CN117820528A - Synthesis of polybutadiene with narrow molecular weight distribution and method for preparing polyethylene-butene elastomer by hydrogenation of polybutadiene - Google Patents
Synthesis of polybutadiene with narrow molecular weight distribution and method for preparing polyethylene-butene elastomer by hydrogenation of polybutadiene Download PDFInfo
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 35
- 229920001971 elastomer Polymers 0.000 title claims abstract description 21
- 239000000806 elastomer Substances 0.000 title claims abstract description 21
- 238000009826 distribution Methods 0.000 title claims description 39
- 239000005062 Polybutadiene Substances 0.000 title claims description 33
- 229920002857 polybutadiene Polymers 0.000 title claims description 33
- 238000000034 method Methods 0.000 title claims description 23
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims description 19
- -1 alkyl lithium Chemical compound 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- 239000012190 activator Substances 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001294 propane Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 15
- 239000005977 Ethylene Substances 0.000 description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000004711 α-olefin Substances 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920006124 polyolefin elastomer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OEQMCMBXMGAHDM-UHFFFAOYSA-N C1=CC=CC1[Ti](CCCC)(CCCC)C1C=CC=C1 Chemical compound C1=CC=CC1[Ti](CCCC)(CCCC)C1C=CC=C1 OEQMCMBXMGAHDM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MFRXMZYAKSRDMT-UHFFFAOYSA-L [Br-].[Br-].C1(C=CC=C1)[Ti+2]C1C=CC=C1 Chemical compound [Br-].[Br-].C1(C=CC=C1)[Ti+2]C1C=CC=C1 MFRXMZYAKSRDMT-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- YNBJMIXWGPOBGE-UHFFFAOYSA-N carbanide;cyclopenta-1,3-diene;titanium(4+) Chemical compound [CH3-].[CH3-].[Ti+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 YNBJMIXWGPOBGE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- OWJHNUOZBNPLDR-UHFFFAOYSA-N C1=CC=CC1[Ti](CC)(CC)C1C=CC=C1 Chemical compound C1=CC=CC1[Ti](CC)(CC)C1C=CC=C1 OWJHNUOZBNPLDR-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- IPTJKFGGRLMTIC-UHFFFAOYSA-L [I-].[I-].C1(C=CC=C1)[Ti+2]C1C=CC=C1 Chemical compound [I-].[I-].C1(C=CC=C1)[Ti+2]C1C=CC=C1 IPTJKFGGRLMTIC-UHFFFAOYSA-L 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KSFCHHFBQJDGFF-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C1C=CC=C1.C1C=CC=C1 KSFCHHFBQJDGFF-UHFFFAOYSA-L 0.000 description 1
- WDGICGVEWQIMTQ-UHFFFAOYSA-L cyclopentane;difluorotitanium Chemical compound F[Ti]F.[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 WDGICGVEWQIMTQ-UHFFFAOYSA-L 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Abstract
The invention relates to the technical field of polyolefin, in particular to a preparation method of a polyethylene-butene elastomer, which is prepared from a single butadiene monomer through a polymerization reaction and a hydrogenation reaction in two steps.
Description
Technical field:
the invention belongs to the field of polymer synthesis, and particularly relates to the technical field of polyolefin elastomers.
The background technology is as follows:
polyolefin elastomer POE is an ethylene/higher alpha-olefin random copolymer with higher comonomer content, belongs to a novel thermoplastic elastomer, has elasticity without vulcanization, has high comonomer content (10-30 wt%) and excellent cold resistance, ageing resistance, mechanical property and processability, can partially replace ethylene propylene rubber, can be widely used as an impact modifier of polyolefin materials such as polypropylene and the like, is used for preparing instrument boards, bumpers, connectors and plugs, pipelines, instrument parts, sheets, gardening tools and building materials, can be directly prepared into molded products and extrusion molded products, and is a novel elastomer material with high performance and high added value. At present, only few petrochemical enterprises such as the Dow chemical industry, the Ekkimen mobil chemical industry, the Sanjing chemical industry, the SK industry and the like can produce the products, but the petrochemical enterprises in China cannot produce the products.
