WO2016202175A1 - 一种衣康酸酯/丁二烯共聚物型生物工程橡胶及其制备方法 - Google Patents
一种衣康酸酯/丁二烯共聚物型生物工程橡胶及其制备方法 Download PDFInfo
- Publication number
- WO2016202175A1 WO2016202175A1 PCT/CN2016/084508 CN2016084508W WO2016202175A1 WO 2016202175 A1 WO2016202175 A1 WO 2016202175A1 CN 2016084508 W CN2016084508 W CN 2016084508W WO 2016202175 A1 WO2016202175 A1 WO 2016202175A1
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- WO
- WIPO (PCT)
- Prior art keywords
- rubber
- itaconate
- butadiene
- butadiene copolymer
- sodium
- Prior art date
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 142
- 239000005060 rubber Substances 0.000 title claims abstract description 139
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229920001577 copolymer Polymers 0.000 title claims abstract description 81
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000004073 vulcanization Methods 0.000 claims abstract description 19
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 239000000344 soap Substances 0.000 claims description 21
- -1 Sodium dialkyl sulfate Chemical class 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 15
- 229930195729 fatty acid Natural products 0.000 claims description 15
- 239000000194 fatty acid Substances 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- 150000004665 fatty acids Chemical class 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 5
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- MKWYFZFMAMBPQK-UHFFFAOYSA-J sodium feredetate Chemical compound [Na+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O MKWYFZFMAMBPQK-UHFFFAOYSA-J 0.000 claims description 4
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 claims description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
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- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000013040 rubber vulcanization Methods 0.000 claims description 2
- 229940078031 sodium ironedetate Drugs 0.000 claims description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012936 vulcanization activator Substances 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims 1
- 235000011009 potassium phosphates Nutrition 0.000 claims 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims 1
- 238000010382 chemical cross-linking Methods 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 4
- 230000009477 glass transition Effects 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 229920003051 synthetic elastomer Polymers 0.000 abstract description 3
- 239000005061 synthetic rubber Substances 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 23
- 229920000126 latex Polymers 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 14
- 235000021355 Stearic acid Nutrition 0.000 description 14
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 14
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 14
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 14
- 239000008117 stearic acid Substances 0.000 description 14
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- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 13
- 239000011787 zinc oxide Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
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- 244000043261 Hevea brasiliensis Species 0.000 description 10
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- PPPIIDSEUCJLLC-UHFFFAOYSA-N 3-(3-methylbutoxycarbonyl)but-3-enoic acid Chemical compound CC(C)CCOC(=O)C(=C)CC(O)=O PPPIIDSEUCJLLC-UHFFFAOYSA-N 0.000 description 4
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Images
Classifications
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- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65G—TRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
- B65G15/00—Conveyors having endless load-conveying surfaces, i.e. belts and like continuous members, to which tractive effort is transmitted by means other than endless driving elements of similar configuration
- B65G15/30—Belts or like endless load-carriers
- B65G15/32—Belts or like endless load-carriers made of rubber or plastics
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/16—Aqueous medium
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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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
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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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/14—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/16—Esters having free carboxylic acid groups, e.g. monoalkyl maleates or fumarates
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/01—High molecular weight, e.g. >800,000 Da.
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
Definitions
- the present invention relates to a process for preparing an itaconate/butadiene copolymer type bioengineered rubber by emulsion polymerization initiated by a redox initiation system under low temperature conditions.
- bio-based engineering rubber should have the following characteristics: (1) The main raw materials are renewable resources; (2) It has good environmental stability; (3) It can be processed by traditional rubber processing technology; (4) It has good mechanical properties to meet engineering applications.
- the applicant discloses an unsaturated aliphatic polyester bioengineered rubber which is polycondensed from a bio-based chemical in "A polyester bio-engineered rubber and its preparation method" (ZL 200910076032.9).
- the polyester bioengineered rubber is synthesized by direct polycondensation using a glycol derived from a renewable resource, and has a number average molecular weight of between 19,800 and 55,000 and a weight average molecular weight of between 88,810 and 222,500.
- the peroxide is chemically cross-linked, and a reinforcing agent may be added during the crosslinking process, which can be formed by a conventional rubber processing process.
- the applicant discloses a bio-based chemical itaconate and isoprene in "A itaconate/isoprene copolymer type bioengineered rubber and a preparation method thereof" (ZL 2011 1 0440400.0) Bio-based engineering rubber prepared by emulsion polymerization of a diene and a preparation method thereof.
