CN115073666B - High molecular weight iron-based bio-based rubber, preparation method and application thereof, and rubber composition based on high molecular weight iron-based bio-based rubber - Google Patents
High molecular weight iron-based bio-based rubber, preparation method and application thereof, and rubber composition based on high molecular weight iron-based bio-based rubber Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 252
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 119
- 229920001971 elastomer Polymers 0.000 title claims abstract description 105
- 239000005060 rubber Substances 0.000 title claims abstract description 105
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 79
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 230000009477 glass transition Effects 0.000 claims abstract description 25
- 238000009826 distribution Methods 0.000 claims abstract description 24
- 239000003208 petroleum Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- JSNRRGGBADWTMC-UHFFFAOYSA-N (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene Chemical compound CC(C)=CCCC(C)=CCCC(=C)C=C JSNRRGGBADWTMC-UHFFFAOYSA-N 0.000 claims description 82
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 80
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 78
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 63
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 claims description 40
- CXENHBSYCFFKJS-UHFFFAOYSA-N (3E,6E)-3,7,11-Trimethyl-1,3,6,10-dodecatetraene Natural products CC(C)=CCCC(C)=CCC=C(C)C=C CXENHBSYCFFKJS-UHFFFAOYSA-N 0.000 claims description 39
- 229930009668 farnesene Natural products 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 claims description 19
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000012380 dealkylating agent Substances 0.000 claims description 8
- 238000004073 vulcanization Methods 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 235000014121 butter Nutrition 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 230000020335 dealkylation Effects 0.000 claims description 4
- 238000006900 dealkylation reaction Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002168 alkylating agent Substances 0.000 claims description 2
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 claims description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 58
- 238000006116 polymerization reaction Methods 0.000 description 20
- 230000003712 anti-aging effect Effects 0.000 description 19
- 239000007788 liquid Substances 0.000 description 19
- 238000010791 quenching Methods 0.000 description 19
- 230000000171 quenching effect Effects 0.000 description 19
- 238000001291 vacuum drying Methods 0.000 description 19
- 238000005406 washing Methods 0.000 description 19
- 238000007334 copolymerization reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 4
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- -1 rare earth lanthanide Chemical class 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- JSNRRGGBADWTMC-QINSGFPZSA-N (E)-beta-Farnesene Natural products CC(C)=CCC\C(C)=C/CCC(=C)C=C JSNRRGGBADWTMC-QINSGFPZSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- YSNRTFFURISHOU-UHFFFAOYSA-N beta-farnesene Natural products C=CC(C)CCC=C(C)CCC=C(C)C YSNRTFFURISHOU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940052367 sulfur,colloidal Drugs 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- C08F236/22—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 three or more carbon-to-carbon double bonds
-
- 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
- C08F236/06—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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- 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
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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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A high molecular weight iron-based bio-based rubber, a method for preparing the same, an application thereof, and a rubber composition based thereon. The invention belongs to the field of bio-based rubber and preparation thereof. The invention aims to solve the technical problems of low molecular weight, high glass transition temperature, high cost and low efficiency of the existing preparation method of the existing bio-based rubber. The iron-based bio-based rubber is prepared by catalyzing and copolymerizing petroleum-based monomers and bio-based monomers through an iron-based catalyst, and the number average molecular weight of the high molecular weight iron-based bio-based rubber is 5.0 multiplied by 10 5 g/mol～20.0×10 5 g/mol, molecular weight distribution is 1.5-3.0, and glass transition temperature Tg is minus 100 ℃ to minus 20 ℃. The method comprises the following steps: under the anhydrous and anaerobic condition, the bio-based monomer, the petroleum-based monomer, the iron-based catalyst, the solvent and the cocatalyst are added into a reactor to react completely, and then the reaction is quenched, so that the high molecular weight iron-based bio-based rubber is obtained. Application: used for manufacturing chemical protective clothing, tires or soles. The rubber composition comprises high molecular weight iron-based bio-based rubber and has high mechanical properties.
Description
Technical Field
The invention belongs to the field of bio-based rubber and preparation thereof, and particularly relates to high molecular weight iron bio-based rubber, a preparation method and application thereof, and a rubber composition based on the high molecular weight iron bio-based rubber.
