CN117247485A - Rare earth catalyst containing bis (benzimidazolyl) methylamine lanthanum complex and preparation and application thereof - Google Patents
Rare earth catalyst containing bis (benzimidazolyl) methylamine lanthanum complex and preparation and application thereof Download PDFInfo
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- -1 bis (benzimidazolyl) methylamine lanthanum Chemical compound 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 56
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000010668 complexation reaction Methods 0.000 title abstract description 4
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 39
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 32
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 13
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 13
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 claims abstract description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 47
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 72
- 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
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 239000012190 activator Substances 0.000 description 11
- 229920001971 elastomer Polymers 0.000 description 11
- 239000005060 rubber Substances 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229920002554 vinyl polymer Polymers 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 8
- 238000011049 filling Methods 0.000 description 8
- 239000002608 ionic liquid Substances 0.000 description 8
- 239000012041 precatalyst Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- XWSGEVNYFYKXCP-UHFFFAOYSA-N 2-[carboxymethyl(methyl)amino]acetic acid Chemical compound OC(=O)CN(C)CC(O)=O XWSGEVNYFYKXCP-UHFFFAOYSA-N 0.000 description 1
- UZGARMTXYXKNQR-UHFFFAOYSA-K 7,7-dimethyloctanoate;neodymium(3+) Chemical compound [Nd+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O UZGARMTXYXKNQR-UHFFFAOYSA-K 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000009566 Mao-to Substances 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
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation 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
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 150000003956 methylamines Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- BMHHUDTYDROHFH-UHFFFAOYSA-N n-(1h-benzimidazol-2-yl)-1h-benzimidazol-2-amine Chemical compound C1=CC=C2NC(NC=3NC4=CC=CC=C4N=3)=NC2=C1 BMHHUDTYDROHFH-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 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
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a rare earth catalyst containing bis (benzimidazolyl) methylamine lanthanum complex, and preparation and application thereof. The rare earth catalyst containing the bis (benzimidazolyl) methylamine lanthanum complex is prepared from the bis (benzimidazolyl) methylamine lanthanum complex, triisobutyl aluminum and tributyl monomethyl ammonium chloride, wherein the bis (benzimidazolyl) methylamine lanthanum complex is prepared from N, N-bis (2-benzimidazolemethylene) methylamine and LnCl 3 (THF) n Obtained by a sufficient reaction in THF, wherein Ln represents a lanthanide. The invention provides an application of the rare earth catalyst containing bis (benzimidazolyl) methylamine lanthanum complex in preparing polybutadiene. The rare earth catalyst provided by the invention has the advantages of high activity, high conversion rate and the like, can be used for preparing high-quality polybutadiene with ultrahigh cis-form, high molecular weight and narrow molecular weight distribution, and has high product yield.
Description
Technical Field
The invention relates to a rare earth catalyst containing bis (benzimidazolyl) methylamine lanthanum complex, and preparation 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 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%).
Renan Cariou et al [ Renan Cariou, juan Chirinos, vernon C.Gibson, grant Jacobsen, atanas K.Tomov, and Mark R.J.Elsegood.1,3-Butadiene Polymerization by Bis (Benzimidazolyl) amine Metal Complexes: remarkable Microstructural Control and a Protocol for In-Reactor Blending of trans-1,4-, cis-1,4-, and cis-1,4-co-1,2-Vinyl polybutadiene. Macromolecules 2009,42,1443-1444 ]]Treatment of CrCl with bis (benzimidazol-2-alkyl) methylamines 3 (thf) 3 And cobalt chloride, preparing a chromium pre-catalyst 1 and a cobalt pre-catalyst 2, and forming a catalytic system by the chromium pre-catalyst 1 or the cobalt pre-catalyst 2 and an activator MAO to catalyze the polymerization of butadiene, wherein the 1, 4-trans selectivity in polybutadiene obtained by the catalysis of the MAO activated chromium pre-catalyst 1 is as high as 99%; while MAO activated cobalt pre-catalyst 2 obtained a high cis-1,4 microstructure (-97%) with a molecular weight of (560-720) x 10 3 In the g/mol range, but the conversion of butadiene under the catalysis of MAO-activated cobalt pre-catalyst 2 is only 50.9% at maximum.
