CN117126319B - Pre-catalyst, rare earth catalyst and preparation of polybutadiene - Google Patents
Pre-catalyst, rare earth catalyst and preparation of polybutadiene Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 68
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 63
- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 43
- 239000012041 precatalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000005062 Polybutadiene Substances 0.000 title claims abstract description 20
- 239000013207 UiO-66 Substances 0.000 claims abstract description 112
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 93
- -1 alcohol compound Chemical class 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 13
- HJHUXWBTVVFLQI-UHFFFAOYSA-N tributyl(methyl)azanium Chemical compound CCCC[N+](C)(CCCC)CCCC HJHUXWBTVVFLQI-UHFFFAOYSA-N 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 114
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 10
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 9
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 40
- 239000000243 solution Substances 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 229920001971 elastomer Polymers 0.000 description 14
- 239000005060 rubber Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 11
- 238000011049 filling Methods 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 229920002554 vinyl polymer Polymers 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 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
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 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
- 239000003513 alkali Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 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
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 239000013241 lanthanide-based metal–organic framework Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 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
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
Abstract
The invention discloses a pre-catalyst, a rare earth catalyst and preparation of polybutadiene. The rare earth catalyst is prepared from Nd-UiO-66 pre-catalyst, alcohol compound, tributyl-methyl ammonium chloroaluminate and diene compound. The invention also provides a preparation method of the polybutadiene, which comprises the following steps: the rare earth catalyst is adopted to catalyze the polymerization reaction of the 1, 3-butadiene monomer, and the polybutadiene product is obtained. The rare earth catalyst containing Nd-UiO-66 has the advantages of high activity, stability and the like, can be used for preparing high-quality polybutadiene products with the characteristics of ultrahigh cis, high molecular weight, narrow molecular weight distribution and the like, and has high product yield.
Description
Technical Field
The invention relates to an Nd-UiO-66 pre-catalyst, a rare earth catalyst containing Nd-UiO-66 and a preparation method of polybutadiene catalyzed by the catalyst.
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%).
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.
UiO-66 (uio= University of Oslo) is a rigid metal-organic framework material with Zr as a metal center and terephthalic acid as an organic ligand, has superior hydrothermal stability and chemical stability, and the crystal structure of UiO-66 can be kept stable at 500 ℃, and the framework structure can bear mechanical pressure of 1.0 MPa. The UiO-66 can keep stable structure in solvents such as water, DMF (N, N-dimethylformamide), benzene or acetone, and has strong acid resistance and alkali resistance.
Therefore, it is an expected research direction to develop a novel rare earth catalyst for the synthesis of polybutadiene rubber based on UiO-66 material 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 an Nd-UiO-66 pre-catalyst, a rare earth catalyst containing Nd-UiO-66 and a preparation method of polybutadiene catalyzed by the rare earth 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 a first aspect of the present invention, there is provided an Nd-UiO-66 pre-catalyst prepared by: weighing a UiO-66 sample, ultrasonically dispersing the sample in methanol to obtain a UiO-66 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 UiO-66 suspension, magnetically stirring the solution for 8-12 h, fully washing (washing reagents are preferably methanol and ethanol), and drying the solution at 50-80 ℃ for 8-24 h to obtain an Nd-UiO-66 precatalyst; the feeding mass ratio of the UIO-66 sample to the neodymium chloride is 0.1-1 g:0.1 to 0.5g. The UIO-66 sample can be prepared according to the method reported in the literature.
Preferably, the feeding mass ratio of the UIO-66 sample to the neodymium chloride is 0.1-0.2 g:0.1 to 0.5g.
The Nd-UiO-66 pre-catalyst provided by the invention has high catalytic activity and high stereostructure selectivity for polymerization reaction of 1, 3-butadiene after being activated.
