CN117106115B - Butadiene polymerization pre-catalyst and preparation method thereof, catalyst and preparation method of polybutadiene - Google Patents
Butadiene polymerization pre-catalyst and preparation method thereof, catalyst and preparation method of polybutadiene Download PDFInfo
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 188
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 44
- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 43
- 239000012041 precatalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000005062 Polybutadiene Substances 0.000 title claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 150
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 80
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 44
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims abstract description 31
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 89
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 38
- 239000000243 solution Substances 0.000 description 36
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 14
- 229920001971 elastomer Polymers 0.000 description 14
- 239000005060 rubber Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 238000011049 filling Methods 0.000 description 10
- 239000012621 metal-organic framework Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 229920002554 vinyl polymer Polymers 0.000 description 10
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 9
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 229910052779 Neodymium Inorganic materials 0.000 description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ZJJGTEYQUYIFGN-UHFFFAOYSA-N 4,5-dimethyl-1H-imidazole 2-methyl-1H-imidazole Chemical compound CC=1NC=CN1.CC1=C(N=CN1)C ZJJGTEYQUYIFGN-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000013241 lanthanide-based metal–organic framework Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 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
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-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
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- 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 butadiene polymerization pre-catalyst and a preparation method thereof, a catalyst and a preparation method of polybutadiene. The butadiene polymerization pre-catalyst is prepared by the following method: taking a ZIF-8 sample, ultrasonically dispersing the ZIF-8 sample in methanol, taking neodymium chloride, ultrasonically dissolving the neodymium chloride in deionized water, dropwise adding the neodymium chloride solution into ZIF-8 suspension, and magnetically stirring the solution at room temperature for 8-12 hours; fully washing and drying to obtain Nd-ZIF-8; and mixing pyridine, a solvent and Nd-ZIF-8, stirring for 12-24 hours at room temperature, and removing the solvent to obtain the butadiene polymerization precatalyst. The invention provides a butadiene polymerization catalyst comprising a butadiene polymerization pre-catalyst, an alcohol and a modified methylaluminoxane. The invention also provides a preparation method of polybutadiene based on the catalyst, which not only can achieve higher polybutadiene yield, but also can prepare polybutadiene with ultrahigh cis-form, high molecular weight and narrow molecular weight distribution.
Description
Technical Field
The invention relates to a butadiene polymerization pre-catalyst and a preparation method thereof, a butadiene polymerization catalyst and a preparation method of polybutadiene based on the catalyst.
Background
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%).
Among catalysts for producing butadiene rubber, neodymium-based catalysts are more widely used than other metal catalysts because of their high activity and the economical and convenient preparation of the catalyst precursor. In addition, neodymium catalyst residues do not catalyze the aging of rubber.
In recent years, atomic ordered porous Metal Organic Frameworks (MOFs) have received widespread attention in the field of single-site heterogeneous catalysis. MOFs offer unique opportunities for single-site heterogeneous catalysis due to the monodispersed and well-defined transition metal coordination environment. The Secondary Building Units (SBUs) can be used as site isolation platforms of small molecules such as transition metal catalysts in high-surface-area solid carriers. Also, many SBUs are capable of cation exchange while maintaining a localized coordination structure, which also provides the possibility of incorporating rare earth metals into the desired coordination geometry.
Marta J, victorino et al [ Marta J, victorino, thomas Devic, moniek Tromp, G eard F earey, marc visleaux, lanthanide Metal-Organic Frameworks as Ziegler-Natta Catalysts for the Selective Polymerization of Isoprene, macromol chem. Phys 2009, 210, 1923-1932] disclose the ability of MIL-103 (Nd) as a pre-catalyst for isoprene polymerization in combination with Methylaluminoxane (MAO) or Modified MAO (MMAO), which mainly provides cis-selective polyisoprene up to 90.7%. And indicates that: the higher the porosity of the MOF precatalyst, the higher the efficiency of the catalyst. However, the high conversion rate and the high selectivity of the isoprene polymerization reaction under the catalyst system cannot be achieved, and the catalyst system has poor effect of catalyzing the polymerization reaction of butadiene.
The Zeolitic Imidazolate Frameworks (ZIFs) are MOFs materials that have been widely studied in recent years. The ZIFs material is self-assembled by four coordination modes of Zn or Co and N on an imidazole (or imidazole derivative) ring. The pore structure of ZIFs is relatively similar to that of an aluminosilicate zeolite. ZIFs have a range of structures and are easily functionalized. In addition, ZIFs have better thermal and chemical stability than other MOFs. Among ZIFs, ZIF-8 and ZIF-67 are most commonly synthesized, and are formed by coordinating Zn and Co with dimethyl imidazole (2-methylimidazole), respectively. These two ZIFs are relatively easy to synthesize and can be crystallized even at room temperature. In particular ZIF-8 has excellent stability.
