CN107522816B - Method for synthesizing high cis-diene polymer - Google Patents
Method for synthesizing high cis-diene polymer Download PDFInfo
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- CN107522816B CN107522816B CN201710882579.2A CN201710882579A CN107522816B CN 107522816 B CN107522816 B CN 107522816B CN 201710882579 A CN201710882579 A CN 201710882579A CN 107522816 B CN107522816 B CN 107522816B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 71
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 70
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 58
- 239000000178 monomer Substances 0.000 claims abstract description 57
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 150000001993 dienes Chemical class 0.000 claims abstract description 29
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 21
- -1 rare earth compound Chemical class 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 229910052736 halogen Inorganic materials 0.000 claims description 27
- 150000002367 halogens Chemical class 0.000 claims description 27
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 24
- 238000007334 copolymerization reaction Methods 0.000 claims description 14
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010008 shearing Methods 0.000 claims description 6
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910001502 inorganic halide Inorganic materials 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 23
- 238000009835 boiling Methods 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 14
- 238000007710 freezing Methods 0.000 description 14
- 230000008014 freezing Effects 0.000 description 14
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 14
- 229920002857 polybutadiene Polymers 0.000 description 14
- 239000005062 Polybutadiene Substances 0.000 description 13
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 12
- 229920001195 polyisoprene Polymers 0.000 description 12
- UZGARMTXYXKNQR-UHFFFAOYSA-K 7,7-dimethyloctanoate;neodymium(3+) Chemical compound [Nd+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O UZGARMTXYXKNQR-UHFFFAOYSA-K 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 7
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002954 polymerization reaction product Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010981 drying operation Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910001504 inorganic chloride Inorganic materials 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DZNFWGVDYGAMJB-UHFFFAOYSA-K neodymium(3+);phosphate Chemical compound [Nd+3].[O-]P([O-])([O-])=O DZNFWGVDYGAMJB-UHFFFAOYSA-K 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011592 zinc chloride 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—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
- C08F236/04—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
- C08F236/08—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
- C08F136/06—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
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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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a method for synthesizing a high cis-diene polymer, which comprises the following steps: in an anhydrous and oxygen-free closed container, carrying out polymerization reaction on a reaction solution containing a diene monomer, liquid pentane and a rare earth composite catalyst to obtain a high cis-diene polymer; the diene monomer is liquid butadiene and/or isoprene; the filling degree of the reaction solution in the closed container is 30-70%. According to the invention, liquid butadiene and/or isoprene is used as a raw material, pentane with a low boiling point is used as a solvent, and polymerization is carried out under the catalysis of the rare earth composite catalyst under the anhydrous and oxygen-free closed conditions, after the reaction is finished, pentane can be volatilized at room temperature, so that the solvent residue in the product is reduced, the obtained product is easy to recover and separate, the post-treatment temperature of the product is reduced, and energy is saved.
Description
Technical Field
The invention relates to the technical field of polymer preparation, in particular to a method for synthesizing a high cis-diene polymer.
Background
With the rapid development of the automobile industry, the world demand for rubber with excellent performance is more and more intense. The rare earth polybutadiene rubber has the characteristics of high strength, flex resistance, low heat generation, wet skid resistance, low rolling resistance and the like, and is a preferred rubber seed for developing high-performance tires and energy-saving tires; the rare earth polyisoprene rubber has a structure and performance similar to those of natural rubber, is universal rubber with good comprehensive performance, and has water resistance and insulativity superior to those of the natural rubber; the rare earth butadiene-isoprene copolymer rubber (butadiene-isoprene rubber) can be used for preparing various high-performance tires due to the excellent low-temperature resistance, wear resistance, low-temperature rolling resistance and other performances which meet modern standards, has wide development potential in the future, and the butadiene-isoprene (Bd-Ip) copolymer rubber polymerized by rare earth catalysis has Tg of-104 ℃, is difficult to generate crystals at low temperature, has low-temperature performance similar to that of silicon rubber and mechanical performance superior to that of the silicon rubber, but can also form crystals when vulcanized rubber is used at-55 ℃ for a long time (synthetic rubber industry, 1986,9(5): 354-.