In a second aspect of the present invention, there is provided a rare earth catalyst comprising Nd-UiO-66, which is prepared from Nd-UiO-66 pre-catalyst, alcohol compound, tributyl-monomethyl-ammonium chloroaluminate and diene compound, the chemical formula of the tributyl-monomethyl-ammonium chloroaluminate is [ N ] 4,4,4,1 ]Cl-xAlCl 3 Wherein x=1 to 3; the alcohol compound is isopropylAlcohol or butanol, wherein the diene compound is isoprene or piperylene;
the molar ratio of Nd element to alcohol compound in the Nd-UiO-66 precatalyst is 1:100-1:1000, the molar ratio of Nd element to tributyl monoammonium chloroaluminate in the Nd-UiO-66 precatalyst is 1:30-1:300, and the molar ratio of Nd element to diene compound in the Nd-UiO-66 precatalyst is 1:30-1:300.
Preferably, the molar ratio of Nd element to alcohol compound in the Nd-UiO-66 pre-catalyst is 1:200-1:500.
Preferably, the molar ratio of Nd element to tributyl-monomethyl ammonium chloroaluminate in the Nd-UiO-66 pre-catalyst is 1:50-1:150.
Preferably, the molar ratio of Nd element to diene compound in the Nd-UiO-66 pre-catalyst is 1:50-1:150.
Preferably, the rare earth catalyst containing Nd-UiO-66 is prepared by the following steps: mixing an Nd-UiO-66 pre-catalyst, an alcohol compound and tributyl-monoammonium chloroaluminate, aging for 5-60 minutes at 10-40 ℃, adding a diene compound, mixing, and aging for 5-60 minutes at 10-40 ℃ to obtain the rare earth catalyst containing Nd-UiO-66.
As a further preference, the preparation of the catalyst is carried out under inert gas protection to further facilitate the efficiency of the catalyst preparation. The inert gas adopted in the invention is not strictly limited, for example, more economical nitrogen (N) 2 ) Etc.
In still another aspect of the present invention, there is provided a method for preparing polybutadiene, comprising: the rare earth catalyst containing Nd-UiO-66 is adopted to catalyze the polymerization reaction of the 1, 3-butadiene monomer, and the polybutadiene product is obtained.
Specifically, 1, 3-butadiene monomer and rare earth catalyst containing Nd-UiO-66 may be mixed in a solvent, and then subjected to polymerization reaction, and the reaction process is carried out under the protection of inert gas, thereby obtaining polybutadiene.
Preferably, the solvent is toluene.
Preferably, the inert gas is nitrogen.
Preferably, the amount of the Nd-UiO-66-containing rare earth catalyst is controlled so that the molar ratio of the rare earth element to the butadiene monomer is 1.0X10 -5 ~1.2×10 -3 。
Preferably, the 1, 3-butadiene monomer is fed to the polymerization reaction system at a concentration of 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:
the rare earth catalyst containing Nd-UIO-66 has the advantages of high activity, high stability and the like, and can be prepared to have ultrahigh cis structure content (cis 1, 4-structure content is more than 99.5 percent) and high molecular weight (Mn is more than 8.7X10) 5 ) High quality polybutadiene rubber products with narrow molecular weight distribution (Mw/Mn as low as 1.43), and high yield (up to 87% or more).
Detailed Description
The invention is illustrated below by means of specific examples. It is to be noted that the examples are only for further explanation of the present invention and are not to be construed as limiting the scope of the present invention in any way. Those skilled in the art will be able to make numerous insubstantial modifications and adaptations in light of the above disclosure.
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 UiO-66 vector: weighing 0.1623 g terephthalic acid, placing the terephthalic acid in a 100 mL beaker, taking 50 mL of N, N-Dimethylformamide (DMF) solution in the beaker by using a cylinder, and performing ultrasonic dissolution; then weighing zirconium chloride 0.2332 g in the solution, and carrying out ultrasonic treatment on the solution; acetic acid (36%) 1 mL was added with a pipette, the mixed solution was placed in a 100 mL reactor, sealed, and reacted under heating at 120 ℃ for 24 h. After cooling to room temperature, the sample was centrifuged, washed three times with DMF and methanol, and finally dried in a vacuum oven at 100deg.C for 12h to give 0.27g of white zirconium metal organic framework (UiO-66).
