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 PDF

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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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Prior art keywords
rubber
itaconate
butadiene
butadiene copolymer
sodium
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PCT/CN2016/084508
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English (en)
French (fr)
Inventor
张立群
周鑫鑫
王润国
雷巍巍
乔荷
花·国智
库里格·约瑟夫
查瓦拉·萨伦德拉
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北京化工大学
美国固特异轮胎橡胶公司
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Application filed by 北京化工大学, 美国固特异轮胎橡胶公司 filed Critical 北京化工大学
Priority to JP2017557307A priority Critical patent/JP6688319B2/ja
Priority to EP16810916.3A priority patent/EP3305819B1/en
Priority to US15/736,198 priority patent/US11890896B2/en
Publication of WO2016202175A1 publication Critical patent/WO2016202175A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • 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
    • 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

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属于生物工程橡胶领域。本发明提供的生物工程橡胶，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，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。衣康酸酯单体与丁二烯经乳液聚合制备衣康酸酯/丁二烯共聚物；然后，将衣康酸酯/丁二烯共聚物经化学交联制得生物工程橡胶。上述的化学交联过程可以通过添加传统的硫化/促进剂硫化体系实现。本发明的生物工程橡胶具有高分子量、低玻璃化转变温度，能够通过硫化/促进剂硫化体系硫化，并使其具有与现有合成橡胶相当的物理机械性能和加工性能。能满足如轮胎胎面、传送带等工程应用的要求。

Description

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 技术领域：
本发明涉及一种由氧化还原引发体系引发，低温条件下通过乳液聚合制备衣康酸酯/丁二烯共聚物型生物工程橡胶的方法。
背景技术：
随着人们对化石资源枯竭和环境污染等问题的关注，充分利用低碳、环保、可再生资源越来越受到世界各国的重视。橡胶由于其独特的高弹性，被广泛应用于国防民生的各个领域，橡胶材料被称作重要的战略资源。然而，橡胶合成工业长期严重依赖不可再生的化石资源，同时，不可再生资源的加速消耗增加了橡胶合成的成本，加速了环境的破坏，限制了橡胶工业的发展。因此，充分利用低碳、环保、可再生资源，减少对不可再生化石资源的依赖对保护环境、促进橡胶产业的可持续发展具有十分重大的意义。