In the prior art, various methods for preparing homopolymers and copolymers of butadiene and isoprene are reported, but high boiling point solvents such as hexane, cyclohexane or heptane are mostly adopted as organic solvents. For example, chinese patent publication No. CN101831032B reports a method for preparing a butadiene-isoprene copolymer by controlling the molecular weight and molecular weight distribution of the butadiene-isoprene copolymer by controlling the molar ratio of the reaction monomers and the catalyst, and terminating the polymerization reaction by the hydroxyl group in ethanol to prepare a butadiene-isoprene copolymer having a low molecular weight and a narrow molecular weight distribution, using hexane, cyclohexane or heptane as an organic solvent. Chinese patent with publication number CN103724378A reports an isoprene-butadiene binary copolymer and a preparation method thereof, and the method adopts a butadiene isoprene monomer, a rare earth complex, alkylaluminum and a halogen donor containing alkylaluminum halide as a catalytic system, and provides a preparation method of the isoprene-butadiene binary copolymer with a high 1, 4-structure polybutadiene chain segment and a 3, 4-structure polyisoprene chain segment.
In the technical scheme, high-boiling-point solvents such as hexane, cyclohexane or heptane are mostly adopted as organic solvents, and because the boiling points are high, such as the boiling point of hexane is 69 ℃, the boiling point of cyclohexane is 80.7 ℃ and the boiling point of heptane is 98.42 ℃, solvent residues are easily caused in products, the content of volatile components is increased, and the aftertreatment of the products needs to reach a certain temperature, so that energy waste is caused.
Disclosure of Invention
The invention aims to provide a method for synthesizing a high cis-diene polymer. The method for synthesizing the high cis-diene polymer provided by the invention has the advantages that the boiling point of the solvent is low, and the solvent residue in the product is reduced.
The invention provides a method for synthesizing a high cis-diene polymer, which comprises the following steps:
in an anhydrous and oxygen-free closed container, carrying out polymerization reaction on a reaction solution containing a diene monomer, liquid pentane and a rare earth composite catalyst to obtain a high cis-diene polymer; the diene monomer is liquid butadiene and/or isoprene; the filling degree of the reaction solution in the closed container is 30-70%.
Preferably, the reaction solution is obtained by mixing a diene monomer, liquid pentane and a rare earth composite catalyst, and the mixing temperature is below-100 ℃.
Preferably, the rare earth composite catalyst comprises a rare earth compound, an alkyl aluminum and a halogen-containing compound.
Preferably, the molar ratio of the rare earth compound, the alkyl aluminum and the halogen-containing compound is 1 (1-100) to 1-50.
Preferably, the molar ratio of the rare earth compound to the diene monomer is (1-200) x 10-4:1。
Preferably, the rare earth compound comprises a rare earth-beta-diketone complex.
Preferably, the aluminum alkyl comprises one or more of triethylaluminum, diisobutylaluminum hydride and triisobutylaluminum.
Preferably, the halogen-containing compound comprises one or more of an alkylaluminum halide, a halosilane, and an inorganic halide.
Preferably, the temperature of the polymerization reaction is 0-50 ℃, and the time of the polymerization reaction is 0.5-6 h.
Preferably, the polymerization reaction is terminated by adding a terminating agent to the closed vessel.
The invention provides a method for synthesizing a high cis-diene polymer, which comprises the following steps: in an anhydrous and oxygen-free closed container, carrying out polymerization reaction on a reaction solution containing a diene monomer, liquid pentane and a rare earth composite catalyst to obtain a high cis-diene polymer; the diene monomer is liquid butadiene and/or isoprene; the filling degree of the reaction solution in the closed container is 30-70%. According to the invention, liquid butadiene and/or isoprene is used as a raw material, pentane with a low boiling point is used as a solvent, and polymerization is carried out under the catalysis of the rare earth composite catalyst under the anhydrous and oxygen-free closed conditions, after the reaction is finished, pentane can be volatilized at room temperature, so that the solvent residue in the product is reduced, the obtained product is easy to recover and separate, the post-treatment temperature of the product is reduced, and energy is saved. Experimental results show that the method provided by the invention does not need to carry out additional treatment on a solvent, the conversion rate of the product is 88.0%, the cis-structure of a polybutadiene chain segment in the product reaches 97.9%, and the cis-structure of a polyisoprene chain segment in the product reaches 97.9%.
