CN117487073A - Bio-based low-temperature-resistant elastomer, preparation method thereof and rubber composition - Google Patents
Bio-based low-temperature-resistant elastomer, preparation method thereof and rubber composition Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 146
- 239000000806 elastomer Substances 0.000 title claims abstract description 98
- 239000005060 rubber Substances 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 17
- -1 terpene compound Chemical class 0.000 claims abstract description 46
- 150000001993 dienes Chemical class 0.000 claims abstract description 36
- 235000007586 terpenes Nutrition 0.000 claims abstract description 36
- 238000009826 distribution Methods 0.000 claims abstract description 11
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 claims description 41
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 229910052779 Neodymium Inorganic materials 0.000 claims description 23
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 23
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- 238000012718 coordination polymerization Methods 0.000 claims description 12
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 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 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 4
- 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 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 3
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 claims description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- JSNRRGGBADWTMC-QINSGFPZSA-N (E)-beta-Farnesene Natural products CC(C)=CCC\C(C)=C/CCC(=C)C=C JSNRRGGBADWTMC-QINSGFPZSA-N 0.000 claims description 2
- IHPKGUQCSIINRJ-CSKARUKUSA-N (E)-beta-ocimene Chemical compound CC(C)=CC\C=C(/C)C=C IHPKGUQCSIINRJ-CSKARUKUSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- YSNRTFFURISHOU-UHFFFAOYSA-N beta-farnesene Natural products C=CC(C)CCC=C(C)CCC=C(C)C YSNRTFFURISHOU-UHFFFAOYSA-N 0.000 claims description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims description 2
- ACOLQZDYRBEHEV-UHFFFAOYSA-K decanoate;neodymium(3+) Chemical compound [Nd+3].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O ACOLQZDYRBEHEV-UHFFFAOYSA-K 0.000 claims description 2
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 claims description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- ARWCRSVRKCNEDI-UHFFFAOYSA-K neodymium(3+);octanoate Chemical compound [Nd+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O ARWCRSVRKCNEDI-UHFFFAOYSA-K 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- IHPKGUQCSIINRJ-UHFFFAOYSA-N β-ocimene Natural products CC(C)=CCC=C(C)C=C IHPKGUQCSIINRJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 abstract description 20
- 238000011161 development Methods 0.000 abstract description 8
- 238000002425 crystallisation Methods 0.000 abstract description 6
- 230000008025 crystallization Effects 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 238000002156 mixing Methods 0.000 description 27
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 26
- 230000003712 anti-aging effect Effects 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 229920001577 copolymer Polymers 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 235000021355 Stearic acid Nutrition 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 239000006229 carbon black Substances 0.000 description 13
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 13
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 239000008117 stearic acid Substances 0.000 description 13
- 229910052717 sulfur Inorganic materials 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 13
- 239000011787 zinc oxide Substances 0.000 description 13
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 229920003051 synthetic elastomer Polymers 0.000 description 11
- 239000005061 synthetic rubber Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 8
- 238000011056 performance test Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 244000043261 Hevea brasiliensis Species 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- MJFCTNUEAJRLHN-UHFFFAOYSA-N hexane neodymium Chemical compound CCCCCC.[Nd] MJFCTNUEAJRLHN-UHFFFAOYSA-N 0.000 description 6
- 229920003052 natural elastomer Polymers 0.000 description 6
- 229920001194 natural rubber Polymers 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- KISFFWNZZFRNSC-UHFFFAOYSA-M diethylalumanylium;hexane;chloride Chemical compound [Cl-].CC[Al+]CC.CCCCCC KISFFWNZZFRNSC-UHFFFAOYSA-M 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- HEVGGTGPGPKZHF-UHFFFAOYSA-N 1-(1,2-dimethyl-3-methylidenecyclopentyl)-4-methylbenzene Chemical compound CC1C(=C)CCC1(C)C1=CC=C(C)C=C1 HEVGGTGPGPKZHF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- ZDVHQYVXWOYBEH-UHFFFAOYSA-N bis(2-methylpropyl)alumane hexane Chemical compound CCCCCC.[H][Al](CC(C)C)CC(C)C ZDVHQYVXWOYBEH-UHFFFAOYSA-N 0.000 description 2
- 238000012711 chain transfer polymerization Methods 0.000 description 2
- 238000007571 dilatometry Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000010057 rubber processing Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 238000013421 nuclear magnetic resonance imaging Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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)
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- Medicinal Chemistry (AREA)
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Abstract
The invention discloses a bio-based low temperature resistant elastomer, a preparation method thereof and a rubber composition. The bio-based low temperature resistant elastomer comprises conjugated diene structural units and terpene compound structural units; the mol content of the terpene compound structural unit is 5-60% and the mol content of the conjugated diene structural unit is 40-95% based on 100% of the total mol of the conjugated diene structural unit and the terpene compound structural unit; the number average molecular weight of the bio-based low temperature resistant elastomer is 2-30 ten thousand, and the molecular weight distribution coefficient PDI=2.0-4.5. The bio-based low temperature resistant elastomer has 90-96% of cis-1, 4 structure, low glass transition temperature and no crystallization at low temperature, is applied to low temperature resistant winter tires, meets the requirement of green development, can alleviate the problem of increasingly depleted fossil resources, and has important significance for sustainable development.