The ionic liquid is a salt composed of an organic cation and an inorganic or organic anion in a liquid state at room temperature, and is widely used for acylation, polymerization, isomerization, alkylation, epoxidation and other reactions as a novel green solvent and catalyst, and has excellent properties such as stable physicochemical properties, good conductivity, low vapor pressure and the like. RamInd n D i-az de Le-n et al [ RamNDi-az de Le-n, mari a Teresa Alonso C D ova, francisco Javier Enr i-quez Medrano, jos i-Ez Elizondo, odilia P-rez Camach, alo Romo Quiroz, rosa Idalia Narro C e seeds, adaliFacio.Polymerization of 1,3-Butadiene with Several Catalytic Systems Based on Neodymium or Lithiumin Presence of Ionic Liquids.Macromol.Symp.2013,325-326,194-202]Disclosed is a process for polymerizing 1,3 butadiene by adding an ionic liquid to a NdV (neodymium neodecanoate)/TIBA (triisobutylaluminum)/DEAC (diethylaluminum chloride) Ziegler-Natta polymerization catalyst system, the presence of the ionic liquid reducing the exotherm of the reaction, promoting the production of higher molecular weights and reducing the molecular weight distribution, but the yield of polybutadiene is significantly reduced, especially by adding a chlorine-containing ionic liquid [ EMIM][Cl]In this case, the polybutadiene yield was only 19% when the polymerization reaction was carried out for 180 minutes, and the cis-selectivity was significantly lowered.
Therefore, the development of a novel rare earth catalyst for synthesizing polybutadiene rubber to obtain high-quality polybutadiene rubber with ultrahigh cis structure content, high molecular weight and narrow molecular weight distribution in high yield is a problem to be solved urgently at present.
Disclosure of Invention
The primary aim of the invention is to provide a rare earth catalyst containing bis (benzimidazolyl) methylamine lanthanum complex, which has the advantages of high catalytic activity, high selectivity and the like.
The second object of the present invention is to provide a method for preparing a rare earth catalyst containing bis (benzimidazolyl) lanthanum methylamine complex, which can prepare the rare earth catalyst.
The third object of the invention is to provide the application of the rare earth catalyst containing bis (benzimidazolyl) methylamine lanthanum complex in preparing polybutadiene, the method can remarkably improve the yield of polybutadiene by adopting the rare earth catalyst, and the polybutadiene product has ultrahigh cis structure content, high molecular weight and narrow molecular weight distribution.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a rare earth catalyst comprising a bis (benzimidazolyl) lanthanum methylamine complex, which is prepared from a bis (benzimidazolyl) lanthanum methylamine complex, triisobutylaluminum (Al (iBu) 3 ) And tributyl monomethyl ammonium chloride ([ N) 4,4,4,1 ][Cl]) Is prepared from N, N-di (2-benzimidazole methylene) methylamine and LnCl 3 (THF) n Fully reacting in THF to obtain the catalyst, wherein Ln represents lanthanide, specifically one of lanthanum (La), cerium (Ce), praseodymium (Pr) and neodymium (Nd), and when Ln is La or Ce, n=4; when Ln is Pr or Nd, n=3;
in the rare earth catalyst, the mol ratio of the lanthanide to the triisobutylaluminum is 1:10-1:200; the molar ratio of tributyl monomethyl ammonium chloride to lanthanide is 10-1000.
The preparation of the bis (benzimidazolyl) lanthanum methylamine complex precatalyst can be referred to the literature [ Atanas K Tomov, etc. an Unprecedenta alpha-Olefin Distribution Arising From a Homogeneous Ethylene Oligomerization catalyst.J Am Chem Soc.2006Jun 21;128 7704-5] can be prepared generally according to a preparation process comprising the following steps:
n, N-bis (2-benzimidazole methylene) methylamine and LnCl 3 (THF) n The mixture of (2) is stirred in THF for 10-15 hours, the product is filtered, washed thoroughly with THF, washed with diethyl ether and then dried under vacuum to obtain a solid, namely the bis (benzimidazolyl) methylamine lanthanum complex. Preferably, the N, N-bis (2-benzimidazole methylene) methylamine and LnCl 3 (THF) n The feeding mole ratio of (2) is 1-1.5: 1.
preferably, the molar ratio of the lanthanide element to triisobutylaluminum in the bis (benzimidazolyl) lanthanum methylamine complex is 1:10-1:50.