In 2015, the market demand of China for POEs is about 15 ten thousand tons/year, all depend on import, the imported market price is about 18000-23000 yuan/ton, the domestic market demand for POEs is increased year by year, the annual growth rate is about 13%, and 20 ten thousand tons/year is expected to be reached in 2018. Exxon, dow, mitsui and LG four companies have been realized for POE industry production abroad. In 1993, the Dow company in the United states synthesized Engage series by titanium catalyst technology at the earliest and succeeded in 5.5 ten thousand tons/year industrialization equipment, then in 2004 synthesized Affinity series POE by using the site technology, and in 2005 Exxon Mobil company developed Exact series POE by using metallocene catalyst and high pressure ion production technology; the POE basic production process is as follows: the metallocene catalyst is used as a catalytic system, and a solution polymerization method is adopted, wherein the polymerization temperature is 80-150 ℃ and the polymerization pressure is 1-4.9MPa. The Insite technology can effectively control the introduction of long-chain branches into the linear short-chain branching structure of the polymer, thereby improving the processing rheological property (Mooney viscosity 5-35) of the polymer and improving the transparency of the material. At present, no POE production technology exists in China, most scientific research units stay in the research and development stage of the catalyst, and the price of imported POE products is high, so that the POE application field in China is greatly limited.
CN104774361a discloses a polyethylene/polybutene thermoplastic elastomer alloy material and its preparation method, the obtained material contains polybutene 5% -98.9% by weight, polyethylene 1% -80% by weight, ethylene-butene copolymer 0.1-20% by weight. The invention adopts a supported titanium and/or vanadium catalyst to synthesize the catalyst by a multistage sequential polymerization method. CN109942734a discloses a process for synthesizing POE elastomer, in which ethylene and alpha-olefin are copolymerized as monomer, alkyl aluminium is used as catalyst, operation is easy, investment cost is low, and its molecular weight distribution PID is 2-2.3. CN111247157a provides a novel transition metal compound based on cyclopenta-naphthyl, a transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and at least one α -olefin having high catalytic activity, a process for preparing an ethylene homopolymer or a copolymer of ethylene and α -olefin using the same, and the prepared ethylene homopolymer or copolymer of ethylene and α -olefin. CN111148748A provides a novel indene-based transition metal complex, a transition metal catalyst composition comprising the indene-based transition metal complex with high catalyst activity for preparing an ethylene homopolymer or a copolymer of ethylene and one or more alpha-olefins, a process for preparing an ethylene homopolymer or a copolymer of ethylene and alpha-olefins using the indene-based transition metal complex, and an ethylene homopolymer or copolymer of ethylene and alpha-olefins prepared thereby. The molecular weight distribution in the method is narrow and is between 2.0 and 10.0, and the narrow molecular weight distribution ensures that the method is not easy to flex during injection and extrusion processing and has certain dimensional stability. Patent CN103788276a discloses a method for controlling the molecular weight distribution in an ethylene/α -olefin composition, which can effectively control the size of the molecular weight distribution by controlling the relative monomer concentration during the contact with the pre-catalyst or the specific catalyst, but the narrowest molecular weight distribution is 2.87 from the result.
The invention comprises the following steps:
aiming at the problem of wider molecular weight distribution of the existing polyethylene-butene elastomer, the invention obtains polybutadiene through butadiene polymerization, and then hydrogenation is carried out to finally obtain the polyethylene-butene elastomer with narrower molecular weight distribution.
The first object of the present invention is to produce polybutadiene having a molecular weight distribution (PID) of 1.1 or less by a lithium-based anionic polymerization method.
The second object of the present invention is to provide a process for the preparation of a polyethylene-butene elastomer having a narrow distribution of molecular weights, aimed at obtaining a polyethylene-butene elastomer having a PID less than 1.1.