Description
Technical Field
The invention relates to the technical field of chemical synthetic rubber, in particular to a bio-based low temperature resistant elastomer, a preparation method thereof and a rubber composition.
Background
The automobile tire commonly used in China is a four-season tire, and compared with the traditional tire, the winter tire needs the tread rubber material to have better low temperature resistance in terms of materials, so that the tire has higher gripping force and wet skid resistance on ice and snow roads; the tire is required to have wider and deeper patterns in terms of the structural appearance of the tire, so that the tire can keep higher performance such as steering and braking on wet and slippery roads in winter. The tread rubber materials of winter tyres commonly used at present mainly comprise butadiene rubber (with lower Tg) and solution polymerized styrene-butadiene rubber (with better wet skid resistance). The monomer for synthesizing butadiene rubber and styrene butadiene rubber is mainly derived from fossil resources, and development of a brand new bio-based low temperature resistant rubber has important significance for sustainable development of tires.
The low temperature resistance of rubber is mainly determined by the crystallinity and glass transition temperature of rubber, and the rubber becomes hard and loses elasticity as the temperature decreases or the glass transition temperature is reached. The natural rubber commonly used is mainly polyisoprene with a high cis-1, 4 structure, which has a low glass transition temperature but slowly crystallizes at a low temperature. Styrene-butadiene rubber is not crystallized at low temperature due to the existence of benzene rings, and also causes an increase in glass transition temperature. In order to better meet the use requirement of the rubber material in a low-temperature environment and reduce the utilization of fossil resources, the development of the environment-friendly bio-based low-temperature resistant elastomer has important significance.
Thus, there is a need for an environmentally friendly low temperature resistant rubber material.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a bio-based low temperature resistant elastomer, a preparation method thereof and a rubber composition. The preparation method of the bio-based low temperature resistant elastomer comprises the following steps: and carrying out coordination chain transfer polymerization on the bio-based monomer terpene compound and conjugated diene to obtain a random copolymer (namely the bio-based low temperature resistant elastomer), wherein the structural units of the terpene compound account for 5-60 mol% of the random copolymer. The copolymer has 90-96% of cis-1, 4 structure, low glass transition temperature and no crystallization at low temperature, and can be applied to winter tires to meet the use requirement of the winter tires in low-temperature environment. The invention applies coordination chain transfer polymerization capable of controlling the polymer structure to the bio-based terpene compound monomer, can synthesize the bio-based low temperature resistant elastomer with high cis-1, 4 structure content and high molecular weight, has important significance for sustainable development, is applied to low temperature resistant winter tires, meets the requirement of green development, and can alleviate the problem of increasingly depleted fossil resources.
The invention aims to provide a bio-based low temperature resistant elastomer, which contains conjugated diene structural units and terpene compound structural units;
the conjugated diene structural unit is shown as a formula (I):
wherein R is 1 Is H or CH 3 Preferably CH 3 ；
The terpene compound structural unit is at least one structural unit shown in the formula (II), the formula (III) and the formula (IV);
the molar content of the terpene compound structural unit is 5 to 60%, preferably 5 to 50%, more preferably 10 to 40%, and the molar content of the conjugated diene structural unit is 40 to 95%, preferably 50 to 95%, more preferably 60 to 90%, based on 100% of the total molar amount of the conjugated diene structural unit and the terpene compound structural unit; the number average molecular weight of the bio-based low temperature resistant elastomer is 2 to 30 ten thousand, preferably 10 to 30 ten thousand, and the molecular weight distribution coefficient pdi=2.0 to 4.5, preferably pdi=2.0 to 3.0.
In a preferred embodiment of the present invention,
90 to 96 percent of the structural units of the bio-based low temperature resistant elastomer are in a 1,4 cis structure, and 91 to 94 percent of the structural units are in a 1,4 cis structure.
The second object of the present invention is to provide a method for producing a bio-based low temperature resistant elastomer according to one of the objects of the present invention, comprising the step of carrying out a coordination polymerization reaction of a terpene compound and a conjugated diene in a solvent in the presence of a neodymium catalyst system.
In a preferred embodiment of the present invention,
the terpene compound is at least one of myrcene, beta-farnesene and ocimene, preferably myrcene; and/or the number of the groups of groups,
the conjugated diene is at least one of isoprene and butadiene, preferably isoprene; and/or the number of the groups of groups,
the solvent is at least one of n-hexane and cyclohexane; and/or the number of the groups of groups,
the mol dosage of the terpene compound is 5% -60% of the total mol dosage of the terpene compound and the conjugated diene, preferably 5% -50%, more preferably 5% -30%; and/or the number of the groups of groups,
the mass ratio of the total mass of the terpene compound and the conjugated diene to the solvent is 1:3-10, preferably 1:4-10, and more preferably 1:4-6.
