CN116715790A - Preparation method of conjugated diene polymer with high side group content - Google Patents
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- CN116715790A CN116715790A CN202310607858.3A CN202310607858A CN116715790A CN 116715790 A CN116715790 A CN 116715790A CN 202310607858 A CN202310607858 A CN 202310607858A CN 116715790 A CN116715790 A CN 116715790A
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- 150000001993 dienes Chemical class 0.000 title claims abstract description 46
- 229920000642 polymer Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 14
- -1 ether compound Chemical class 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 11
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000011112 process operation Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 21
- 229920002857 polybutadiene Polymers 0.000 description 11
- 239000005062 Polybutadiene Substances 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 9
- 230000003078 antioxidant effect Effects 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000001979 organolithium group Chemical group 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005065 High vinyl polybutadiene Substances 0.000 description 1
- 239000005064 Low cis polybutadiene Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 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
- 239000007787 solid Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
-
- 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
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
- C08F4/48—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from lithium, rubidium, caesium or francium
- C08F4/482—Metallic lithium, rubidium, caesium or francium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention discloses a preparation method of a conjugated diene polymer with high side group content, which uses metallic lithium as an initiator, and carries out anionic polymerization reaction on conjugated diene monomer in the presence of ether compound to obtain the conjugated diene polymer. The method provided by the invention can stably obtain the conjugated diene polymers with different molecular weights and high side group content, and has the advantages of simple and convenient process operation, mild reaction conditions, low raw material cost, no need of rare gas protection, repeated use of metal lithium, stable product structure and performance and satisfaction of industrial production requirements.
Description
Technical Field
The invention relates to the field of polymer synthesis, in particular to a preparation method of conjugated diene polymer with high side group content.
Background
Lithium is mainly present as metallic lithium, organolithium, lithium complex when used as an initiator for polymerization of conjugated dienes.
The lithium metal can initiate polymerization of the conjugated diene in a hydrocarbon solvent. U.S. patent No. 3317918a discloses a process for preparing polybutadiene by initiating polymerization of butadiene in petroleum ether using a lithium dispersion having a particle size of 20 μm as an initiator. The method requires expensive lithium dispersion as an initiator, has low lithium utilization rate, and simultaneously requires the reaction under argon or helium, and the obtained product has high gel content and low vinyl content.
Organolithium is currently the most predominant initiator in the synthesis of commercial polymers by anionic methods. Bulk industrial products such as styrene-butadiene-styrene block copolymers, medium and high vinyl polybutadiene rubber, low cis polybutadiene, etc. are synthesized using butyllithium as an initiator. However, organolithium is expensive, and the cost per mole of initiator is more than 10 times that of metallic lithium.
Homogeneous complex formed by lithium and polycyclic aromatic hydrocarbon in ether solvent. Chinese patent CN1070198A discloses a method for preparing initiator for anion polymerization, in which polycyclic aromatic hydrocarbon and metallic lithium are reacted in mixed solvent composed of aromatic hydrocarbon and small amount of ethers or amines to prepare initiator, and the initiator can be used for polymerization of conjugated diene or styrene monomer to prepare various homo-and copolymers. The method needs to prepare the initiator in advance, has complex process, is difficult to recycle the mixed solvent, and contains cancerogenic polycyclic aromatic hydrocarbon impurities.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a conjugated diene polymer with high side group content, which uses commercial metallic lithium particles as an initiator and uses an ether compound as a reaction catalyst and a solvent, so that the commercial metallic lithium particles can directly initiate the polymerization of conjugated diene, and unreacted metallic lithium can be continuously used without treatment.
The technical scheme of the invention is as follows:
a process for preparing the conjugated diene polymer with high content of lateral group includes such steps as anionic polymerizing the conjugated diene monomer in the presence of ether compound to obtain conjugated diene polymer.