Detailed Description
The invention provides a method for synthesizing a high cis-diene polymer, which comprises the following steps:
in an anhydrous and oxygen-free closed container, carrying out polymerization reaction on a reaction solution containing a diene monomer, liquid pentane and a rare earth composite catalyst to obtain a high cis-diene polymer; the diene monomer is liquid butadiene and/or isoprene; the filling degree of the reaction solution in the closed container is 30-70%.
In the present invention, the diene monomer is liquid butadiene and/or isoprene. In the present invention, when the diene monomer is liquid butadiene, the diene polymer is polybutadiene; when the diene monomer is isoprene, the diene polymer is polyisoprene; when the diene monomer is liquid butadiene and isoprene, the diene polymer is a butadiene-isoprene copolymer. The molar ratio of the liquid butadiene to the liquid isoprene is not particularly limited, and may be adjusted according to the desired product.
In the present invention, the liquid pentane preferably comprises one or more of n-pentane, isopentane and neopentane. In the invention, the boiling point of the n-pentane is 36.1 ℃, the boiling point of the isopentane is 27.8 ℃, the n-pentane is liquid at room temperature and is greatly lower than the boiling points of common solvents such as hexane and cyclohexane, the n-pentane can volatilize at a lower temperature, the neopentane has the boiling point of 9.5 ℃, and the neopentane can volatilize at room temperature, so that the solvent residue in the product is greatly reduced, the obtained product is easy to recover and separate, the post-treatment temperature of the product can be greatly reduced, and energy sources are saved.
In the present invention, the rare earth composite catalyst preferably includes a rare earth compound, an alkyl aluminum, and a halogen-containing compound. In the invention, the molar ratio of the rare earth compound, the alkyl aluminum and the halogen-containing compound is preferably 1 (1-100): 1-50, more preferably 1 (10-80): 2-30, and most preferably 1 (15-40): 3-15. In the invention, the molar ratio of the rare earth compound to the diene monomer is preferably (1-200) x 10-41, more preferably (2 to 100). times.10-41, most preferably (3 to 50). times.10-4:1. Hair brushThe amount of the liquid pentane is not particularly limited, and any solvent known to those skilled in the art may be used.
In the present invention, the rare earth compound preferably comprises a rare earth- β -diketone complex, more preferably comprises one or more of rare earth naphthenate, rare earth neodecanoate and rare earth phosphate. In the present invention, the rare earth element in the rare earth compound is preferably Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu. In embodiments of the invention, the rare earth compound is preferably one or more of neodymium naphthenate, neodymium neodecanoate, neodymium phosphate, and neodymium isooctanoate.
In the present invention, the alkyl aluminum preferably includes one or more of triethyl aluminum, diisobutyl aluminum hydride, and triisobutyl aluminum. In the present invention, the halogen-containing compound preferably includes one or more of alkylaluminum halide, halosilane, and inorganic halide, and more preferably includes one or more of alkylaluminum chloride, chlorosilane, and inorganic chloride. In the embodiment of the present invention, the halogen-containing compound is preferably diethylaluminum chloride, diisobutylaluminum chloride, chloroform, SiCl4、SnCl4、MgCl2And ZnCl2One or more of (a).
The preparation method of the rare earth composite catalyst is not particularly limited, and the technical scheme for preparing the rare earth composite catalyst, which is well known to those skilled in the art, can be adopted. In the present invention, the preparation of the rare earth composite catalyst is preferably referred to chinese patent CN 101831032B. In the invention, the rare earth compound in the rare earth composite catalyst and alkyl aluminum are subjected to alkylation reaction and halogen exchange reaction with a halogen-containing compound to finally generate a double-metal double-core active complex or a multi-core active complex.
In the present invention, the anhydrous and oxygen-free environment is preferably a vacuum or an inert atmosphere, more preferably a high purity nitrogen atmosphere. In the present invention, the water-and oxygen-free closed container is preferably obtained by: vacuumizing the clean and dry closed container under the heating condition, and filling high-purity nitrogen when the pressure of the closed container reaches negative pressure; and repeating the steps for 3-5 times after the closed container is kept at the constant temperature. In the present invention, the purity of the high-purity nitrogen is preferably 99.999% or more. In the invention, the anhydrous and anaerobic condition can avoid the inactivation of the catalyst with stronger chemical activity due to violent reaction of water and oxygen.