A process for preparing polybutadiene with narrow molecular weight distribution features that the single butadiene monomers are polymerized with each other. The present invention has innovatively found that polybutadiene with a narrow molecular weight distribution can be obtained by polymerizing a butadiene-only monomer.
Preferably, the polybutadiene according to the invention is prepared from a single butadiene monomer by anionic polymerization, comprising the steps of: and (3) carrying out anionic polymerization on a raw material solution consisting of a solvent, butadiene and alkyl lithium.
In the invention, butadiene is taken as the only monomer, and an anionic polymerization mode is adopted, which is beneficial to the cooperative preparation of polybutadiene with narrow molecular weight distribution.
In the invention, the solvent is at least one of cyclohexane, n-hexane and cyclopentane.
Preferably, the alkyl lithium is alkyl lithium with 3-6 carbon atoms; at least one of n-butyllithium and sec-butyllithium is preferable. The amount of alkyllithium may be determined based on the target molecular weight of the polymer.
Preferably, the concentration of butadiene monomer in the raw material solution is 50-200g/L.
The invention also provides another preferable preparation scheme of polybutadiene with narrow molecular weight distribution, which is obtained by carrying out anionic polymerization on a raw material solution consisting of at least one of a regulator and an activator, a solvent, butadiene and alkyl lithium. Preferably, the preferable scheme of the invention can be obtained by carrying out anion polymerization on a raw material solution consisting of an activating agent, a solvent, butadiene and alkyl lithium; or, carrying out anion polymerization on a raw material solution consisting of a regulator, a solvent, butadiene and alkyl lithium; or the raw material solution consisting of a regulator, an activator, a solvent, butadiene and alkyl lithium is subjected to anionic polymerization.
In the invention, the activator is THF.
Preferably, the concentration of the activator in the stock solution is less than or equal to 1g/L, preferably from 0.05 to 0.5g/L.
According to the invention, butadiene is taken as a single monomer, and the alkyl lithium and the regulator are matched, so that the narrow distribution is ensured, the flexible regulation and control of 1,2 structures and the performance of the structure are facilitated, and the performance of the structure is flexibly regulated and controlled.
In the invention, the regulator is at least one of diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol ethyl ether, triethylamine, hexamethylphosphoric triamide, tetramethyl ethylenediamine, ditetrahydrofurfuryl propane and N, N-dimethyl tetrahydrofurfuryl amine;
preferably, the content of the regulator in the raw material solution is less than or equal to 0.5g/L, preferably 0.01 to 0.1g/L.
In the invention, the temperature of the polymerization reaction is 30-100 ℃; the pressure is 0.1-0.5MPa.
In the invention, the data molecular weight of polybutadiene obtained by controlled polymerization is less than or equal to 20 ten thousand, preferably 5 to 15 ten thousand;
preferably, in the polybutadiene, the PID is less than or equal to 1.1, preferably 1 to 1.05.
The invention also provides a preparation method of the polyethylene-butene elastomer with narrow molecular weight distribution, which is adopted to prepare the polybutadiene with narrow molecular weight distribution, and then the polybutadiene with narrow molecular weight distribution is subjected to hydrogenation reaction, so that the polybutadiene is obtained.
In the invention, a single butadiene is innovatively adopted as a monomer to carry out polymerization and hydrogenation two-step reaction, and a brand new thought and scheme are provided for the preparation of the polyethylene-butene polymer elastomer.
In the present invention, the hydrogenation reaction can be carried out based on the existing means.
Preferably, the hydrogenation catalyst is a metallocene catalyst system;
preferably, the catalyst (mg) is present in a weight ratio of monomers (g) of 0.1 to 1mg/g, preferably 0.3 to 0.7mg/g.
The hydrogenation reaction temperature is 50 to 90 ℃, preferably 70 to 80 ℃.
Preferably, the hydrogenation reaction pressure is 1-3MPa;
the hydrogenation reaction time is 1-3h;
preferably, the hydrogenation degree is not less than 97%.