Therefore, it is an expected research direction to develop a novel rare earth catalyst for synthesizing polybutadiene rubber based on ZIFs materials in order to obtain high quality polybutadiene rubber having ultra-high cis, high molecular weight and narrow molecular weight distribution in high yield.
Disclosure of Invention
The invention aims to provide a butadiene polymerization pre-catalyst and a preparation method thereof, a butadiene polymerization catalyst and a preparation method of polybutadiene based on the catalyst, wherein the catalyst has the advantages of high catalytic activity, high selectivity and the like, and can be used for preparing high-quality polybutadiene products with 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 one aspect of the present invention, there is provided a butadiene polymerization pre-catalyst prepared by the method comprising:
weighing a ZIF-8 sample, ultrasonically dispersing the ZIF-8 sample in methanol to obtain a ZIF-8 suspension, weighing neodymium chloride, ultrasonically dissolving the neodymium chloride in deionized water to obtain a neodymium chloride solution, dropwise adding the neodymium chloride solution into the ZIF-8 suspension, and magnetically stirring the neodymium chloride solution for 8-12 hours at room temperature; fully washing (preferably methanol and ethanol are used as washing reagents), and then drying in a vacuum oven at 50-80 ℃ for 8-24 hours to obtain Nd-ZIF-8; mixing pyridine, a solvent and Nd-ZIF-8, stirring for 12-24 hours at room temperature, enabling pyridine to enter a MOF gap through capillary action, and removing the solvent to obtain a solid, namely a butadiene polymerization precatalyst, namely Nd-ZIF-8 (py); the feeding mass ratio of the ZIF-8 sample to neodymium chloride to pyridine is 0.1 g: 0.1-0.2 g: 5-15 mg.
Preferably, the feeding mass ratio of the ZIF-8 sample to neodymium chloride to pyridine is 0.1 g: 0.1-0.15 g:5 to 15mg, more preferably 0.1 to g: 0.1-0.15 g:10mg.
The ZIF-8 sample provided by the invention can be synthesized according to a method reported in literature, and is specifically recommended to be synthesized according to the following method: dissolving 2-methylimidazole in methanol (MeOH) to form a clear solution; zn (NO) dissolved in methanol 3 ) 2 ·6H 2 O is added into the solution, and then the solution is vigorously stirred for 1 hour; after the resulting mixture was allowed to stand at room temperature for 24 hours, the product was separated into a white powder by centrifugation, and washed several times with deionized water and MeOH, and finally dried overnight under vacuum to give a ZIF-8 sample; the 2-methylimidazole is mixed with Zn (NO) 3 ) 2 ·6H 2 The mass ratio of O is 0.1-1 g:0.1 to 0.3g.
The butadiene polymerization pre-catalyst prepared by the invention has the advantages of high catalytic activity, high selectivity and the like after being activated.
In a second aspect, the present invention provides a method for preparing a butadiene polymerization pre-catalyst, the method comprising: weighing a ZIF-8 sample, ultrasonically dispersing the ZIF-8 sample in methanol to obtain a ZIF-8 suspension, weighing neodymium chloride, ultrasonically dissolving the neodymium chloride in deionized water to obtain a neodymium chloride solution, dropwise adding the neodymium chloride solution into the ZIF-8 suspension, and magnetically stirring the neodymium chloride solution for 8-12 hours at room temperature; fully washing (preferably methanol and ethanol are used as washing reagents), and then drying in a vacuum oven at 50-80 ℃ for 8-24 hours to obtain Nd-ZIF-8; mixing pyridine, a solvent and Nd-ZIF-8, stirring for 12-24 hours at room temperature, enabling pyridine to enter a MOF gap through capillary action, and removing the solvent to obtain a solid, namely a butadiene polymerization precatalyst, namely Nd-ZIF-8 (py); the feeding mass ratio of the ZIF-8 sample to neodymium chloride to pyridine is 0.1 g: 0.1-0.2 g: 5-15 mg.
Preferably, the feeding mass ratio of the ZIF-8 sample to neodymium chloride to pyridine is 0.1 g: 0.1-0.15 g:5 to 15mg, more preferably 0.1 to g: 0.1-0.15 g:10mg.