The preparation method of the conjugated diene polymer comprises the following steps:
(1) Under the protection of nitrogen, adding a metallic lithium initiator and an ether compound into a reactor, and uniformly stirring;
(2) Adding conjugated diene monomer or conjugated diene-ether compound solution to carry out anionic polymerization reaction;
(3) Terminating the reaction after the polymerization is finished, and obtaining the conjugated diene polymer through post-treatment.
The purity of the metal lithium is required to be more than 98%, and the metal lithium particles with the diameter and the length of 2-6 mm and 98.0-99.9% of 2-6 mm are preferable.
The ether compound simultaneously plays roles of a reaction catalyst, a side group content regulator and a solvent, and is one or a mixture of more of diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether tetrahydrate, anisole and the like, and is preferably diethyl ether or tetrahydrofuran.
The conjugated diene monomer is one or a mixture of several of butadiene, isoprene, 2, 3-dimethylbutadiene and 1, 4-dimethylbutadiene, preferably butadiene and isoprene.
The polymerization reaction temperature is-20-80 ℃, preferably 0-30 ℃; the polymerization time is 0.5 to 6 hours, preferably 1 to 3 hours.
The step (3) is preferably carried out by filtering the reaction solution after the polymerization is finished, removing unreacted metallic lithium, adding a terminator to terminate the reaction, washing with water, and drying to obtain the conjugated diene homopolymer or copolymer product. The terminator is one or a mixture of several of methanol, ethanol and isopropanol, preferably methanol or ethanol.
The molecular weight and molecular weight distribution of the conjugated diene polymer can be effectively controlled by changing the amount of the metal lithium and the conjugated diene monomer, the molar ratio of the metal lithium to the conjugated diene monomer is 10:1-1:50, the number average molecular weight of the conjugated diene polymer is 2000-20000, the molecular weight distribution index is 1.1-1.4, and the side group structure content of the obtained product is 70% -95%.
Compared with other lithium polymerization processes, the method has the advantages that other substances are not introduced, metal lithium and ether compounds in a reaction system can be recycled, only lithium salt waste liquid is generated in a water washing step, the method is simple and convenient in process operation, mild in reaction conditions, low in raw material cost, free of rare gas protection such as argon and the like, capable of being repeatedly used, high-side group content conjugated diene polymers with different molecular weights can be stably obtained, high in product purity, stable in structure and performance, and capable of meeting industrial production requirements.
The method provided by the invention can stably obtain conjugated diene polymers with different molecular weights, and the obtained product has the appearance of colorless transparent viscous liquid or pale yellow solid according to different types of conjugated dienes when the conjugated diene polymers react with fixed feeding amount, and has stable molecular weight, symmetrical unipeak molecular weight distribution, and better mechanical property and processability.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
Under the protection of nitrogen, 2 g metal lithium particles and 100 mL tetrahydrofuran are sequentially added into a dry and sealed 500 and mL three-neck flask, stirring is started and fully stirred, and after the temperature in the kettle reaches 0 ℃,100 g of butadiene-tetrahydrofuran solution with 25w% of butadiene content is added for polymerization reaction. In the whole process, the temperature is controlled between 0 and 10 ℃. After reaction 1 h, the reaction solution was filtered and poured into ethanol to recover unreacted metallic lithium particles. Washing the reaction solution with water, adding antioxidant, and distilling under reduced pressure using GPC and 1 the obtained polybutadiene was examined by H NMR to have a number average molecular weight of 3000, a molecular weight distribution index of 1.20 and a vinyl content of 95%.
Example 2
Under the protection of nitrogen, the recovered metal lithium particles in the example 1, 100 mL tetrahydrofuran are sequentially added into a dry and sealed 500-mL three-neck flask, stirring is started and fully stirred, and after the temperature in the kettle reaches 0 ℃,100 g of butadiene-tetrahydrofuran solution with 25w% of butadiene content is added for polymerization reaction. In the whole process, the temperature is controlled between 0 and 10 ℃. After reaction 1 h, the reaction solution was filtered and poured into ethanol to recover unreacted metallic lithium particles. The reaction solution is washed with water, an antioxidant is added, reduced pressure distillation is carried out, and the obtained polybutadiene has a number average molecular weight of 3200, a molecular weight distribution index of 1.22 and a vinyl content of 95 percent.
