CN117229432B - Organic rare earth phosphate catalyst and preparation method and application thereof - Google Patents
Organic rare earth phosphate catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 47
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 43
- 239000010452 phosphate Substances 0.000 title claims abstract description 43
- -1 rare earth phosphate Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 36
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 31
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 30
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002608 ionic liquid Substances 0.000 claims abstract description 19
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 9
- LUTCIFPQNFPSIZ-UHFFFAOYSA-K n,n-diethylethanamine;trichloroalumane;hydrochloride Chemical compound [Al+3].Cl.[Cl-].[Cl-].[Cl-].CCN(CC)CC LUTCIFPQNFPSIZ-UHFFFAOYSA-K 0.000 claims abstract description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 54
- 239000007983 Tris buffer Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 78
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 229920001971 elastomer Polymers 0.000 description 11
- 239000005060 rubber Substances 0.000 description 11
- XEHAPDQZMHKJAD-UHFFFAOYSA-N bis[2,6-di(propan-2-yl)phenyl] hydrogen phosphate Chemical compound CC(C)C1=CC=CC(C(C)C)=C1OP(O)(=O)OC1=C(C(C)C)C=CC=C1C(C)C XEHAPDQZMHKJAD-UHFFFAOYSA-N 0.000 description 10
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002798 neodymium compounds Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- HJHUXWBTVVFLQI-UHFFFAOYSA-N tributyl(methyl)azanium Chemical compound CCCC[N+](C)(CCCC)CCCC HJHUXWBTVVFLQI-UHFFFAOYSA-N 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000863902 Odilia Species 0.000 description 1
- 235000011449 Rosa Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- OLBCVFGFOZPWHH-UHFFFAOYSA-N propofol Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O OLBCVFGFOZPWHH-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses an organic rare earth phosphate catalyst, a preparation method and application thereof. The organic rare earth phosphate catalyst is prepared from tri [ bis (2, 6-diisopropylphenyl) phosphate ] neodymium and triethylamine hydrochloride-aluminum trichloride ionic liquid according to a molar ratio of 1:5-1:200. The invention provides an application of the organic rare earth phosphate catalyst in preparing polybutadiene, which comprises the following steps: the rare earth organic phosphate catalyst is adopted to catalyze the polymerization reaction of the 1,3-butadiene monomer, and the polybutadiene product is obtained. The rare earth catalyst provided by the invention has the advantages of high activity and high selectivity, and can be used for preparing high-quality polybutadiene products with ultrahigh cis, high molecular weight and narrow molecular weight distribution, and the yield of the products is high.
Description
Technical Field
The invention relates to an organic rare earth phosphate catalyst, a preparation method thereof and application thereof in preparing polybutadiene.
Technical Field
Cis-1, 4 polybutadiene rubber, abbreviated as butadiene rubber, is the second most versatile synthetic rubber worldwide, which is widely used in various rubber products with excellent properties such as good low temperature properties, high abrasion resistance and high temperature change elasticity.
Butadiene rubber is polymerized from 1,3-Butadiene (BD) as a monomer, which is a highly stereotactic reaction that provides various Polybutadiene (PB) with different microstructures and affects the basic properties of the rubber. The stereoselectivity of 1,3-butadiene is mainly controlled by adjusting the polymerization parameters (i.e., reaction temperature, solvent used and specific metal/ligand catalyst system).
Ilya E, nifant 'ev et al [ Ilya E, nifant' ev etc. Neodymium tris-dialkylphosphinates Systematic study of the structure-reactivity relationship in butadiene and isoprene Polymerisation.Applied Catalysis A: General 478 (2014) 219–227]A tris [ bis (2, 6-diisopropylphenyl) phosphate was reported]Neodymium compound, and diene polymerization catalyst based on the neodymium compound, which is prepared from tris [ bis (2, 6-diisopropylphenyl) phosphate]Neodymium compound, iBu 3 Al、Et 3 Al 2 Cl 3 And a diene (isoprene or piperylene) in a molar ratio Nd: iBu 3 Al: cl: diene=1:30:2.5:20, and the catalyst is used for polymerization of 1,3-butadiene, and the yield and cis-selectivity reach 89%, 98.3% (isoprene) and 93%, 97.8% (piperylene). However, the catalyst system is relatively complicated in composition and preparation, and there is room for improvement in molecular weight and molecular weight distribution.