Background
Terpenes are one of the largest families of natural compounds synthesized by conifers and various plants. Among the bulky terpene-based monomers, β -myrcene having a unique conjugated diene structure is attracting increasing attention. After Johanson et al first reported on myrcene in 1948, scientists began to study myrcene polymers in different polymerization modes. In 1987, cawse et al used a free radical polymerization method with hydrogen peroxide as an initiator and n-butanol as a solvent to obtain low molecular weight (3100 g/mol to 4030 g/mol) polylaurene. But the selectivity of myrcene is not easy to be regulated. Meanwhile, due to the defect of the performance of the homopolymer of a single monomer, researchers start to study copolymers of myrcene and other monomers.
In 1993, david studied the copolymerization of myrcene and styrene/methyl methacrylate by emulsion polymerization using AIBN as an initiator, wherein the copolymer has a high molecular weight (20000 g/mol) but a low conversion (5% -13%). Compared with cationic polymerization, the free radical polymerization has long reaction time, uncontrollable microstructure and unsatisfactory conversion rate. Compared with the method, the anionic polymerization has high speed, high conversion rate, narrow molecular weight distribution and controllable molecular weight and molecular structure, and the myrton and the Quirk successfully obtain the myrcene-styrene copolymer with narrow molecular weight distribution (PDI=1.09) by using the anionic polymerization method. However, the severe conditions of the anionic polymerization reaction and the sensitivity to water and oxygen make the industrial production difficult.
In recent years, many scientists have developed coordination polymerization to study the copolymerization of myrcene. In 2015, the Cui Dongmei subject group realized copolymerization of isoprene and myrcene by a rare earth lanthanide series catalytic system. In 2020, the Dirong subject group successfully realized the copolymerization of myrcene and isoprene, and myrcene and butadiene using a neodymium rare earth catalyst. 2021, kotohiro Nomura et al successfully achieved the copolymerization of myrcene with ethylene by half-titanocene catalysts. Beta-farnesene is relatively less studied at present due to its lower monomer productivity. With the development of industrial preparation technology and biological preparation technology in recent years, research on bio-based monomers is expanded to beta-farnesene. Under the action of a novel lanthanide catalyst, eval L researches the copolymerization reaction of myrcene and farnesene with styrene. The blend amount of myrcene and farnesene in the copolymer is 5.6-30.8% and 2.5-9.8% respectively. However, because rare earth metals are expensive, titanium metals have toxicity, free radical polymerization can generate gel, monomer conversion rate is low and the like, so that industrial production of bio-based rubber still faces a plurality of problems, and therefore, how to realize green and environment-friendly industrial preparation of bio-based rubber with better performance is important.
Disclosure of Invention
The invention aims to solve the technical problems of low molecular weight, high glass transition temperature, high cost and low efficiency of the existing preparation method of the existing bio-based rubber, and provides a high molecular weight iron-based bio-based rubber, a preparation method and application thereof, and a rubber composition based on the high molecular weight iron-based bio-based rubber.
The high molecular weight iron-based biobased rubber is prepared by catalyzing and copolymerizing a petroleum-based monomer and a biobased monomer through an iron-based catalyst, and the number average molecular weight of the high molecular weight iron-based biobased rubber is 5.0 multiplied by 10 5 g/mol～20.0×10 5 g/mol, molecular weight distribution is 1.5-3.0, and glass transition temperature Tg is minus 100 ℃ to minus 20 ℃.
Further defined, the petroleum-based monomer is isoprene or butadiene and the bio-based monomer is myrcene or farnesene.
Further defined, the molar ratio of petroleum-based monomer to bio-based monomer is (1:19) - (19:1).
Further, the molar ratio of the sum of the molar amounts of the petroleum-based monomer and the bio-based monomer to the iron element in the iron-based catalyst is (500 to 20000): 1. The sum of the molar amounts of the petroleum-based monomer and the bio-based monomer refers to the sum of the amounts of the materials of the petroleum-based monomer and the bio-based monomer.