Preferably, the molar ratio of tributyl monomethyl ammonium chloride to lanthanide in the bis (benzimidazolyl) methylamine lanthanum complex is 200-1000:1.
In a second aspect of the present invention, there is provided a method for preparing a rare earth catalyst containing a bis (benzimidazolyl) lanthanum methylamine complex, comprising the steps of: mixing bis (benzimidazolyl) lanthanum methylamine complex, triisobutylaluminum and tributyl monomethyl ammonium chloride, and aging for 5-60 minutes at 10-40 ℃ to obtain the rare earth catalyst containing the bis (benzimidazolyl) lanthanum methylamine complex. To further facilitate the catalyst preparation efficiency, the above preparation process can be generally carried out under the protection of inert gas, and the inert gas adopted is not strictly limited in the inventionFor example, more economical nitrogen (N) 2 ) Etc.
Preferably, the aging conditions are: aging at 20-25deg.C for 10-30 min. More preferred aging conditions are: aging at 20-25deg.C for 20-30 min.
In a third aspect of the present invention, there is also provided the use of the rare earth catalyst containing bis (benzimidazolyl) lanthanum methylamine complex in the preparation of polybutadiene, comprising: and catalyzing the 1,3-butadiene monomer to carry out polymerization reaction by adopting the rare earth catalyst containing the bis (benzimidazolyl) methylamine lanthanum complex to obtain a polybutadiene product.
Specifically, the implementation steps of the application are as follows: mixing 1,3-butadiene monomer and rare earth catalyst containing bis (benzimidazolyl) methylamine lanthanum complex in solvent, and then carrying out polymerization reaction at 20-80 ℃; the reaction process is carried out under the protection of inert gas.
Preferably, the solvent is toluene.
Preferably, the inert gas is nitrogen.
Preferably, the amount of rare earth catalyst containing bis (benzimidazolyl) lanthanum methylamine complex is controlled so that the molar ratio of lanthanide to butadiene monomer is 1.0X10 -5 ~1.0×10 -3 。
Preferably, the 1,3-butadiene is fed in a polymerization reaction system at a concentration of 1.5 to 4M.
The preparation method of the invention adopts the high-activity rare earth catalyst, so that the polymerization reaction can be carried out at room temperature, and the operation is simple and convenient. Under the polymerization conditions of the invention, higher polymerization efficiency can be achieved, and the polymerization can be completed within 15-60 min.
Compared with the prior art, the invention has at least the following beneficial effects:
the rare earth catalyst provided by the invention is a novel rare earth catalytic system based on N, N-di (2-benzimidazole methylene) methylamine, has the advantages of high activity, high conversion rate 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 8.5x10) 5 ) Narrow molecular weight fractionCloth (Mw/Mn is as low as 1.60), and the yield of the product is high (more than 91%).
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 rare earth catalyst
(1) Synthesis of N, N-bis (2-benzimidazole methylene) methylamine: o-phenylenediamine (5.88 g,54.4 mmol) and methyliminodiacetic acid (4.00 g,27.2 mmol) were stirred in ethylene glycol (20 ml) at 190℃for 4h. The water produced during the reaction was removed by distillation. After cooling the reaction mixture to room temperature, the product was triturated with water (120 ml), filtered, washed with water (4×20 ml), recrystallized from a hot methanol-water mixture (volume ratio 1:1) and dried under vacuum at 60 ℃ for 48 hours. A pale pink solid was obtained, yield 6.88g (87%).
(2) Synthesis of bis (benzimidazolyl) neodymium methylamine complex: n, N-bis (2-benzimidazolemethylene) methylamine (2.00 g,6.9 mmol) and NdCl 3 (THF) 3 A mixture of (3.22 g,6.9 mmol) was stirred in THF (20 ml) for 12 hours. The product was filtered, washed twice with THF (2×20 ml), once with diethyl ether (20 ml) and then dried under vacuum to give 3.46g of solid as bis (benzimidazolyl) methylamine neodymium complex.
