CN117209638A - Amphoteric ion rare earth element alkyl catalyst and preparation method and application thereof - Google Patents
Amphoteric ion rare earth element alkyl catalyst and preparation method and application thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 17
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 9
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 125000003944 tolyl group Chemical group 0.000 claims abstract description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 57
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000007787 solid Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 11
- 239000002608 ionic liquid Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000012041 precatalyst Substances 0.000 description 9
- 150000002910 rare earth metals Chemical class 0.000 description 9
- KMJZIGLLNWFDIG-UHFFFAOYSA-N buta-1,3-diene;toluene Chemical compound C=CC=C.CC1=CC=CC=C1 KMJZIGLLNWFDIG-UHFFFAOYSA-N 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- 238000005406 washing Methods 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 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- LSQZJLSUYDQPKJ-NJBDSQKTSA-N amoxicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=C(O)C=C1 LSQZJLSUYDQPKJ-NJBDSQKTSA-N 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 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
- LUTCIFPQNFPSIZ-UHFFFAOYSA-K n,n-diethylethanamine;trichloroalumane;hydrochloride Chemical compound [Al+3].Cl.[Cl-].[Cl-].[Cl-].CCN(CC)CC LUTCIFPQNFPSIZ-UHFFFAOYSA-K 0.000 description 1
- JPYAHQUNMYHNDY-MHECFPHRSA-N n-[(1r,2s)-2-(3,4-dimethoxyphenyl)-7-methoxy-6-propan-2-yloxy-1,2,3,4-tetrahydronaphthalen-1-yl]-n-methylformamide Chemical compound C1=C(OC)C(OC)=CC=C1[C@H]1[C@@H](N(C)C=O)C2=CC(OC)=C(OC(C)C)C=C2CC1 JPYAHQUNMYHNDY-MHECFPHRSA-N 0.000 description 1
- -1 neodymium amide Chemical class 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- HJHUXWBTVVFLQI-UHFFFAOYSA-N tributyl(methyl)azanium Chemical compound CCCC[N+](C)(CCCC)CCCC HJHUXWBTVVFLQI-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- 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
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a zwitterionic rare earth element alkyl catalyst and a preparation method and application thereof. The zwitterionic rare earth element alkyl catalyst is prepared from a zwitterionic complex, 1-butylpyridinium chloroaluminate and a solvent, wherein the zwitterionic complex has the chemical formula of LnC (SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Wherein Ln represents rare earth element selected from one of lanthanum, cerium, praseodymium and neodymium, and the solvent is toluene and/or hexane. The invention provides application of the zwitterionic rare earth element alkyl catalyst in preparing polybutadiene. The amphoteric ion rare earth element alkyl catalyst has the advantages of high catalytic activity, high selectivity and the like, and can be used for preparing high-quality polybutadiene rubber products with ultrahigh cis, high molecular weight and narrow molecular weight distribution.
Description
Technical Field
The invention relates to a zwitterionic rare earth element alkyl catalyst, a preparation method thereof and application thereof in preparing polybutadiene rubber products.
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 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). However, commercial heterogeneous catalysts have not achieved 1,3-butadiene polymerization reactions with high 1, 4-cis selectivity (> 99%).
Moneil et al [ Moneil V, spitz R, boisson C. Polymerization of butadiene and copolymerization of butadiene with styrene using neodymium amide catalysts, polym Int 2004, 53 (5): 576-81).]Using a complex based on Nd { N (SiMe 3 ) 2 } 3 The catalyst of (2) is used for polymerizing butadiene. Catalytic system Nd { N (SiMe 3 ) 2 } 3 /[HNMe 2 Ph][B(C 6 F 5 ) 4 ]/Al(iBu) 3 At the ratio Al/nd=10/1, high activity and stereospecificity for butadiene polymerization were shown, with a cis-1, 4 structure content of 86%.
