated and the solution viscosity at 25℃was found to be 118 mPas, the chloride ion content in the solution was found to be 6.2ug/g and the concentration was found to be 0.118mol/L. When the concentration was 0.1mol/L, the chloride ion content in the solution was 5.3ug/g.
The obtained neodymium phosphonate solution was diluted to 0.1mol/L with n-hexane, and the solution viscosity measured at 25℃was 87 mPas.
Example 4
Into a 1000mL three-necked flask, 120mL of an aqueous solution of neodymium chloride having a concentration of 0.25mol/L, 200mL of n-hexane and 40g of di (2-ethylhexyl) phosphonate were charged, and heated to 50℃in a water bath. Stirring was started, then, dropwise adding a sodium hydroxide aqueous solution having a concentration of 0.50mol/L to the flask via a constant pressure funnel was started, 190ml was added dropwise (40 minutes elapsed), the reaction was continued for 30 minutes, and the pH of the aqueous phase was measured to be 5.0. Wherein the molar ratio of phosphonate to neodymium is 4.1. After the reaction is finished, standing and layering are carried out, oil-water phase layering is good, and the interface is free of turbid impurities. The oil phase was separated and the solution viscosity at 25℃was found to be 198 mPas, the chloride ion content in the solution was found to be 7.4ug/g and the concentration was found to be 0.151mol/L. When the concentration was 0.1mol/L, the chloride ion content in the solution was 4.9ug/g.
The obtained neodymium phosphonate solution was diluted to 0.1mol/L with n-hexane, and the solution viscosity measured at 25℃was 112 mPas.
Example 5
Into a 1000mL three-necked flask, 120mL of an aqueous solution of neodymium chloride having a concentration of 0.25mol/L, 100mL of n-hexane and 52g of di (2-ethylhexyl) phosphonate were charged, and heated to 50℃in a water bath. Stirring was started, then an aqueous sodium hydroxide solution (0.50 mol/L) was added dropwise to the flask via a constant pressure funnel, and the reaction was continued for 30 minutes after 170ml was added dropwise (40 minutes elapsed), and the pH of the aqueous phase was measured to be 4.0. Wherein the molar ratio of phosphonate to neodymium is 5.4. After the reaction is finished, standing and layering are carried out, oil-water phase layering is good, and the interface is free of turbid impurities. The oil phase was separated and the solution viscosity at 25℃was found to be 369 mPas, the chloride ion content in the solution was found to be 9.8ug/g and the concentration was found to be 0.292mol/L. When the concentration was 0.1mol/L, the chloride ion content in the solution was 3.4ug/g.
The obtained neodymium phosphonate solution was diluted to 0.1mol/L with n-hexane, and the solution viscosity measured at 25℃was 173 mPas.
Example 6
Into a 1000mL three-necked flask, 120mL of an aqueous solution of neodymium chloride having a concentration of 0.25mol/L, 200mL of n-hexane and 56g of di (n-hexyl) phosphonate were charged, and heated to 50℃in a water bath. Stirring was started, then an aqueous sodium hydroxide solution (0.50 mol/L) was added dropwise to the flask via a constant pressure funnel, and after 170ml was added dropwise (30 minutes elapsed), the reaction was continued for 30 minutes, and the pH of the aqueous phase was measured to be 4.2. Wherein the molar ratio of phosphonate to neodymium is 5.5. After the reaction is finished, standing and layering are carried out, oil-water phase layering is good, and the interface is free of turbid impurities. The oil phase was separated and the solution viscosity at 25℃was 108 mPas, the chloride ion content in the solution was 7.2ug/g and the concentration was 0.141mol/L. When the concentration was 0.1mol/L, the chloride ion content in the solution was 5.1ug/g.
The obtained neodymium phosphonate solution was diluted to 0.1mol/L with n-hexane, and the solution viscosity was 66 mPas measured at 25 ℃.
Comparative example 1
Otherwise as in example 1, the amount of di (2-ethylhexyl) phosphonate was changed to 36g only, with a molar ratio of phosphonate to neodymium of 3.7. The pH of the aqueous phase was measured to be 3.5. After the reaction is finished, the oil-water phase is difficult to separate after standing, and a plurality of white unidentified substances are arranged on the interface. The oil phase was withdrawn and the solution viscosity at 25℃was found to be 12184 mPa.s, the chloride ion content in the solution was 35.7ug/g and the concentration was found to be 0.124mol/L. When the concentration was 0.1mol/L, the chloride ion content in the solution was 28.8ug/g.