The invention relates to a method for preparing a preferable polyethylene-butene elastomer, which adopts an anion polymerization method, a solvent, a regulator, an activator (alkyl lithium) and an initiator are added into a polymerization kettle which is replaced by dry nitrogen, the temperature of the polymerization kettle is kept between 30 and 100 ℃, the pressure is kept between 0.1 and 0.5MPa, a butadiene monomer is firstly added, and the reaction is carried out for 20 minutes after the high temperature, so as to obtain polybutadiene with very narrow molecular weight distribution; then adopting a metallocene catalytic system to carry out hydrogenation reaction, wherein the hydrogenation degree is more than or equal to 97%, and obtaining a finished product through solvent removal and drying. The solvent adopted in the synthesis method is cyclohexane, n-hexane or cyclopentane; the initiator is n-butyllithium or sec-butyllithium; the activator is tetrahydrofuran; the regulator is at least one of diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol ethyl ether, triethylamine, hexamethylphosphoric triamide, tetramethyl ethylenediamine, ditetrahydrofurfuryl propane and N, N-dimethyl tetrahydrofurfuryl amine, preferably ditetrahydrofurfuryl propane. The process conditions are as follows: the content of the activator in the solvent system is less than or equal to 1g/L, preferably 0.05-0.5 g/L; the content of the regulator in the solvent system is less than or equal to 0.5g/L, preferably 0.01-0.1 g/L; the number average molecular weight of the polymer is controlled to be less than or equal to 20 ten thousand, preferably 5 to 15 ten thousand; the vinyl content of the butadiene segment is controlled to be less than or equal to 80%, preferably less than or equal to 40%; the hydrogenation reaction pressure is 1-3MPa; hydrogenation reaction time: 1-3h; the hydrogenation catalyst is as follows: a metallocene catalyst.
Advantageous effects
The invention innovatively adopts butadiene as a single monomer to polymerize, thus being capable of unexpectedly preparing polybutadiene with narrow molecular weight distribution and a polyethylene-butene elastomer, wherein the hard segment of the elastomer is polyethylene crystal, and the soft segment is poly-1-butene.
The research shows that the molecular weight distribution of the polyethylene-butene elastomer of the polybutadiene prepared by the invention can be controlled between 1 and 1.1, the polybutadiene is not easy to flex in the processing and using processes, and the size stability is good.
According to the preparation process, polymerization innovation is carried out by taking the single butadiene as a monomer, and the polymerization temperature, the regulator and other controls are further matched, so that the preparation process is beneficial to further flexibly regulating and controlling the 1,2 structure, the density, the tensile strength, the hardness and the melting point of the prepared polymer under the condition of ensuring narrow molecular weight distribution, and has excellent process suitability.
Detailed Description
To further illustrate the details of the invention, several embodiments are set forth. The following examples are intended to illustrate the present invention and are not intended to limit the scope of the invention as claimed.
Polymerization conditions: the monomer concentration is 50-200g/L; the initiator is n-butyllithium or sec-butyllithium, the addition amount is set according to the molecular weight, the addition amount is small, and the addition amount is large; the activator is tetrahydrofuran, and the activator mainly activates the catalyst to improve the reaction rate, and the addition amount is less than or equal to 1g/L, preferably 0.05-0.5 g/L; the addition amount of the regulator is less than or equal to 0.5g/L, preferably 0.01-0.1 g/L, and the regulator has the function of improving the 1,2 structure content of the butadiene chain segment in the polymerization reaction process, converting the butadiene chain segment into a 1-butene structure after hydrogenation, and improving the product elasticity as a soft segment of an elastomer; the pressure of the polymerization kettle is between 0.2 and 0.5MPa, and the initiation temperature is more than or equal to 40 ℃; the reaction temperature is less than or equal to 100 ℃, and the reaction time is more than or equal to 30min.