Further defined, the structure of the iron-based catalyst is any one of the following:
the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
under the anhydrous and anaerobic condition, the bio-based monomer, the petroleum-based monomer, the iron-based catalyst, the solvent and the cocatalyst are added into a reactor, and the reaction is quenched for 10min to 240min at the temperature of 0 ℃ to 100 ℃ under the condition of stirring, and the reaction is repeatedly washed by ethanol and dried in vacuum, thus obtaining the high molecular weight iron-based bio-based rubber.
Further defined, the cocatalyst is one of MAO, MMAO, DMAO, or a mixture of an aluminum alkyl and a dealkylating agent, the aluminum alkyl being Al i Bu 3 、AlEt 3 、AlMe 3 One of the dealkylating agents is [ Ph ] 3 C] + [B(CF 5 ) 4 ] - Or B (C) 6 F 5 ) 3 。
Further defined, when the promoter is one of MAO, MMAO, DMAO, the molar ratio of the aluminum element in the promoter to the iron element in the iron-based catalyst is (10 to 1000): 1, when the cocatalyst is a mixture of aluminum alkyl and dealkylating agent, the mol ratio of aluminum element in aluminum alkyl to iron element in iron catalyst is (10-100): 1, and the mol ratio of boron element in dealkylating agent to iron element in iron catalyst is (1-10): 1.
Further defined, when the promoter is one of MAO, MMAO, DMAO, the molar ratio of aluminum element in the promoter to iron element in the iron-based catalyst is 500:1, when the cocatalyst is a mixture of aluminum alkyl and a dealkylation reagent, the molar ratio of aluminum element in the aluminum alkyl to iron element in the iron-based catalyst is 40:1, and the molar ratio of boron element in the dealkylation reagent to iron element in the iron-based catalyst is 1:1.
Further limited, the solvent is one or two of toluene, xylene, petroleum ether, n-hexane, cyclohexane, n-heptane, n-octane, methylene dichloride and hydrogenated gasoline, and the ratio of the solvent to the total volume of the bio-based monomer and the petroleum-based monomer is (1-50): 1.
Further defined, the reaction is carried out at 25℃for 60min.
The invention relates to a high molecular weight iron-based bio-based rubber for manufacturing chemical protective clothing, tires or soles.
The rubber composition based on the high molecular weight iron-based bio-based rubber is prepared from 100 parts by weight of the high molecular weight iron-based bio-based rubber, 10-75 parts by weight of carbon black, 1-3 parts by weight of a vulcanization accelerator, 0.1-15 parts by weight of a vulcanizing agent, 1-10 parts by weight of zinc oxide and 1-9 parts by weight of hard butter.
Further limited, the tensile strength of the rubber composition is more than or equal to 18MPa, the elongation at break is more than or equal to 350%, the tearing strength is more than or equal to 40N/mm, and the 100% stretching stress is more than or equal to 3MPa.
Further defined, the carbon black is one or a mixture of several of N330, N220 and N660 according to any ratio.
Further defined, the vulcanization accelerator is one or more of CZ, NA-22, DCBS, MBT, TT, DZ and TMTD.
Further defined, the vulcanizing agent is sulfur, including powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur.
Compared with the prior art, the invention has the remarkable effects that:
1) The iron-based bio-based rubber prepared by the invention has high molecular weight, low glass transition temperature, good physical and mechanical properties and good processability. The storage stability of the alloy can be improved while ensuring better mechanical strength. The application field of the synthetic rubber is further expanded.
2) The main catalyst adopted by the invention is an iron catalyst, and is green, environment-friendly, good in biocompatibility and simple to prepare.
3) The catalyst system provided by the invention has higher copolymerization activity on petroleum-based monomers such as butadiene and isoprene and biological-based monomers such as myrcene and farnesene, and can obtain more environment-friendly and sustainable biological-based rubber through the introduction of the biological-based monomers, thereby relieving the dependence on the petrochemical industry field and having important industrial application value.
Drawings
FIG. 1 is GPC of the iron-based bio-based rubber of example 1;
FIG. 2 is a DSC of the iron-based bio-based rubber of example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range. In the present specification and claims, the range limitations may be combined and/or interchanged, such ranges including all the sub-ranges contained therein if not expressly stated.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" is to be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the plural reference is obvious that there is a singular reference
Example 1: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 10:10), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield is>99%. Polymer M n (number average molecular weight, g/mol) 106.6 ten thousand, PDI (molecular weight distribution) 2.3, glass transition temperature-63.6 ℃.