In a preferred embodiment of the present invention,
the neodymium catalyst system comprises a neodymium carboxylate compound, aluminum alkyl, a halogen-containing compound and conjugated diene A;
preferably, the method comprises the steps of,
the carboxylic acid neodymium compound is at least one of neodymium naphthenate, neodymium octoate, neodymium decanoate and neodymium neodecanoate, and more preferably is neodymium neodecanoate; and/or the number of the groups of groups,
the alkyl aluminum is at least one of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, diethyl aluminum hydride and diisobutyl aluminum hydride, and is more preferably triisobutyl aluminum and diisobutyl aluminum hydride; and/or the number of the groups of groups,
the halogen-containing compound is at least one of aluminum sesquiethyl chloride, diethyl aluminum monochloride, dimethyl chlorosilane and dimethyl dichlorosilane, and more preferably at least one of aluminum sesquiethyl chloride and diethyl aluminum monochloride; and/or the number of the groups of groups,
the conjugated diene A is at least one of butadiene, isoprene, 1, 3-pentadiene and 1, 3-hexadiene, and more preferably at least one of butadiene and isoprene; and/or the number of the groups of groups,
the molar ratio of the neodymium carboxylate compound to the aluminum alkyl to the halogen-containing compound to the conjugated diene A is 1 (10-30): 1-10): 5-20; and/or the number of the groups of groups,
the molar ratio of the neodymium carboxylate compound to the total mole number of the terpene compound and the conjugated diene is 1.5X10 -4 ～1.5×10 -3 Preferably 1X 10 -3 ～1.5×10 -3 。
In a preferred embodiment of the present invention,
the temperature of the coordination polymerization reaction is 30-100 ℃, preferably 50-80 ℃, more preferably 40-60 ℃; and/or the coordination polymerization reaction time is 4 to 12 hours, preferably 4 to 10 hours, more preferably 6 to 8 hours.
The preparation method of the bio-based low temperature resistant elastomer preferably comprises the following steps:
under the protection of nitrogen or inert gas, sequentially adding a neodymium carboxylate compound, aluminum alkyl, a halogen-containing compound and conjugated diene A into a vacuum reaction bottle, aging for 40-60 min at 40-60 ℃ under the condition of stirring, adding a solvent, a terpene compound and conjugated diene, polymerizing for 4-12 h at 30-100 ℃, adding methanol into a reaction system to terminate the reaction, pouring out a polymer solution, and flocculating out the copolymer with methanol or ethanol. And (3) after vacuum drying, obtaining the bio-based low temperature resistant elastomer.
The order of addition of the neodymium carboxylate, the aluminum alkyl, the halogen-containing compound, and the conjugated diene A in the neodymium catalyst system may affect the activity of the catalyst system, and the order of addition of the neodymium carboxylate, the aluminum alkyl, the halogen-containing compound, and the conjugated diene A is preferably used in the present invention.
It is still another object of the present invention to provide a rubber composition comprising the biobased low temperature resistant elastomer of one of the objects of the present invention or the biobased low temperature resistant elastomer produced by the method of the second object of the present invention.
The bio-based low temperature resistant elastomer can be chemically crosslinked to prepare the synthetic rubber, and the chemical crosslinking can be realized through a traditional vulcanization system.
The rubber composition of the invention can contain various common assistants in the field, such as zinc oxide, stearic acid, white carbon black, silicon 69, accelerator CZ, accelerator DM, anti-aging agent 4020, sulfur and the like, and the dosage of the rubber composition is conventional or is adjusted according to the requirements of actual situations.
The fourth object of the present invention is to provide a process for producing a rubber composition according to the third object of the present invention, comprising a step of kneading and then vulcanizing components including the bio-based low temperature resistant elastomer.
In the preparation process, the mixing, mixing and vulcanizing processes of the raw material components can adopt the rubber processing process which is common in the prior art. The equipment used is also equipment in rubber processing in the prior art, such as an internal mixer, an open mill, a flat vulcanizing machine and the like.
Specifically, the preparation method comprises the steps of blending 100 parts by weight of the bio-based low temperature resistant elastomer with the rubber auxiliary agent through an internal mixer, and carrying out mould pressing vulcanization at 140-160 ℃ to obtain the rubber composite material.
The rubber auxiliary agent is a conventional auxiliary agent in the prior art, the dosage of the rubber auxiliary agent is also conventional, and the inventor can add the rubber auxiliary agent according to actual conditions.
It is a fifth object of the present invention to provide the use of a biobased low temperature resistant elastomer as one of the objects of the present invention or prepared by the process of the second object of the present invention in a tyre, in particular in a winter tyre.
The beneficial effects of the invention are as follows:
the bio-based low temperature resistant elastomer has high molecular weight, high cis-1, 4 structure content of 90-96%, lower glass transition temperature, no crystallization at low temperature and simple preparation process.
The invention catalyzes the copolymerization of terpene compounds and conjugated diene by using a neodymium catalyst system to obtain the high molecular weight bio-based low temperature resistant elastomer. The terpene compound monomer is firstly a bio-based monomer, which accords with the concept of sustainable development at present; secondly, the side group of the terpene compound can damage the crystallization of a molecular chain, and simultaneously reduce the glass transition temperature of the bio-based low temperature resistant elastomer, wherein the glass transition temperature is between 70 ℃ below zero and 60 ℃ below zero, so that the bio-based low temperature resistant elastomer has good low temperature resistance.