(3) Sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; under nitrogen, 0.22mmol of activator Al (iBu) was added 3 0.022mmol of bis (benzimidazolyl) methylamineNeodymium Complex and 4.4mmol [ N ] 4,4,4,1 ][Cl]Mix and age for 10 minutes at 21 ℃.
2. Synthetic polydiene rubber
1, 3-butadiene-toluene solution (3.63mL,18.5mmol 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 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 93.7% by weight, stereoselectivity: 99.6% of 1, 4-cis, 0.3% of 1, 4-trans, 0.1% of 1,2-vinyl, mn 9.32X10 5 Mw/Mn was 1.60.
Example 2 (different from example 1 aging time)
1. Preparation of rare earth catalyst
(1) Synthesis of N, N-bis (2-benzimidazole methylene) methylamine: the same embodiment.
(2) Synthesis of bis (benzimidazolyl) neodymium methylamine complex: 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, 0.22mmol of activator Al (iBu) was added 3 0.022mmol of bis (benzimidazolyl) neodymium methylamine complex and 4.4mmol of [ N ] 4,4,4,1 ][Cl]Mix and age at 21 ℃ for 20 minutes.
2. Synthetic polydiene rubber
1, 3-butadiene-toluene solution (3.63mL,18.5mmol 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 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.
By weight ofThe yield was measured by quantitative method, the yield of polybutadiene rubber was 94.2%, stereoselectivity: 99.2% of 1, 4-cis, 0.5% of 1, 4-trans, 0.3% of 1,2-vinyl, mn 8.78X10 5 Mw/Mn was 1.83.
Example 3 (different from the amount of ionic liquid used in example 1)
1. Preparation of rare earth catalyst
(1) Synthesis of N, N-bis (2-benzimidazole methylene) methylamine: as in example 1.
(2) Synthesis of bis (benzimidazolyl) neodymium methylamine complex: 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, 0.22mmol of activator Al (iBu) was added 3 0.022mmol of bis (benzimidazolyl) neodymium methylamine complex and 22mmol of [ N ] 4,4,4,1 ][Cl]Mix and age for 10 minutes at 21 ℃.
2. Synthetic polydiene rubber
1, 3-butadiene-toluene solution (3.63mL,18.5mmol 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 21℃for 2 hours. 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 determination, yield of polybutadiene rubber was 92.8%, stereoselectivity: 99.3% of 1, 4-cis, 0.5% of 1, 4-trans, 0.2% of 1,2-vinyl, mn 8.53×10 5 Mw/Mn was 2.13.
Example 4 (different from the rare earth element type of the catalyst in example 1)
1. Preparation of rare earth catalyst
(1) Synthesis of N, N-bis (2-benzimidazole methylene) methylamine: as in example 1.
(2) Synthesis of bis (benzimidazolyl) ceryl methylamine complexes: n, N-bis (2-benzimidazolemethylene) methylamine (2.00 g,6.9 mmol) and CeCl 3 (THF) 3 A mixture of (3.19 g,6.9 mmol) was stirred in THF (20 ml) for 12 hours. The product was filtered, washed twice with THF (2×20 ml), once with diethyl ether (20 ml) and then dried under vacuum to give 3.24g (91% yield) of solid as bis (benzimidazolyl) methylamine cerium complex.
(3) Sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; under nitrogen, 0.22mmol of activator Al (iBu) was added 3 0.022mmol of bis (benzimidazolyl) methylamine cerium complex and 4.4mmol of [ N ] 4,4,4,1 ][Cl]Mix and age for 10 minutes at 21 ℃.
2. Synthetic polydiene rubber
1, 3-butadiene-toluene solution (3.63mL,18.5mmol 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 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, 91.7%, stereoselectivity: 99.0% of 1, 4-cis, 0.6% of 1, 4-trans, 0.4% of 1,2-vinyl, mn 8.96×10 5 Mw/Mn was 1.55.
Comparative example 1 (different from the activator in example 1)
1. Preparation of rare earth catalyst
(1) Synthesis of N, N-bis (2-benzimidazole methylene) methylamine: as in example 1.