生物基化学品的发展越来越受到世界各国的重视，利用生物基化学品合成橡胶材料具有广阔的发展前景。正是在这一前提下，本申请人提出了生物基工程橡胶(Bio-based Engineering Elastomer)的概念，并指出生物基工程橡胶应该具有以下几个特点：(1)主要原料为可再生资源；(2)具有良好的环境稳定性；(3)能够通过传统的橡胶加工工艺进行加工；(4)具有良好的力学性能能够满足工程应用。本申请人在“一种聚酯型生物工程橡胶及其制备方法”(ZL 200910076032.9)中公开了一种由生物基化学品缩聚合成的不饱和脂肪族聚酯型生物工程橡胶。该聚酯型生物工程橡胶使用来源于可再生资源的二元醇和二元酸，通过直接缩聚的方法合成，数均分子量在19800～55000之间，重均分子量在88610～222500之间，可使用过氧化物进行化学交联，交联过程中还可添加增强剂，可以采用传统的橡胶加工工艺来成型。
本申请人在“一种衣康酸酯/异戊二烯共聚物型生物工程橡胶及其制备方法”(ZL 2011 1 0440400.0)中公开了一种由生物基化学品衣康酸酯和异戊二烯经乳液聚合制备的生物基工程橡胶及其制备方法。该方法通过引发剂的热裂解产生自由基，在高温高压下引发衣康酸酯和异戊二烯的共聚，制得的生 物基工程橡胶的数均分子量为52500～502563，重均分子量为135230～1503263，力学性能相对较低，尚不能满足部分工程领域(如轮胎，传送带等)的应用。
本申请人在“一种低温乳液聚合制备衣康酸酯/异戊二烯共聚物型生物工程橡胶生胶的方法”(ZL 2011 1 0440385.X)中公开了一种在低温下制备衣康酸酯/异戊二烯共聚物型生物工程橡胶生胶的方法。该方法采用氧化还原反应产生自由基，可在常温常压下引发聚合反应，降低了聚合过程的能耗及操作难度。制得的生物基工程橡胶数均分子量为145200～705678，重均分子量为290400～2540440。
丁二烯是一种具有共轭结构的二烯烃类单体。与异戊二烯相比，丁二烯结构中不含侧基，在聚合过程中受位阻效应的影响小，更容易发生加成反应，生成高分子量的聚合物，而且生成的聚合玻璃化温度更低。此外，丁二烯的价格比异戊二烯低，从而可以降低生产成本。全球生物能源(Global Bioenergies)公司于2014年11月28号宣布，已经通过直接发酵成功地生产出生物来源的丁二烯，这是第一次通过一个完全的生物生产过程，即没有任何化学步骤，生产出重要的石化原料丁二烯，是生物基丁二烯生产的突破性进展。
利用生物基单体衣康酸酯为主体原料，通过与丁二烯发生自由基引发的乳液共聚合方法制备高分子量、低玻璃化转变温度、有优异力学性能的聚合物，尤其是可利用传统橡胶加工工艺进行加工的衣康酸酯/丁二烯共聚物型生物工程橡胶，在国内外均无报道。
动态力学分析(DMTA)是研究聚合物结构和性能的重要手段，它能得到聚合物的损耗因子(tanδ)与试验温度的对应关系，tanδ是决定聚合物使用特性的重要参数。对轮胎用橡胶复合材料而言，0℃时tanδ值越大，表明用该材料制备出的轮胎抗湿滑性越好，越安全；60℃时tanδ值越小，表明用该材料制备出的轮胎滚动阻力越小，越节油。本发明的另一目的是通过改变衣康酸酯与丁二烯的投料比，调控衣康酸酯/丁二烯共聚物型生物工程橡胶的粘弹性，从而获得最优的动态力学性能，即0℃时tanδ值较高，60℃时tanδ值较低。使用具有最优动态力学性能的衣康酸酯/丁二烯共聚物型生物工程橡胶制 备高性能的绿色轮胎，在国内外均无报道。
发明内容：
本发明的目的在于提供一种衣康酸酯/丁二烯共聚物型生物工程橡胶及其制备方法，使得其具有高分子量、低玻璃化转变温度，能够通过硫化/促进剂硫化体系硫化，并使其具有与现有合成橡胶相当的物理机械性能和加工性能。
本发明提供的一种衣康酸酯/丁二烯共聚物型生物工程橡胶，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，其特征是：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。
衣康酸酯单体与丁二烯经乳液聚合制备衣康酸酯/丁二烯共聚物；然后，将衣康酸酯/丁二烯共聚物经化学交联制得衣康酸酯/丁二烯共聚物型生物工程橡胶。上述的化学交联过程可以通过添加传统的硫化/促进剂硫化体系实现。具体反应条件和步骤如下：
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：