According to the invention, through reasonable structural design, the structure of the terpene compound and the conjugated diene is regulated, so that the bio-based low temperature resistant elastomer has good low temperature resistance, and an effective thought is provided for the preparation of winter tires.
The invention uses coordination polymerization mode to copolymerize laurene and isoprene, and controls microstructure of copolymer, thus obtaining bio-based low temperature resistant elastomer. The prepared bio-based low temperature resistant elastomer has narrower molecular weight distribution and 90-96% of high cis-1, 4 structure, and can meet the use requirement of the low temperature resistant elastomer.
Drawings
FIG. 1 is a DSC curve of the bio-based low temperature resistant elastomer of examples 1, 2, 3, 4, 5, and 6, as measured by Differential Scanning Calorimetry (DSC), and a curve a, b, c, d, e, f sequentially corresponds to the bio-based low temperature resistant elastomer 1 (20% of myrcene in the comonomer), the bio-based low temperature resistant elastomer 2 (20% of myrcene in the comonomer), the bio-based low temperature resistant elastomer 3 (20% of myrcene in the comonomer), the bio-based low temperature resistant elastomer 4 (30% of myrcene in the comonomer), the bio-based low temperature resistant elastomer 5 (10% of myrcene in the comonomer), and the bio-based low temperature resistant elastomer 6 (40% of myrcene in the comonomer) obtained in the examples;
FIG. 2 is a nuclear magnetic resonance spectrum of bio-based low temperature resistant elastomers of examples 1, 2, 3, 4, 5, and 6. In the figure, curves 1, 2, 3, 4, 5 and 6 correspond to the bio-based low temperature resistant elastomer 1, the bio-based low temperature resistant elastomer 2, the bio-based low temperature resistant elastomer 3, the bio-based low temperature resistant elastomer 4, the bio-based low temperature resistant elastomer 5 and the bio-based low temperature resistant elastomer 6 obtained in the embodiment in sequence;
FIG. 3 is a graph showing the comparison of the change rates of rubber volumes of example 7, comparative example 1 and comparative example 2 at-25℃measured by capillary dilatometry.
Detailed Description
The present invention will be described in detail with reference to the following specific embodiments and the accompanying drawings, and it is necessary to point out that the following embodiments are merely for further explanation of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adaptations of the invention based on the present disclosure will remain within the scope of the invention.
The starting materials used in the examples were all conventional commercially available.
The model and manufacturer of the detection instrument used in the invention are shown in table 1:
TABLE 1
| Instrument name | Instrument model | Manufacturing factories |
| Differential scanning calorimeter | STARe | Mettler-Tooledo, switzerland |
| Nuclear magnetic resonance spectrometer | AV400 | Bruker Germany |
| Gel permeation chromatograph | Waters1515 | Waters Co., ltd |
The rubbers prepared in the examples and comparative examples were tested according to the following criteria: tensile strength (GB/T528-2009), tensile stress (100%) (GB/T528-2009), tensile stress (300%) (GB/T528-2009), elongation at break (GB/T528-2009), and compression cold resistance coefficient (HG/T3866-2008).
The mole content of myrcene units and the proportion of 1,4 microstructures of the bio-based low temperature resistant elastomer in the examples are obtained through nuclear magnetic resonance imaging integration.
Example 1
The preparation method of the bio-based low temperature resistant elastomer 1 comprises the following steps:
firstly, drying a vacuum reaction bottle, vacuumizing, introducing nitrogen, and completely removing oxygen and water, thus circulating for 3 times. Under the protection of nitrogen, 1ml of neodecanoic neodymium n-hexane solution (0.45 mol/L), 7ml of diisobutyl aluminum hydride n-hexane solution (1 mol/L) and 1ml of mono-hexane are sequentially addedThe n-hexane solution (1 mol/L) of diethylaluminum chloride and 0.005mol of isoprene were sequentially added to a vacuum reaction flask, and aged at 50℃under stirring for 50 minutes, to obtain the desired neodymium catalyst system. 10g (0.073 mol) of myrcene, 20g (0.294 mol) of isoprene and 120g of n-hexane were added under nitrogen protection. The reaction was allowed to react at 40℃for 4 hours, after which methanol was added to terminate the reaction. The polymer solution was poured off and the copolymer was flocculated out with methanol. And then the polymer is placed in a vacuum oven for drying to constant weight, so as to obtain the bio-based low temperature resistant elastomer 1. Calculated, the conversion was 96%, the mole content of myrcene units in the copolymer was 25%, and the cis 1,4 structure content was 94%. Number average molecular weight mn=9.2×10 of biobased low temperature resistant elastomer 1 as measured by Gel Permeation Chromatography (GPC) 4 The molecular weight distribution coefficient pdi=3.17.