RamInd n D i az de Le Lon et al [ RamInd n D i az de Le Lon, mari a Teresa Alonso C Lord ova, francisco Javier Enr i quez Medrano, jos i Iz Elizondo, odilia Pirez Camacho, alo Romo Quiroz, rosa Idalia Narro C e speed, adali Casta ñ eda Facio Polymerization of 1,3-Butadiene with Several Catalytic Systems Based on Neodymium or Lithium in Presence of Ionic liquids, macromol. Symp. 3, 325-326, 194-202] disclose that the addition of ionic liquid to NdV/TIBA/DEAC Ziegler-Natta polymerization catalyst system in a 1,3 butadiene polymerization reaction reduces the exothermic heat of reaction, promotes higher molecular weight production, and reduces the molecular weight distribution, but significantly reduces the yield of the chlorinated ionic liquid [ EMIM ] [ Cl ] especially when the polymerization reaction is carried out at 180% for polybutadiene.
Therefore, developing a novel rare earth catalyst for synthesizing polybutadiene rubber, simplifying the catalyst preparation process, and improving the molecular quality characteristics while maintaining good yield and microstructure (with cis content of more than 99%) is a problem to be solved at present.
Disclosure of Invention
The primary aim of the invention is to provide an organic rare earth phosphate catalyst which has the advantages of high catalytic activity, high selectivity and the like.
The second object of the invention is to provide a preparation method of the rare earth organic phosphate catalyst, which can prepare the rare earth organic phosphate catalyst.
The invention also provides a preparation method of polybutadiene, which adopts the rare earth catalyst to prepare high-quality polybutadiene products with ultrahigh cis-structure content, high molecular weight and narrow molecular weight distribution, and can achieve higher yield.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in one aspect of the invention, a rare earth organophosphate catalyst is provided that is prepared from tris [ bis (2, 6-diisopropylphenyl) phosphate]Neodymium and triethylamine hydrochloride-aluminum trichloride Ionic liquid ([ Et) 3 HN]Cl/AlCl 3 ) The preparation method comprises the following steps of (1:5) - (1:200).
The tris [ bis (2, 6-diisopropylphenyl) phosphate ] Neodymium of the present invention can be prepared by the method reported in the literature [ Ilya E. Nifant' ev etc. Neodymium tris-dialkylphosphinates: systematic study of the structure-reactivity relationship in butadiene and isoprene Polymer. Applied Catalysis A:general 478 (2014) 219-227 ].
Preferably, the tris [ bis (2, 6-diisopropylphenyl) phosphate]Neodymium and triethylamine hydrochloride-aluminum trichloride Ionic liquid ([ Et) 3 HN]Cl/AlCl 3 ) The molar ratio of (1:5) to (1:50), more preferably 1: 5-15.
In a second aspect, the invention provides a method for preparing an organic rare earth phosphate catalyst, comprising the following steps: tris [ bis (2, 6-diisopropylphenyl) phosphate]Neodymium and triethylamine hydrochloride-aluminum trichlorideIonic liquids ([ Et) 3 HN]Cl/AlCl 3 ) Mixing and aging for 5-60 minutes at the temperature of 10-40 ℃ to obtain the organic phosphoric acid rare earth catalyst.
Preferably, the aging conditions are: aging is carried out at 20-25 ℃ for 10-30 minutes, more preferably at 21 ℃ for 30 minutes.
In order to further facilitate the preparation efficiency of the catalyst, the preparation process can be generally carried out under the protection of inert gas, and the inert gas adopted in the invention is not strictly limited, for example, more economic nitrogen (N) 2 ) Etc.
In a third aspect of the present invention, there is also provided an application of the rare earth organophosphate catalyst in preparing polybutadiene, comprising: the rare earth organic phosphate catalyst is adopted to catalyze the polymerization reaction of the 1,3-butadiene monomer, and the polybutadiene product is obtained.