The type of the closed container is not particularly limited in the present invention, and a container capable of sealing and withstanding high pressure, which is well known to those skilled in the art, may be used. In the present invention, the closed container is preferably a polymerization bottle.
In the invention, the reaction solution is preferably obtained by mixing a diene monomer, liquid pentane and a rare earth composite catalyst; the temperature of the mixing is preferably-100 ℃ or lower, more preferably-150 ℃ or lower. According to the invention, the diene monomer, the liquid pentane and the rare earth composite catalyst are preferably mixed under the condition of freezing by liquid nitrogen. In the invention, the mixture of the diene monomer, the liquid pentane and the rare earth composite catalyst is preferably as follows: the diene monomer is put into an anhydrous and oxygen-free closed container, then liquid pentane is added under the condition of freezing by liquid nitrogen, and finally the rare earth composite catalyst is added.
In the present invention, the filling degree of the reaction solution in the closed container is 30 to 70%, preferably 40 to 60%, and more preferably 45 to 55%. In the present invention, the degree of filling ensures that butadiene and pentane in the closed vessel can exist in the liquid phase at the polymerization temperature.
After the reaction solution is obtained, the invention carries out polymerization reaction on the reaction solution in the closed container to obtain the high cis-diene polymer. In the invention, the temperature of the polymerization reaction is preferably 0-50 ℃, more preferably 10-40 ℃, and most preferably 20-30 ℃; the time of the polymerization reaction is preferably 0.5-6 h, more preferably 1-5 h, and most preferably 2-4 h. In the present invention, the polymerization reaction is preferably carried out under water bath conditions. In the invention, the diolefin monomer is polymerized under the catalysis of the rare earth composite catalyst to obtain the high cis-diolefin polymer.
In the present invention, the polymerization reaction is preferably terminated by adding a terminator to the closed vessel. The type of the terminator is not particularly limited in the present invention, and any terminator known to those skilled in the art for use in polymerization reactions may be used. In the present invention, the terminator is preferably an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (anti-aging agent 264); the mass content of the 2, 6-di-tert-butyl-4-methylphenol in the terminator is preferably 1-2%.
After the polymerization reaction is terminated, the closed container is preferably opened, so that the environment in the closed container is restored to normal temperature and normal pressure. In the invention, the pentane solvent can be volatilized at a lower temperature to obtain a polymerization reaction product. In the invention, when the pentane solvent is n-pentane or isopentane, evaporating the solvent at 20-30 ℃; when the pentane solvent is neopentane, the pentane solvent can be volatilized at room temperature.
After obtaining the polymerization reaction product, the present invention preferably sequentially washes and dries the polymerization reaction product to obtain the high cis-diene polymer. The washing and drying operation is not particularly limited in the present invention, and washing and drying operations well known to those skilled in the art may be used. In the present invention, the washing detergent is preferably absolute ethanol; the number of washing is preferably 3 to 5. In the present invention, the drying is preferably normal temperature drying; the drying time is preferably 8-10 h.
The pentane solvent can be volatilized at room temperature after the reaction is finished, so that the solvent residue in the product is reduced, the obtained product is easy to recover and separate, the post-treatment temperature of the product is reduced, and the energy is saved.
To further illustrate the present invention, the process for synthesizing high cis diene polymers provided by the present invention is described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1:
under the vacuum state, 7mL of isoprene monomer and 6mL of butadiene monomer are sequentially added into a clean and dry 100mL polymerization bottle, and 20mL of n-pentane is introduced into the polymerization bottle under the condition of liquid nitrogen freezing to form a monomerThe molar ratio of butadiene to isoprene was 1: 1, and about 6mL of the prepared catalyst solution was added, the molar ratio of catalyst [ Nd ]]/[Al]/[Cl]/═ 1/20/2, molar ratio of rare earth compound to monomer in catalyst [ Nd]/[M]＝10.5×10-41, preparing a catalyst; the catalyst and solvent hexane are prepared into a solution, the rare earth compound is prepared into a solution of 0.1mol/L, the alkyl aluminum is prepared into a solution of 1.0mol/L, and the halogen-containing compound is prepared into a solution of 0.1mol/L, and the solution is convenient to meter.
In the catalyst, the rare earth compound is neodymium neodecanoate, the alkylaluminium is triisobutylaluminium, and the halogen-containing compound is diisobutylaluminium chloride.