The obtained neodymium phosphonate solution was diluted to 0.1mol/L with n-hexane, and the solution viscosity was 9840 mPas measured at 25 ℃.
Comparative example 2
The pH of the aqueous phase was measured to be 6.5 by changing the amount of the aqueous sodium hydroxide solution to 300mL in the same manner as in example 1. After the reaction is finished, the oil-water phase is very difficult to separate after standing, and obvious interfaces are basically difficult to observe. The oil phase was withdrawn, and the solution viscosity at 25℃was found to be 8908 mPas, the chloride ion content in the solution was found to be 67.2ug/g, and the concentration was found to be 0.082mol/L. When the concentration was 0.1mol/L, the chloride ion content in the solution was 82.0ug/g.
The obtained neodymium phosphonate solution was concentrated to 0.1mol/L, and the solution viscosity measured at 25℃was 11076 mPa.s.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (30)
1. A neodymium phosphonate solution is characterized in that the solution viscosity of the neodymium phosphonate solution is lower than 200 mPa.s when the concentration of the neodymium phosphonate solution is 0.1mol/L at 25 ℃, the chloride ion content of the neodymium phosphonate solution is not higher than 10ug/g when the concentration of the neodymium phosphonate is 0.1mol/L, and the preparation method of the neodymium phosphonate solution comprises the step of contacting an aqueous neodymium chloride solution, an organic phosphonate, an organic solvent and an alkaline compound, wherein the molar ratio of the organic phosphonate to the neodymium chloride in the aqueous neodymium chloride solution is 4-6:1, and the alkaline compound is used in an amount such that the pH value of an aqueous phase is less than or equal to 5.
2. The neodymium phosphonate solution according to claim 1, wherein the neodymium phosphonate solution has a solution viscosity of less than 100 mPa-s measured at a concentration of 0.1mol/L at 25 ℃.
3. The neodymium phosphonate solution according to claim 1, wherein the chloride ion content of the neodymium phosphonate solution is not higher than 7ug/g at a neodymium phosphonate concentration of 0.1 mol/L.
4. A neodymium phosphonate solution according to any one of claims 1-3, wherein the concentration of the neodymium phosphonate solution is 0.04-0.5mol/L.
5. The neodymium phosphonate solution according to claim 4, wherein the concentration of the neodymium phosphonate solution is 0.1-0.2mol/L.
6. A neodymium phosphonate solution according to any one of claims 1-3, wherein the solvent of the neodymium phosphonate solution is n-hexane.
7. A preparation method of a neodymium phosphonate solution is characterized by comprising the step of contacting a neodymium chloride aqueous solution, an organic phosphonate, an organic solvent and an alkaline compound, wherein the molar ratio of the organic phosphonate to the neodymium chloride in the neodymium chloride aqueous solution is 4-6:1, the alkaline compound is used in an amount such that the pH value of an aqueous phase is less than or equal to 5,
The organic phosphonate is of a structure shown in formula (1), wherein R d1、Rd2 and R d3 are each independently hydrogen, hydroxy, C 1-C20 alkyl or C 1-C20 alkoxy, and at least one of R d1、Rd2 and R d3 is C 1-C20 alkyl or C 1-C20 alkoxy,
8. The process of claim 7 wherein the contacting comprises first contacting the aqueous neodymium chloride solution with the organic phosphonate and the organic solvent followed by second contacting the first contact product with the basic compound.
9. The method of claim 8, wherein the neodymium chloride content in the neodymium chloride aqueous solution is 0.1-0.5 mol/L.
10. The method of claim 8, wherein the molar ratio of the organophosphonate to neodymium chloride in the aqueous solution of neodymium chloride is 4-5:1.