Example 2
The preparation method of the bio-based low temperature resistant elastomer 2 comprises the following steps:
firstly, drying a vacuum reaction bottle, vacuumizing, introducing nitrogen, and completely removing oxygen and water, thus circulating for 3 times. 1ml of neodecanoic acid neodymium n-hexane solution (0.45 mol/L), 7ml of diisobutyl aluminum hydride n-hexane solution (1 mol/L), 1ml of diethyl aluminum monochloride n-hexane solution (1 mol/L) and 0.005mol of isoprene were sequentially added into a vacuum reaction flask under the protection of nitrogen, and aged at 50 ℃ under stirring for 50 minutes to obtain the required neodymium catalyst system. 10g (0.073 mol) of myrcene, 20.0g (0.294 mol) of isoprene and 120g of n-hexane were added under nitrogen protection. The reaction was allowed to react at 50℃for 6 hours, after which methanol was added to terminate the reaction. The polymer solution was poured off and the copolymer was flocculated out with methanol. And then the polymer is placed in a vacuum oven for drying to constant weight, so as to obtain the bio-based low temperature resistant elastomer 2. Calculated, the conversion was 94%, the molar content of myrcene units in the copolymer was 23%, and the cis 1,4 structure content was 92%. Number average molecular weight mn=9.5×10 of the biobased low temperature resistant elastomer 2 as measured by Gel Permeation Chromatography (GPC) 4 The molecular weight distribution coefficient pdi=3.12.
Example 3
The preparation method of the bio-based low temperature resistant elastomer 3 comprises the following steps:
firstly, drying a vacuum reaction bottle, vacuumizing, introducing nitrogen, and completely removing oxygen and water, thus circulating for 3 times. 1ml of neodecanoic acid neodymium n-hexane solution (0.45 mol/L), 7ml of triisobutyl aluminum n-hexane solution (1 mol/L), 1ml of diethyl aluminum monochloride n-hexane solution (1 mol/L) and 0.005mol of isoprene were sequentially added into a vacuum reaction flask under the protection of nitrogen, and aged at 50 ℃ under stirring for 50 minutes to obtain the desired neodymium catalyst system. 10g of myrcene, 20g of isoprene and 120g of n-hexane were added under nitrogen protection. The reaction was allowed to react at 50℃for 6 hours, after which methanol was added to terminate the reaction. The polymer solution was poured off and the copolymer was flocculated out with methanol. And then the polymer is placed in a vacuum oven for drying to constant weight, so as to obtain the bio-based low temperature resistant elastomer 3. Calculated, the conversion was 89%, the molar content of myrcene units in the copolymer was 23%, and the cis 1,4 structure content was 91%. Number average molecular weight mn=12.3×10 of biobased low temperature resistant elastomer 3 as measured by Gel Permeation Chromatography (GPC) 4 Molecular weight distribution coefficient pdi=2.17.
Example 4
The preparation method of the bio-based low temperature resistant elastomer 4 comprises the following steps:
firstly, drying a vacuum reaction bottle, vacuumizing, introducing nitrogen, and completely removing oxygen and water, thus circulating for 3 times. 1ml of neodecanoic acid neodymium n-hexane solution (0.45 mol/L), 7ml of triisobutyl aluminum n-hexane solution (1 mol/L), 1ml of diethyl aluminum monochloride n-hexane solution (1 mol/L) and 0.005mol of isoprene were sequentially added into a vacuum reaction flask under the protection of nitrogen, and aged at 50 ℃ under stirring for 50 minutes to obtain the desired neodymium catalyst system. 13.7g of myrcene, 16.0g of isoprene and 120g of n-hexane were added under nitrogen protection. The reaction was allowed to react at 50℃for 6 hours, after which methanol was added to terminate the reaction. The polymer solution was poured off and the copolymer was flocculated out with methanol. The polymer was then dried in a vacuum oven to constant weight to give biobased low temperature resistant elastomer 4. Calculated, the conversion was 92%, the molar content of myrcene units in the copolymer was 32%, and the cis 1,4 structure content was 93%. Gel Permeation Chromatography (GPC) of organismsNumber average molecular weight mn=11.7x10 of the base low temperature resistant elastomer 4 4 Molecular weight distribution coefficient pdi=2.21.
Example 5
The preparation method of the bio-based low temperature resistant elastomer 5 comprises the following steps:
firstly, drying a vacuum reaction bottle, vacuumizing, introducing nitrogen, and completely removing oxygen and water, thus circulating for 3 times. 1ml of neodecanoic acid neodymium n-hexane solution (0.45 mol/L), 7ml of triisobutyl aluminum n-hexane solution (1 mol/L), 1ml of sesquiethyl aluminum n-hexane solution (1 mol/L) and 0.005mol of isoprene were sequentially added into a vacuum reaction flask under the protection of nitrogen, and aged for 50 minutes at 50 ℃ under stirring to obtain the desired neodymium catalyst system. 4.4g (0.032 mol) of myrcene, 20.0g (0.294 mol) of isoprene and 120g of n-hexane were added under nitrogen protection. The reaction was allowed to react at 60℃for 6 hours, after which methanol was added to terminate the reaction. The polymer solution was poured off and the copolymer was flocculated out with methanol. The polymer was then dried in a vacuum oven to constant weight to give biobased low temperature resistant elastomer 5. Calculated, the conversion was 89%, the mole content of myrcene units in the copolymer was 13%, and the cis 1,4 structure content was 94%. Number average molecular weight mn=13.1×10 of the biobased low temperature resistant elastomer 5 as measured by Gel Permeation Chromatography (GPC) 4 The molecular weight distribution coefficient pdi=2.18.
