CN118406172B - Soluble rare earth chloride catalyst, preparation method thereof and isoprene polymerization method - Google Patents
Soluble rare earth chloride catalyst, preparation method thereof and isoprene polymerization method Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 106
- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 60
- -1 rare earth chloride Chemical class 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 53
- 230000032683 aging Effects 0.000 claims abstract description 34
- 150000001993 dienes Chemical class 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000002612 dispersion medium Substances 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 9
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 7
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 7
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 3
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical group C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-UHFFFAOYSA-N 0.000 claims description 3
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 claims description 3
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 3
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 2
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000002431 foraging effect Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 229920001195 polyisoprene Polymers 0.000 abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000000379 polymerizing effect Effects 0.000 description 7
- 239000003708 ampul Substances 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- HHRAWPICZKGGFQ-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethylidene)cyclohex-2-en-1-ol Chemical compound C(CCCCCCC)SC=C1C(C(=CC(C1)=CSCCCCCCCC)C)O HHRAWPICZKGGFQ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- GBCZSUVDRWNVFP-UHFFFAOYSA-K C(C)(C)O.[Cl-].[Nd+3].O.[Cl-].[Cl-] Chemical compound C(C)(C)O.[Cl-].[Nd+3].O.[Cl-].[Cl-] GBCZSUVDRWNVFP-UHFFFAOYSA-K 0.000 description 2
- CQJMNYHBWYQEOR-UHFFFAOYSA-N C=CC(C)=C.[Nd] Chemical compound C=CC(C)=C.[Nd] CQJMNYHBWYQEOR-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 241000863480 Vinca Species 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ROHFMCNIVFLSTQ-UHFFFAOYSA-K trichloroneodymium;hydrate Chemical compound O.Cl[Nd](Cl)Cl ROHFMCNIVFLSTQ-UHFFFAOYSA-K 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- 229910017544 NdCl3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers 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
- C08F36/04—Homopolymers and copolymers 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
- C08F36/08—Isoprene
-
- 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
- C08F136/08—Isoprene
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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)
- Polymerization Catalysts (AREA)
Abstract
The invention discloses a soluble rare earth chloride catalyst, a preparation method thereof and an isoprene polymerization method, wherein the soluble rare earth chloride catalyst reacts with alkyl aluminum at a reaction temperature for a certain time by taking an organic solvent as a dispersion medium in the presence of a small amount of conjugated diene monomer, and then the aging rare earth catalyst is obtained. The soluble rare earth chloride catalyst belongs to a catalyst system for isoprene polymerization, and can be aged for a short time to obtain an aged rare earth catalyst with high catalytic activity; when the aging rare earth catalyst is used for isoprene polymerization, high conversion rate can be achieved by isoprene polymerization in a short time; the prepared polyisoprene has high stereoregularity and high molecular weight.
Description
Technical Field
The invention relates to the field of synthetic rubber, in particular to a soluble rare earth chloride catalyst and a preparation method thereof, an isoprene polymerization method, an aging rare earth catalyst and a preparation method thereof.
Background
Since the last sixties of century, research on polymerization of isoprene and butadiene by rare earth catalysts has been carried out in China, and it is clear that a coordination complex catalytic system containing rare earth compounds is particularly suitable for directional polymerization of conjugated olefins. Since the use of YCl 3—Al(C2H5)3 system to prepare high cis-polybutadiene was reported in 1964, a series of rare earth catalysts for the oriented polymerization of diolefins have been developed and studied, and the activity of the LnCl 3—AlR3 system which is the simplest to be composed has been low. Later, the research finds that adding proper amount of ethanol into a binary rare earth chloride system according to a certain sequence can improve the polymerization activity. Researchers in the Changchun applied chemistry institute inspired by this, developed a study of diene polymerization by a catalytic system composed of rare earth chloride complexes; however, rare earth chloride complex is indissolvable in hydrocarbon solvent, which causes inconvenient operation, difficult transportation and low catalyst utilization rate, thus limiting the development of rare earth chloride catalytic system.
The polymerization research of butadiene is carried out by Sun Tao et al of the national academy of sciences of China using a binary catalyst system composed of NdCl 3.3P350 and alkyl aluminum (oriented polymerization of diolefin by the NdCl 3·3P350—AlR3 binary catalyst system, china's rare earth school newspaper, 1990, stage 2, page 185), but the catalyst system needs to be aged overnight at room temperature in the process of preparing the catalyst, i.e. the catalyst system needs to be aged for a long time, which leads to complex catalyst aging process and is unfavorable for the development of industrialized technology.