(2) Synthesis of bis (benzimidazolyl) neodymium methylamine complex: 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 activator diethylaluminum chloride (Et) 2 AlCl), 0.022mmol bis (benzimidazolyl) methylamine neodymium complex and 4.4mmol [ N ] 4,4,4,1 ][Cl]Mix and age for 10 minutes at 21 ℃.
2. Synthetic polydiene rubber
1, 3-butadiene-toluene solution (3.63mL,18.5mmol 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 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 the polybutadiene rubber was 73.1% by weight, the stereoselectivity was 81.5%1, 4-cis, 10.3%1, 4-trans, 8.2%1, 2-vinyl and Mn was 6.14X10 5 Mw/Mn was 2.64.
Comparative example 2 (different from the activator in example 1)
1. Preparation of rare earth catalyst
(1) Synthesis of N, N-bis (2-benzimidazole methylene) methylamine: as in example 1.
(2) Synthesis of bis (benzimidazolyl) neodymium methylamine complex: 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, 0.095ml of MMAO-12 toluene solution with mass fraction of 7% Al (density of 0.895g/ml, containing 0.22mmol Al), 0.022mmol of bis (benzimidazolyl) methylamine neodymium complex and 4.4mmol of [ N ] 4,4,4,1 ][Cl]Mix and age for 10 minutes at 21 ℃.
2. Synthetic polydiene rubber
1, 3-butadiene-toluene solution (3.63mL,18.5mmol 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 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 64.1% and stereoselectivity90.3% of 1, 4-cis, 6.4% of 1, 4-trans, 3.3% of 1,2-vinyl, mn 7.89X 10 5 Mw/Mn was 2.86.
As can be seen from a comparison of example 1 with comparative examples 1-2, the rare earth catalyst of the present invention containing bis (benzimidazolyl) lanthanum methylamine complex uses Al (iBu) 3 As activator, as compared with the use of diethylaluminum chloride (Et) 2 AlCl), modified methylaluminoxane (MMAO-12), higher polybutadiene yields can be obtained, the resulting polybutadiene having higher molecular weight, higher 1, 4-cis selectivity and narrower molecular weight distribution.
Comparative example 3
1. Preparation of rare earth catalyst
(1) Synthesis of N, N-bis (2-benzimidazole methylene) methylamine: as in example 1.
(2) Synthesis of bis (benzimidazolyl) neodymium methylamine complex: 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, 0.035g (0.22 mmol) of activator Al (iBu) was added 3 0.022mmol of bis (benzimidazolyl) methylamine neodymium complex was mixed with solvent toluene (1 mL) and aged at 21 ℃ for 10 min.
2. Synthetic polydiene rubber
1, 3-butadiene-toluene solution (3.63mL,18.5mmol 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 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 87.3%, stereoselectivity: 82.7% of 1, 4-cis, 9.3% of 1, 4-trans, 7% of 1,2-vinyl, mn 4.15X10 5 Mw/Mn was 2.86.
Comparative example 4 (type of ionic liquid different from that in example 1)
1. Preparation of rare earth catalyst
(1) Synthesis of N, N-bis (2-benzimidazole methylene) methylamine: as in example 1.
(2) Synthesis of bis (benzimidazolyl) neodymium methylamine complex: 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, 0.22mmol of activator Al (iBu) was added 3 0.022mmol of bis (benzimidazolyl) methylamine neodymium complex and 4.4mmol of 1-butyl-3-methylimidazole tetrafluoroborate salt [ BMIM ]][BF 4 ]Mix and age for 10 minutes at 21 ℃.
2. Synthetic polydiene rubber
1, 3-butadiene-toluene solution (3.63mL,18.5mmol 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 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 88.2% by weight, stereoselectivity: 85.6%1, 4-cis, 9.9%1, 4-trans, 4.5%1, 2-vinyl, mn 6.95×10 5 Mw/Mn was 2.79.
As can be seen from a comparison of example 1 with comparative example 4, the rare earth catalyst containing bis (benzimidazolyl) lanthanum methylamine complex according to the invention uses [ N ] 4,4,4,1 ][Cl](1 mL) the polybutadiene yield can be significantly increased and the 1, 4-cis selectivity, molecular weight and molecular weight distribution of the polybutadiene product can be improved compared to the use of conventional solution toluene or ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate.