Specifically, the implementation steps of the application are as follows: adding a 1,3-butadiene monomer and an organic rare earth phosphate catalyst into a solvent, mixing, and then carrying out polymerization reaction at 30-80 ℃; the reaction process is carried out under the protection of inert gas.
Preferably, the solvent is hexane.
Preferably, the inert gas is nitrogen.
Preferably, the rare earth organophosphate catalyst is used in an amount such that the molar ratio of neodymium element to 1,3-butadiene monomer is 1.0X10 -5 ~3.0×10 -3 。
Preferably, the initial butadiene concentration in the polymerization reaction system is 1.5 to 4M.
Under the polymerization condition, the high polymerization efficiency can be achieved, and the polymerization can be completed within 30-120 min generally.
Compared with the prior art, the invention has at least the following beneficial effects:
the rare earth catalyst provided by the invention is based on tris [ bis (2, 6-diisopropylphenyl) phosphate]The novel rare earth catalytic system of neodymium and ionic liquid has the advantages of high activity, high selectivity and the like, and can be prepared to have the ultrahigh cis structure content (cis 1, 4-structure content is more than 9)9%), high molecular weight (Mn greater than 10 6 ) High quality polybutadiene rubber products with narrow molecular weight distribution (Mw/Mn as low as 1.48), and high yield (up to 95% or more).
Detailed Description
The invention is illustrated below by means of specific examples. It is to be noted that the examples are only for further explanation of the present invention and are not to be construed as limiting the scope of the present invention in any way. Those skilled in the art will be able to make numerous insubstantial modifications and adaptations in light of the above disclosure.
Example 1
1. Preparation of rare earth catalyst
(1) Synthesis of bis (2, 6-diisopropylphenyl) -phosphoric acid: pyridine (100 mmol) was added to a solution of 2, 6-diisopropylphenol (19.5 mL, 105 mmol) and phosphorus oxychloride (50 mmol) in benzene (50 mL) with stirring. The reaction mixture was refluxed for 5h. Then, water (10 mL) was added, and after stirring for 10 minutes, the organic layer was separated using a separation funnel and the solvent was evaporated. The resulting solution was refluxed in a mixture of acetone and water (50 mL of acetone+5 mL of water) for 1 hour, and extracted with chloroform. The solvent was evaporated and recrystallized from toluene to yield 14.9g of the product.
(2) Synthesis of tris [ bis (2, 6-diisopropylphenyl) phosphate ] neodymium: lithium metal (6 mmol) was dissolved in methanol (20 mL) and bis (2, 6-diisopropylphenyl) -phosphoric acid (6 mmol) was added. To the resulting solution was added a solution of neodymium chloride (2 mmol) in methanol (10 mL). The mixture was refluxed for 8 hours, then precipitated pink needle crystals were filtered off and washed with methanol and dried under vacuum at 120 ℃ to a constant weight, yielding 2.26g of product.
(3) Sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; under nitrogen protection, 0.22mmol of ionic liquid [ Et ] 3 HN]Cl/AlCl 3 0.022mmol of tris [ bis (2, 6-diisopropylphenyl) phosphate]Neodymium was mixed and aged at 21℃for 30 minutes.
2. Synthetic polydiene rubber
Hexane (1 mL) and a hexane solution of 1,3-butadiene (3.63 mL,18.5 mmol 1,3-butadiene) were rapidly poured into the above-mentioned Schlenk flask charged with the rare earth catalyst, and the flask was immediately sealed Shi Laike and stirred at 60℃for 1h. After completion, the flask was carefully opened and the flask was closed with a hydrochloric acid/methanol solution (15 mL, V) Concentrated hydrochloric acid ：V Methanol =1:5) quenched and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was determined by gravimetric method to be 96.4%, stereoselectivity: 99.3% of 1, 4-cis, 0.4% of 1, 4-trans, 0.3% of 1, 2-vinyl, mn 1.07×10 6 Mw/Mn was 1.56.
Example 2 (different from the aging time in example 1)
1. Preparation of rare earth catalyst
(1) Synthesis of bis (2, 6-diisopropylphenyl) -phosphoric acid: as in example 1.
(2) Synthesis of tris [ bis (2, 6-diisopropylphenyl) phosphate ] neodymium: as in example 1.