In a third aspect, the present invention provides a butadiene polymerization catalyst comprising the butadiene polymerization pre-catalyst of the first aspect, an alcohol, and a modified methylaluminoxane (MMAO-12); the alcohol is one or a mixture of more of isopropanol, methanol, ethanol and n-propanol;
the molar ratio of Nd element to alcohol in the butadiene polymerization pre-catalyst is 1:100-1:1000, and the molar ratio of Nd element to aluminum element in the modified methylaluminoxane in the butadiene polymerization pre-catalyst is 1:30-1:300.
Preferably, the molar ratio of Nd element to alcohol in the butadiene polymerization pre-catalyst is 1:200-1:500.
Preferably, the molar ratio of Nd element in the butadiene polymerization pre-catalyst to aluminum element in the modified methylaluminoxane is 1:50-1:150.
The modified methylaluminoxane (MMAO-12) used in the present invention may be commercially available, which may be in the form of a solution, and the preparation catalyst may be directly added thereto, so that the butadiene polymerization catalyst of the present invention may further comprise a solvent in the modified methylaluminoxane (MMAO-12) reagent. In a specific embodiment, the modified methylaluminoxane (MMAO-12) used is present in the form of its toluene solution and is added to prepare a butadiene polymerization catalyst.
The catalyst of the invention can be generally prepared according to the preparation process comprising the following steps: mixing a butadiene polymerization pre-catalyst and alcohol, aging for 5-60 minutes at 10-40 ℃, adding modified methylaluminoxane, mixing, and aging for 5-60 minutes at 10-40 ℃ to obtain the butadiene polymerization catalyst. 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.
Preferably, the aging conditions are: aging for 10-30 minutes at 20-25 ℃.
In a fourth aspect, the present invention provides a process for the preparation of polybutadiene comprising: the butadiene polymerization catalyst is adopted to catalyze the polymerization reaction of the 1, 3-butadiene monomer, and the polybutadiene product is obtained.
Specifically, the polybutadiene may be obtained by mixing a 1, 3-butadiene monomer and a butadiene polymerization catalyst in a solvent and then performing polymerization under the protection of an inert gas.
Preferably, the solvent is toluene.
Preferably, the inert gas is nitrogen.
Preferably, the amount of the butadiene polymerization catalyst is controlled so that the molar ratio of Nd element to 1, 3-butadiene monomer is 1.0X10 -5 ~1.0×10 -3 。
Preferably, the 1, 3-butadiene charge concentration in the polymerization reaction system is 1.5 to 4M.
Preferably, the polymerization reaction is carried out at room temperature, and the operation is simple and convenient. Under the polymerization conditions, the high polymerization efficiency can be achieved, and the polymerization can be completed within 1-2 hours generally.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, neodymium element and pyridine are introduced into a ZIF-8 structure to obtain the precatalyst, so that the catalytic performance of the butadiene polymerization catalyst mainly containing the precatalyst is improved.
(2) The butadiene polymerization catalyst prepared by the invention has the advantages of high activity, high selectivity and the like, and in practical application, the catalyst not only can achieve higher polybutadiene yield (up to more than 94 percent), but also can prepare the catalyst with ultrahigh cis-form (cis-1, 4-structure content is more than 98 percent) and high molecular weight (Mn is more than 9.5x10) 5 ) And polybutadiene rubber products of good properties such as narrow molecular weight distribution (Mw/Mn as low as 1.45).
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 the catalyst
(1) Synthesis of ZIF-8 vector: 0.4g of 2-methylimidazole was dissolved in 6 mL methanol (MeOH) to form a clear solution. 0.168 g Zn (NO) dissolved in 2 ml methanol 3 ) 2 ·6H 2 O was added to the above solution, followed by vigorous stirring for 1 hour. After the mixture was allowed to stand at room temperature for 24 hours, the product was isolated as a white powder by centrifugation and washed several times with deionized water and MeOH, and finally dried under vacuum overnight to give 0.11g ZIF-8.