Claims (10)
1. A rare earth catalyst containing bis (benzimidazolyl) lanthanum methylamine complex, characterized in that: the rare earth catalyst containing the bis (benzimidazolyl) lanthanum methylamine complex consists of the bis (benzimidazolyl) lanthanum methylamine complex, triisobutylaluminum and triButyl monomethyl ammonium chloride salt, wherein the bis (benzimidazolyl) methylamine lanthanum complex is prepared from N, N-bis (2-benzimidazolylmethylene) methylamine and LnCl 3 (THF) n Fully reacting in THF to obtain, wherein Ln represents a lanthanide element, specifically selected from one of lanthanum, cerium, praseodymium and neodymium, and when Ln is La or Ce, n=4; when Ln is Pr or Nd, n=3;
in the rare earth catalyst, the mol ratio of the lanthanide to the triisobutylaluminum is 1:10-1:200; the molar ratio of tributyl monomethyl ammonium chloride to lanthanide is 10-1000.
2. The rare earth catalyst containing bis (benzimidazolyl) lanthanum methylamine complex as claimed in claim 1, wherein: the bis (benzimidazolyl) lanthanum methylamine complex is prepared according to the preparation process comprising the following steps:
n, N-bis (2-benzimidazole methylene) methylamine and LnCl 3 (THF) n The mixture of (2) is stirred in THF for 10-15 hours, the product is filtered, washed thoroughly with THF, washed with diethyl ether and then dried under vacuum to obtain a solid, namely the bis (benzimidazolyl) methylamine lanthanum complex.
3. The rare earth catalyst containing bis (benzimidazolyl) lanthanum methylamine complex as claimed in claim 2, wherein: the N, N-di (2-benzimidazole methylene) methylamine and LnCl 3 (THF) n The feeding mole ratio of (2) is 1-1.5: 1.
4. the rare earth catalyst containing bis (benzimidazolyl) lanthanum methylamine complex as claimed in claim 1, wherein: the molar ratio of the lanthanide element to the triisobutylaluminum in the bis (benzimidazolyl) lanthanum methylamine complex is 1:10-1:50.
5. The rare earth catalyst containing bis (benzimidazolyl) lanthanum methylamine complex as claimed in claim 1, wherein: the molar ratio of tributyl monomethyl ammonium chloride to lanthanide in the bis (benzimidazolyl) methylamine lanthanum complex is 200-1000:1.
6. A method for preparing the rare earth catalyst containing bis (benzimidazolyl) lanthanum methylamine complex as claimed in claim 1, wherein: the preparation method comprises the following steps: mixing bis (benzimidazolyl) lanthanum methylamine complex, triisobutylaluminum and tributyl monomethyl ammonium chloride, and aging for 5-60 minutes at 10-40 ℃ to obtain the rare earth catalyst containing the bis (benzimidazolyl) lanthanum methylamine complex.
7. The method of manufacturing according to claim 6, wherein: the preparation process of the preparation method is implemented under the protection of inert gas.
8. Use of a rare earth catalyst containing bis (benzimidazolyl) lanthanum methylamine complex as claimed in claim 1, in the preparation of polybutadiene, comprising: and catalyzing the 1,3-butadiene monomer to carry out polymerization reaction by adopting the rare earth catalyst containing the bis (benzimidazolyl) methylamine lanthanum complex to obtain a polybutadiene product.
9. The use according to claim 8, wherein: the application implementation steps are as follows: mixing 1,3-butadiene monomer and rare earth catalyst containing bis (benzimidazolyl) methylamine lanthanum complex in solvent, and then carrying out polymerization reaction at 20-80 ℃; the reaction process is carried out under the protection of inert gas.
10. The use according to claim 9, wherein: the amount of rare earth catalyst containing bis (benzimidazolyl) lanthanum methylamine complex is controlled so that the molar ratio of lanthanide to butadiene monomer is 1.0X10 -5 ~1.0×10 -3 The method comprises the steps of carrying out a first treatment on the surface of the The feeding concentration of 1,3-butadiene in the polymerization reaction system is 1.5-4M.
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