Hydrogenation reaction conditions: the catalyst is one of bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium dibromide, bis (cyclopentadienyl) titanium diiodide, bis (cyclopentadienyl) titanium difluoride, bis (cyclopentadienyl) titanium dicarbonate, bis (cyclopentadienyl) dimethyl titanium, bis (cyclopentadienyl) diethyl titanium, bis (cyclopentadienyl) dibutyl titanium and the like, the hydrogenation pressure is 1-3MPa, the hydrogenation reaction time is 1-3 hours, the hydrogenation initial temperature is 70-80 ℃, the dosage of the hydrogenation catalyst is 0.1-1 mg/g, and the preferred dosage of the hydrogenation catalyst is 0.3-0.7 mg/g.
Example 1
Adding 3000ml of cyclohexane and 1.5mmol of n-butyllithium into a polymerization kettle, heating the kettle to 40 ℃, controlling the temperature of the kettle to be 0.20MPa, adding 150g of butadiene monomer, and controlling the high temperature to be 85 ℃ through circulating water for 30min; and then pressing the polymerized glue solution into a hydrogenation kettle, heating to 72 ℃, adding 100mg of dicyclopentadiene titanium dichloride, introducing hydrogen (the pressure is 1.2 MPa), reacting for 2 hours, and obtaining a finished product after condensation and drying.
Example 2
3000ml of cyclohexane, 0.25g of tetrahydrofuran, 1.92mmol of sec-butyllithium and 0.25MPa of pressure of the polymerization kettle are added into a polymerization kettle, 250g of butadiene monomer is added, the high temperature is controlled to be 75 ℃ through circulating water, the reaction time is 40min, then the polymerization glue solution is pressed into a hydrogenation kettle, the temperature is increased to be 75 ℃, 80mg of bis (cyclopentadienyl) titanium dibromide is added, hydrogen (the pressure is 1.5 MPa) is introduced, the reaction time is 1.5 hours, and the finished product is obtained after condensation and drying.
Example 3
Adding 3000ml of cyclohexane, 1g of tetrahydrofuran, 3.2mmol of n-butyllithium into a polymerization kettle, raising the temperature of the kettle to 45 ℃, controlling the pressure of the polymerization kettle to 0.4MPa, adding 300g of butadiene monomer, and controlling the high temperature to 98 ℃ through circulating water for 35min; then the polymerized glue solution is pressed into a hydrogenation kettle, the temperature is raised to 77 ℃, 150mg of bis (cyclopentadienyl) dibutyl titanium is added, hydrogen (pressure is 2 MPa) is introduced, the reaction time is 1 hour, and the finished product is obtained after condensation and drying.
Example 4
3000ml of cyclohexane, 0.75g of tetrahydrofuran, 0.2g of ditetrahydrofuran propane and 3.74mmol of sec-butyllithium are added into a polymerization kettle, the kettle temperature is raised to 45 ℃, the pressure of the polymerization kettle is 0.3MPa, then 400g of butadiene monomer is added, the high temperature is controlled to 78 ℃ through circulating water, the reaction time is 40min, then the polymerization glue solution is pressed into a hydrogenation kettle, the temperature is raised to 80 ℃, 250mg of bis (cyclopentadienyl) dimethyl titanium is added, hydrogen (the pressure is 2 MPa) is introduced, the reaction time is 1 hour, and the finished product is obtained after condensation and drying.
The microstructure and properties of the finished product obtained by the method are shown in Table 1:
table 1: typical microstructure and performance table of polyethylene-butene elastomer
| Test item | Example 1 | Example 2 | Example 3 | Example 4 |
| Mn molecular weight (Wan) | 10 | 13 | 9.4 | 10.7 |
| Molecular weight distribution | 1.04 | 1.05 | 1.03 | 1.05 |
| Butadiene section 1,2 Structure content (%) | 10 | 12.6 | 21 | 35 |
| Density (g/cm) 3 ) | 0.905 | 0.881 | 0.872 | 0.863 |
| Melting point (. Degree. C.) | 86 | 79 | 45 | 12 |
| 300% strength at definite elongation (MPa) | 11 | 9.4 | 5.2 | 2.18 |
| Tensile Strength (MPa) | 40 | 36.8 | 26 | 2.65 |
| Elongation at break (%) | 476 | 582 | 658 | 483 |
| Hardness (Shore A) | 92 | 90 | 82 | 53 |
The invention relates to the field of polyolefin elastomer, in particular to a polyethylene-butene elastomer obtained by adopting a two-step method of lithium series anion polymerization and metallocene series hydrogenation technology, which is characterized by having narrower molecular weight distribution, 1-1.1 and 1,2 structure content of 10-40% and a density of 0.86-0.91g/cm 3 The tensile strength is 2-45MPa, the elongation at break is 400-700%, the hardness is 53-92 Shore A, and the melting point is 12-86 ℃.