(3) Sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; under nitrogen protection, 0.22mmol of ionic liquid [ Et ] 3 HN]Cl/AlCl 3 0.022mmol of tris [ bis (2, 6-diisopropylphenyl) phosphate]Neodymium was mixed and aged at 21℃for 10 minutes.
2. Synthetic polydiene rubber
Hexane (1 mL) and a hexane solution of 1,3-butadiene (3.63 mL,18.5 mmol 1,3-butadiene) were rapidly poured into the above-mentioned Schlenk flask charged with the rare earth catalyst, and the flask was immediately sealed Shi Laike and stirred at 60℃for 1h. After completion, the flask was carefully opened and the flask was closed with a hydrochloric acid/methanol solution (15 mL, V) Concentrated hydrochloric acid ：V Methanol =1:5) quenched and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was 95.3% by weight, immediatelyBody selectivity: 99.2% of 1, 4-cis, 0.5% of 1, 4-trans, 0.3% of 1, 2-vinyl, mn 1.02X10 6 Mw/Mn was 1.76.
Example 3 (different from the amount of neodymium tris [ bis (2, 6-diisopropylphenyl) phosphate ] in example 1)
1. Preparation of rare earth catalyst
(1) Synthesis of bis (2, 6-diisopropylphenyl) -phosphoric acid: as in example 1.
(2) Synthesis of tris [ bis (2, 6-diisopropylphenyl) phosphate ] neodymium: as in example 1.
(3) Sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; under nitrogen protection, 0.22mmol of ionic liquid [ Et ] 3 HN]Cl/AlCl 3 0.044mmol of tris [ bis (2, 6-diisopropylphenyl) phosphate]Neodymium was mixed and aged at 21℃for 30 minutes.
2. Synthetic polydiene rubber
Hexane (1 mL) and a hexane solution of 1,3-butadiene (3.63 mL,18.5 mmol 1,3-butadiene) were rapidly poured into the above-mentioned Schlenk flask charged with the rare earth catalyst, and the flask was immediately sealed Shi Laike and stirred at 60℃for 1h. After completion, the flask was carefully opened and the flask was closed with a hydrochloric acid/methanol solution (15 mL, V) Concentrated hydrochloric acid ：V Methanol =1:5) quenched and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was 97.6% by weight, stereoselectivity: 99.8% of 1, 4-cis, 0.8% of 1, 4-trans, 0.4% of 1, 2-vinyl, mn 1.12X10 6 Mw/Mn was 1.48.
Example 4 (different from the 1,3-butadiene solution monomer concentration of example 1)
1. Preparation of rare earth catalyst
(1) Synthesis of bis (2, 6-diisopropylphenyl) -phosphoric acid: as in example 1.
(2) Synthesis of tris [ bis (2, 6-diisopropylphenyl) phosphate ] neodymium: as in example 1.
（3）Sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; under nitrogen protection, 0.22mmol of ionic liquid [ Et ] 3 HN]Cl/AlCl 3 0.022mmol of tris [ bis (2, 6-diisopropylphenyl) phosphate]Neodymium was mixed and aged at 21℃for 30 minutes.
2. Synthetic polydiene rubber
Hexane (5 mL) and a hexane solution of 1,3-butadiene (3.63 mL,18.5 mmol 1,3-butadiene) were rapidly poured into the above-described Schlenk flask charged with the rare earth catalyst, and the flask was immediately sealed Shi Laike and stirred at 60℃for 1h. After completion, the flask was carefully opened and the flask was closed with a hydrochloric acid/methanol solution (15 mL, V) Concentrated hydrochloric acid ：V Methanol =1:5) quenched and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was determined by gravimetric method and was 95.4%, stereoselectivity: 99.3% of 1, 4-cis, 0.3% of 1, 4-trans, 0.4% of 1, 2-vinyl, mn 1.05X10 6 Mw/Mn was 1.71.
Comparative example 1
1. Preparation of rare earth catalyst
(1) Synthesis of bis (2, 6-diisopropylphenyl) -phosphoric acid: as in example 1.
(2) Synthesis of tris [ bis (2, 6-diisopropylphenyl) phosphate ] neodymium: as in example 1.