And (3) putting the polymerization bottle into a constant-temperature water bath, reacting for 5 hours at the constant temperature of 40 ℃, and adding an absolute ethyl alcohol solution containing 1% of the antioxidant 264 by mass fraction to terminate the reaction.
After the obtained copolymerization product is washed by absolute ethyl alcohol repeatedly for three times, the copolymerization product is cut into pieces and is placed on a culture dish for drying for 8 hours at the temperature of 20-30 ℃, and the conversion rate of the product is 86.1 percent, the cis-1, 4-structure content of the polybutadiene chain segment is 97.6 percent, and the cis-1, 4-structure content of the polyisoprene chain segment is 97.1 percent.
Example 2:
under the vacuum state, 7mL of isoprene monomer and 6mL of butadiene monomer are sequentially added into a clean and dry 100mL polymerization bottle, 20mL of n-pentane is added into the polymerization bottle under the condition of liquid nitrogen freezing to form a monomer solution, the molar ratio of butadiene to isoprene is 1: 1, and then about 6mL of prepared catalyst solution is added, wherein the molar ratio of the catalyst is [ Nd ]]/[Al]/[Cl]1/25/2 molar ratio of rare earth compound to monomer in catalyst [ Nd]/[M]＝10.5×10-4:1；
In the catalyst, the rare earth compound is neodymium neodecanoate, the alkylaluminium is triisobutylaluminium, and the halogen-containing compound is diisobutylaluminium chloride.
And (3) putting the polymerization bottle into a constant-temperature water bath, reacting for 5 hours at the constant temperature of 40 ℃, and adding an absolute ethyl alcohol solution containing 1% of the antioxidant 264 by mass fraction to terminate the reaction.
After the obtained copolymerization product is washed by absolute ethyl alcohol repeatedly for three times, shearing the copolymerization product, placing the product on a culture dish at the temperature of 20-30 ℃ and drying for 8 hours, and measuring the product conversion rate to be 87.2%; it was found that the cis 1, 4-structure content of the polybutadiene block was 97.2%, and the cis 1, 4-structure content of the polyisoprene block was 96.4%.
Example 3:
under the vacuum state, adding 7mL of isoprene monomer and 6mL of butadiene monomer into a clean and dry 100mL polymerization bottle in sequence, adding 20mL of isopentane into the polymerization bottle under the condition of liquid nitrogen freezing to form a monomer solution, wherein the molar ratio of butadiene to isoprene is 1: 1, and then adding about 6mL of prepared catalyst solution, wherein the molar ratio of the catalyst is [ Nd ]]/[Al]/[Cl]1/20/2 molar ratio of rare earth compound to monomer in catalyst [ Nd]/[M]＝10.5×10-4:1；
In the catalyst, the rare earth compound is neodymium neodecanoate, the alkylaluminium is triisobutylaluminium, and the halogen-containing compound is diisobutylaluminium chloride.
And (3) putting the polymerization bottle into a constant-temperature water bath, reacting for 5 hours at the constant temperature of 40 ℃, and adding an absolute ethyl alcohol solution containing 1% of the antioxidant 264 by mass fraction to terminate the reaction.
After the obtained copolymerization product is washed by absolute ethyl alcohol repeatedly for three times, the copolymerization product is cut into pieces and is placed on a culture dish for drying for 8 hours at the temperature of 20-30 ℃, the conversion rate of the product is 85.7 percent, the cis 1, 4-structure content of the polybutadiene chain segment is 96.6 percent, and the cis 1, 4-structure content of the polyisoprene chain segment is 95.1 percent.
Example 4:
under the vacuum state, adding 7mL of isoprene monomer and 6mL of butadiene monomer into a clean and dry 100mL polymerization bottle in sequence, adding 20mL of isopentane into the polymerization bottle under the condition of liquid nitrogen freezing to form a monomer solution, wherein the molar ratio of butadiene to isoprene is 1: 1, and then adding about 6mL of prepared catalyst solution, wherein the molar ratio of the catalyst is [ Nd ]]/[Al]/[Cl]1/25/2 molar ratio of rare earth compound to monomer in catalyst [ Nd]/[M]＝10.5×10-4:1；
In the catalyst, the rare earth compound is neodymium neosilicate, the alkyl aluminum is triisobutyl aluminum, and the halogen-containing compound is diisobutyl aluminum chloride.