Claims (12)
1. A process for preparing polybutadiene with a narrow molecular weight distribution, which is characterized by polymerizing a single butadiene monomer.
2. The process for preparing polybutadiene having a narrow molecular weight distribution according to claim 1, wherein said polybutadiene is prepared from a single butadiene monomer by anionic polymerization, comprising the steps of: and (3) carrying out anionic polymerization on a raw material solution consisting of a solvent, butadiene and alkyl lithium.
3. The method for producing a polybutadiene having a narrow molecular weight distribution as set forth in claim 2, wherein said solvent is at least one of cyclohexane, n-hexane and cyclopentane.
4. The method for producing a polybutadiene having a narrow molecular weight distribution according to claim 2, wherein said alkyllithium is an alkyllithium having 3 to 6 carbon atoms; at least one of n-butyllithium and sec-butyllithium is preferable.
5. The process for preparing a polybutadiene having a narrow molecular weight distribution as claimed in claim 2, wherein the concentration of the butadiene monomer in the raw material solution is 50 to 200g/L.
6. The process for producing a polybutadiene having a narrow molecular weight distribution according to any one of claims 2 to 5, wherein said polybutadiene is obtained by anionic polymerization of a raw material solution comprising at least one of a regulator and an activator, a solvent, butadiene and alkyl lithium.
7. The method for preparing polybutadiene with narrow molecular weight distribution according to claim 6, wherein the regulator is at least one of diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol ethyl ether, triethylamine, hexamethylphosphoric triamide, tetramethyl ethylenediamine, ditetrahydrofurfuryl propane and N, N-dimethyl tetrahydrofurfuryl amine;
preferably, the content of the regulator in the raw material solution is less than or equal to 0.5g/L, preferably 0.01-0.1 g/L;
preferably, the activator is THF;
preferably, the concentration of activator is less than or equal to 1g/L, preferably 0.05 to 0.5g/L.
8. The process for the preparation of a polybutadiene having a narrow molecular weight distribution according to any one of claims 1 to 7, wherein the polymerization temperature is from 30 to 100 ℃; the pressure is 0.1-0.5MPa.
9. The process for the preparation of polybutadiene having a narrow molecular weight distribution according to any of claims 1 to 7, wherein the data molecular weight of the polyethylene-butene polymer obtained by controlled polymerization is less than or equal to 20 ten thousand, preferably from 5 to 15 ten thousand;
preferably, in the polybutadiene, the PID is less than or equal to 1.1, preferably 1 to 1.05.
10. A method for preparing a polyethylene-butene elastomer with narrow molecular weight distribution, which is characterized in that the polybutadiene with narrow molecular weight distribution is prepared by adopting the preparation method of any one of claims 1 to 9, and is obtained by hydrogenation reaction.
11. The process for preparing a narrow molecular weight distribution polyethylene-butene elastomer according to claim 10 wherein the catalyst of the hydrogenation reaction is a metallocene-based catalyst system;
preferably, the catalyst (mg) is present in a weight ratio of monomers (g) of 0.1 to 1mg/g, preferably 0.3 to 0.7mg/g.
12. The process for preparing a narrow molecular weight distribution polyethylene-butene elastomer according to claim 10 wherein the hydrogenation reaction pressure is from 1 to 3MPa;
the temperature of hydrogenation reaction is 50-90 ℃;
the hydrogenation reaction time is 1-3h;
preferably, the hydrogenation degree is not less than 97%.
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