Herba Hyperici Japonici synthesizes multiple complexes of neodymium chloride and polyether (ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, crown ether), and uses binary catalytic system composed of the complex and aluminum alkyl for polymerization of butadiene and isoprene to obtain polyisoprene rubber and polybutadiene rubber with high cis-1,4 structure content and high molecular weight, and the molecular weight and microstructure of the polymer can be regulated by changing experimental conditions (preparation of neodymium chloride polyether complex and olefin polymerization research, university of vinca and university of vinca, 2012). The complex can be directly prepared from cheaper neodymium oxide, and the cost is greatly reduced.
Patent CN106916240a discloses a method for preparing rare earth isoprene rubber catalyst, comprising the following steps: (1) preparing triisobutylaluminum toluene solution; (2) Preparing a mixture of triisobutylaluminum toluene solution and piperylene; (3) preparing a neodymium chloride monohydrate isopropyl alcohol complex: adding neodymium chloride monohydrate and isopropanol into toluene to carry out coordination reaction to obtain a neodymium chloride monohydrate isopropanol complex; (4) preparation of a catalyst: adding neodymium chloride-isopropanol monohydrate complex into a mixture of triisobutylaluminum toluene solution and piperylene, and reacting to obtain a catalyst, wherein the reaction temperature is below-5 ℃ for 5-10 min, and the reaction should be carried out under stirring; (5) catalyst aging: aging the catalyst prepared in the step (4) for more than 16 hours, wherein the aging temperature is 20-40 ℃. The technology for preparing the rare earth rubber catalyst provided by the invention has the advantages of simple and easy process, easily available raw materials, less side reaction and high catalyst activity.
Patent CN105418810a discloses a preparation method and application of neodymium isoprene polymerized rubber rare earth catalyst. Rare earth compounds, organic aluminum compounds or corresponding mixtures, conjugated dienes, organic solvents and alcohols are used as rare earth catalytic systems. The molar ratio of neodymium element to isopropanol is 1:1-5, the mass fraction of triisobutylaluminum in triisobutylaluminum toluene solution is 7% -25%, the molar ratio of Nd element to A1 element to piperylene is 1:5-20:1-10, and the aging time is 15-20 hours, so that the neodymium isoprene polymerized rubber rare earth catalyst is prepared. The preparation method provided by the invention can effectively improve the service efficiency of the rare earth catalyst and the performance index of the rubber product, realizes the purpose of being applicable to industrialized and continuous polymerization production of isoprene rubber, and has wide application value.
Most rare earth chloride complexes are insoluble in hydrocarbon solvents and can only be formulated as a solid, resulting in low effective utilization of the catalyst. In order to improve the effective utilization rate of the rare earth chloride catalyst, the NdCl 3.2 THF complex is prepared into nano dispersion （Morphology and Activity of Nanosized NdCl3 Catalyst for 1,3-Butadiene Polymerization[J],J. Appl. Polym. Sci.,2005,97:1278-1283） in cyclohexane or the NdCl 3.nROH complex is prepared into colloid in hexane (research on the reaction characteristics of the rare earth chloride complex polymerized isoprene, national academy of sciences of China, national institute of sciences, shuo Jiu, 2006) both obviously improve the catalytic activity.
Disclosure of Invention
The invention aims to provide a soluble rare earth chloride catalyst, a preparation method thereof and a method for polymerizing isoprene, wherein the soluble rare earth chloride catalyst belongs to a catalyst system for polymerizing isoprene, and can obtain an aged rare earth catalyst with high catalytic activity after short-time aging.
In a first aspect, the invention provides a preparation method of a soluble rare earth chloride catalyst, wherein pentaerythritol diphosphite is added into an organic solvent (such as toluene) and stirred for dissolution, then anhydrous rare earth chloride is added, the anhydrous rare earth chloride reacts with the pentaerythritol diphosphite, and the mixture is stirred until the anhydrous rare earth chloride is completely dissolved and dispersed, so as to obtain the soluble rare earth chloride catalyst.
In the preparation method of the soluble rare earth chloride catalyst, the molar ratio of pentaerythritol diphosphite to anhydrous rare earth chloride is 0.5-4.0.
In the preparation method of the soluble rare earth chloride catalyst, anhydrous neodymium chloride is preferentially selected as anhydrous rare earth chloride; the pentaerythritol diphosphite is preferably selected from bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite or distearyl pentaerythritol diphosphite.
In a second aspect, the invention provides a soluble rare earth chloride catalyst, which is prepared according to the preparation method of the soluble rare earth chloride catalyst.