And (3) putting the polymerization bottle into a constant-temperature water bath, reacting for 5 hours at the constant temperature of 40 ℃, and adding an absolute ethyl alcohol solution containing 1% of the antioxidant 264 by mass fraction to terminate the reaction.
After the obtained copolymerization product is washed by absolute ethyl alcohol repeatedly for three times, the copolymerization product is cut into pieces and is placed on a culture dish for drying for 8 hours at the temperature of 20-30 ℃, and the conversion rate of the product is measured to be 87.9 percent, the cis-1, 4-structure content of the polybutadiene chain segment is 96.4 percent, and the cis-1, 4-structure content of the polyisoprene chain segment is 95.8 percent.
Example 5:
under the vacuum state, 7mL of isoprene monomer and 6mL of butadiene monomer are sequentially added into a clean and dry 100mL polymerization bottle, 20mL of neopentane is added into the polymerization bottle under the condition of liquid nitrogen freezing to form a monomer solution, the molar ratio of butadiene to isoprene is 1: 1, and then about 6mL of prepared catalyst solution is added, and the molar ratio of the catalyst [ Nd ] is]/[Al]/[Cl]1/20/2 molar ratio of rare earth compound to monomer in catalyst [ Nd]/[M]＝10.5×10-4:1；
In the catalyst, the rare earth compound is alkyl aluminum, and the halogen-containing compound is alkyl aluminum.
And (3) putting the polymerization bottle into a constant-temperature water bath, reacting for 5 hours at the constant temperature of 40 ℃, and adding an absolute ethyl alcohol solution containing 1% of the antioxidant 264 by mass fraction to terminate the reaction.
After the obtained copolymerization product is washed by absolute ethyl alcohol repeatedly for three times, shearing the copolymerization product, placing the product on a culture dish, and drying the product for 8 hours at normal temperature, wherein the conversion rate of the product is 84.3 percent; it was found that the cis 1, 4-structure content of the polybutadiene block was 96.9%, and the cis 1, 4-structure content of the polyisoprene block was 95.6%.
Example 6:
under the vacuum state, 7mL of isoprene monomer and 6mL of butadiene monomer are sequentially added into a clean and dry 100mL polymerization bottle, 20mL of neopentane is added into the polymerization bottle under the condition of liquid nitrogen freezing to form a monomer solution, the molar ratio of butadiene to isoprene is 1: 1, and then about 2.4mL of prepared catalyst solution is added, wherein the molar ratio of the catalyst is [ Nd ]]/[Al]/[Cl]1/25/2, the mole ratio of rare earth compound to monomer in the catalystNd]/[M]＝4.2×10-4:1；
In the catalyst, the rare earth compound is neodymium neodecanoate, the alkylaluminium is triisobutylaluminium, and the halogen-containing compound is diisobutylaluminium chloride.
And (3) putting the polymerization bottle into a constant-temperature water bath, reacting for 5 hours at the constant temperature of 40 ℃, and adding an absolute ethyl alcohol solution containing 1% of the antioxidant 264 by mass fraction to terminate the reaction.
After the obtained copolymerization product was washed with absolute ethanol repeatedly three times, the copolymerization product was cut into pieces and placed on a petri dish to dry at room temperature for 8 hours, and the conversion rate of the product was found to be 86.8%, the cis 1, 4-structure content of the polybutadiene chain segment was found to be 97.8%, and the cis 1, 4-structure content of the polyisoprene chain segment was found to be 96.6%.
Example 7:
under vacuum, 12mL of butadiene monomer was added to a clean and dry 100mL polymerization flask, 25mL of n-pentane was added to the polymerization flask under liquid nitrogen freezing conditions to form a monomer solution, and about 2.5mL of the prepared catalyst solution was added at a catalyst molar ratio [ Nd []/[Al]/[Cl]1/20/2 molar ratio of rare earth compound to monomer in catalyst [ Nd]/[M]＝4.0×10-4:1；
In the catalyst, the rare earth compound is neodymium neodecanoate, the alkylaluminium is triisobutylaluminium, and the halogen-containing compound is diisobutylaluminium chloride.
And (3) putting the polymerization bottle into a constant-temperature water bath, reacting for 5 hours at the constant temperature of 30 ℃, and adding an absolute ethanol solution containing 1% of the antioxidant 264 by mass fraction to terminate the reaction.