(2) Synthesis of Nd-UiO-66 Pre-catalyst: 0.17 g of UiO-66 sample is weighed and dispersed in 30mL methanol by ultrasonic, 0.2g of neodymium chloride is weighed and dissolved in 3mL deionized water by ultrasonic, the neodymium chloride solution is dripped into the UiO-66 suspension, and the magnetic stirring is carried out for 10 h; the methanol and ethanol were washed three times each, and dried at oven 60℃for 12h to give an Nd-UiO-66 catalyst, the Nd content (mass ratio) of which was 22.5% was detected.
(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, 6.39mg of Nd-UiO-66 (10 mu mol of Nd) and 1mmol of [ N 4,4,4,1 ]Cl-2AlCl 3 0.46ml of butanol (5 mmol) was mixed, aged at 21℃for 10 minutes, 1mmol of piperylene was added and aged at 21℃for 20 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 Schlenk flask containing the aged rare earth catalyst, wherein the molar ratio of rare earth element to 1, 3-butadiene 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 in vacuo at 80℃for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was 89.3% by weight, stereoselectivity: 99.7% of 1, 4-cis, 0.2% of 1, 4-trans, 0.1% of 1, 2-vinyl, mn 9.11X10 5 Mw/Mn was 1.49.
Example 2 (different from the Nd content in the catalyst of example 1)
1. Preparation of rare earth catalyst
(1) Synthesis of UiO-66 vector: as in example 1.
(2) Synthesis of Nd-UiO-66 Pre-catalyst: 0.17 g of UiO-66 sample is weighed and dispersed in 30mL methanol by ultrasonic, 0.35 g neodymium chloride is weighed and dissolved in 3mL deionized water by ultrasonic, neodymium chloride solution is dripped into the UiO-66 suspension, and the magnetic stirring is carried out for 10 h; the methanol and ethanol were washed three times each, and dried at oven 60℃for 12h to give an Nd-UiO-66 catalyst, the Nd content (mass ratio) of which was 34.0% was detected.
(3) Preparation of rare earth catalyst containing Nd-UiO-66: 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, 8.45mg of Nd-UiO-66 (20 mu mol of Nd) and 1mmol of [ N 4,4,4,1 ]Cl-2AlCl 3 0.46ml of butanol was mixed, aged at 21℃for 10 minutes, 1mmol of piperylene was added thereto, and aged at 21℃for 20 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 Schlenk flask containing the aged rare earth catalyst, 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 in vacuo at 80℃for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was determined by gravimetric method and was 95.4%, stereoselectivity: 99.8% of 1, 4-cis, 0.1% of 1, 4-trans, 0.1% of 1, 2-vinyl, mn 9.87×10 5 Mw/Mn was 1.43.
Example 3 (different from example 1 aging time)
1. Preparation of rare earth catalyst
(1) Synthesis of UiO-66 vector: as in example 1.
(2) Synthesis of Nd-UiO-66 Pre-catalyst: as in example 1.
(3) Preparation of rare earth catalyst containing Nd-UiO-66: 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, 6.39mg of Nd-UiO-66 (10 mu mol of Nd) and 1mmol of [ N 4,4,4,1 ]Cl-2AlCl 3 0.46ml of butanol was mixed, aged at 21℃for 20 minutes, 1mmol of piperylene was added thereto, and aged at 21℃for 40 minutes.
2. Synthetic polydiene rubber
A toluene solution of toluene (1 mL) and 1, 3-butadiene (3.63 mL,18.5 mmol 1,3-butadiene) was rapidly injected into the above-described Schlenk flask charged with the aged rare earth catalyst, wherein the molar ratio of Nd to butadiene 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 in vacuo at 80℃for 20h to give polybutadiene rubber.
The yield was determined by gravimetric method, the yield of polybutadiene rubber was 87.7%, stereoselectivity: 99.6% of 1, 4-cis, 0.3% of 1, 4-trans, 0.1% of 1, 2-vinyl, mn 9.26×10 5 Mw/Mn was 1.53.
Example 4 (different from the 1, 3-butadiene solution monomer concentration of example 1)
1. Preparation of rare earth catalyst
(1) Synthesis of UiO-66 vector: as in example 1.
(2) Synthesis of Nd-UiO-66 Pre-catalyst: as in example 1.