Schmidt et al [ Bradley M Schmidt, aradhana Pindwal, amrit Venkatesh, arkady Ellern, aaron J. Rossini, and Aaron D. Sadow Zwitterionic Trivalent (Alkyls) lanthanide Complexes in Ziegler-type Butadiene Polymerization.ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.8b04025 • Publication Date (Web): 12 Dec 2018]Discloses a zwitterionic complex LnC (SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 And provides a method for preparing the same from the zwitterionic complex LnC (SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 The rare earth catalyst consists of triisobutylaluminum and an organic solvent, and is used for the synthesis of polybutadiene. The results showed that the best results were obtained with NdC (SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 As a pre-catalyst, the 1, 4-cis structure content of the polybutadiene obtained varies from 40% to 75% and Mn is less than. And it indicates that NdC (SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 With 10 or 50 equivalents of iBu 2 AlCl or AliBu 3 And iBu 2 The 9:1 mixture of AlCl is not an active catalyst for butadiene polymerization and this chlorination process is ineffective in obtaining polybutadiene with a high 1,4 cis content. NdC (SiHMe) 2 ) 3 {HB(C 6 F 5 ) 3 } 2 And iBu 2 AlH (50 equivalents) alone provided the oligomer after 15 minutes of combined reaction. By NdC (SiHMe) 2 ) 3 {HB(C 6 F 5 ) 3 } 2 The cis content of butadiene polymerization with MAO was slightly higher (80%), but the activity was lower and the molecular weight distribution was broader (Mw/mn=3.28).
The ionic liquid is a salt which is formed by organic cations and inorganic or organic anions and is in a liquid state at room temperature, and the ionic liquid is used as a novel green solvent and a catalyst, has excellent properties of stable physicochemical properties, good conductivity, low vapor pressure and the like, and is widely used for acylation, polymerization, isomerization, alkylation, epoxidation and the like. RamInd n D i az de Le Lon et al [ RamInd n D i az de Le Lon, mari a Teresa Alonso C D ova, francisco Javier Enr i quez Medrano, jos i D i az Elizondo, odilia P rez Camacho, alo Romo Quiroz, rosa Idalia Narro C e seeds, 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 the addition of an ionic liquid to the NdV/TIBA/DEAC Ziegler-Natta polymerization catalyst system in a 1,3-butadiene polymerization reaction, which results in the presence of an ionic liquid reduces the reaction exotherm and reduces the molecular weight distribution, but the yield of polybutadiene is significantly reduced, especially when the addition of a chlorine-containing ionic liquid [ Cl ] is carried out, and the yield of polybutadiene is significantly reduced by 180% and only cis-19% is selected.
Disclosure of Invention
The primary aim of the invention is to provide a zwitterionic rare earth element alkyl catalyst which has the advantages of high catalytic activity, high selectivity and the like, and can be used for preparing high-quality polybutadiene rubber products with ultrahigh cis structure content, high molecular weight and narrow molecular weight distribution.
The second object of the invention is to provide a preparation method of the amphoteric ion rare earth element alkyl catalyst, which can prepare the rare earth element alkyl catalyst.
A third object of the present invention is to provide an application of the zwitterionic rare earth element alkyl catalyst in preparing polybutadiene, which can prepare high-quality polybutadiene products with ultra-high cis structure content, high molecular weight and low molecular weight distribution by adopting the zwitterionic rare earth element alkyl catalyst.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in one aspect of the invention, a zwitterionic rare earth alkyl catalyst is provided that is formed from a zwitterionic complex, 1-butylpyridinium chloroaluminate ([ C) 4 Py]Cl/AlCl 3 ) And a solvent; the chemical formula of the zwitterionic complex is LnC (SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Wherein Ln represents a rare earth element selected from one of lanthanum (La), cerium (Ce), praseodymium (Pr) and neodymium (Nd), and the solvent is toluene and/or hexane; in the zwitterionic rare earth element alkyl catalyst, the molar ratio of the rare earth element in the zwitterionic complex to the 1-butylpyridinium chloroaluminate is 1:10-1:200, and the molar ratio of the solvent to the zwitterionic complex is 100-3000.