Figure PCTCN2016084508-appb-000001
其中，R1、R2为H原子或C1～10的烷基，R1、R2可以相同，也可不同，优选正丁基、正戊基或异戊基。
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。
所述的电解质为下列中的一种或它们的混合物：氯化钾(KCl)、磷酸钾(K3PO4)、乙二胺四乙酸(EDTA)、间次甲基二萘磺酸钠(TAOM-L)、磷酸(H3PO4)、氢氧化钾(KOH)。
所述的活化剂为甲醛次硫酸氢钠和乙二胺四乙酸铁(EDTA-Fe)的混合物，或甲醛次硫酸氢钠和乙二胺四乙酸铁钠(EDTA-Fe·Na)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。
所述的除氧剂为连二亚硫酸钠，俗称保险粉。
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。
衣康酸酯与丁二烯单体可以任意质量比配合，优选衣康酸酯与丁二烯单体的质量比为100:10～60。
所述的破乳干燥过程中破乳剂可以采用氢离子浓度为0.1～0.5mol/L的盐酸溶液、1wt％～5wt％的氯化钙水溶液、无水甲醇或无水乙醇。
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。
上述制备方法中所涉及的橡胶加工制备工艺和硫化配合体系均是传统的橡胶加工手段，使用原则是公知的。
上述的硫化配合体系包括硫化活化剂(如：氧化锌、硬脂酸)和硫化促进剂(如：2-巯醇基苯并噻唑(促进剂M)、N-环已基-2-苯骈噻唑次磺酰胺(促进剂CZ)、二苯胍(促进剂D))和硫化剂(如：硫磺)。
为提高强度，可添加白炭黑或炭黑作为增强剂。以白炭黑作为增强剂时，还可以加入硅烷偶联剂Si69提高复合效果。
本发明的效果在于：采用氧化还原引发体系，在1～20℃下，通过乳液聚合合成了一种衣康酸酯/丁二烯共聚物型生物工程橡胶。该橡胶的数均分子量可以达到100万以上，分子量分布窄，并且可以利用传统的橡胶加工工艺进 行加工成型。通过加入补强填料，能有效提高该橡胶的机械性能，其性能满足对力学性能要求较高的如轮胎胎面，传送带等工程应用的要求。利用该橡胶成功试制了首批衣康酸酯/丁二烯共聚物型生物工程橡胶轮胎，经测试表明，该轮胎是一种低滚阻、高抗湿滑的高性能绿色轮胎，具有广阔的市场前景。
附图说明：
图1为本发明实施例4制备的衣康酸丁酯/丁二烯共聚物型生物工程橡胶生胶照片。
图2为本发明实施例4制备的衣康酸丁酯/丁二烯共聚物型生物工程橡胶生胶的1H-NMR谱图，在化学位移4.94-5.68ppm处的峰位表示衣康酸丁酯/丁二烯共聚物型生物工程橡胶生胶中有双键存在，可以为后续的化学交联过程提供交联点。
图3为本发明实施例11制备的白炭黑补强衣康酸丁酯/丁二烯共聚物型生物工程橡胶透射电子显微镜照片。可以看出，填料在衣康酸丁酯/丁二烯共聚物型生物工程橡胶中有较好的分散效果。
具体实施方式：
本发明将对实施例和对比例进行更详细的描述，但不是对本发明的限制。
下列实施例和对比例中所采用的所有材料均为市售的化工产品。聚合部分的材料均为分析纯试剂，混炼部分的材料均为化学纯试剂。下列实施例中的衣康酸酯/丁二烯共聚物型生物工程橡胶材料和对比例中的橡胶复合材料，在-80℃至100℃的温度范围，10Hz频率和3℃/min加热速率以及0.1％的动态应力的拉伸模式下，通过动态粘弹谱仪测试其损耗因子(tanδ)，测试片大小为20mm长×10mm宽×1mm厚。
实施例1
在1升的聚合装置中，加入500克去离子水，150克衣康酸甲酯，3克脂肪酸钾皂，4克脂肪酸钠皂，2克H3PO4，1.2克KOH，0.02克EDTA，0.25克TAOM-L，0.01克EDTA-Fe，0.05克甲醛次硫酸氢钠；将装置密封后，抽真空、充氮气，操作1次，然后加入50克丁二烯，0.02克连二亚硫酸钠和0.03克过氧化氢对孟烷，在1℃，0.1MPa压力条件下反应15小时，加入1克羟胺 终止反应，得到衣康酸甲酯/丁二烯共聚物型生物工程橡胶胶乳，将胶乳倒入0.1mol/L的盐酸溶液中破乳干燥后得到衣康酸甲酯/丁二烯共聚物型生物工程橡胶生胶。
将100克上述衣康酸甲酯/丁二烯共聚物型生物工程橡胶生胶，5克氧化锌，2克硬脂酸，1克硫磺，0.7克促进剂M，1克促进剂CZ，50克白炭黑、5克Si69在双辊开炼机上混合均匀得到混炼胶，混炼胶在140℃下模压硫化制备成衣康酸甲酯/丁二烯共聚物型生物工程橡胶。