- the method generates free radicals by thermal cracking of an initiator, and initiates copolymerization of itaconate and isoprene under high temperature and high pressure, and the obtained raw
- the number average molecular weight of the base-based engineering rubber is 52500-502563, the weight average molecular weight is 135230-1503263, and the mechanical properties are relatively low, which cannot meet the application of some engineering fields (such as tires, conveyor belts, etc.).
- the present applicant discloses a method for preparing Yikang at a low temperature in "a method for preparing an itaconate/isoprene copolymer type bioengineered rubber raw rubber by low temperature emulsion polymerization” (ZL 2011 1 0440385.X).
- the obtained bio-based engineering rubber has a number average molecular weight of 145,200 to 705,678 and a weight average molecular weight of 290,400 to 2,540,440.
- Butadiene is a diene monomer having a conjugated structure. Compared with isoprene, the butadiene structure does not contain pendant groups, and is less affected by the steric hindrance effect during the polymerization process. The addition reaction is more likely to occur, and a high molecular weight polymer is formed, and the resulting polymerized vitrification is formed. The temperature is lower. In addition, butadiene is less expensive than isoprene, which can reduce production costs. Global Bioenergies announced on November 28, 2014 that it has successfully produced bio-derived butadiene by direct fermentation, which is the first time that a complete biological process has been passed, ie without any chemical steps. The production of important petrochemical raw material butadiene is a breakthrough in the production of bio-based butadiene.
- a bio-based monomer itaconate as a main raw material, a high molecular weight, low glass transition temperature, excellent mechanical properties of a polymer can be prepared by a free radical initiated emulsion copolymerization process with butadiene, especially using conventional
- the itaconate/butadiene copolymer bioengineered rubber processed by the rubber processing process has not been reported at home and abroad.
- DMTA Dynamic mechanical analysis
- Another object of the present invention is to control the viscoelasticity of the itaconate/butadiene copolymer type bioengineered rubber by changing the feed ratio of itaconate to butadiene, thereby obtaining optimal dynamic mechanical properties, that is, The tan ⁇ value is higher at 0 ° C, and the tan ⁇ value is lower at 60 ° C.
- Use of itaconate/butadiene copolymer bioengineered rubber with optimal dynamic mechanical properties There are no reports on high-performance green tires at home and abroad.
- the object of the present invention is to provide an itaconate/butadiene copolymer type bioengineered rubber and a preparation method thereof, which have high molecular weight, low glass transition temperature, and can be vulcanized by a vulcanization/accelerator vulcanization system, and It has the same physical and mechanical properties and processing properties as existing synthetic rubber.
- the present invention provides an itaconate/butadiene copolymer type bioengineered rubber which is obtained by chemically crosslinking a copolymer obtained by emulsion polymerization of itaconate and butadiene, and is characterized in that:
- the itaconate/butadiene copolymer has a number average molecular weight of 53,000 to 1.64 million and a weight average molecular weight of 110,000 to 289,2000.
- the itaconate/butadiene copolymer is prepared by emulsion polymerization of itaconate monomer and butadiene; then, the itaconate/butadiene copolymer is chemically crosslinked to obtain itaconate/butylate. Diene copolymer type bioengineered rubber.
- the above chemical crosslinking process can be achieved by adding a conventional vulcanization/accelerator vulcanization system.
- the specific reaction conditions and steps are as follows:
- the polymerization device adding itaconate, emulsifier, electrolyte, activator, deionized water, the polymerization device is closed, first vacuuming, and then filling with nitrogen, operating 1 to 5 times; The diene, the oxygen scavenger and the initiator are added to the polymerization apparatus, and reacted at 1 to 20 ° C under a pressure of 0.1 to 5 MPa for 5 to 15 hours; and the terminator is added to terminate the reaction.
- the mass ratio of itaconate, butadiene, emulsifier, electrolyte, activator, oxygen scavenger, initiator, terminator and deionized water is: 100:1 ⁇ 100:1 ⁇ 10:0.1 ⁇ 5 : 0.01 to 5: 0.1 to 5: 0.01 to 5: 1 to 10: 100 to 1000.
- the emulsion is demulsified and dried to obtain a itaconic acid ester/butadiene copolymer bioengineered elastomer raw rubber having a number average molecular weight of 53,000 to 16.46 million and a weight average molecular weight of 110,000 to 2892,000.
- R 1 and R 2 are a H atom or a C 1-10 alkyl group, and R 1 and R 2 may be the same or different, and a n-butyl group, a n-pentyl group or an isopentyl group is preferable.
- the emulsifier is a mixture of one or more of the following: disproportionated rosin sodium soap, disproportionation Potassium rosin acid soap, fatty acid sodium soap, fatty acid potassium soap, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate.