LnC (SiHMe) 2 ) 3 {HB(C 6 F 5 ) 3 } 2 The preparation of the precatalyst is carried out by methods reported in the literature and can generally be carried out by a preparation process comprising the steps of:
（1）Ln{C(SiHMe 2 ) 3 } 3 is synthesized by the following steps: lnI 3 (THF) n (La, ce: n=4; pr, nd: n=3) and KC (SiHMe 2 ) 3 (molar ratio is 1:3) stirring in benzene solvent at room temperature for 1.5-12 h, evaporating volatile substances, extracting with pentane, evaporating pentane to obtain solid, namely Ln { C (SiHMe) 2 ) 3 } 3 ；
（2）LnC(SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Is synthesized by the following steps: b (C) 6 F 5 ) 3 With Ln { C (SiHMe) 2 ) 3 } 3 Dissolving (molar ratio of 2:1) in benzene solvent, stirring at room temperature for 10-50 min, washing the obtained product with pentane, and vacuum drying to obtain solid, namely LnC (SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 。
Preferably, ln is cerium (Ce) or neodymium (Nd).
Preferably, the molar ratio of the rare earth element in the amphoteric ion complex to the 1-butylpyridinium chloroaluminate is 1:10-1:50.
Preferably, the molar ratio of the solvent to the zwitterionic complex is 300-600.
In a second aspect, the invention provides a method for preparing a zwitterionic rare earth element alkyl catalyst, comprising the steps of: zwitterionic complexes, 1-butylpyridinium chloroaluminate ([ C) 4 Py]Cl/AlCl 3 ) Mixing the solvents and aging for 5-60 minutes at the temperature of 10-40 ℃ to obtain the amphoteric ion rare earth element alkyl catalyst.
Preferably, the aging conditions are: aging at 20-25deg.C for 10-30 min. Further preferred aging conditions are: aging at 20-25deg.C for 20-30 min.
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 the use of the zwitterionic rare earth element alkyl catalyst in the preparation of polybutadiene, comprising: the zwitterionic rare earth element alkyl 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: mixing 1,3-butadiene monomer and amphoteric ion rare earth element alkyl catalyst in a solvent, and then carrying out polymerization reaction at 10-80 ℃ under the protection of inert gas.
Preferably, the solvent is toluene.
Preferably, the inert gas is nitrogen.
Preferably, the amount of the zwitterionic rare earth element alkyl catalyst is controlled such that the molar ratio of rare earth element to 1,3-butadiene monomer therein is 1.0X10 -5 ~1.2×10 -3 。
Preferably, the 1,3-butadiene is fed in a concentration of 1.5 to 4M in the polymerization reaction system.
Preferably, the polymerization reaction temperature is 20-60 ℃ and the reaction time is 15-60 min. Under the polymerization conditions of the invention, higher polymerization efficiency can be achieved.
Compared with the prior art, the invention has at least the following beneficial effects:
the amphoteric ion rare earth element alkyl catalyst provided by the invention is a novel rare earth catalytic system based on a zwitterionic complex and specific ionic liquid, has the advantages of high activity, high selectivity and the like, and can be prepared to have ultrahigh cis structure content (cis 1, 4-structure content is more than 99%) and high molecular weight (Mn is more than 8 multiplied by 10) 5 ) High quality polybutadiene rubber products with narrow molecular weight distribution (Mw/Mn as low as 1.52), and high yield (up to more than 85%).
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.
The specific conditions are not noted in the examples of the present invention, and are carried out according to conventional conditions or conditions suggested by the manufacturer. The reagents or apparatus used are conventional products, which are available by conventional technical means or commercially available, without the manufacturer's knowledge.
Example 1
1. Preparation of zwitterionic rare earth alkyl catalysts
（1）Nd{C(SiHMe 2 ) 3 } 3 Is synthesized by the following steps: 0.052g (0.071 mmol) of NdI 3 (THF) 3 With 0.05g (0.21 mmol) KC (SiHMe) 2 ) 3 (molar ratio 1:3) was stirred at room temperature in 5mL of benzene solvent for 12h, during which time the solution color changed from red to yellow. After evaporation of the volatiles, extraction with pentane (3X 5 mL) gave after evaporation of pentane 0.047g (0.066 mmol) of a viscous yellow solid (92.2% yield) as Nd { C (SiHMe) 2 ) 3 } 3 。
（2）NdC(SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Is synthesized by the following steps: 0.067g (0.132 mmol) of B (C 6 F 5 ) 3 With 0.047g (0.066 mmol) Nd { C (SiHMe) 2 ) 3 } 3 (molar ratio 2:1) was dissolved in 5mL benzene and stirred at room temperature for 30min, the resulting product was washed with pentane (2X 5 mL) and then dried in vacuo to give 0.076g (0.056 mmol) of pale green solid (yield 85%) as NdC (SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 。
(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 [ C 4 Py]Cl/AlCl 3 0.022mmol of precatalyst NdC (SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Mixed with toluene (1 mL) solvent and aged at 21 ℃ for 10 minutes to obtain the zwitterionic rare earth element alkyl catalyst.