实施例2
在1升的聚合装置中，加入500克去离子水，160克衣康酸乙酯，5克脂肪酸钾皂，5克歧化松香酸钠皂，0.3克K3PO4，0.15克KCl，0.03克EDTA，0.25克TAOM-L，1克EDTA-Fe·Na，4克甲醛次硫酸氢钠；将装置密封后，抽真空、充氮气，连续操作3次，然后加入40克丁二烯，0.01克连二亚硫酸钠和0.05克过氧化氢对孟烷，在5℃，1MPa压力条件下反应10小时，加入5克羟胺终止反应，得到衣康酸乙酯/丁二烯共聚物型生物工程橡胶胶乳，将胶乳倒入无水乙醇中破乳干燥后得到衣康酸乙酯/丁二烯共聚物型生物工程橡胶生胶。
将100克上述衣康酸乙酯/丁二烯共聚物型生物工程橡胶生胶，5克氧化锌，2克硬脂酸，1克硫磺，0.7克促进剂M，1克促进剂CZ，40克白炭黑、4克Si69在双辊开炼机上混合均匀得到混炼胶，混炼胶在150℃下模压硫化制备成衣康酸乙酯/丁二烯共聚物型生物工程橡胶。
实施例3
在1升的聚合装置中，加入500克去离子水，140克衣康酸丁酯，3克脂肪酸钾皂，4克脂肪酸钠皂，0.2克H3PO4，0.12克KOH，0.02克EDTA，0.25克TAOM-L，0.01克EDTA-Fe，0.05克甲醛次硫酸氢钠；将装置密封后，抽真空、充氮气，连续操作5次，然后加入60克丁二烯，2克连二亚硫酸钠和5克过氧化氢对孟烷，在5℃，1MPa压力条件下反应8小时，加入3克羟胺终止反应，得到衣康酸丁酯/丁二烯共聚物型生物工程橡胶胶乳，将胶乳倒入1wt％氯化钙溶液中破乳干燥后得到衣康酸丁酯/丁二烯共聚物型生物工程橡 胶生胶。
将100克上述衣康酸丁酯/丁二烯共聚物型生物工程橡胶生胶，5克氧化锌，2克硬脂酸，1克硫磺，0.7克促进剂M，1克促进剂CZ，60克白炭黑、6克Si69在双辊开炼机上混合均匀得到混炼胶，混炼胶在160℃下模压硫化制备成衣康酸丁酯/丁二烯共聚物型生物工程橡胶。
实施例4
在1升的聚合装置中，加入500克去离子水，120克衣康酸丁酯，3克脂肪酸钾皂，4克脂肪酸钠皂，0.2克H3PO4，0.12克KOH，0.02克EDTA，0.25克TAOM-L，0.02克EDTA-Fe，0.05克甲醛次硫酸氢钠；将装置密封后，抽真空、充氮气，连续操作4次，然后加入80克丁二烯，0.01克连二亚硫酸钠和0.01克过氧化氢对孟烷，在5℃，1MPa压力条件下反应9小时后加入10克羟胺终止反应，得到衣康酸丁酯/丁二烯共聚物型生物工程橡胶胶乳，将胶乳倒入1wt％氯化钙溶液中破乳干燥后得到衣康酸丁酯/丁二烯共聚物型生物工程橡胶生胶。
将100克上述衣康酸丁酯/丁二烯共聚物型生物工程橡胶生胶，5克氧化锌，2克硬脂酸，1克硫磺，0.7克促进剂M，1克促进剂CZ，60克白炭黑、6克Si69在双辊开炼机上混合均匀得到混炼胶，混炼胶在150℃下模压硫化制备成衣康酸丁酯/丁二烯共聚物型生物工程橡胶。
实施例5
在1升的聚合装置中，加入400克去离子水，140克衣康酸正戊酯，5克歧化松香酸钾皂，2克H3PO4，1.2克KOH，0.5克EDTA，1.3克TAOM-L，0.01克EDTA-Fe·Na，0.05克甲醛次硫酸氢钠；将装置密封后，抽真空、充氮气，连续操作3次，然后加入60克丁二烯，0.02克连二亚硫酸钠和0.03克过氧化氢对孟烷，在5℃，0.5MPa压力条件下反应10小时，加入10克羟胺终止反应，得到衣康酸正戊酯/丁二烯共聚物型生物工程橡胶胶乳，将胶乳倒入1wt％氯化钙水溶液中破乳干燥后得到衣康酸正戊酯/丁二烯共聚物型生物工程橡胶生胶。
将100克上述衣康酸正戊酯/丁二烯共聚物型生物工程橡胶生胶，5克氧 化锌，2克硬脂酸，1克硫磺，0.7克促进剂M，1克促进剂CZ，80克白炭黑和8克Si69在双辊开炼机上混合均匀得到混炼胶，混炼胶在150℃下模压硫化制备成衣康酸正戊酯/丁二烯共聚物型生物工程橡胶。
实施例6
在1升的聚合装置中，加入600克去离子水，140克衣康酸丁酯，6克十二烷基硫酸钠，0.2克K3PO4，0.4克KCl，0.02克EDTA，0.2克TAOM-L，0.02克EDTA-Fe，0.05克甲醛次硫酸氢钠；将装置密封后，抽真空、充氮气，连续操作4次，然后加入60克丁二烯，0.02克连二亚硫酸钠和0.03克过氧化氢对孟烷，在5℃，2MPa压力条件下反应10小时后加入1克二甲基二硫代氨基甲酸钠终止反应，得到衣康酸丁酯/丁二烯共聚物型生物工程橡胶胶乳，将胶乳倒入5wt％氯化钙水溶液中破乳干燥后得到衣康酸丁酯/丁二烯共聚物型生物工程橡胶生胶。