(2) Synthesis of Nd-ZIF-8 (py): 0.1 g of ZIF-8 sample is weighed and dispersed in 20mL of methanol by ultrasonic, 0.1 g of g neodymium chloride is weighed and dissolved in 5mL deionized water by ultrasonic, the neodymium chloride solution is dripped into ZIF-8 suspension, and magnetic stirring is carried out at room temperature for 10 h; washing methanol and ethanol three times, drying 12h under vacuum oven at 60deg.C, adding mixed solution of 10mg pyridine and 5mL ethanol into the product, mixing and stirring at room temperature for 12h, allowing pyridine to enter MOF gap by capillary action, evaporating ethanol at 80deg.C to obtain Nd-ZIF-8 (py), detecting neodymium mass fraction in the catalyst by ICP-OES to 23.7%, and Soxhlet extracting 0.05g of Nd-ZIF-8 (py) prepared above: the extract was extracted with 150 mL acetone at 100℃for 24 hours, and 2.4mg of pyridine was contained in the extract by HPLC, whereby the mass fraction of pyridine in Nd-ZIF-8 (py) was calculated to be 4.8%.
(3) Sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; nd-ZIF-8 (py) (6.08 mg, 10. Mu. Mol Nd) was mixed with 0.38ml of isopropyl alcohol (5 mmol) under nitrogen, and aged at 21℃for 10 minutes, and 0.43ml of MMAO-12 toluene solution (density: 0.895g/ml, containing 1mmol of Al) having a mass fraction of 7% Al was added thereto to mix, and aged at 21℃for 10 minutes to prepare a catalyst.
2. Synthetic polydiene rubber
A toluene solution (3.63 mL,18.5 mmol 1,3-butadiene) of toluene (1 mL) and 1, 3-butadiene was rapidly injected into the above catalyst-loaded Schlemk flask, wherein the molar ratio of Nd element to 1, 3-butadiene in the catalyst was 5.4X10 -4 The Shi Laike flask was immediately sealed and stirred at 21 ℃ for 2 hours. After completion, the flask was carefully opened, quenched with a 1:5 volume ratio of concentrated hydrochloric acid to methanol in hydrochloric acid/methanol (15 mL) and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum at 80℃for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was 94.7% by weight, stereoselectivity: 98.5% of 1, 4-cis, 0.3% of 1, 4-trans, 0.2% of 1, 2-vinyl, mn 9.52×10 5 Mw/Mn was 1.50.
Example 2 (different from the Nd content in the catalyst of example 1)
1. Preparation of the catalyst
(1) Synthesis of ZIF-8 vector: as in example 1.
(2) Synthesis of Nd-ZIF-8 (py): 0.1 g of ZIF-8 sample is weighed and dispersed in 20mL of methanol by ultrasonic, 0.15 g of g neodymium chloride is weighed and dissolved in 10 mL deionized water by ultrasonic, neodymium chloride solution is dripped into ZIF-8 suspension, and magnetic stirring is carried out at room temperature for 10 h; washing methanol and ethanol for three times, drying 12h in a vacuum oven at 60 ℃, adding a mixed solution of 10mg pyridine and 5mL ethanol into the product, mixing and stirring for 12 hours at room temperature, allowing pyridine to enter a MOF gap through capillary action, evaporating ethanol at 80 ℃ to obtain Nd-ZIF-8 (py), and detecting that the mass fraction of neodymium in the catalyst is 33.8% and the mass fraction of pyridine is 4.3% according to the method of example 1.
(3) Sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; nd-ZIF-8 (py) (8.52 mg, 20. Mu. Mol Nd) was mixed with 0.38ml of isopropyl alcohol (5 mmol) under nitrogen, and aged at 21℃for 10 minutes, and 0.43ml of MMAO-12 toluene solution (density: 0.895g/ml, containing 1mmol of Al) having a mass fraction of 7% Al was added thereto to mix, and aged at 21℃for 10 minutes to prepare a catalyst.
2. Synthetic polydiene rubber
A toluene solution (3.63 mL,18.5 mmol 1,3-butadiene) of toluene (1 mL) and 1, 3-butadiene was rapidly injected into the above catalyst-loaded Schlemk flask, wherein the molar ratio of Nd element to 1, 3-butadiene in the catalyst was 1.1X10 -3 The Shi Laike flask was immediately sealed and stirred at 21 ℃ for 2 hours. After completion, the flask was carefully opened, quenched with a 1:5 volume ratio of concentrated hydrochloric acid to methanol in hydrochloric acid/methanol (15 mL) and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum at 80℃for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was determined by gravimetric method to be 96.9%, stereoselectivity: 98.7% of 1, 4-cis, 0.2% of 1, 4-trans, 0.1% of 1, 2-vinyl, mn 1.05X10 6 Mw/Mn was 1.45.
Example 3 (different from example 1 aging time)
1. Preparation of the catalyst
(1) Synthesis of ZIF-8 vector: as in example 1.