The molecular weight information table of the high molecular weight iron-based biobased rubber of this example is shown in table 1.
TABLE 1 molecular weight information Table
| Peak | Mp(g/mol) | Mn(g/mol) | Mw(g/mol) | Mz(g/mol) | Mz+1(g/mol) | Mv(g/mol) | PD |
| Peak1 | 2154548 | 1066144 | 2414918 | 4037159 | 5471657 | 3817224 | 2.265 |
The rubber composition based on the high molecular weight iron-based bio-based rubber of example 1 was prepared from 100 parts by mass of the high molecular weight iron-based bio-based rubber of example 1, 30 parts by mass of N220, 2 parts by mass of a vulcanization accelerator CZ, 3 parts by mass of sulfur, 3 parts by mass of zinc oxide, 2 parts by mass of hard butter.
The properties of the obtained rubber composition were found to be 18.03MPa in tensile strength, 456.81% in elongation at break, 42.30N/mm in tear strength and 4.45MPa in 100% elongation stress.
Example 2: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 4:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield was 89%. Polymer M n (number average molecular weight, g/mol) 71.4 ten thousand, PDI (molecular weight distribution) 3.0, glass transition temperature-70.1 ℃.
Example 3: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:3), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield is>99%. Polymer M n (number average molecular weight, g/mol) 169.6 ten thousand, PDI (molecular weight distribution) 2.0, glass transition temperature-42.6 ℃.
The rubber composition based on the high molecular weight iron-based bio-based rubber of example 3 was prepared from 100 parts by mass of the high molecular weight iron-based bio-based rubber of example 3, 20 parts by mass of N220, 2 parts by mass of a vulcanization accelerator CZ, 3 parts by mass of sulfur, 2 parts by mass of zinc oxide, 2 parts by mass of hard butter.
The properties of the obtained rubber composition were found to be 18.78MPa in tensile strength, 374.5% in elongation at break, 41.70N/mm in tear strength and 4.89MPa in 100% elongation stress.
Example 4: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:9), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield is>99%. Polymer M n (number average molecular weight, g/mol) was 139.6 ten thousand, PDI (molecular weight distribution) was 2.2, and glass transition temperature was-45.7 ℃.
Example 5: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:19), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield is>99%. Polymer M n (number average molecular weight, g/mol) 121.6 ten thousand, PDI (molecular weight distribution) 1.9, glass transition temperature-28.7 ℃.
Example 6: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 50 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield was 87%. Polymer M n (number average molecular weight, g/mol) 74.9 ten thousand, PDI (molecular weight distribution) 2.5, glass transition temperature-53.7 ℃.
Example 7: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst E (20 mu mol,1equiv.,4.24 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield was 95%. Polymer M n (number average molecular weight, g/mol) was 127.3 ten thousand, PDI (molecular weight distribution) was 2.4, and glass transition temperature was-59.6 ℃.
The rubber composition based on the high molecular weight iron-based bio-based rubber of example 7 was prepared from 100 parts by mass of the high molecular weight iron-based bio-based rubber of example 7, 30 parts by mass of N220, 2 parts by mass of a vulcanization accelerator CZ, 3 parts by mass of sulfur, 3 parts by mass of zinc oxide, 2 parts by mass of hard butter.
The properties of the obtained rubber composition were found to be 18.65MPa in tensile strength, 432.79% in elongation at break, 43.57N/mm in tear strength and 4.27MPa in 100% elongation stress.
Example 8: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst H (20 mu mol,1equiv.,4.72 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield was 99%. Polymer M n (number average molecular weight, g/mol) was 115.5 ten thousand, PDI (molecular weight distribution) was 2.1, and glass transition temperature was-61.7 ℃.
Example 9: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst I (20 mu mol,1equiv.,6.76 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield was 94%. Polymer M n (number average molecular weight, g/mol) was 83.5 ten thousand, PDI (molecular weight distribution) was 2.3, and glass transition temperature was-65.2 ℃.
Example 10: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst N (20 mu mol,1equiv.,18.3 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
Yield rate>99%. Polymer M n The (number average molecular weight, g/mol) was 95.6 ten thousand, the PDI (molecular weight distribution) was 2.6, and the glass transition temperature was-66.3 ℃.