- the electrolyte is one of the following or a mixture thereof: potassium chloride (KCl), potassium phosphate (K 3 PO 4 ), ethylenediaminetetraacetic acid (EDTA), sodium m-dimethylnaphthalenesulfonate (TAOM-L), phosphoric acid (H 3 PO 4 ), potassium hydroxide (KOH).
- the activator is a mixture of sodium formaldehyde sulfoxylate and iron EDTA-Fe, or a mixture of sodium formaldehyde sulfoxylate and sodium iron edetate (EDTA-Fe.Na).
- the initiator is hydrogen peroxide to montan, tert-butyl hydroperoxide or cumene hydroperoxide.
- the oxygen scavenger is sodium dithionite, commonly known as insurance powder.
- the terminator is sodium dimethyl dithiocarbamate, sodium diethylaminodithiocarbamate, hydroxylamine or sodium polysulfide.
- the itaconate ester and the butadiene monomer may be blended in any mass ratio, and preferably the mass ratio of itaconate to butadiene monomer is from 100:10 to 60.
- the demulsifier in the demulsification drying process may be a hydrochloric acid solution having a hydrogen ion concentration of 0.1 to 0.5 mol/L, a 1 wt% to 5 wt% aqueous calcium chloride solution, anhydrous methanol or absolute ethanol.
- the itaconate/butadiene copolymer bioengineering rubber is prepared by using a sulfur as a crosslinking agent and a conventional vulcanization/accelerator vulcanization system at 140-160 ° C for compression vulcanization.
- the rubber processing preparation process and the vulcanization compounding system involved in the above preparation method are conventional rubber processing means, and the use principle is well known.
- the above vulcanization compounding system includes a vulcanization activator (such as zinc oxide, stearic acid) and a vulcanization accelerator (for example, 2-nonyl benzothiazole (accelerator M), N-cyclohexyl-2-phenyl hydrazine) Thiazole sulfenamide (promoter CZ), diphenyl hydrazine (accelerator D)) and vulcanizing agent (eg sulphur).
- a vulcanization activator such as zinc oxide, stearic acid
- a vulcanization accelerator for example, 2-nonyl benzothiazole (accelerator M), N-cyclohexyl-2-phenyl hydrazine) Thiazole sulfenamide (promoter CZ), diphenyl hydrazine (accelerator D)
- vulcanizing agent eg sulphur
- white carbon black or carbon black may be added as a reinforcing agent.
- a silane coupling agent Si69 may also be added to enhance the composite effect.
- the effect of the present invention is that an itaconate/butadiene copolymer type bioengineered rubber is synthesized by emulsion polymerization at a temperature of 1 to 20 ° C using a redox initiation system.
- the rubber has a number average molecular weight of more than 1 million and a narrow molecular weight distribution, and can be processed by a conventional rubber processing process. Processing and forming.
- reinforcing filler By adding reinforcing filler, the mechanical properties of the rubber can be effectively improved, and its performance satisfies the requirements of engineering applications such as tire tread and conveyor belt which have high requirements on mechanical properties.
- the first batch of itaconate/butadiene copolymer bioengineered rubber tires was successfully trial-produced with this rubber. The test shows that the tire is a high-performance green tire with low rolling resistance and high resistance to slippery. market expectation.
- Fig. 1 is a photograph of a bio-engineered rubber raw rubber of butyl acetate/butadiene copolymer prepared in Example 4 of the present invention.
- Example 2 is a 1 H-NMR spectrum of a butyl butyl acrylate/butadiene copolymer bioengineered rubber raw rubber prepared in Example 4 of the present invention, and the peak position at a chemical shift of 4.94 - 5.68 ppm represents itaconic acid.
- the butyl ester/butadiene copolymer type bioengineered rubber raw rubber has a double bond and can provide a crosslinking point for the subsequent chemical crosslinking process.
- Example 3 is a transmission electron micrograph of a white carbon black reinforcing butyl phthalate/butadiene copolymer bioengineered rubber prepared in Example 11 of the present invention. It can be seen that the filler has a good dispersing effect in the butyl butylate/butadiene copolymer bioengineered rubber.
- the materials of the polymerization part are analytically pure reagents, and the materials of the kneading part are all chemically pure reagents.
- the itaconate/butadiene copolymer type bioengineered rubber material in the following examples and the rubber composite material in the comparative example in the temperature range of -80 ° C to 100 ° C, the frequency of 10 Hz and the heating rate of 3 ° C / min, and
- the tensile factor (tan ⁇ ) was measured by a dynamic viscoelastic spectrometer in a tensile mode of 0.1% dynamic stress, and the test piece size was 20 mm long ⁇ 10 mm wide ⁇ 1 mm thick.