(2) Synthesis of Nd-ZIF-8 (py): 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; nd-ZIF-8 (py) (6.08 mg, 10. Mu. Mol Nd) was mixed with 0.38ml of isopropyl alcohol under nitrogen, and aged at 21℃for 20 minutes, and 0.43ml of MMAO-12 toluene solution (density: 0.895g/ml, containing 1mmol of Al) having a mass fraction of 7% Al was added, mixed, and aged at 21℃for 20 minutes to prepare a catalyst.
2. Synthetic polydiene rubber
A toluene solution (3.63 mL,18.5 mmol 1,3-butadiene) of toluene (1 mL) and 1, 3-butadiene was rapidly injected into the above catalyst-loaded Schlemk flask, wherein the molar ratio of Nd element to 1, 3-butadiene in the catalyst was 5.4X10 -4 The Shi Laike flask was immediately sealed and stirred at 21 ℃ for 2 hours. After completion, the flask was carefully opened and quenched with concentrated hydrochloric acid and a 1:5 volume ratio of hydrochloric acid/methanol solution (15 mL)And performing deintercalation and ultrasonic treatment for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum at 80℃for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was determined by gravimetric method, 95.8% and stereoselectivity: 98.7% of 1, 4-cis, 0.2% of 1, 4-trans, 0.1% of 1, 2-vinyl, mn 9.63×10 5 Mw/Mn was 1.54.
Example 4 (different from the 1, 3-butadiene solution monomer concentration of example 1)
1. Preparation of the catalyst
(1) Synthesis of ZIF-8 vector: as in example 1.
(2) Synthesis of Nd-ZIF-8 (py): as in example 2.
(3) Sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; nd-ZIF-8 (py) (6.08 mg, 10. Mu. Mol Nd) was mixed with 0.38ml of isopropyl alcohol under nitrogen, and aged at 21℃for 10 minutes, and 0.43ml of MMAO-12 toluene solution (density: 0.895g/ml, containing 1mmol of Al) having a mass fraction of 7% Al was added, mixed, and aged at 21℃for 10 minutes to prepare a catalyst.
2. Synthetic polydiene rubber
Toluene (4.96 mL) and a toluene solution of 1, 3-butadiene (3.63 mL,18.5 mmol 1, 3-butadiene) were rapidly injected into the above catalyst-loaded Schlemk flask, wherein the molar ratio of Nd element to 1, 3-butadiene in the catalyst was 5.4X10 -4 The Shi Laike flask was immediately sealed and stirred at 21 ℃ for 2 hours. After completion, the flask was carefully opened, quenched with a 1:5 volume ratio of concentrated hydrochloric acid to methanol in hydrochloric acid/methanol (15 mL) and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum at 80℃for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was 92.4% by weight, stereoselectivity: 98.5% of 1, 4-cis, 0.4% of 1, 4-trans, 0.1% of 1, 2-vinyl, mn 9.52×10 5 Mw/Mn was 1.92.
Comparative example 1 (in contrast to example 1, no pyridine was added to the catalyst)
1. Preparation of the catalyst
(1) Synthesis of ZIF-8 vector: as in example 1.
(2) Synthesis of Nd-ZIF-8: 0.1 g of ZIF-8 sample is weighed and dispersed in 20mL of methanol by ultrasonic, 0.1 g of g neodymium chloride is weighed and dissolved in 5mL deionized water by ultrasonic, neodymium chloride solution is dripped into ZIF-8 suspension, and magnetic stirring is carried out for 10 h; the catalyst was washed three times with methanol and ethanol, dried in a vacuum oven at 60℃for 12h, and cooled to give a Nd-ZIF-8 catalyst, the mass fraction of Nd in the catalyst was 24.9% as measured in the method of example 1.
(3) Sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; nd-ZIF-8 (5.78 mg, 10. Mu. Mol of Nd) was mixed with 0.38ml of isopropyl alcohol under nitrogen atmosphere, and aged at 21℃for 10 minutes, and 0.43ml of MMAO-12 toluene solution (density: 0.895g/ml, containing 1mmol of Al) having a mass fraction of 7% Al was added thereto, mixed, and aged at 21℃for 10 minutes to obtain a catalyst.