Example 3
Under the protection of nitrogen, sequentially adding 1 g metal lithium particles and 100 mL tetrahydrofuran into a dry and sealed 500 and mL three-neck flask, stirring thoroughly, stirring uniformly, and adding 200g butadiene-tetrahydrofuran solution with 25w% butadiene content after the temperature in the kettle reaches 0 ℃ for polymerization reaction. In the whole process, the temperature is controlled between 0 and 10 ℃. After reaction 1 h, the reaction solution was filtered and poured into ethanol to recover unreacted metallic lithium particles. Washing the reaction solution with water, adding antioxidant, and distilling under reduced pressure using GPC and 1 the number average molecular weight of the polybutadiene obtained was 11000, the molecular weight distribution index was 1.33, and the vinyl content was 95% by H NMR.
Example 4
Under the protection of nitrogen, sequentially adding 2 g metal lithium particles and 100 mL tetrahydrofuran into a dry and sealed 500 and mL three-neck flask, stirring thoroughly, and adding 25 g isoprene after the temperature in the kettle reaches 0 ℃ for polymerization reaction. In the whole process, the temperature is controlled between 0 and 10 ℃. After reaction 1 h, the reaction solution was filtered and poured into ethanol to recover unreacted metallic lithium particles. Washing the reaction solution with water, adding antioxidant, and distilling under reduced pressure using GPC and 1 the obtained polyisoprene was subjected to H NMR to detect a number average molecular weight of 4000, a molecular weight distribution index of 1.30 and a side group content of 90%.
Example 5
Under the protection of nitrogen, sequentially adding 2 g metal lithium particles and 100 mL diethyl ether into a dry and sealed 500 and mL three-neck flask, stirring thoroughly, stirring uniformly, and adding 100g butadiene-diethyl ether solution with 25w% butadiene content after the temperature in the kettle reaches 0 ℃ for polymerization reaction. In the whole process, the temperature is controlled between 0 and 10 ℃. After reaction 1 h, the reaction solution was filtered and poured into ethanol to recover unreacted metallic lithium particles. The reaction solution was washed with water and then distilled under reduced pressure with the addition of an antioxidant, and the obtained polybutadiene was subjected to detection by GPC to have a number average molecular weight of 3000, a molecular weight distribution index of 1.25 and a vinyl content of 75%.
Example 6
Under the protection of nitrogen, sequentially adding 2 g metal lithium particles and 100 mL ethylene glycol dimethyl ether into a dry and sealed 500 and mL three-neck flask, stirring thoroughly, stirring uniformly, and adding 100g butadiene-ethylene glycol dimethyl ether solution with 25w% of butadiene content after the temperature in the kettle reaches 0 ℃ for polymerization reaction. In the whole process, the temperature is controlled between 0 and 10 ℃. After reaction 1 h, the reaction solution was filtered and poured into ethanol to recover unreacted metallic lithium particles. The reaction solution was washed with water and then distilled under reduced pressure with the addition of an antioxidant, and the obtained polybutadiene was subjected to detection by GPC to give a number average molecular weight of 3000, a molecular weight distribution index of 1.30 and a vinyl content of 70%.
Example 7
Under the protection of nitrogen, sequentially adding 20 g metal lithium particles and 1000 mL tetrahydrofuran into a dry and sealed 2L reaction kettle, stirring thoroughly, and adding 250 g butadiene after the temperature in the kettle reaches 0 ℃ for polymerization reaction. In the whole process, the temperature is controlled between 0 and 10 ℃. After reaction 1 h, the reaction solution was filtered and poured into ethanol to recover unreacted metallic lithium particles. The reaction solution was washed with water and distilled under reduced pressure with the addition of an antioxidant, and the obtained polybutadiene was examined for a number average molecular weight of 3100, a molecular weight distribution index of 1.19 and a vinyl content of 95%.