2. Synthetic polybutadiene rubber
1, 3-butadiene-toluene solution (3.63 mL,18.5 mmol 1,3-butadiene) was rapidly poured into the Schlenk flask containing the zwitterionic rare earth alkyl catalyst described above, the flask was immediately sealed Shi Laike and stirred at 60℃for 15min. After completion, the flask was carefully opened and a hydrochloric acid/methanol solution (15 mL, wherein 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 86.4% by weight, stereoselectivity: 99.3% of 1, 4-cis, 0.5% of 1, 4-trans, 0.2% of 1, 2-vinyl, mn 8.12X10 5 Mw/Mn was 1.60.
Example 2 (different from example 1 aging time)
1. Preparation of zwitterionic rare earth alkyl catalysts
（1）Nd{C(SiHMe 2 ) 3 } 3 Is synthesized by the following steps: as in example 1.
（2）NdC(SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Is synthesized by the following steps: 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 [ C 4 Py]Cl/AlCl 3 0.022mmol of precatalyst NdC (SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Mix with solvent toluene (1 mL) and age at 21 ℃ for 20 minutes.
2. Synthetic polybutadiene rubber
1, 3-butadiene-toluene solution (3.63 mL,18.5 mmol 1,3-butadiene) was rapidly injected into the above-described Schlenk flask charged with the rare earth catalyst, and the Shi Laike flask was immediately sealed and stirred at 40℃for 30 minutes. After completion, the flask was carefully opened and a hydrochloric acid/methanol solution (15 mL, wherein 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 was determined by gravimetric method, the yield of polybutadiene rubber was 87.2%, stereoselectivity: 99.4% of 1, 4-cis, 0.4% of 1, 4-trans, 0.2% of 1, 2-vinyl, mn 8.56X10 5 Mw/Mn was 1.52.
Example 3 (different from the 1,3-butadiene monomer concentration of example 1)
1. Preparation of zwitterionic rare earth alkyl catalysts
（1）Nd{C(SiHMe 2 ) 3 } 3 Is synthesized by the following steps: as in example 1.
（2）NdC(SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Is synthesized by the following steps: 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 [ C 4 Py]Cl/AlCl 3 0.022mmol of precatalyst NdC (SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Mixed with toluene (5 mL) solvent and aged at 21 ℃ for 10 minutes to give rare earth catalyst.
2. Synthetic polybutadiene rubber
1, 3-butadiene-toluene solution (3.63 mL,18.5 mmol 1,3-butadiene) was rapidly injected into the above-described Schlemk flask charged with the rare earth catalyst, and the Shi Laike flask was immediately sealed and stirred at 21℃for 1 hour. After completion, the flask was carefully opened and a hydrochloric acid/methanol solution (15 mL, wherein 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, 85.3%, stereoselectivity: 99.2% of 1, 4-cis, 0.6% of 1, 4-trans, 0.2% of 1, 2-vinyl, mn 8.05X10 5 Mw/Mn was 1.98.