In a third aspect, the present invention provides a method for preparing an aged rare earth catalyst, which is essentially obtained by activating the soluble rare earth chloride catalyst, comprising: the soluble rare earth chloride catalyst reacts with alkyl aluminum at a reaction temperature and is aged for a certain time by taking an organic solvent (toluene) as a dispersion medium in the presence of a small amount of conjugated diene monomer, so that the aged rare earth catalyst is obtained.
In the preparation method of the aging rare earth catalyst, the conjugated diene monomer is isoprene, piperylene or butadiene.
In the preparation method of the aging rare earth catalyst, the alkyl aluminum is one or more of triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, diisobutyl aluminum hydride and diethyl aluminum hydride.
In the preparation method of the aging rare earth catalyst, the dosage range of the small amount of conjugated diene monomer is as follows: the molar ratio of the small amount of conjugated diene monomer to Nd element in the soluble rare earth chloride catalyst is 1 to 15.
The invention relates to a preparation method of an aging rare earth catalyst, which comprises the following steps of: the molar ratio of the alkyl aluminum to Nd element in the soluble rare earth chloride catalyst is 10 to 35; the reaction temperature with the aluminum alkyl is specifically in the range of-20 ℃ to 50 ℃, preferably-5 ℃ to 30 ℃.
In the preparation method of the aged rare earth catalyst, the aging time ranges from 10min to 120h, preferably from 20min to 6h.
In a fourth aspect, the invention provides an aged rare earth catalyst prepared according to the method for preparing an aged rare earth catalyst.
In a fifth aspect, the present invention provides a method for polymerizing isoprene, comprising: mixing isoprene and hexane solvent, stirring uniformly, adding an aging rare earth catalyst, polymerizing at a set temperature for a specified time, and adding a terminator to terminate the polymerization to obtain the isoprene polymer.
In the method for polymerizing isoprene according to the present invention, the terminator is an ethanol solution containing 2, 4-bis (n-octylthiomethylene) -6-methylphenol.
In the isoprene polymerization method, the usage range of the aging rare earth catalyst is as follows: aged rare earth catalyst) the molar ratio of Nd element to isoprene is 1:30000 to 1:10000.
In the method for polymerizing isoprene according to the present invention, the specific temperature range is 0℃to 70 ℃.
In the method for polymerizing isoprene according to the present invention, the polymerization reaction is performed for a time period ranging from 1h to 6h.
The soluble rare earth chloride catalyst is soluble in hydrocarbons, so that the problems of conveying and metering of a rare earth chloride catalytic system are solved, meanwhile, an aged rare earth catalyst with high catalytic activity can be obtained through short-time aging of a catalytic system consisting of the soluble rare earth chloride catalyst and aluminum alkyl, and when the aged rare earth catalyst is used for isoprene polymerization, high conversion rate can be achieved through short-time polymerization, and the prepared polyisoprene has high stereoregularity and high molecular weight.
Drawings
FIG. 1 is an infrared absorption spectrum of an isoprene polymer.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments and the like used in the present application are commercially available or may be prepared by existing methods. The percentages in the present application are mass percentages unless otherwise specifically indicated. Room temperature in the present application generally refers to a temperature of 15 ℃ to 25 ℃ and is generally defined as 25 ℃.
The present invention will be described in detail with reference to specific examples.
Example 1
50Ml of toluene and 0.882mmol of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite are sequentially added into an ampoule with the volume of 200ml under the protection of nitrogen and at room temperature, and after stirring and dissolving, 0.441mmol of anhydrous NdCl 3 powder is added, and the mixture is stirred until the powder is completely dissolved and dispersed, so that the soluble rare earth chloride catalyst is obtained for standby.
Under the protection of nitrogen, adding 4.41mmol of piperylene into the soluble rare earth chloride catalyst of the ampoule, uniformly mixing at 10 ℃, then adding 8.82mmol of triisobutyl aluminum, reacting at 10 ℃ and aging for 1h to obtain the aged rare earth catalyst for later use.
Under the protection of nitrogen, 1700g of hexane and 300g of isoprene are sequentially added into a 5L polymerization kettle, and uniformly stirred, then all the aged rare earth catalyst prepared in the previous step is added into the polymerization kettle, and the polymerization is carried out for 4 hours at the polymerization temperature of 40 ℃, and then an ethanol solution containing 2, 4-di (n-octyl thiomethylene) -6-methylphenol is added to terminate the polymerization, so that 283g of isoprene polymer is obtained, the polymerization yield is 94.3 percent, the Cis-1,4 structure (Cis-1, 4) content of the polymer is 96.1 percent, the weight average relative molecular weight (Mw) is 289.9 ten thousand, the molecular weight distribution (PDI) is 2.61, and no gel exists.