2. Synthetic polydiene rubber
A toluene solution (3.63 mL,18.5 mmol 1,3-butadiene) of toluene (1 mL) and 1, 3-butadiene was rapidly injected into the above catalyst-loaded Schlemk flask, wherein the molar ratio of Nd element to 1, 3-butadiene in the catalyst was 5.4X10 -4 The Shi Laike flask was immediately sealed and stirred at 21 ℃ for 2 hours. After completion, the flask was carefully opened, quenched with a 1:5 volume ratio of concentrated hydrochloric acid to methanol in hydrochloric acid/methanol (15 mL) and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum at 80℃for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was determined by gravimetric method as 85.1%, stereoselectivity: 89%,1, 4-cis, 6.4%1, 4-trans, 4.6%1, 2-vinyl, mn 6.75X10 5 Mw/Mn was 2.90.
As can be seen from a comparison of example 1 with comparative example 1, the addition of pyridine in the preparation of the precatalyst significantly increases the product yield, stereoselectivity, molecular weight and molecular weight distribution.
Comparative example 2 (different from the aluminum alkyl in example 1)
1. Preparation of the catalyst
(1) Synthesis of ZIF-8 vector: as in example 1.
(2) Synthesis of Nd-ZIF-8 (py): 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; nd-ZIF-8 (py) (6.08 mg, 10. Mu. Mol Nd) was mixed with 0.38ml of isopropanol under nitrogen and aged at 21℃for 10 minutes, and 1mmol of diethylaluminum chloride (Et) 2 AlCl) and aged at 21℃for 10 minutes.
2. Synthetic polydiene rubber
A toluene solution (3.63 mL,18.5 mmol 1,3-butadiene) of toluene (1 mL) and 1, 3-butadiene was rapidly injected into the above catalyst-loaded Schlemk flask, wherein the molar ratio of Nd element to 1, 3-butadiene in the catalyst was 5.4X10 -4 The Shi Laike flask was immediately sealed and stirred at 21 ℃ for 2 hours. After completion, the flask was carefully opened, quenched with a 1:5 volume ratio of concentrated hydrochloric acid to methanol in hydrochloric acid/methanol (15 mL) and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum at 80℃for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was 88.3% by weight, stereoselectivity: 86.6%,1, 4-cis, 9.5%1, 4-trans, 3.9%1, 2-vinyl, mn 5.95×10 5 Mw/Mn was 3.02.
Comparative example 3 (different from the aluminum alkyl in example 1)
1. Preparation of the catalyst
(1) Synthesis of ZIF-8 vector: as in example 1.
(2) Synthesis of Nd-ZIF-8 (py): 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; nd-ZIF-8 (py) (6.08 mg, 10. Mu. Mol Nd) was mixed with 0.38ml of isopropanol under nitrogen and aged at 21℃for 10 minutes, followed by1mmol of triisobutylaluminum (Al (iBu) was added 3 ) The catalyst was prepared after mixing and aging at 21℃for 10 minutes.
2. Synthetic polydiene rubber
Toluene (1 mL) and 1, 3-butadiene in toluene solution (3.63 mL,18.5 mmol 1,3-butadiene) were rapidly injected into a Schlenk flask for the above catalyst, wherein the molar ratio of Nd element to 1, 3-butadiene in the catalyst was 5.4X10 -4 The Shi Laike flask was immediately sealed and stirred at 21 ℃ for 2 hours. After completion, the flask was carefully opened, quenched with a 1:5 volume ratio of concentrated hydrochloric acid to methanol in hydrochloric acid/methanol (15 mL) and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum at 80℃for 20h to give polybutadiene rubber.
Yield by gravimetric determination, yield of polybutadiene rubber 79.2%, stereoselectivity: 77.4%,1, 4-cis, 12.9%1, 4-trans, 9.7%1, 2-vinyl, mn 5.98X10 5 Mw/Mn was 2.97.
Comparative example 4 (different from the aluminum alkyl in example 1)
1. Preparation of the catalyst
(1) Synthesis of ZIF-8 vector: as in example 1.
(2) Synthesis of Nd-ZIF-8 (py): 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; nd-ZIF-8 (py) (6.08 mg, 10. Mu. Mol Nd) was mixed with 0.38ml of isopropanol under nitrogen and aged at 21℃for 10 min, and 1mmol of triethylaluminum (AlEt) was added 3 ) The catalyst was prepared after mixing and aging at 21℃for 10 minutes.
2. Synthetic polydiene rubber
Toluene (1 mL) and 1, 3-butadiene in toluene solution (3.63 mL,18.5 mmol 1,3-butadiene) were rapidly injected into a Schlenk flask for the above catalyst, wherein the molar ratio of Nd element to 1, 3-butadiene in the catalyst was 5.4X10 -4 The Shi Laike flask was immediately sealed and stirred at 21 ℃ for 2 hours. After completion, the flask was carefully opened with concentrated hydrochloric acid and formazanHydrochloric acid/methanol solution (15 mL) with an alcohol volume ratio of 1:5 was quenched and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum at 80℃for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was 76.6% by weight, stereoselectivity: 84.8%,1, 4-cis, 11.2%1, 4-trans, 4%1, 2-vinyl, mn 7.7X10 5 Mw/Mn was 2.99.