- EDTA 0.25 g TAOM-L, 1 g EDTA-Fe ⁇ Na, 4 g sodium formaldehyde sulfoxylate; after sealing the device, vacuum, nitrogen, continuous operation 3 times, then add 40 g butadiene, 0.01 g Sodium dithionite and 0.05 g of hydrogen peroxide were reacted for 10 hours at 5 ° C under a pressure of 1 MPa, and 5 g of hydroxylamine was added to terminate the reaction to obtain an itaconic acid ethyl ester/butadiene copolymer type bioengineered rubber latex. The latex was poured into absolute ethanol and demulsified to obtain an itaconate/butadiene copolymer type bioengineered rubber raw rubber.
- SBR1502 styrene butadiene rubber
- 5 g of zinc oxide 2 g of stearic acid, 1 g of sulfur, 0.7 g of accelerator M, 1 g of accelerator CZ, 60 g of silica and 6 g of Si69 in a double roll
- the mixture was uniformly mixed to obtain a rubber compound, and the rubber compound was molded and vulcanized at 150 ° C to prepare a white carbon black/styrene-butadiene rubber composite material.
- the itaconate/butadiene copolymer type bioengineered rubber raw rubber prepared by the invention has a relatively high molecular weight, a narrow molecular weight distribution, and the polymerization process is carried out at a low temperature. Reduced energy consumption and suitable for industrial production.
- the itaconate/butadiene copolymer bioengineered rubber prepared by the invention exhibits excellent physical and mechanical properties after being reinforced by the filler, and the tensile strength and elongation at break are both achieved. Or exceed the performance of traditional styrene butadiene rubber and natural rubber, to meet the requirements of engineering applications (such as tires, conveyor belts) that require high mechanical properties.
- the loss factor (tan ⁇ ) of the itaconate/butadiene copolymer type bioengineered rubber material prepared by the present invention at 0 ° C is significantly higher than the loss factor of styrene-butadiene rubber and natural rubber, and the loss factor at 60 ° C and
- the loss factor of styrene-butadiene rubber and natural rubber is equivalent to or lower than the loss factor of styrene-butadiene rubber and natural rubber, indicating that the itaconate/butadiene copolymer bio-engineered rubber material prepared by the invention has excellent dynamic mechanical properties. It can be used as a rubber material for preparing tires with low rolling resistance and high wet resistance.
- the butyl butylate/butadiene copolymer type bioengineered rubber prepared in Examples 9 to 15 has the same type and quality of other reagents except that the amount of butyl itaconate and butadiene is different, and the preparation process is the same.
- the route is also the same, and the amounts of butyl butyrate and butadiene are given in Table 3.
- the specific preparation steps and methods are as follows:
- TAOM-L 0.01 g EDTA-Fe, 0.05 g sodium formaldehyde sulfoxylate; after sealing the device, vacuum, nitrogen, continuous operation 5 times, then add butadiene, 0.02 g sodium dithionite and 0.03 g peroxidation Hydrogen to montan, reacted at 5 ° C, 1 MPa pressure for 8 hours, added 1 g of hydroxylamine to terminate the reaction, to obtain a butyl butyl acrylate / butadiene copolymer bioengineered rubber latex, pour the latex into 1 wt% chlorination After breaking and drying in the calcium solution, a butyl butyrate/butadiene copolymer type bioengineered rubber raw rubber is obtained.
- styrene butadiene rubber 100 g of styrene butadiene rubber (SSBR2503), 5 g of zinc oxide, 2 g of stearic acid, 1 g of sulfur, 0.7 g of accelerator M, 1 g of accelerator CZ, 60 g of silica and 6 g of Si69 in a double roll
- the mixture was uniformly mixed to obtain a rubber compound, and the rubber compound was molded and vulcanized at 150 ° C to prepare a white carbon black/styrene-butadiene rubber composite material.
- the physical and mechanical properties and dynamic mechanical properties of the butyl butylate/butadiene copolymer bioengineered rubber prepared by the present invention can be controlled by controlling the butyl itaconate during the polymerization reaction. It is regulated with the amount of butadiene charged.
- the physical and mechanical properties of the itaconate/butadiene copolymer bioengineered rubber prepared in the examples can meet the requirements of engineering applications (such as tires, conveyor belts, etc.).