And (3) repeatedly washing the obtained product with absolute ethyl alcohol for three times, shearing the product, placing the cut product on a culture dish at the temperature of 20-30 ℃, and drying for 8 hours to obtain that the conversion rate of the product is 87.8 percent, and the cis-1, 4-structure content of the polybutadiene chain segment is 97.9 percent.
Example 8
Adding 14mL of isoprene monomer into a clean and dry 100mL polymerization bottle under a vacuum state, adding 25mL of n-pentane into the polymerization bottle under the condition of liquid nitrogen freezing to form a monomer solution, and then adding about 2.5mL of prepared catalyst solution, wherein the molar ratio of the catalyst is [ Nd ]]/[Al]/[Cl]/＝1/20/2 molar ratio of rare earth compound to monomer in catalyst [ Nd]/[M]＝4.0×10-4:1；
In the catalyst, the rare earth compound is neodymium neodecanoate, the alkylaluminium is triisobutylaluminium, and the halogen-containing compound is diisobutylaluminium chloride.
And (3) putting the polymerization bottle into a constant-temperature water bath, reacting for 5 hours at the constant temperature of 30 ℃, and adding an absolute ethanol solution containing 1% of the antioxidant 264 by mass fraction to terminate the reaction.
After the obtained product is washed by absolute ethyl alcohol repeatedly for three times, shearing the product, placing the product on a culture dish at the temperature of 20-30 ℃ and drying for 8 hours, and measuring the conversion rate of the product to be 85.9%; the cis 1, 4-structure content of the polyisoprene segment was found to be 97.9%.
Example 9
Under the vacuum state, adding 12mL of butadiene monomer into a clean and dry 100mL polymerization bottle, introducing 25mL of isopentane into the polymerization bottle under the condition of liquid nitrogen freezing to form a monomer solution, and then adding about 2.5mL of a prepared catalyst solution, wherein the molar ratio of the catalyst is [ Nd ]]/[Al]/[Cl]/═ 1/20/2, molar ratio of rare earth compound to monomer in catalyst [ Nd]/[M]＝4.0×10-4:1；
In the catalyst, the rare earth compound is neodymium neodecanoate, the alkylaluminium is triisobutylaluminium, and the halogen-containing compound is diisobutylaluminium chloride.
And (3) putting the polymerization bottle into a constant-temperature water bath, reacting for 5 hours at the constant temperature of 30 ℃, and adding an absolute ethanol solution containing 1% of the antioxidant 264 by mass fraction to terminate the reaction.
And (3) repeatedly washing the obtained product with absolute ethyl alcohol for three times, shearing the product, placing the product on a culture dish at the temperature of 20-30 ℃, and drying for 8 hours to obtain that the conversion rate of the product is 88.0 percent, and the cis-1, 4-structure content of the polybutadiene chain segment is 96.7 percent.
Example 10
Adding 14mL of isoprene monomer into a clean and dry 100mL polymerization bottle under a vacuum state, adding 25mL of isopentane into the polymerization bottle under the condition of liquid nitrogen freezing to form a monomer solution, and then adding about 2.5mL of prepared catalyst solution with the catalyst molar ratio [ Nd ]]/[Al]/[Cl]/＝1/20/2 molar ratio of rare earth compound to monomer in catalyst [ Nd]/[M]＝4.0×10-4:1；
In the catalyst, the rare earth compound is neodymium neodecanoate, the alkylaluminium is triisobutylaluminium, and the halogen-containing compound is diisobutylaluminium chloride.
And (3) putting the polymerization bottle into a constant-temperature water bath, reacting for 5 hours at the constant temperature of 30 ℃, and adding an absolute ethanol solution containing 1% of the antioxidant 264 by mass fraction to terminate the reaction.
After the obtained product is washed by absolute ethyl alcohol repeatedly for three times, the product is cut into pieces and is placed on a culture dish to be dried for 8 hours at normal temperature, and the conversion rate of the product is measured to be 87.9 percent, and the cis-1, 4-structure content of the polybutadiene chain segment is measured to be 95.7 percent.