Example 4 (different from the rare earth element type of the catalyst in example 1)
1. Preparation of zwitterionic rare earth alkyl catalysts
（1）Ce{C(SiHMe 2 ) 3 } 3 Is synthesized by the following steps: 0.183g (0.226 mmol) CeI 3 (THF) 3 With 0.175g (0.735 mmol) KC (SiHMe) 2 ) 3 (molar ratio 1:3) in 5mL of benzene solvent at room temperature for 12h, during the reaction, the color of the solution changed from red toYellow. After evaporation of the volatiles, extraction with pentane (3X 5 mL) gave after evaporation of pentane 0.141g (0.195 mmol) of a viscous yellow solid (88.2% yield) as Ce { C (SiHMe) 2 ) 3 } 3 。
（2）CeC(SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Is synthesized by the following steps: 0.199g (0.389 mmol) of B (C 6 F 5 ) 3 With 0.138g (0.195 mmol) Ce { C (SiHMe 2 ) 3 } 3 (molar ratio 2:1) in 5mL benzene, stirring at room temperature for 30min, washing the resulting product with pentane (2X 5 mL), and then drying in vacuo gave 0.218g (0.163 mmol) of a yellow solid (yield 83%), ceC (SiHMe) 2 ) 3 {HB(C 6 F 5 ) 3 } 2 。
(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 [ C 4 Py]Cl/AlCl 3 0.022mmol of precatalyst CeC (SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Mix with solvent toluene (1 mL) and age for 10 minutes at 21 ℃.
2. Synthetic polybutadiene rubber
1, 3-butadiene-toluene solution (3.63 mL,18.5 mmol 1,3-butadiene) was rapidly injected 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 15 minutes. After completion, the flask was carefully opened and a hydrochloric acid/methanol solution (15 mL, wherein 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 as 85.7%, stereoselectivity: 99.0% of 1, 4-cis, 0.6% of 1, 4-trans, 0.4% of 1, 2-vinyl, mn 8.67×10 5 Mw/Mn was 1.55.
Comparative example 1 (different from the ionic liquid used in example 1)
1. Preparation of zwitterionic rare earth alkyl catalysts
（1）Nd{C(SiHMe 2 ) 3 } 3 Is synthesized by the following steps: as in example 1.
（2）NdC(SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Is synthesized by the following steps: 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 1-butyl-3-methylimidazole chloroaluminate ([ BMIM)]Cl-2AlCl 3 ) 0.022mmol of precatalyst NdC (SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Mix with solvent toluene (1 mL) and age for 10 minutes at 21 ℃.
2. Synthetic polybutadiene rubber
1, 3-butadiene-toluene solution (3.63 mL,18.5 mmol 1,3-butadiene) was rapidly injected into the above-described Schlenk flask charged with the rare earth catalyst, and the Shi Laike flask was immediately sealed and stirred at 40℃for 30 minutes. After completion, the flask was carefully opened and a hydrochloric acid/methanol solution (15 mL, wherein 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 determination, yield of polybutadiene rubber 79.8%, stereoselectivity: 65.7% of 1, 4-cis, 21.4% of 1, 4-trans, 12.9% of 1, 2-vinyl, mn 8.98X10 5 Mw/Mn was 3.12.
Comparative example 2 (different from the ionic liquid used in example 1)
1. Preparation of zwitterionic rare earth alkyl catalysts
（1）Nd{C(SiHMe 2 ) 3 } 3 Is synthesized by the following steps: as in example 1.
（2）NdC(SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Is synthesized by the following steps: as in example 1.
(3) Sequentially vacuumizing and baking the clean Schlenk reaction bottle without foreign matters at high temperatureThen, nitrogen is filled for three times; under nitrogen protection, 0.22mmol of tributyl-monomethyl-ammonium chloroaluminate ([ N) 4,4,4,1 ]Cl-2AlCl 3 ) 0.022mmol of precatalyst NdC (SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Mix with solvent toluene (1 mL) and age for 10 minutes at 21 ℃.
2. Synthetic polybutadiene rubber
1, 3-butadiene-toluene solution (3.63 mL,18.5 mmol 1,3-butadiene) was rapidly injected into the above-described Schlenk flask charged with the rare earth catalyst, and the Shi Laike flask was immediately sealed and stirred at 40℃for 30 minutes. After completion, the flask was carefully opened and a hydrochloric acid/methanol solution (15 mL, wherein 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, 81.8% and stereoselectivity: 51.7%1, 4-cis, 27.3%1, 4-trans, 21%1, 2-vinyl, mn 8.87×10 5 Mw/Mn was 2.76.
Comparative example 3 (different from the ionic liquid used in example 1)
1. Preparation of zwitterionic rare earth alkyl catalysts
（1）Nd{C(SiHMe 2 ) 3 } 3 Is synthesized by the following steps: as in example 1.