Comparative example 1
Under the protection of argon, 8 g metal lithium particles, 400 mL petroleum ether and 100g butadiene are sequentially added into a dry and sealed 1L reaction kettle, stirring is fully carried out, and polymerization reaction is carried out after the temperature in the kettle reaches 40 ℃. In the whole process, the temperature is controlled between 40 and 50 ℃. After reaction 6 h, the reaction solution was filtered and poured into ethanol to stop the reaction. After the reaction liquid is washed by water, an antioxidant is added, and reduced pressure distillation is carried out, so that any polybutadiene product can not be obtained.
In contrast to US3317918A, polybutadiene was not formed after replacing the lithium dispersion in US3317918A with lithium metal lithium.
Comparative example 2
Under the protection of nitrogen, sequentially adding 2 g metal lithium particles, 100 mL cyclohexane and stirring fully and uniformly into a dry and sealed 500 and mL three-neck flask, and after the temperature in the kettle reaches 0 ℃, adding 100g of butadiene-cyclohexane solution with 25w% of butadiene content for polymerization reaction. In the whole process, the temperature is controlled between 0 and 10 ℃. After reaction 1 h, the reaction solution was filtered and poured into ethanol to recover unreacted metallic lithium particles. The reaction solution was washed with water and was added with an antioxidant, and distilled under reduced pressure, whereby any polybutadiene product could not be obtained.
It should be understood that the foregoing examples of the present invention are provided merely for the purpose of clearly illustrating the invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (10)
1. A process for preparing the conjugated diene polymer with high content of lateral group includes such steps as anionic polymerizing the conjugated diene monomer in the presence of ether compound to obtain conjugated diene polymer.
2. The method for producing a conjugated diene polymer according to claim 1, comprising the steps of:
(1) Under the protection of nitrogen, adding a metallic lithium initiator and an ether compound into a reactor, and uniformly stirring;
(2) Adding conjugated diene monomer or conjugated diene-ether compound solution to carry out anionic polymerization reaction;
(3) Terminating the reaction after the polymerization is finished, and obtaining the conjugated diene polymer through post-treatment.
3. The method for producing a conjugated diene polymer according to claim 1, wherein the ether compound is one or a mixture of several of diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether tetrahydrate, anisole, etc., preferably diethyl ether or tetrahydrofuran.
4. The method for producing a conjugated diene polymer according to claim 1, wherein the conjugated diene monomer is one or a mixture of several of butadiene, isoprene, 2, 3-dimethylbutadiene and 1, 4-dimethylbutadiene, preferably butadiene and isoprene.
5. The method for producing a conjugated diene polymer according to claim 1, wherein the polymerization reaction temperature is-20 to 80 ℃, preferably 0 to 30 ℃.
6. The method for producing a conjugated diene polymer according to claim 1, wherein the polymerization time is 0.5 to 6 hours, preferably 1 to 3 hours.
7. The process for producing a conjugated diene polymer according to claim 2, wherein the step (3) is carried out by filtering the reaction solution after completion of the polymerization to remove unreacted metallic lithium and adding a terminator to terminate the reaction, and washing with water and drying to obtain a conjugated diene homopolymer or copolymer product.
8. The process for producing a conjugated diene polymer according to claim 7, wherein the terminator is one or a mixture of several of methanol, ethanol and isopropanol, preferably methanol or ethanol.
9. The method for producing a conjugated diene polymer according to claim 1, wherein the molar ratio of the metal lithium to the conjugated diene monomer is 10:1 to 1:50.
10. The method for producing a conjugated diene polymer according to claim 1, wherein the conjugated diene polymer has a number average molecular weight of 2000 to 20000, a molecular weight distribution index of 1.1 to 1.4, and a side group structure content of 70% to 95%.
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