- the dynamic mechanical properties of the butyl butyl acrylate/butadiene copolymer bioengineered rubber are optimal, 0 ° C
- the loss factor is significantly higher than the loss factor of styrene-butadiene rubber and natural rubber, the loss factor is equivalent to the loss factor of styrene-butadiene rubber and natural rubber at 60 °C.
- a green tire having a low rolling resistance and a high wet skid resistance was prepared by using the butyl itaconate/butadiene copolymer type bioengineered rubber synthesized in Example 11.
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Abstract
Description
Claims (10)
- 一种衣康酸酯/丁二烯共聚物型生物工程橡胶,其特征是:是由衣康酸酯和丁二烯乳液聚合而成的共聚物经化学交联而成,所述的衣康酸酯/丁二烯共聚物的数均分子量为53000~1640000,重均分子量为110000~2892000。
- 根据权利要求1所述的一种衣康酸酯/丁二烯共聚物型生物工程橡胶的制备方法,其特征在于,步骤如下:A:衣康酸酯与丁二烯的乳液聚合反应在聚合装置中,加入衣康酸酯、乳化剂、电解质、活化剂、去离子水,将聚合装置封闭,先抽真空,再充氮气,操作1~5次;最后一次充完氮气后将丁二烯、除氧剂和引发剂加入到聚合装置中,在1~20℃,0.1~5MPa压力条件下反应5~15小时;加入终止剂终止反应;其中,衣康酸酯、丁二烯、乳化剂、电解质、活化剂、除氧剂、引发剂、终止剂和去离子水的质量比是:100:1~100:1~10:0.1~5:0.01~5:0.1~5:0.01~5:1~10:100~1000;乳液经破乳干燥得到衣康酸酯/丁二烯共聚物型生物工程弹性体生胶,生胶数均分子量为53000~1640000,重均分子量为110000~2892000;所述的衣康酸酯的分子式如下:其中,R1、R2为H原子或C1~10的烷基,R1、R2相同,或者不同;B、橡胶硫化过程以硫磺为交联剂,利用传统的硫化/促进剂硫化体系,在140~160℃下模压硫化制成衣康酸酯/丁二烯共聚物型生物工程橡胶。
- 根据权利要求2所述方法,其特征在于,R1、R2为正丁基、正戊基或异戊基。
- 根据权利要求2所述方法,其特征在于,所述的乳化剂为下列中的一种或几种的混合物:歧化松香酸钠皂、歧化松香酸钾皂、脂肪酸钠皂、脂肪酸钾皂、十二烷基硫酸钠、十二烷基苯磺酸钠、十二烷基磺酸钠。
- 根据权利要求2所述方法,其特征在于,所述的电解质为下列中的一种或它们的混合物:氯化钾、磷酸钾、乙二胺四乙酸、间次甲基二萘磺酸钠、磷酸、氢氧化钾。
- 根据权利要求2所述方法,其特征在于,所述的活化剂为甲醛次硫酸氢钠和乙二胺四乙酸铁的混合物,或甲醛次硫酸氢钠和乙二胺四乙酸铁钠的混合物;所述的引发剂为过氧化氢对孟烷、叔丁基过氧化氢或过氧化氢异丙苯。
- 根据权利要求2所述方法,其特征在于,所述的终止剂二甲基二硫代氨基甲酸钠、二 乙胺基二硫代氨基甲酸钠、羟胺或多硫化钠。
- 根据权利要求2所述方法,其特征在于,衣康酸酯与丁二烯单体的质量比为100:10~60。
- 根据权利要求2所述方法,其特征在于,上述的硫化配合体系包括硫化活化剂、硫化促进剂和硫化剂。
- 根据权利要求2-9任意一项所述方法,其特征在于,应用于包括轮胎胎面或传送带工程应用。
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US15/736,198 US11890896B2 (en) | 2015-06-15 | 2016-06-02 | Preparation method of itaconate-butadiene bio-based engineering rubber |
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CN112521553B (zh) * | 2019-09-19 | 2022-02-01 | 北京化工大学 | 一种衣康酸酯/苯乙烯/丁二烯共聚物及其制备方法和橡胶组合物 |
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CN115627044B (zh) * | 2022-10-27 | 2024-02-20 | 山东京博中聚新材料有限公司 | 一种生物基衣康酸酯橡胶白炭黑复合材料及其制备方法 |
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JP2018536719A (ja) | 2018-12-13 |
US20180250984A1 (en) | 2018-09-06 |
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CN104945817A (zh) | 2015-09-30 |
US11890896B2 (en) | 2024-02-06 |
CN104945817B (zh) | 2017-12-29 |
EP3305819A1 (en) | 2018-04-11 |
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