Example 11: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of myrcene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000equiv., and the molar ratio of the myrcene to the isoprene is 1:1) and a cocatalyst MAO (10 mmol,500equiv.,6.66 mL) under the condition of anhydrous and anaerobic argon, carrying out polymerization reaction for 60min at 25 ℃ under the condition of stirring, adding 1mL of an anti-aging agent, carrying out ethanol quenching reaction, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
Yield rate>99%. M of polymer n The (number average molecular weight, g/mol) was 93.5 ten thousand, the PDI (molecular weight distribution) was 2.2, and the glass transition temperature was-45.1 ℃.
The rubber composition based on the high molecular weight iron-based bio-based rubber of example 11 was prepared from 100 parts by mass of the high molecular weight iron-based bio-based rubber of example 11, 20 parts by mass of N220, 2 parts by mass of a vulcanization accelerator CZ, 3 parts by mass of sulfur, 3 parts by mass of zinc oxide, and 4 parts by mass of hard butter.
The properties of the obtained rubber composition were found to be 20.14MPa in tensile strength, 398.5% in elongation at break, 43.7N/mm in tear strength and 4.83MPa in 100% elongation stress.
Example 12: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and butadiene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the butadiene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL) under the condition of no water and no oxygen argon, carrying out polymerization at 25 ℃ for 60min under the condition of stirring, adding 1mL of an anti-aging agent, quenching the mixture by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
Yield rate>99%. M of polymer n (number average molecular weight, g/mol) 90.8 ten thousand, PDI (molecular weight distribution) 2.1, glass transition temperature-55.7 ℃.
Example 13: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of myrcene and butadiene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the myrcene to the butadiene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL) under the condition of anhydrous and anaerobic argon, carrying out polymerization at 25 ℃ for 60min under the condition of stirring, adding 1mL of an anti-aging agent, carrying out ethanol quenching reaction, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield thereof was found to be 99%. M of polymer n (number average molecular weight, g/mol) 86.1 tens of thousands, PDI (molecular weight distribution) 2.4, glass transition temperature-40.2 ℃.
Example 14: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MMAO (10 mmol,500equiv.,5.34 mL) under the condition of no water and no oxygen argon, carrying out polymerization reaction at 25 ℃ for 60min under the condition of stirring, adding 1mL of an anti-aging agent, carrying out ethanol quenching reaction, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield was 95%. Polymer M n The (number average molecular weight, g/mol) was 120 ten thousand, the PDI (molecular weight distribution) was 2.2, and the glass transition temperature was-66.1 ℃.
Example 15: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 3000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL) under the condition of no water and no oxygen argon, carrying out polymerization at 25 ℃ for 240min under the condition of stirring, adding 1mL of an anti-aging agent, quenching by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield was 98%. Micro M of polymer n (number average molecular weight, g/mol) 130.1 tens of thousands, PDI (molecular weight distribution) 2.3, glass transition temperature-62.8 ℃.
Example 16: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (6 mmol,300equiv.,4.0 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield thereof was found to be 93%. M of polymer n (number average molecular weight, g/mol) 133.5 ten thousand, PDI (molecular weight distribution) 2.3, glass transition temperature-64.1 ℃.
Example 17: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst J (20 mu mol,1equiv.,7.06 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL) under the condition of no water and no oxygen argon, carrying out polymerization reaction at 25 ℃ for 60min under the condition of stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield thereof was found to be 99%. M of polymer n (number average molecular weight, g/mol) was 89.1 ten thousand, PDI (molecular weight distribution) was 2.3, and glass transition temperature was-62.8 ℃.
Example 18: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst O (20 mu mol,1equiv.,17.72 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield thereof was found to be 99%. M of polymer n (number average molecular weight, g/mol) 113.4 ten thousand, PDI (molecular weight distribution) 2.3, glass transition temperature-60.8 ℃.
Example 19: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL) under the condition of no water and no oxygen argon, carrying out polymerization reaction at 25 ℃ for 30min under the condition of stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield was 90%. M of polymer n (number average molecular weight, g/mol) 98.1 tens of thousands, PDI (molecular weight distribution) 2.4, glass transition temperature-63.3 ℃.