11. The method of claim 8, wherein in formula (1), R d1 is hydroxy, and R d2 and R d3 are both 2-ethylhexyloxy.
12. The method of claim 8, wherein in formula (1), R d1 is hydroxy, and R d2 and R d3 are both 2-ethylhexyl.
13. The method of claim 8, wherein in formula (1), R d1 is hydroxy, R d2 is 2-ethylhexyl, and R d3 is 2-ethylhexyloxy.
14. The method of claim 8, wherein the organic solvent is one or more of a C 5-C10 alkane, a C 5-C10 cycloalkane, and a C 6-C12 arene.
15. The method of claim 14, wherein the organic solvent is one or more of hexane, cyclohexane, heptane, pentane, isopentane, octane, methylcyclohexane, benzene, toluene, xylene, and cumene.
16. The method of claim 8, wherein the organic solvent is used in an amount such that the volume of the organic phase and the volume of the aqueous phase are 0.3-2:1.
17. The method of any one of claims 8-16, wherein the alkaline compound is used in an amount such that the PH of the aqueous phase is 4-5.
18. The method according to claim 17, wherein the basic compound is used in the form of an aqueous solution, and the content of the basic compound in the aqueous solution of the basic compound is 0.1 to 5.0mol/L.
19. The method according to claim 18, wherein the second contacting is performed by dropping the aqueous alkaline compound solution into the first contact product.
20. The method of claim 19, wherein the drop rate is 2.0-20.0 ml/min.
21. The method of claim 8, wherein the basic compound is one or more of hydroxide and ammonia.
22. The method of any of claims 8-16, wherein the second contact temperature is 30-80 ℃.
23. A neodymium phosphonate solution prepared by the method of any one of claims 7-22.
24. The neodymium phosphonate solution according to claim 23, wherein the neodymium phosphonate solution has a solution viscosity of less than 200 mPa-s measured at a concentration of 0.1mol/L at 25 ℃ and a chloride ion content of not more than 10ug/g at a neodymium phosphonate concentration of 0.1 mol/L.
25. The neodymium phosphonate solution according to claim 23, wherein the neodymium phosphonate solution has a solution viscosity of less than 100 mPa-s measured at a concentration of 0.1mol/L at 25 ℃.
26. The neodymium phosphonate solution according to claim 23, wherein the chloride ion content of the neodymium phosphonate solution is not higher than 7ug/g at a neodymium phosphonate concentration of 0.1 mol/L.
27. The neodymium phosphonate solution of claim 23, wherein the concentration of the neodymium phosphonate solution is 0.04-0.5mol/L.
28. The neodymium phosphonate solution of claim 27, wherein the concentration of the neodymium phosphonate solution is 0.1-0.2mol/L.
29. The neodymium phosphonate solution of claim 23, wherein the solvent of the neodymium phosphonate solution is n-hexane.
30. Use of a neodymium phosphonate solution according to any one of claims 1 to 6 or a neodymium phosphonate solution according to any one of claims 7 to 22 in the preparation of an olefin polymerization catalyst.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2506181A1 (en) * | 2002-11-18 | 2004-06-03 | Michelin Recherche Et Technique S.A. | Method for obtaining a butadiene hompolymer in the presence of mono-olefin(s) with 4 carbon atoms |
| 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 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6111082A (en) * | 1998-04-17 | 2000-08-29 | Rhodia Rare Earths Inc. | Stable concentrated rare earth carboxylate liquids |
| BR0309644B8 (en) * | 2002-05-16 | 2013-02-19 | catalytic system usable for preparing polymerized polybutadienes and processes for preparing a catalytic system and a polybutadiene. | |
| FR2919871B1 (en) * | 2007-08-08 | 2010-04-23 | Rhodia Operations | PROCESS FOR PREPARING A SOLUTION OF A RARE EARTH ORGANOPHOSPHATE IN AN ORGANIC SOLVENT |
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| CN101824050B (en) * | 2009-12-28 | 2012-12-12 | 中国科学院长春应用化学研究所 | Preparation method of soluble neodymium chloride complex |
| CN103694386B (en) * | 2013-12-19 | 2017-03-08 | 华宇橡胶有限责任公司 | A kind of preparation method of organic neodymium phosphate catalyst system |
| CN103694378B (en) * | 2013-12-19 | 2016-08-31 | 华宇橡胶有限责任公司 | A kind of method of synthetic solvent type rare-earth rubber catalyst |
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|---|---|---|---|---|
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| 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 |
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