As can be seen from a comparison of example 1 with comparative examples 2-4, MMAO-12 is most suitable as a cocatalyst in the present invention.
Comparative example 5 (in comparison with example 1, no pyridine or isopropanol was added to the catalyst)
1. Preparation of the catalyst
(1) Synthesis of ZIF-8 vector: as in example 1.
(2) Synthesis of Nd-ZIF-8: as in comparative example 1.
(3) Sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; nd-ZIF-8 (5.78 mg, 10. Mu. Mol of Nd) was mixed with 0.38ml of toluene under nitrogen atmosphere, and aged at 21℃for 10 minutes, and then 0.43ml of MMAO-12 toluene solution (density: 0.895g/ml, containing 1mmol of Al) having a mass fraction of 7% Al was added, mixed, and aged at 21℃for 10 minutes to obtain a catalyst.
2. Synthetic polydiene rubber
A toluene solution (3.63 mL,18.5 mmol 1,3-butadiene) of toluene (1 mL) and 1, 3-butadiene was rapidly injected into the above catalyst-loaded Schlemk flask, wherein the molar ratio of Nd element to 1, 3-butadiene in the catalyst was 5.4X10 -4 The Shi Laike flask was immediately sealed and stirred at 21 ℃ for 2 hours. After completion, the flask was carefully opened, quenched with a 1:5 volume ratio of concentrated hydrochloric acid to methanol in hydrochloric acid/methanol (15 mL) and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum at 80℃for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was determined by gravimetric method to be 65.3%, stereoselectivity: 71.5%,1, 4-cis12.6% of 1, 4-trans, 15.9% of 1, 2-vinyl, mn 4.96×10 5 Mw/Mn was 3.64.
As is clear from a comparison of example 1, comparative example 1 and comparative example 5, the catalytic system Nd-ZIF-8/MMAO-12 has a poor catalytic effect on the polymerization of 1, 4-butadiene, and the addition of isopropanol is favorable to some extent for improving the catalytic effect, but the reaction yield and the 1, 4-cis structure selectivity are still not good enough. It follows that the importance of the introduction of pyridine into Nd-ZIF-8 is evident.
Comparative example 6
1. Preparation of the catalyst
(1) Synthesis of ZIF-8 vector: as in example 1.
(2) Synthesis of Nd-ZIF-8: as in comparative example 1.
(3) Sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; nd-ZIF-8 (5.78 mg, 10. Mu. Mol of Nd) and pyridine (10. Mu. Mol) were mixed with 0.38ml of isopropyl alcohol under nitrogen protection, and aged at 21℃for 10 minutes, and then 0.43ml of MMAO-12 toluene solution (density: 0.895g/ml, containing 1mmol of Al) having a mass fraction of 7% Al was added, mixed, and aged at 21℃for 10 minutes to prepare a catalyst.
2. Synthetic polydiene rubber
A toluene solution (3.63 mL,18.5 mmol 1,3-butadiene) of toluene (1 mL) and 1, 3-butadiene was rapidly injected into the above catalyst-loaded Schlemk flask, wherein the molar ratio of Nd element to 1, 3-butadiene in the catalyst was 5.4X10 -4 The Shi Laike flask was immediately sealed and stirred at 21 ℃ for 2 hours. After completion, the flask was carefully opened, quenched with a 1:5 volume ratio of concentrated hydrochloric acid to methanol in hydrochloric acid/methanol (15 mL) and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried under vacuum at 80℃for 20h to give polybutadiene rubber.
The yield was determined by gravimetric method, the yield of polybutadiene rubber was 91.2%, stereoselectivity: 90.9%,1, 4-cis, 5.9%1, 4-trans, 3.2%1, 2-vinyl, mn 7.54×10 5 Mw/Mn was 1.98.
It is evident from a comparison of example 1 with comparative example 6 that the introduction of pyridine into the pre-catalyst structure can improve the product yield, stereoselectivity, molecular weight and molecular weight distribution more significantly than the addition of pyridine into the catalyst system.