Example 6
The preparation method of the bio-based low temperature resistant elastomer 6 comprises the following steps:
firstly, drying a vacuum reaction bottle, vacuumizing, introducing nitrogen, and completely removing oxygen and water, thus circulating for 3 times. 1ml of neodecanoic acid neodymium n-hexane solution (0.45 mol/L), 7ml of triisobutyl aluminum n-hexane solution (1 mol/L), 1ml of sesquiethyl aluminum n-hexane solution (1 mol/L) and 0.005mol of isoprene were sequentially added into a vacuum reaction flask under the protection of nitrogen, and aged for 50 minutes at 50 ℃ under stirring to obtain the desired neodymium catalyst system. 20g (0.147 mol) of myrcene, 15g (0.22 mol) of isoprene and 120g of n-hexane were added under nitrogen protection. The reaction was allowed to react at 50℃for 6 hours, after which methanol was added to terminate the reaction. Will polymerizeThe solution was poured off and the copolymer was flocculated out with methanol. The polymer was then dried in a vacuum oven to constant weight to give biobased low temperature resistant elastomer 6. Calculated, the conversion was 89%, the mole content of myrcene units in the copolymer was 44%, and the cis 1,4 structure content was 93%. Number average molecular weight mn=12.1×10 of the biobased low temperature resistant elastomer 6 as measured by Gel Permeation Chromatography (GPC) 4 Molecular weight distribution coefficient pdi=2.35.
As can be seen from fig. 1, the glass transition temperature of the bio-based low temperature resistant elastomer 1 is-65.7 ℃, the glass transition temperature of the bio-based low temperature resistant elastomer 2 is-65.50 ℃, the glass transition temperature of the bio-based low temperature resistant elastomer 3 is-65.5 ℃, the glass transition temperature of the bio-based low temperature resistant elastomer 4 is-66.1 ℃, the glass transition temperature of the bio-based low temperature resistant elastomer 5 is-64.7 ℃, and the glass transition temperature of the bio-based low temperature resistant elastomer 6 is-66.7 ℃; the glass transition temperature of the bio-based low temperature resistant elastomer prepared in the embodiment is below-64 ℃, the content of myrcene in the bio-based low temperature resistant elastomer with great influence on the glass transition temperature is not obviously influenced by the temperature time, and when the content of terpene compounds-myrcene in the comonomer accounts for 5% -30%, the glass transition temperature of the polymer is also reduced along with the increase of the fraction of terpene compounds-myrcene.
Example 7
The bio-based low temperature resistant elastomer synthetic rubber prepared based on coordination polymerization comprises the following specific components in parts by weight:
100 parts of crude rubber (bio-based low temperature resistant elastomer 5 (PIMy 10%)), 60 parts of white carbon black (VN 3), 6 parts of silicon 69 (Si 69), 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of an anti-aging agent (4020), 1 part of an anti-aging agent (RD), 1 part of an accelerator (CZ), 1.2 parts of an accelerator (NS) and 1.5 parts of sulfur.
Placing the raw rubber into an internal mixer for plasticating for 1min, adding zinc oxide and stearic acid, mixing for 2min, adding an anti-aging agent, mixing for 2min, adding white carbon black and silicon 69, mixing for 5min, performing heat treatment for 5min at 150 ℃, cooling, and adding an accelerator and sulfur, mixing for 5min to obtain the final rubber. Hot press vulcanization was performed at 150 ℃ on a platen vulcanizer to prepare a test sample. The tensile strength, elongation at break, and the like of the sample were measured. The results of the performance tests are shown in Table 2.
Example 8
The bio-based low temperature resistant elastomer synthetic rubber prepared based on coordination polymerization comprises the following specific components in parts by weight:
100 parts of crude rubber (bio-based low temperature resistant elastomer 1 (PIMy 20%)), 60 parts of white carbon black (VN 3), 6 parts of silicon 69 (Si 69), 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of an anti-aging agent (4020), 1 part of an anti-aging agent (RD), 1 part of an accelerator (CZ), 1.2 parts of an accelerator (NS) and 1.5 parts of sulfur.
Placing the raw rubber into an internal mixer for plasticating for 1min, adding zinc oxide and stearic acid, mixing for 2min, adding an anti-aging agent, mixing for 2min, adding white carbon black and silicon 69, mixing for 5min, performing heat treatment for 5min at 150 ℃, cooling, and adding an accelerator and sulfur, mixing for 5min to obtain the final rubber. Hot press vulcanization was performed at 150 ℃ on a platen vulcanizer to prepare a test sample. The tensile strength, elongation at break, and the like of the sample were measured. The results of the performance tests are shown in Table 2.