Claims (8)
1. A method for preparing high molecular weight iron-based bio-based rubber, characterized in that the iron-based bio-based rubber is formed by catalyzing and copolymerizing petroleum-based monomers and bio-based monomers through an iron-based catalyst, and the number average molecular weight of the high molecular weight iron-based bio-based rubber is 5.0x10 5 g/mol～20.0×10 5 g/mol, molecular weight distribution of 1.5-3.0, glass transition temperature Tg of minus 100 ℃ to minus 20 ℃, petroleum-based monomer of isoprene or butadiene, biological-based monomer of myrcene or farnesene, molar ratio of petroleum-based monomer to biological-based monomer of (1:19) - (19:1), molar ratio of sum of petroleum-based monomer and biological-based monomer to iron element in iron-based catalyst of (500-20000): 1, the structure of iron-based catalyst is any one of the following:
the preparation method comprises the following steps:
under the anhydrous and anaerobic condition, the bio-based monomer, the petroleum-based monomer, the iron-based catalyst, the solvent and the cocatalyst are added into a reactor, and the reaction is quenched for 60min at 25 ℃ under the condition of stirring, and the reaction is repeatedly washed by ethanol and dried in vacuum, thus obtaining the high molecular weight iron-based bio-based rubber.
2. The method of claim 1, wherein the cocatalyst is one of MAO, MMAO, DMAO, or a mixture of an aluminum alkyl and a dealkylating agent, and the aluminum alkyl is Al i Bu 3 、AlEt 3 、AlMe 3 One of the dealkylating agents is [ Ph ] 3 C] + [B(CF 5 ) 4 ] - Or B (C) 6 F 5 ) 3 When the cocatalyst is one of MAO, MMAO, DMAO, the molar ratio of the aluminum element in the cocatalyst to the iron element in the iron-based catalyst is (10-1000): 1, when the cocatalyst is a mixture of aluminum alkyl and dealkylating agent, the mol ratio of aluminum element in aluminum alkyl to iron element in iron catalyst is (10-100): 1, and the mol ratio of boron element in dealkylating agent to iron element in iron catalyst is (1-10): 1.
3. The method according to claim 2, wherein when the cocatalyst is one of MAO, MMAO, DMAO, the molar ratio of aluminum element in the cocatalyst to iron element in the iron-based catalyst is 500:1, when the cocatalyst is a mixture of aluminum alkyl and a dealkylation reagent, the molar ratio of aluminum element in the aluminum alkyl to iron element in the iron-based catalyst is 40:1, and the molar ratio of boron element in the dealkylation reagent to iron element in the iron-based catalyst is 1:1.
4. The method according to claim 1, wherein the solvent is one or two of toluene, xylene, petroleum ether, n-hexane, cyclohexane, n-heptane, n-octane, methylene chloride and hydrogenated gasoline, and the ratio of the solvent to the total volume of the bio-based monomer and petroleum-based monomer is (1-50): 1.
5. the high molecular weight iron-based biobased rubber produced by the method of any one of claims 1 to 4 for use in the manufacture of chemical protective clothing, tires or shoe soles.
6. The rubber composition based on the high molecular weight iron-based bio-based rubber prepared by the method according to any one of claims 1 to 4, wherein the rubber composition is prepared from 100 parts by mass of the high molecular weight iron-based bio-based rubber, 10 to 75 parts by mass of carbon black, 1 to 3 parts by mass of a vulcanization accelerator, 0.1 to 15 parts by mass of a vulcanizing agent, 1 to 10 parts by mass of zinc oxide and 1 to 9 parts by mass of hard butter.
7. The rubber composition according to claim 6, wherein the tensile strength of the rubber composition is not less than 18MPa, the elongation at break is not less than 350%, the tear strength is not less than 40N/mm, and the 100% tensile stress is not less than 3MPa.
8. The rubber composition according to claim 6, wherein the carbon black is one or a mixture of several of N330, N220 and N660, the vulcanization accelerator is one or a mixture of several of CZ, NA-22, DCBS, MBT, TT, DZ and TMTD, and the vulcanizing agent is sulfur.
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