（2）NdC(SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Is synthesized by the following steps: 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 triethylamine hydrochloride-aluminum trichloride ionic liquid ([ Et) 3 HN]Cl/AlCl 3 ) 0.022mmol of precatalyst NdC (SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Mix with solvent toluene (1 mL) and age for 10 minutes at 21 ℃.
2. Synthetic polybutadiene rubber
1, 3-butadiene-toluene solution (3.63 mL,18.5 mmol 1,3-butadiene) was rapidly injected into the above-described Schlenk flask charged with the rare earth catalyst, and the Shi Laike flask was immediately sealed and stirred at 40℃for 30 minutes. After completion, the flask was carefully opened and a hydrochloric acid/methanol solution (15 mL, wherein 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 84.6%, stereoselectivity: 58.4%1, 4-cis, 26.1%1, 4-trans, 15.5%1, 2-vinyl, mn 8.54×10 5 Mw/Mn was 2.71.
As can be seen from a comparison of example 1 with comparative examples 1-3, an activator [ C ] was used 4 Py]Cl/AlCl 3 Compared to catalysts using activators [ BMIM ]]Cl-2AlCl 3 、[N 4,4,4,1 ]Cl-2AlCl 3 、[Et 3 HN]Cl/AlCl 3 The catalyst of (2) can obtain higher polybutadiene yield and higher cis-selectivity, and the molecular weight distribution of the obtained polybutadiene is narrower but the molecular weight is slightly lower.
Claims (10)
1. A zwitterionic rare earth element alkyl catalyst characterized by: the zwitterionic rare earth element alkyl catalyst is prepared from a zwitterionic complex, 1-butylpyridinium chloroaluminate and a solvent, wherein the zwitterionic complex has the chemical formula of LnC (SiHMe 2 ) 3 {HB(C 6 F 5 ) 3 } 2 Wherein Ln represents rare earth element selected from one of lanthanum, cerium, praseodymium and neodymium, and the solvent is toluene and/or hexane; in the zwitterionic rare earth element alkyl catalyst, the molar ratio of the rare earth element in the zwitterionic complex to the 1-butylpyridinium chloroaluminate is 1:10-1:200, and the molar ratio of the solvent to the zwitterionic complex is 100-3000.
2. The zwitterionic rare earth element alkyl catalyst of claim 1 wherein: the molar ratio of the rare earth element to the 1-butylpyridinium chloroaluminate in the zwitterionic complex is 1:10-1:50.
3. The zwitterionic rare earth element alkyl catalyst of claim 1 wherein: the molar ratio of the solvent to the zwitterionic complex is 300-600.
4. A method for preparing the zwitterionic rare earth element alkyl catalyst as claimed in any one of claims 1 to 3, characterized in that: the preparation method comprises the following steps: mixing the zwitterionic complex, the 1-butyl pyridine chloroaluminate and the solvent, and aging for 5-60 minutes at the temperature of 10-40 ℃ to obtain the zwitterionic rare earth element alkyl catalyst.
5. The method of manufacturing according to claim 4, wherein: the aging conditions are as follows: aging at 20-25deg.C for 10-30 min.
6. The method of manufacturing according to claim 4, wherein: the preparation process of the preparation method is implemented under the protection of inert gas.
7. Use of a zwitterionic rare earth element alkyl catalyst according to any one of claims 1 to 3 in the preparation of polybutadiene, comprising: the amphoteric ion rare earth element alkyl catalyst is adopted to catalyze the polymerization reaction of the 1,3-butadiene monomer, and the polybutadiene product is obtained.
8. The use according to claim 7, wherein: the application implementation steps are as follows: mixing 1,3-butadiene monomer and amphoteric ion rare earth element alkyl catalyst in a solvent, and then carrying out polymerization reaction at 10-80 ℃ under the protection of inert gas.
9. The use according to claim 8, wherein: the amount of the zwitterionic rare earth element alkyl catalyst is controlled to be such that the molar ratio of the rare earth element to the 1,3-butadiene monomer is 1.0X10 -5 ~1.2×10 -3 。
10. The use according to claim 8, wherein: in the polymerization reaction system, the feeding concentration of the 1,3-butadiene is 1.5-4M.
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