The infrared absorption spectrum of the isoprene polymer obtained in example 1 is shown in FIG. 1.
In fig. 1, the infrared characteristic peaks of polyisoprene:
cis-1,4:836cm -1、1130cm-1 and 1375cm -1;3,4-：890cm-1;trans-1,4：1150cm-1 and 1385cm -1;1,2-：910cm-1.
As can be seen from FIG. 1, the polyisoprene of the present invention has no 1, 2-and trans-1, 4 structures.
Examples 2 to 11
Example 1 was identical except that the reaction temperature and aging time during the preparation of the aged rare earth catalyst are shown in Table 1.
As shown in Table 1, when the reaction temperature is-5 ℃ to 30 ℃ and the aging time is 20min to 6h, the obtained aging rare earth catalyst is used for isoprene polymerization, the polymerization efficiency of isoprene reaches over 94.5%, the polymerization efficiency of Cis-1, 4-structure isoprene polymer reaches over 95.5%, and especially in example 5, the polymerization efficiency reaches 96.7%.
Example 12
50Ml of toluene and 0.882mmol of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite are sequentially added into an ampoule with the volume of 200ml under the protection of nitrogen and at room temperature, and after stirring and dissolving, 0.441mmol of anhydrous NdCl 3 powder is added, and the mixture is stirred until the mixture is completely dissolved and dispersed, so as to obtain the soluble rare earth chloride catalyst for standby.
Under the protection of nitrogen, adding 4.41mmol of isoprene into the soluble rare earth chloride catalyst of the ampoule, uniformly mixing at 10 ℃, then adding 8.82mmol of triisobutylaluminum, reacting at 10 ℃ and aging for 1h to obtain the aged rare earth catalyst for later use.
Under the protection of nitrogen, 1700g of hexane and 300g of isoprene are sequentially added into a 5L polymerization kettle, and uniformly stirred, then all the aged rare earth catalyst prepared in the previous step is added into the polymerization kettle, and the polymerization is carried out for 4 hours at the polymerization temperature of 40 ℃, and then an ethanol solution containing 2, 4-di (n-octyl thiomethylene) -6-methylphenol is added to terminate the polymerization, so that 287g of isoprene polymer is obtained, the polymerization yield is 95.7% through calculation, the cis-1, 4 structure content of the polymer is 96.4%, the weight average molecular weight is 292.8 ten thousand, the molecular weight distribution is 2.63, and no gel exists.
Examples 13 to 18
Example 12 was identical except for the amount of anhydrous NdCl 3, the amount of conjugated diene (isoprene), the amount and type of aluminum alkyls used in the preparation of the soluble rare earth chloride catalyst (see table 2 below).
As is clear from Table 2, when the obtained aged rare earth catalyst was used for isoprene polymerization, the polymerization efficiency was 100% in the case where the amounts of anhydrous NdCl 3 and conjugated diene were 1.47mmol, the amount of aluminum alkyl was 14.7mmol, and the amounts of anhydrous NdCl 3, conjugated diene and aluminum alkyl were 0.882mmol, 2.65mmol, and 13.23mmol, respectively, and the isoprene polymers obtained in examples 13 to 17 were 90% or more in Cis-1,4 structure.
Example 19
50Ml of toluene and 0.882mmol of distearyl pentaerythritol diphosphite are added into an ampoule with the volume of 200ml in sequence under the protection of nitrogen and at room temperature, after stirring and dissolving, 0.441mmol of anhydrous NdCl 3 powder is added, and stirring is carried out until all the powder is dissolved and dispersed, thus obtaining the soluble rare earth chloride catalyst for standby.
Under the protection of nitrogen, adding 4.41mmol of isoprene into the soluble rare earth chloride catalyst of the ampoule, uniformly mixing at 10 ℃, then adding 8.82mmol of trioctylaluminum, reacting at 10 ℃ and aging for 1h to obtain the aged rare earth catalyst for later use.
Under the protection of nitrogen, 1700g of hexane and 900g of isoprene are sequentially added into a 5L polymerization kettle, and are uniformly stirred, then all the aged rare earth catalyst prepared in the previous step is added into the polymerization kettle, and is polymerized for 4 hours at the polymerization temperature of 30 ℃, then an ethanol solution containing 2, 4-di (n-octyl thiomethylene) -6-methylphenol is added to terminate the polymerization, so that 281g of isoprene polymer is obtained, the polymerization yield is 93.7% through calculation, the cis-1, 4 structure content of the polymer is 96.5%, the weight average molecular weight is 274.5 ten thousand, the molecular weight distribution is 2.79, and no gel exists.