Example 9
The bio-based low temperature resistant elastomer synthetic rubber prepared based on coordination polymerization comprises the following specific components in parts by weight:
100 parts of crude rubber (bio-based low temperature resistant elastomer 4 (PIMy 30%)), 60 parts of white carbon black (VN 3), 6 parts of silicon 69 (Si 69), 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of an anti-aging agent (4020), 1 part of an anti-aging agent (RD), 1 part of an accelerator (CZ), 1.2 parts of an accelerator (NS) and 1.5 parts of sulfur.
Placing the raw rubber into an internal mixer for plasticating for 1min, adding zinc oxide and stearic acid, mixing for 2min, adding an anti-aging agent, mixing for 2min, adding white carbon black and silicon 69, mixing for 5min, performing heat treatment for 5min at 150 ℃, cooling, and adding an accelerator and sulfur, mixing for 5min to obtain the final rubber. Hot press vulcanization was performed at 150 ℃ on a platen vulcanizer to prepare a test sample. The tensile strength, elongation at break, and the like of the sample were measured. The results of the performance tests are shown in Table 2.
Example 10
The bio-based low temperature resistant elastomer synthetic rubber prepared based on coordination polymerization comprises the following specific components in parts by weight:
100 parts of crude rubber (bio-based low temperature resistant elastomer 6 (PIMy 40%)), 60 parts of white carbon black (VN 3), 6 parts of silicon 69 (Si 69), 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of an anti-aging agent (4020), 1 part of an anti-aging agent (RD), 1 part of an accelerator (CZ), 1.2 parts of an accelerator (NS) and 1.5 parts of sulfur.
Placing the raw rubber into an internal mixer for plasticating for 1min, adding zinc oxide and stearic acid, mixing for 2min, adding an anti-aging agent, mixing for 2min, adding white carbon black and silicon 69, mixing for 5min, performing heat treatment for 5min at 150 ℃, cooling, and adding an accelerator and sulfur, mixing for 5min to obtain the final rubber. Hot press vulcanization was performed at 150 ℃ on a platen vulcanizer to prepare a test sample. The tensile strength, elongation at break, and the like of the sample were measured. The results of the performance tests are shown in Table 2.
Comparative example 1
100 parts of styrene-butadiene rubber (ESBR 1502), 60 parts of white carbon black (VN 3), 6 parts of silicon 69 (Si 69), 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of an anti-aging agent (4020), 1 part of an anti-aging agent (RD), 1 part of an accelerator (CZ), 1.2 parts of an accelerator (NS) and 1.5 parts of sulfur.
Placing the raw rubber into an internal mixer for plasticating for 1min, adding zinc oxide and stearic acid, mixing for 2min, adding an anti-aging agent, mixing for 2min, adding white carbon black and silicon 69, mixing for 5min, performing heat treatment for 5min at 150 ℃, cooling, and adding an accelerator and sulfur, mixing for 5min to obtain the final rubber. Hot press vulcanization was performed at 150 ℃ on a platen vulcanizer to prepare a test sample. The tensile strength, elongation at break, and the like of the sample were measured. The results of the performance tests are shown in Table 2.
Comparative example 2
100 parts of crude rubber (natural rubber NR), 60 parts of white carbon black (VN 3), 6 parts of silicon 69 (Si 69), 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of an anti-aging agent (4020), 1 part of an anti-aging agent (RD), 1 part of an accelerator (CZ), 1.2 parts of an accelerator (NS) and 1.5 parts of sulfur.
Placing the raw rubber into an internal mixer for plasticating for 1min, adding zinc oxide and stearic acid, mixing for 2min, adding an anti-aging agent, mixing for 2min, adding white carbon black and silicon 69, mixing for 5min, performing heat treatment for 5min at 150 ℃, cooling, and adding an accelerator and sulfur, mixing for 5min to obtain the final rubber. Hot press vulcanization was performed at 150 ℃ on a platen vulcanizer to prepare a test sample. The tensile strength, elongation at break, and the like of the sample were measured. The results of the performance tests are shown in Table 2.
TABLE 2 Performance test results for the samples of examples 7-10 and comparative examples 1-2
FIG. 3 is a graph showing the comparison of the change rates of rubber volumes of example 7, comparative example 1 and comparative example 2 at-25℃measured by capillary dilatometry. Since crystallization reduces the volume of the rubber, the volume will not change if not crystallized, and thus it can be seen from FIG. 3: at low temperatures (-25 ℃), the rubber of comparative example 2 crystallized, whereas the synthetic rubber based on the bio-based low temperature resistant elastomer prepared by coordination polymerization of example 7 of the present invention and the rubber of comparative example 1 did not crystallize. In addition, the synthetic rubbers of examples 8 to 10 according to the invention based on the bio-based low temperature resistant elastomers prepared by coordination polymerization also do not crystallize under these conditions.