Claims (8)
1. A butadiene polymerization catalyst characterized by: the butadiene polymerization catalyst comprises a butadiene polymerization pre-catalyst, an alcohol and a modified methylaluminoxane; the alcohol is one or a mixture of more of isopropanol, methanol, ethanol and n-propanol; the butadiene polymerization pre-catalyst is prepared by the following method: weighing a ZIF-8 sample, ultrasonically dispersing the ZIF-8 sample in methanol to obtain a ZIF-8 suspension, weighing neodymium chloride, ultrasonically dissolving the neodymium chloride in deionized water to obtain a neodymium chloride solution, dropwise adding the neodymium chloride solution into the ZIF-8 suspension, and magnetically stirring the neodymium chloride solution for 8-12 hours at room temperature; sufficiently washing, and then placing in a vacuum oven to be dried for 8-24 hours at 50-80 ℃ to obtain Nd-ZIF-8; mixing pyridine, a solvent and Nd-ZIF-8, stirring for 12-24 hours at room temperature, and removing the solvent to obtain a solid, namely a butadiene polymerization precatalyst; the feeding mass ratio of the ZIF-8 sample to neodymium chloride to pyridine is 0.1 g: 0.1-0.2 g: 5-15 mg;
the molar ratio of Nd element to alcohol in the butadiene polymerization pre-catalyst is 1:100-1:1000, and the molar ratio of Nd element to aluminum element in the modified methylaluminoxane in the butadiene polymerization pre-catalyst is 1:30-1:300.
2. The butadiene polymerization catalyst of claim 1, wherein: the feeding mass ratio of the ZIF-8 sample to neodymium chloride to pyridine is 0.1 g: 0.1-0.15 g: 5-15 mg.
3. The butadiene polymerization catalyst of claim 2, wherein: the feeding mass ratio of the ZIF-8 sample to neodymium chloride to pyridine is 0.1 g: 0.1-0.15 g:10mg.
4. A butadiene polymerisation catalyst as claimed in any one of claims 1 to 3 characterised in that: the molar ratio of Nd element to alcohol in the butadiene polymerization pre-catalyst is 1:200-1:500.
5. A butadiene polymerisation catalyst as claimed in any one of claims 1 to 3 characterised in that: the molar ratio of Nd element in the butadiene polymerization pre-catalyst to aluminum element in the modified methylaluminoxane is 1:50-1:150.
6. A butadiene polymerisation catalyst as claimed in any one of claims 1 to 3 characterised in that: the butadiene polymerization catalyst is prepared according to the preparation process comprising the following steps: mixing a butadiene polymerization pre-catalyst and alcohol, aging for 5-60 minutes at 10-40 ℃, adding modified methylaluminoxane, mixing, and aging for 5-60 minutes at 10-40 ℃ to obtain the butadiene polymerization catalyst.
7. A preparation method of polybutadiene rubber is characterized in that: the preparation method comprises the following steps: the method for preparing the polybutadiene rubber by using the butadiene polymerization catalyst as claimed in claim 1 to catalyze the polymerization of 1, 3-butadiene monomers.
8. The method of manufacturing according to claim 7, wherein: the preparation method comprises the steps of mixing 1, 3-butadiene monomer and butadiene polymerization catalyst in a solvent, and then carrying out polymerization reaction under the protection of inert gas to obtain polybutadiene; wherein the amount of the butadiene polymerization catalyst is controlled so that the molar ratio of Nd element to 1, 3-butadiene monomer is 1.0X10 -5 ~1.0×10 -3 The feeding concentration of butadiene in the polymerization reaction system is 1.5-4M.
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Address after: 311215 Xiaoshan economic and Technological Development Zone, Zhejiang, Hangzhou Applicant after: TRANSFAR ZHILIAN CO.,LTD. Applicant after: Zhejiang Chuanhua Synthetic Materials Co.,Ltd. Applicant after: JIANG University OF TECHNOLOGY Applicant after: Zhejiang ChuanHua functional new material Co.,Ltd. Applicant after: HANGZHOU TRANSFAR FINE CHEMICAL CO.,LTD. Address before: 311215 Xiaoshan economic and Technological Development Zone, Zhejiang, Hangzhou Applicant before: TRANSFAR ZHILIAN CO.,LTD. Applicant before: ZHEJIANG TRANSFAR SYNTHETIC MATERIALS Co.,Ltd. Applicant before: JIANG University OF TECHNOLOGY Applicant before: Zhejiang ChuanHua functional new material Co.,Ltd. Applicant before: HANGZHOU TRANSFAR FINE CHEMICAL CO.,LTD. |
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