(3) Preparation of rare earth catalyst containing Nd-UiO-66: 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, 6.39mg of Nd-UiO-66 (10 mu mol of Nd) and 1mmol of [ N 4,4,4,1 ]Cl-2AlCl 3 Mixing with 0.46ml butanol, aging at 21deg.C for 10 min, and adding 1mmoPiperylene was aged at 21℃for 20 minutes.
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-described Schlenk flask charged with the aged rare earth catalyst, wherein the molar ratio of Nd to butadiene 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 in vacuo at 80℃for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was 89.5% by weight, stereoselectivity: 99.5% of 1, 4-cis, 0.4% of 1, 4-trans, 0.1% of 1, 2-vinyl, mn 8.72×10 5 Mw/Mn was 1.55.
Comparative example 1
1. Preparation of rare earth catalyst
(1) Synthesis of UiO-66 vector: as in example 1.
(2) Synthesis of Nd-UiO-66 Pre-catalyst: as in example 1.
(3) Preparation of rare earth catalyst containing Nd-UiO-66: sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; 6.39mg of Nd-UiO-66 (10. Mu. Mol of Nd), 1mmol of diethylaluminum chloride (Et) 2 AlCl), 0.46ml butanol, aging at 21℃for 10 minutes, further 1mmol piperylene, and aging at 21℃for 20 minutes.
2. Synthetic polydiene rubber
A toluene solution of toluene (1 mL) and 1, 3-butadiene (3.63 mL,18.5 mmol 1,3-butadiene) was rapidly injected into the above-described Schlenk flask charged with the aged rare earth catalyst, wherein the molar ratio of Nd to butadiene 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 the mixture was treated with a 1:5 volume ratio of concentrated hydrochloric acid to methanol in hydrochloric acid/methanol solution (15 mL) Quenched and sonicated for 30s. The precipitate was washed with methanol (30 mL) and the solid was dried in vacuo at 80℃for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was determined by gravimetric method as 85.7%, stereoselectivity: 79.5% of 1, 4-cis, 10.7% of 1, 4-trans, 9.8% of 1, 2-vinyl, mn 6.12X10 5 Mw/Mn was 2.68.
Comparative example 2
1. Preparation of rare earth catalyst
(1) Synthesis of UiO-66 vector: as in example 1.
(2) Synthesis of Nd-UiO-66 Pre-catalyst: as in example 1.
(3) Preparation of rare earth catalyst containing Nd-UiO-66: sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; 6.39mg of Nd-UiO-66 (10. Mu. Mol of Nd), 1mmol of 1-butylpyridinium chloroaluminate ([ C) were reacted under nitrogen 4 Py]Cl/AlCl 3 ) 0.46ml of butanol was mixed, aged at 21℃for 10 minutes, 1mmol of piperylene was added thereto, and aged at 21℃for 20 minutes.
2. Synthetic polydiene rubber
A toluene solution of toluene (1 mL) and 1, 3-butadiene (3.63 mL,18.5 mmol 1,3-butadiene) was rapidly injected into the above-described Schlenk flask charged with the aged rare earth catalyst, wherein the molar ratio of Nd to butadiene 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 in vacuo at 80℃for 20h to give polybutadiene rubber.
The yield of polybutadiene rubber was determined by gravimetric method, 81.6%, stereoselectivity: 63.1% of 1, 4-cis, 22.8% of 1, 4-trans, 14.1% of 1, 2-vinyl, mn 5.67X 10 5 Mw/Mn was 2.95.
Comparative example 3
1. Preparation of rare earth catalyst
(1) Synthesis of UiO-66 vector: as in example 1.
(2) Synthesis of Nd-UiO-66 Pre-catalyst: as in example 1.
(3) Preparation of rare earth catalyst containing Nd-UiO-66: sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; 6.39mg of Nd-UiO-66 (10. Mu. Mol of Nd), 1mmol of 1-butyl-3-methylimidazole chloroaluminate ([ BMIM) were reacted under nitrogen]Cl-2AlCl 3 ) 0.46ml of butanol was mixed, aged at 21℃for 10 minutes, 1mmol of piperylene was added thereto, and aged at 21℃for 20 minutes.