From the properties of examples and comparative examples, it was found that the tensile strength of natural rubber was high due to the presence of tensile crystals, but natural rubber (the 1,4 cis structure content in natural rubber was 97.7%) was slowly crystallized at low temperature, resulting in hardening of rubber and deterioration of properties. Although styrene-butadiene rubber is not crystallized at low temperature, its own glass transition temperature is high, so that the performance at low temperature is lowered, and the compression cold resistance coefficient reflects the lowering of compression rebound performance at low temperature. The glass transition temperature of the bio-based low temperature resistant elastomer is reduced along with the increase of the content of the terpene compound-myrcene, and the synthetic rubber based on the bio-based low temperature resistant elastomer has no crystallization phenomenon at low temperature because the 1,4 cis structure content in the bio-based low temperature resistant elastomer is 90-96 percent. Meanwhile, the elongation at break and the compression cold resistance coefficient of the synthetic rubber based on the bio-based low temperature resistant elastomer are equivalent to those of natural rubber, and the tensile strength and the stretching stress (100%) are equivalent to those of styrene-butadiene rubber, so that the synthetic rubber can meet the use requirement and has better low temperature resistance.
Claims (10)
1. A bio-based low temperature resistant elastomer comprises conjugated diene structural units and terpene compound structural units;
the conjugated diene structural unit is shown as a formula (I):
wherein R is 1 Is H or CH 3 ；
The terpene compound structural unit is at least one structural unit shown in the formula (II), the formula (III) and the formula (IV);
the mol content of the terpene compound structural unit is 5-60% and the mol content of the conjugated diene structural unit is 40-95% based on 100% of the total mol of the conjugated diene structural unit and the terpene compound structural unit; the number average molecular weight of the bio-based low temperature resistant elastomer is 2-30 ten thousand, and the molecular weight distribution coefficient PDI=2.0-4.5.
2. The biobased low temperature resistant elastomer of claim 1, wherein:
the mol content of the terpene compound structural unit is 5-50% and the mol content of the conjugated diene structural unit is 50-95% based on 100% of the total mol of the conjugated diene structural unit and the terpene compound structural unit; the number average molecular weight of the bio-based low temperature resistant elastomer is 10-30 ten thousand, and the molecular weight distribution coefficient PDI=2.0-3.0.
3. The biobased low temperature resistant elastomer of claim 1, wherein:
90 to 96 percent of the structural units of the bio-based low temperature resistant elastomer are in a 1,4 cis structure, and 91 to 94 percent of the structural units are in a 1,4 cis structure.
4. A process for producing the bio-based low temperature resistant elastomer according to any one of claims 1 to 3, comprising the step of coordination-polymerizing a terpene compound and a conjugated diene in a solvent in the presence of a neodymium catalyst system.
5. The method of manufacturing according to claim 4, wherein:
the terpene compound is at least one of myrcene, beta-farnesene and ocimene, preferably myrcene; and/or the number of the groups of groups,
the conjugated diene is at least one of isoprene and butadiene; and/or the number of the groups of groups,
the solvent is at least one of n-hexane and cyclohexane; and/or the number of the groups of groups,
the mol dosage of the terpene compound is 5% -60% of the total mol dosage of the terpene compound and the conjugated diene, preferably 5% -50%, more preferably 5% -30%; and/or the number of the groups of groups,
the mass ratio of the total mass of the terpene compound and the conjugated diene to the solvent is 1:3-10, preferably 1:4-10.
6. The method of manufacturing according to claim 4, wherein:
the neodymium catalyst system comprises a neodymium carboxylate compound, aluminum alkyl, a halogen-containing compound and conjugated diene A;
preferably, the method comprises the steps of,
the carboxylic acid neodymium compound is at least one of neodymium naphthenate, neodymium octoate, neodymium decanoate and neodymium neodecanoate; and/or the number of the groups of groups,
the alkyl aluminum is at least one of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, diethyl aluminum hydride and diisobutyl aluminum hydride; and/or the number of the groups of groups,
the halogen-containing compound is at least one of aluminum sesquiethyl chloride, diethyl aluminum chloride, dimethyl chlorosilane and dimethyl dichlorosilane; and/or the number of the groups of groups,
the conjugated diene A is at least one of butadiene, isoprene, 1, 3-pentadiene and 1, 3-hexadiene, preferably at least one of butadiene and isoprene; and/or the number of the groups of groups,
the molar ratio of the neodymium carboxylate compound to the aluminum alkyl to the halogen-containing compound to the conjugated diene A is 1 (10-30): 1-10): 5-20; and/or the number of the groups of groups,
the molar ratio of the neodymium carboxylate compound to the total mole number of the terpene compound and the conjugated diene is 1.5X10 -4 ～1.5×10 -3 。
7. The method of manufacturing according to claim 4, wherein:
the temperature of the coordination polymerization reaction is 30-100 ℃, preferably 50-80 ℃; and/or the coordination polymerization reaction time is 4 to 12 hours, preferably 4 to 10 hours.
8. A rubber composition comprising the biobased low temperature resistant elastomer of any one of claims 1 to 3 or the biobased low temperature resistant elastomer prepared by the method of any one of claims 4 to 7.
9. A process for producing a rubber composition as described in claim 8, comprising a step of kneading and then vulcanizing components including said bio-based low temperature resistant elastomer.
10. Use of a biobased low temperature resistant elastomer according to any one of claims 1 to 3 or prepared by a method according to any one of claims 4 to 7 in a tyre.
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