将100克上述衣康酸丁酯/丁二烯共聚物型生物工程橡胶生胶，5克氧化锌，2克硬脂酸，1克硫磺，0.7克促进剂M，1克促进剂CZ，60克白炭黑和6克Si69在双辊开炼机上混合均匀得到混炼胶，混炼胶在150℃下模压硫化制备成衣康酸丁酯/丁二烯共聚物型生物工程橡胶。
实施例7
在1升的聚合装置中，加入500克去离子水，150克衣康酸异戊酯，3克脂肪酸钾皂，4克脂肪酸钠皂，0.2克H3PO4，0.12克KOH，0.02克EDTA，0.25克TAOM-L，0.01克EDTA-Fe，0.05克甲醛次硫酸氢钠；将装置密封后，抽真空、充氮气，连续操作3次，然后加入50克丁二烯，0.02克连二亚硫酸钠和0.03克叔丁基过氧化氢，在10℃，3MPa压力条件下反应5小时，加入7克羟胺终止反应，得到衣康酸异戊酯/丁二烯共聚物型生物工程橡胶胶乳，将胶乳倒入乙醇中破乳干燥后得到衣康酸异戊酯/丁二烯共聚物型生物工程橡胶生胶。
将100克上述衣康酸异戊酯/丁二烯共聚物型生物工程橡胶生胶，5克氧化锌，2克硬脂酸，1克硫磺，0.7克促进剂M，1克促进剂CZ，60克炭黑N330在双辊开炼机上混合均匀得到混炼胶，混炼胶在150℃下模压硫化制备 成衣康酸异戊酯/丁二烯共聚物型生物工程橡胶。
实施例8
在1升的聚合装置中，加入500克去离子水，160克衣康酸丁酯，2克十二烷基苯磺酸钠，0.2克K3PO4，0.5克KCl，0.02克EDTA，0.25克TAOM-L，0.01克EDTA-Fe，0.05克甲醛次硫酸氢钠；将装置密封后，抽真空、充氮气，连续操作2次，然后加入40克丁二烯，0.02克连二亚硫酸钠和0.03克过氧化氢异丙苯，在20℃，5MPa压力条件下反应7小时后，入1克羟胺终止反应，得到衣康酸丁酯/丁二烯共聚物型生物工程橡胶胶乳，将胶乳倒入2wt％氯化钙水溶液中破乳干燥后得到衣康酸丁酯/丁二烯共聚物型生物工程橡胶生胶。
将100克上述衣康酸丁酯/丁二烯共聚物型生物工程橡胶生胶，5克氧化锌，2克硬脂酸，1克硫磺，0.7克促进剂M，1克促进剂CZ，40克炭黑N330在双辊开炼机上混合均匀得到混炼胶，混炼胶在150℃下模压硫化制备成衣康酸丁酯/丁二烯共聚物型生物工程橡胶。
对比例1
将100克丁苯橡胶(SBR1502)，5克氧化锌，2克硬脂酸，1克硫磺，0.7克促进剂M，1克促进剂CZ，60克白炭黑和6克Si69在双辊开炼机上混合均匀得到混炼胶，混炼胶在150℃下模压硫化制备成白炭黑/丁苯橡胶复合材料。
对比例2
将100克天然橡胶(云标1#)，5克氧化锌，2克硬脂酸，1克硫磺，0.7克促进剂M，1克促进剂CZ，60克炭黑N330在双辊开炼机上混合均匀得到混炼胶，混炼胶在150℃下模压硫化制备成炭黑/天然橡胶复合材料。
表1 本发明实施例制备的橡胶生胶的性能测试结果
Figure PCTCN2016084508-appb-000002
(注：表1中数据均根据国家标准测试方法获得)
从表1的对比的数据可以看出，本发明制备的衣康酸酯/丁二烯共聚物型生物工程橡胶生胶具有较高的分子量，较窄的分子量分布，聚合过程在低温下进行，降低了能耗，适合工业化生产。
表2 实施例与对比例制备的橡胶复合材料的物理机械性能和动态力学性能
Figure PCTCN2016084508-appb-000003
(注：表2中数据均根据国家标准测试获得)
从表2中可以看出，本发明制备的衣康酸酯/丁二烯共聚物型生物工程橡胶经过填料补强后，表现出优异的物理机械性能，拉伸强度和断裂伸长率均达到或超过了传统的丁苯橡胶和天然橡胶的相应性能，能够满足对力学性能要求较高的工程应用(如轮胎、传送带)的条件。此外，本发明制备的衣康酸酯/丁二烯共聚物型生物工程橡胶材料0℃时的损耗因子(tanδ)明显高于丁苯橡胶和天然橡胶的损耗因子，60℃时的损耗因子与丁苯橡胶和天然橡胶的损耗因子相当甚至低于丁苯橡胶和天然橡胶的损耗因子，说明本发明制备的衣康酸酯/丁二烯共聚物型生物工程橡胶材料具有优异的动态力学性能，可用作制备低滚阻、高抗湿滑性能轮胎的橡胶材料。
实施例9至15
实施例9至15制备的衣康酸丁酯/丁二烯共聚物型生物工程橡胶，除了衣康酸丁酯与丁二烯的投料量不同外，其他试剂的种类和质量均相同，制备工艺路线也相同，衣康酸丁酯与丁二烯的投料量在表3中给出。具体制备步骤和方法如下：