Examples 20 to 27
Example 19 was identical except that the polymerization temperature and polymerization time during polymerization of isoprene monomer were different (see table 3 below).
As is clear from Table 3, when the polymerization temperature was 50℃to 60℃and the polymerization time was 2 hours to 6 hours, the polymerization efficiency of the isoprene polymer was 95% or more, and among the isoprene polymers obtained in examples 24 to 26, cis-1,4 structure isoprene polymer was 95% or more.
Examples 28 to 32
Example 1 was identical except that the amounts and types of conjugated dienes used in the preparation of the aged rare earth catalyst were varied (see Table 4 below).
As can be seen from Table 4, different conjugated dienes and different amounts of the same were used in the preparation of the aged rare earth catalyst to produce different polymerization effects. When isoprene is adopted as conjugated diene and the dosage thereof is 4.41mmol, the polymerization efficiency is as high as 95.9 percent; when piperylene is used as the conjugated diene and the amount thereof is 6.62mmol, the polymerization efficiency is as high as9,7.2%.
In summary, the aging rare earth catalyst with high catalytic activity can be obtained by aging the catalytic system consisting of the soluble rare earth chloride catalyst and the alkyl aluminum for a short time, the aging time is as low as 20 minutes, and the aging time is obviously lower than that of the existing rare earth catalyst. When the aging rare earth catalyst is used for isoprene polymerization, high conversion rate, namely high polymerization efficiency, can be achieved by isoprene polymerization in a short time; and the polyisoprene prepared by using the aging rare earth catalyst has the cis-1, 4 structure content of more than 95 percent and the weight average relative molecular weight of between 100 and 500 ten thousand, namely the prepared polyisoprene has high stereoregularity and high molecular weight.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
Claims (5)
1. A method for preparing an aged rare earth catalyst, comprising: the method comprises the steps of (1) reacting a soluble rare earth chloride catalyst with aluminum alkyl at a reaction temperature for a certain time by taking an organic solvent as a dispersion medium in the presence of a small amount of conjugated diene monomer, and ageing to obtain an aged rare earth catalyst;
Wherein, the soluble rare earth chloride catalyst is obtained by the following steps: adding pentaerythritol diphosphite into an organic solvent, stirring and dissolving, adding anhydrous rare earth chloride, reacting the anhydrous rare earth chloride with the pentaerythritol diphosphite, and stirring until the anhydrous rare earth chloride is completely dissolved and dispersed to obtain a soluble rare earth chloride catalyst;
the anhydrous rare earth chloride is anhydrous neodymium chloride; pentaerythritol diphosphite is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite or distearyl pentaerythritol diphosphite;
The dosage range of the small amount of conjugated diene monomer is as follows: the molar ratio of the small amount of conjugated diene monomer to Nd element in the soluble rare earth chloride catalyst is 1-15; the dosage range of the alkyl aluminum is as follows: the molar ratio of the alkyl aluminum to Nd element in the soluble rare earth chloride catalyst is 10 to 35; the specific range of the reaction temperature with the aluminum alkyl is-5 ℃ to 30 ℃; the aging time ranges from 20min to 6h.
2. The method for preparing an aged rare earth catalyst according to claim 1, wherein the conjugated diene monomer is isoprene, piperylene or butadiene; the alkyl aluminum is one or more of triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, diisobutyl aluminum hydride and diethyl aluminum hydride.
3. The method for preparing an aged rare earth catalyst according to claim 1 or 2, wherein the molar ratio of pentaerythritol diphosphite to anhydrous rare earth chloride is 0.5 to 4.0.
4. An aged rare earth catalyst prepared by the method for preparing an aged rare earth catalyst according to claim 1 or 2 or 3.
5. A method for aging a rare earth catalyst for isoprene polymerization according to claim 4, comprising: mixing isoprene with a solvent, uniformly stirring, and adding an aging rare earth catalyst, wherein the dosage range of the aging rare earth catalyst is as follows: the molar ratio of Nd element to isoprene in the aging rare earth catalyst is 1:30000-1:10000, and the polymerization is carried out for 1h to 6h at the temperature of 0 ℃ to 70 ℃, and then the terminating agent is added to terminate the polymerization, thus obtaining the isoprene polymer.
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