Example 11
Under vacuum, 12mL of butadiene monomer was added to a clean and dry 100mL polymerization flask, 25mL of neopentane was added to the flask under liquid nitrogen freezing conditions to form a monomer solution, and about 2.5mL of the prepared catalyst solution was added at a catalyst molar ratio [ Nd []/[Al]/[Cl]/═ 1/20/2, molar ratio of rare earth compound to monomer in catalyst [ Nd]/[M]＝4.0×10-4:1；
In the catalyst, the rare earth compound is neodymium neodecanoate, the alkylaluminium is triisobutylaluminium, and the halogen-containing compound is diisobutylaluminium chloride.
And (3) putting the polymerization bottle into a constant-temperature water bath, reacting for 5 hours at the constant temperature of 30 ℃, and adding an absolute ethanol solution containing 1% of the antioxidant 264 by mass fraction to terminate the reaction.
After the obtained product was washed with absolute ethanol repeatedly three times, the product was cut into pieces and placed on a petri dish to be dried at normal temperature for 8 hours, and the conversion rate of the product was found to be 87.6%, and the cis 1, 4-structure content of the polybutadiene chain segment was found to be 97.1%.
Example 12
Adding 14mL of isoprene into a clean and dry 100mL polymerization bottle under a vacuum state, adding 25mL of neopentane into the polymerization bottle under the condition of liquid nitrogen freezing to form a monomer solution, and then adding about 2.5mL of prepared catalyst solution with the molar ratio of the catalyst [ Nd ]]/[Al]/[Cl]/═ 1/20/2, catalystMolar ratio of rare earth compound to monomer [ Nd]/[M]＝4.0×10-4:1；
In the catalyst, the rare earth compound is neodymium neodecanoate, the alkylaluminium is triisobutylaluminium, and the halogen-containing compound is diisobutylaluminium chloride.
And (3) putting the polymerization bottle into a constant-temperature water bath, reacting for 5 hours at the constant temperature of 30 ℃, and adding an absolute ethanol solution containing 1% of the antioxidant 264 by mass fraction to terminate the reaction.
After the obtained product is washed by absolute ethyl alcohol repeatedly for three times, the product is cut into pieces and is placed on a culture dish to be dried for 8 hours at normal temperature, and the conversion rate of the product is 86.9 percent, and the cis-1, 4-structure content of the polyisoprene chain segment is 96.1 percent.
It can be seen from the above examples that the solvent can be volatilized at room temperature after the reaction in the method provided by the invention is finished, the solvent residue in the product is reduced, the obtained product is easy to recover and separate, the post-treatment temperature of the product is reduced, the energy is saved, the product conversion rate is high, and the product has a high cis-structure.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (7)
1. A process for synthesizing a high cis diene polymer comprising:
in an anhydrous and oxygen-free closed container, carrying out polymerization reaction on a reaction solution containing a diene monomer, liquid pentane and a rare earth composite catalyst to obtain a high cis-diene polymer; the diene monomer is liquid butadiene and/or isoprene; the filling degree of the reaction solution in the closed container is 30-70%;
the reaction solution is obtained by mixing a diene monomer, liquid pentane and a rare earth composite catalyst, wherein the mixing temperature is below-100 ℃;
the temperature of the polymerization reaction is 40-50 ℃, and the time of the polymerization reaction is 0.5-6 h;
the polymerization reaction is terminated by adding a terminating agent into the closed container;
and (3) repeatedly washing the obtained copolymerization product with absolute ethyl alcohol for three times, shearing the copolymerization product, and drying the product on a culture dish at 20-30 ℃ for 8 hours.
2. The production method according to claim 1, wherein the rare earth composite catalyst comprises a rare earth compound, an alkylaluminum, and a halogen-containing compound.
3. The method according to claim 2, wherein the molar ratio of the halogen element in the rare earth compound, the alkyl aluminum and the halogen-containing compound is 1 (1-100) to (1-50).
4. The method according to claim 2 or 3, wherein the molar ratio of the rare earth compound to the diene monomer is (1 to 200). times.10-4:1。
5. The method according to claim 2 or 3, wherein the rare earth compound comprises a rare earth- β -diketone complex.
6. The method of claim 2 or 3, wherein the aluminum alkyl comprises one or more of triethylaluminum, diisobutylaluminum hydride, and triisobutylaluminum.
7. The method of claim 2 or 3, wherein the halogen-containing compound comprises one or more of an alkylaluminum halide, a halosilane, and an inorganic halide.
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