2. Synthetic polydiene rubber
A toluene solution of toluene (1 mL) and 1, 3-butadiene (3.63 mL,18.5 mmol 1,3-butadiene) was rapidly injected into the above-described Schlenk flask charged with the aged rare earth catalyst, wherein the molar ratio of Nd to butadiene 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 in vacuo at 80℃for 20h to give polybutadiene rubber.
Yield by gravimetric determination, yield of polybutadiene rubber 79.4%, stereoselectivity: 75.2% of 1, 4-cis, 10.4% of 1, 4-trans, 14.4% of 1, 2-vinyl, mn 3.86X 10 5 Mw/Mn was 2.87.
Comparative example 4
1. Preparation of rare earth catalyst
(1) Synthesis of UiO-66 vector: as in example 1.
(2) Synthesis of Nd-UiO-66 Pre-catalyst: as in example 1.
(3) Preparation of rare earth catalyst containing Nd-UiO-66: sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; 6.39mg of Nd-UiO-66 (10 mu mol of Nd), 1mmol of triethylamine hydrochloride and aluminum trichloride are reacted under the protection of nitrogen gas 3 HN]Cl/AlCl 3 ) Mixing 0.46ml butanolAging was carried out at 21℃for 10 minutes, 1mmol of piperylene was added thereto, and aging was carried out at 21℃for 20 minutes.
2. Synthetic polydiene rubber
Toluene (1 mL) and a 1, 3-butadiene solution (3.63 mL,18.5 mmol 1,3-butadiene, resulting monomer concentration 3.5M) were rapidly injected into the above-described Schlenk flask charged with the aged rare earth catalyst, wherein the molar ratio of Nd to butadiene 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 in vacuo at 80℃for 20h to give polybutadiene rubber.
Yield by gravimetric method, yield of polybutadiene rubber 83.2%, stereoselectivity: 62.9% of 1, 4-cis, 25.5% of 1, 4-trans, 11.6% of 1, 2-vinyl, mn 7.31×10 5 Mw/Mn was 3.14.
As can be seen from a comparison of example 1 with comparative examples 1-4, for the Nd-UIO-66 containing rare earth catalyst according to the invention, the choice of promoter is critical for its catalytic performance in the 1, 4-butadiene reaction, in order to [ N 4,4,4,1 ]Cl-2AlCl 3 The best catalytic performance can be obtained as a cocatalyst.
Comparative example 5 (using Nd-UiO-66, aluminum alkyl mixed with toluene as catalyst)
1. Preparation of rare earth catalyst
(1) Synthesis of UiO-66 vector: as in example 1.
(2) Synthesis of Nd-UiO-66 Pre-catalyst: as in example 1.
(3) Preparation of rare earth catalyst containing Nd-UiO-66: sequentially vacuumizing and baking the clean Schlemk reaction bottle without foreign matters at high temperature, and filling nitrogen for three times; 6.39mg of Nd-UiO-66 (10. Mu. Mol of Nd), 0.43ml of MMAO toluene solution with a mass fraction of 7% Al (density 0.895g/ml, containing 1mmol of Al) were mixed under nitrogen, 0.46ml of toluene was mixed, and aged at 21℃for 10 minutes.
2. Synthetic polydiene rubber
Toluene (1 mL) and a 1, 3-butadiene solution (3.63 mL,18.5 mmol 1,3-butadiene, resulting in a monomer concentration of 3.5M) were rapidly injected into the above-described Schlenk flask charged with the aged rare earth catalyst, wherein the molar ratio of rare earth element to butadiene 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 in vacuo at 80℃for 20h to give polybutadiene rubber.
The yield was determined by gravimetric method, the yield of polybutadiene rubber was 3.5%, stereoselectivity: 54.5% of 1, 4-cis, 32.4% of 1, 4-trans, 13.1% of 1, 2-vinyl, mn 2.46×10 5 Mw/Mn was 3.32.
As is evident from a comparison of example 1 with comparative example 5, the rare earth catalyst containing Nd-UiO-66 according to the present invention has a poor catalytic effect for butadiene polymerization if only the conventional cocatalyst MMAO and the conventional solvent toluene are used.