(3) Sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; under nitrogen protection, 0.22mmol of cocatalyst diethylaluminum chloride (Et) 2 AlCl), 0.022mol of tris [ bis (2, 6-diisopropylphenyl) phosphate]Neodymium was mixed with hexane (1 ml) and aged at 21℃for 30 minutes.
2. Synthetic polydiene rubber
A hexane solution of 1,3-butadiene (3.63 mL,18.5 mmol 1,3-butadiene) was rapidly poured into the above-described Schlenk flask charged with the rare earth catalyst, and the Shi Laike flask was immediately sealed and stirred at 60℃for 1 hour. After completion, the flask was carefully opened and dissolved with hydrochloric acid/methanolLiquid (15 mL, V) Concentrated hydrochloric acid ：V Methanol =1:5) quenched and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was determined by gravimetric method to be 87.3%, stereoselectivity: 70.2% of 1, 4-cis, 18.4% of 1, 4-trans, 11.4% of 1, 2-vinyl, mn 6.18X10 5 Mw/Mn was 2.75.
Comparative example 2 (type of ionic liquid different from that in example 1)
1. Preparation of rare earth catalyst
(1) Synthesis of bis (2, 6-diisopropylphenyl) -phosphoric acid: as in example 1.
(2) Synthesis of tris [ bis (2, 6-diisopropylphenyl) phosphate ] neodymium: as in example 1.
(3) Sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; under nitrogen protection, 0.22mmol of ionic liquid 1-butylpyridinium chloroaluminate ([ C) 4 Py]Cl/AlCl 3 ) 0.022mol of tris [ bis (2, 6-diisopropylphenyl) phosphate]Neodymium was mixed and aged at 21℃for 30 minutes.
2. Synthetic polydiene rubber
Hexane (1 mL) and a hexane solution of 1,3-butadiene (3.63 mL,18.5 mmol 1,3-butadiene) were rapidly poured into the above-mentioned Schlenk flask charged with the rare earth catalyst, and the flask was immediately sealed Shi Laike and stirred at 60℃for 1h. After completion, the flask was carefully opened and the flask was closed with a hydrochloric acid/methanol solution (15 mL, V) Concentrated hydrochloric acid ：V Methanol =1:5) quenched and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was determined by gravimetric method to be 84.5%, stereoselectivity: 66.4%1, 4-cis, 19.3%1, 4-trans, 14.3%1, 2-vinyl, mn 7.97X10 5 Mw/Mn was 2.15.
Comparative example 3 (different from the ionic liquid in example 1)
1. Preparation of rare earth catalyst
(1) Synthesis of bis (2, 6-diisopropylphenyl) -phosphoric acid: as in example 1.
(2) Synthesis of tris [ bis (2, 6-diisopropylphenyl) phosphate ] neodymium: as in example 1.
(3) Sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; under nitrogen protection, 0.22mmol of ionic liquid 1-butyl-3-methylimidazole chloroaluminate ([ BMIM)]Cl-2AlCl 3 ) 0.022mol of tris [ bis (2, 6-diisopropylphenyl) phosphate]Neodymium was mixed and aged at 21℃for 30 minutes.
2. Synthetic polydiene rubber
Hexane (1 mL) and a hexane solution of 1,3-butadiene (3.63 mL,18.5 mmol 1,3-butadiene) were rapidly poured into the above-mentioned Schlenk flask charged with the rare earth catalyst, and the flask was immediately sealed Shi Laike and stirred at 60℃for 1h. After completion, the flask was carefully opened and the flask was closed with a hydrochloric acid/methanol solution (15 mL, V) Concentrated hydrochloric acid ：V Methanol =1:5) quenched and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum for 20h to give polybutadiene rubber.
Yield by gravimetric method, yield of polybutadiene rubber 78.3%, stereoselectivity: 69.1% of 1, 4-cis, 16.7% of 1, 4-trans, 14.2% of 1, 2-vinyl, mn 7.86X 10 5 Mw/Mn was 2.29.
Comparative example 4 (type of ionic liquid different from that in example 1)
1. Preparation of rare earth catalyst
(1) Synthesis of bis (2, 6-diisopropylphenyl) -phosphoric acid: as in example 1.