在1升的聚合装置中，加入500克去离子水，衣康酸丁酯，3克脂肪酸钾皂，4克脂肪酸钠皂，0.2克H3PO4，0.12克KOH，0.02克EDTA，0.25克TAOM-L，0.01克EDTA-Fe，0.05克甲醛次硫酸氢钠；将装置密封后，抽真空、充氮气，连续操作5次，然后加入丁二烯，0.02克连二亚硫酸钠和0.03克过氧化氢对孟烷，在5℃，1MPa压力条件下反应8小时，加入1克羟胺终止反应，得到衣康酸丁酯/丁二烯共聚物型生物工程橡胶胶乳，将胶乳倒入1wt％氯化钙溶液中破乳干燥后得到衣康酸丁酯/丁二烯共聚物型生物工程橡胶生胶。
将100克上述衣康酸丁酯/丁二烯共聚物型生物工程橡胶生胶，5克氧化锌，2克硬脂酸，1克硫磺，0.7克促进剂M，1克促进剂CZ，60克白炭黑、6克Si69在双辊开炼机上混合均匀得到混炼胶，混炼胶在150℃下模压硫化制备成衣康酸丁酯/丁二烯共聚物型生物工程橡胶。
对比例3
将100克丁苯橡胶(SSBR2503)，5克氧化锌，2克硬脂酸，1克硫磺，0.7克促进剂M，1克促进剂CZ，60克白炭黑和6克Si69在双辊开炼机上混合均匀得到混炼胶，混炼胶在150℃下模压硫化制备成白炭黑/丁苯橡胶复合材料。
对比例4
将100克天然橡胶(烟片胶)，5克氧化锌，2克硬脂酸，1克硫磺，0.7克促进剂M，1克促进剂CZ，60克炭黑N330在双辊开炼机上混合均匀得到混炼胶，混炼胶在150℃下模压硫化制备成炭黑/天然橡胶复合材料。
表3 本发明实施例与对比例的动态力学性能
Figure PCTCN2016084508-appb-000004
(注：表3中数据均根据国家标准测得)
表4 本发明实施例与对比例制备的橡胶复合材料的物理机械性能测试
Figure PCTCN2016084508-appb-000005
(注：表4中数据均根据国家标准测得)
从表3和表4中可以看出，本发明制备的衣康酸丁酯/丁二烯共聚物型生物工程橡胶的物理机械性能和动态力学性能，可以通过控制聚合反应时衣康酸丁酯与丁二烯的投料量来调控。实施例中制备的衣康酸酯/丁二烯共聚物型生物工程橡胶的物理机械性能均能满足工程应用(如轮胎、输送带等)的要求。当衣康酸丁酯与丁二烯的投料量之比为60:40(实施例11)时，衣康酸丁酯/丁二烯共聚物型生物工程橡胶的动态力学性能最优，0℃时，其损耗因子明显高于丁苯橡胶和天然橡胶的损耗因子，60℃时，其损耗因子与丁苯橡胶和天然橡胶的损耗因子相当。利用实施例11合成的衣康酸丁酯/丁二烯共聚物型生物工程橡胶制备了低滚阻、高抗湿滑的绿色轮胎。

Claims (10)

  1. 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。
  2. 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：
    Figure PCTCN2016084508-appb-100001
    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。
  3. 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。
  4. 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。
  5. 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。
  6. 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。
  7. 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。
  8. 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。
  9. 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。
  10. 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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