Comparative example 6:
1. preparation of rare earth catalyst
(1) Synthesis of UiO-66 vector: as in example 1.
(2) Synthesis of Nd-UiO-66 Pre-catalyst: as in example 1.
(3) Preparation of rare earth catalyst containing Nd-UiO-66: 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, 6.39mg of Nd-UiO-66 (10 mu mol of Nd) and 1mmol of [ N 4,4,4,1 ]Cl-2AlCl 3 Mix and age at 21℃for 10 minutes.
2. Synthetic polydiene rubber
4.63 mL of a toluene solution of 1, 3-butadiene (18.5 mmol of 1, 3-butadiene, obtained as a monomer concentration of 3.5M) was rapidly injected into the above-mentioned Schlenk flask charged with the aged rare earth catalyst, wherein the molar ratio of rare earth element to butadiene was 5.4X10 -4 Immediate seal Schlemk burnThe flask was 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 in vacuo at 80℃for 20h to give polybutadiene rubber.
The yield was determined by gravimetric method, the yield of polybutadiene rubber was 45.7%, stereoselectivity: 56.2%1, 4-cis, 34.1%1, 4-trans, 9.7%1, 2-vinyl, mn 8.35×10 5 Mw/Mn was 1.97.
By comparing example 1 with comparative example 6, it is seen that the addition of diene and alcohol to the rare earth catalyst containing Nd-UIO-66 according to the present invention can significantly improve the yield of polymerization reaction of butadiene and the 1, 4-cis structure selectivity, and in addition, has a certain improvement effect on the molecular weight and molecular weight distribution of polybutadiene.
Claims (9)
1. A rare earth catalyst comprising Nd-UiO-66, characterized in that: the rare earth catalyst containing Nd-UiO-66 is prepared from Nd-UiO-66 pre-catalyst, alcohol compound, tributyl-monoammonium chloroaluminate and diene compound, wherein the chemical formula of the tributyl-monoammonium chloroaluminate is [ N ] 4,4,4,1 ]Cl-xAlCl 3 Whereinx=1 to 3; the alcohol compound is isopropanol or butanol, and the diene compound is isoprene or piperylene;
the molar ratio of Nd element to alcohol compound in the Nd-UiO-66 pre-catalyst is 1:100-1:1000, the molar ratio of Nd element to tributyl monoammonium chloroaluminate in the Nd-UiO-66 pre-catalyst is 1:30-1:300, and the molar ratio of Nd element to diene compound in the Nd-UiO-66 pre-catalyst is 1:30-1:300;
the Nd-UiO-66 pre-catalyst is prepared by the following method: weighing a UiO-66 sample, ultrasonically dispersing the sample in methanol to obtain a UiO-66 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 UiO-66 suspension, magnetically stirring for 8-12 h, fully washing, and drying at 50-80 ℃ for 8-24 h to obtain an Nd-UiO-66 precatalyst; the feeding mass ratio of the UIO-66 sample to the neodymium chloride is 0.1-1: 0.1 to 0.5.
2. A rare earth catalyst containing Nd-UiO-66 as set forth in claim 1, wherein: the feeding mass ratio of the UIO-66 sample to the neodymium chloride is 0.1-0.2: 0.1 to 0.5.
3. A rare earth catalyst containing Nd-UiO-66 as claimed in claim 1 or 2, characterized in that: the molar ratio of Nd element to alcohol compound in the Nd-UiO-66 pre-catalyst is 1:200-1:500.
4. A rare earth catalyst containing Nd-UiO-66 as claimed in claim 1 or 2, characterized in that: the molar ratio of Nd element to tributyl monomethyl ammonium chloroaluminate in the Nd-UiO-66 pre-catalyst is 1:50-1:150.
5. A rare earth catalyst containing Nd-UiO-66 as claimed in claim 1 or 2, characterized in that: the molar ratio of Nd element to diene compound in the Nd-UiO-66 pre-catalyst is 1:50-1:150.