(2) Synthesis of tris [ bis (2, 6-diisopropylphenyl) phosphate ] neodymium: as in example 1.
(3) Sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; under the protection of nitrogen, 0.22mmol of ion liquid tributyl-monomethyl ammonium chloroaluminate ([ N) 4,4,4,1 ]Cl-2AlCl 3 ) 0.022mol of tris [ bis (2, 6-diisopropylphenyl)Phosphoric acid esters]Neodymium was mixed and aged at 21℃for 30 minutes.
2. Synthetic polydiene rubber
Hexane (1 mL) and a hexane solution of 1,3-butadiene (3.63 mL,18.5 mmol 1,3-butadiene) were rapidly poured into the above-mentioned Schlenk flask charged with the rare earth catalyst, and the flask was immediately sealed Shi Laike and stirred at 60℃for 1h. After completion, the flask was carefully opened and the flask was closed with a hydrochloric acid/methanol solution (15 mL, V) Concentrated hydrochloric acid ：V Methanol =1:5) quenched and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum for 20h to give polybutadiene rubber.
The yield by gravimetric determination of the yield of polybutadiene rubber was 69.3%, stereoselectivity: 55.9% of 1, 4-cis, 22.8% of 1, 4-trans, 11.3% of 1, 2-vinyl, mn 6.78X10 5 Mw/Mn was 2.54.
As can be seen from a comparison of example 1 with comparative examples 1-4, the selection of the promoter is critical for the rare earth organophosphate catalyst of the present invention, the promoter [ Et ] selected in the present invention 3 HN]Cl/AlCl 3 In comparison with diethylaluminum chloride (Et) 2 AlCl), 1-butylpyridinium chloroaluminate ([ C ] 4 Py]Cl/AlCl 3 ) 1-butyl-3-methylimidazole chloroaluminate ([ BMIM)]Cl-2AlCl 3 ) And tributyl monomethyl ammonium chloroaluminate ([ N) 4,4,4,1 ]Cl-2AlCl 3 ) Is more beneficial to improving the yield of polybutadiene and improving the quality of polybutadiene products.
Claims (9)
1. An organic phosphoric acid rare earth catalyst for preparing polybutadiene, which is characterized in that: the organic rare earth phosphate catalyst consists of tris [ bis (2, 6-diisopropylphenyl) phosphate]The neodymium and triethylamine hydrochloride-aluminum trichloride ionic liquid is prepared according to a molar ratio of 1:5-1:50, and the molecular formula of the triethylamine hydrochloride-aluminum trichloride ionic liquid is [ Et ] 3 HN]Cl/AlCl 3 。
2. A method for preparing the rare earth organophosphate catalyst according to claim 1, wherein: the preparation method comprises the following steps: mixing tri [ bis (2, 6-diisopropylphenyl) phosphate ] neodymium and triethylamine hydrochloride-aluminum trichloride ionic liquid, and aging for 5-60 minutes at 10-40 ℃ to obtain the organic rare earth phosphate catalyst.
3. The method of manufacturing as claimed in claim 2, wherein: the aging conditions are as follows: aging at 20-25deg.C for 10-30 min.
4. The method of manufacturing as claimed in claim 2, wherein: the preparation process of the preparation method is implemented under the protection of inert gas.
5. Use of the rare earth organophosphate catalyst according to claim 1, for the preparation of polybutadiene, comprising: the rare earth organic phosphate catalyst is adopted to catalyze the polymerization reaction of the 1,3-butadiene monomer, and the polybutadiene product is obtained.
6. The use according to claim 5, wherein: the application implementation steps are as follows: mixing 1,3-butadiene monomer and organic rare earth phosphate catalyst in a solvent, and then carrying out polymerization reaction at 30-80 ℃; the reaction process is carried out under the protection of inert gas.
7. The use according to claim 6, wherein: the solvent is hexane.
8. The use according to claim 6, wherein: the rare earth organic phosphate catalyst is used in such a way that the molar ratio of neodymium element to 1,3-butadiene monomer is 1.0X10 -5 ~3.0×10 -3 。
9. The use according to claim 6, wherein: the initial concentration of butadiene in the polymerization reaction system is 1.5-4M.
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