6. A rare earth catalyst containing Nd-UiO-66 as claimed in claim 1 or 2, characterized in that: the rare earth catalyst containing Nd-UiO-66 is prepared by the following steps: mixing an Nd-UiO-66 pre-catalyst, an alcohol compound and tributyl-monoammonium chloroaluminate, aging for 5-60 minutes at 10-40 ℃, adding a diene compound, mixing, and aging for 5-60 minutes at 10-40 ℃ to obtain a rare earth catalyst containing Nd-UiO-66; the preparation process of the rare earth catalyst containing Nd-UiO-66 is implemented under the protection of inert gas.
7. A method for preparing polybutadiene, which is characterized in that: the preparation method comprises the following steps: the polymerization of 1, 3-butadiene monomer catalyzed by the rare earth catalyst comprising Nd-UiO-66 according to any one of claims 1-6 to obtain polybutadiene product.
8. The method of manufacturing according to claim 7, wherein: the preparation method comprises the following implementation steps: mixing 1, 3-butadiene monomer and rare earth catalyst containing Nd-UiO-66 in solvent, then carrying out polymerization reaction, and carrying out the reaction process under the protection of inert gas to obtain polybutadiene.
9. The method of preparing as claimed in claim 8, wherein: the amount of the Nd-UiO-66-containing rare earth catalyst was controlled so that the molar ratio of the rare earth element to the 1, 3-butadiene monomer was 1.0X10 -5 ~1.2×10 -3 The method comprises the steps of carrying out a first treatment on the surface of the In the polymerization reaction system, the feeding concentration of the 1, 3-butadiene monomer is controlled to be 1.5-4M.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0002353A1 (en) * | 1977-11-29 | 1979-06-13 | Exxon Research And Engineering Company | A process for forming a polymer that contains metalsulphonate |
| EP2098287A1 (en) * | 2008-03-03 | 2009-09-09 | ExxonMobil Chemical Patents Inc. | Method of formulating a molecular sieve catalyst composition by controlling component addition |
| CN108276586A (en) * | 2018-04-10 | 2018-07-13 | 中国石油大学(华东) | A kind of multistage pore canal zirconium/cerium mixed metal uio-66 and preparation method thereof |
| CN113019331A (en) * | 2021-03-16 | 2021-06-25 | 南昌航空大学 | Rare earth element doped defect UiO-66 material and preparation method and application thereof |
| CN114075307A (en) * | 2020-08-13 | 2022-02-22 | 中国石油天然气股份有限公司 | Rare earth catalyst and preparation method and application thereof |
| CN116550387A (en) * | 2023-05-10 | 2023-08-08 | 苏州科技大学 | Ce-UiO-66 composite Ni NPs catalyst and preparation method and application thereof |
-
2023
- 2023-10-26 CN CN202311394862.2A patent/CN117126319B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0002353A1 (en) * | 1977-11-29 | 1979-06-13 | Exxon Research And Engineering Company | A process for forming a polymer that contains metalsulphonate |
| EP2098287A1 (en) * | 2008-03-03 | 2009-09-09 | ExxonMobil Chemical Patents Inc. | Method of formulating a molecular sieve catalyst composition by controlling component addition |
| CN108276586A (en) * | 2018-04-10 | 2018-07-13 | 中国石油大学(华东) | A kind of multistage pore canal zirconium/cerium mixed metal uio-66 and preparation method thereof |
| CN114075307A (en) * | 2020-08-13 | 2022-02-22 | 中国石油天然气股份有限公司 | Rare earth catalyst and preparation method and application thereof |
| CN113019331A (en) * | 2021-03-16 | 2021-06-25 | 南昌航空大学 | Rare earth element doped defect UiO-66 material and preparation method and application thereof |
| CN116550387A (en) * | 2023-05-10 | 2023-08-08 | 苏州科技大学 | Ce-UiO-66 composite Ni NPs catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Lu Li et al.."Heterobimetallic CoCeOx derived from cobalt partially-substituted Ce-UiO-66 for chlorobenzene efficient catalytic destruction".《Journal of Rare Earths》.2023,第810-819. * |
| 高晓庆 等."乙酰丙酸加氢制备γ-戊内酯催化剂研究进展".《低碳化学与化工》.2023,全文. * |
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