WO2017097043A1 - 一种无需硅烷偶联剂的白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料及其制备方法 - Google Patents

一种无需硅烷偶联剂的白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料及其制备方法 Download PDF

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WO2017097043A1
WO2017097043A1 PCT/CN2016/102900 CN2016102900W WO2017097043A1 WO 2017097043 A1 WO2017097043 A1 WO 2017097043A1 CN 2016102900 W CN2016102900 W CN 2016102900W WO 2017097043 A1 WO2017097043 A1 WO 2017097043A1
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itaconate
isoprene
poly
glycidyl methacrylate
bio
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English (en)
French (fr)
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张立群
乔荷
王润国
许文集
雷巍巍
周鑫鑫
晁明远
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北京化工大学
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Priority to EP16872237.9A priority Critical patent/EP3323841B1/en
Priority to JP2017559814A priority patent/JP6628813B2/ja
Priority to US15/761,054 priority patent/US10494514B2/en
Publication of WO2017097043A1 publication Critical patent/WO2017097043A1/zh

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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
    • C08F222/10—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
    • 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
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00—Compositions of rubbers containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or 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, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/02—Homopolymers or copolymers of esters
    • 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
    • C08F22/00—Homopolymers and 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
    • C08F22/02—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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • 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
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/309—Sulfur containing acids
    • 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 

Definitions

  • the invention relates to a white carbon black/bio-based elastomer composite material and a preparation method thereof, in particular to a method for improving the dispersion of white carbon black without improving the mechanical properties of the rubber product and improving the anti-wetting property without the need of a silane coupling agent. And a method for preparing a green rubber composite material which has reduced rolling resistance and is free of VOC gas during preparation.
  • the molecular structure of rubber leads to its high elasticity but poor mechanical strength, and it is generally necessary to use a filler to enhance it to fully exert its use value.
  • the most reinforcing fillers used in the rubber field are carbon black and white carbon black.
  • the production of silica is not dependent on petrochemical resources, and compared with carbon black, silica-filled rubber has better wet skid resistance and lower rolling resistance.
  • the surface of silica has a large amount of hydroxyl groups, which tends to cause filler aggregation, and poor dispersion affects the performance of the silica-filled rubber product.
  • silane coupling agents are mostly used in the industry to improve the dispersion of white carbon black and its interfacial interaction with rubber by coupling white carbon black with rubber.
  • a rubber to which a silane coupling agent is added requires heat treatment, which not only increases the manufacturing cost, but also makes the rubber processing process cumbersome.
  • VOC gas is usually generated, such as methanol, ethanol, etc., causing certain pollution to the environment.
  • Poly(itaconate-isoprene-glycidyl methacrylate) is a novel environmentally friendly bio-based elastomer whose raw materials, itaconic acid, alcohol and isoprene, can be fermented by biological fermentation. Made by law. Poly(itaconate-isoprene-glycidyl methacrylate) molecule contains a large amount of ester groups and a part of epoxy functional groups, and the ester group can improve the white carbon black by forming hydrogen bonds with the surface of the white carbon black.
  • Dispersion, and the epoxy functional group can open-loop cross-link with the hydroxyl group on the surface of silica, thereby greatly improving the dispersion of white carbon in the rubber matrix and the interfacial force between the silica and the rubber matrix. , thereby improving the mechanical properties and wet skid resistance of the green rubber product, reducing the rolling resistance of the product, and avoiding
  • the use of a silane coupling agent simplifies the processing and avoids the generation of VOC gas. Therefore, the silica/poly(itaconate-isoprene-glycidyl methacrylate) bio-based elastomer composite is a promising green bio-based "green tire" rubber material.
  • the addition of glycidyl methacrylate improves the dispersion of white carbon black, improves the mechanical properties and wet skid resistance of rubber products, and reduces the rolling resistance of rubber products, eliminating the introduction of silane coupling agent and simplifying the simplification.
  • the rubber processing process avoids the generation of VOC gas.
  • the invention provides a preparation method of a glycidyl methacrylate functionalized bio-based elastomer poly(itaconic acid-isoprene-glycidyl methacrylate), and the bio-based elastomer and
  • the silica was kneaded and compounded to prepare a silica/poly(itaconate-isoprene-glycidyl methacrylate) biobased elastomer composite.
  • the introduction of a silane coupling agent is not required in the preparation of the composite.
  • the itaconate includes, but is not limited to, dimethyl itaconate, diethyl itaconate, dipropyl itaconate, diisopropyl itaconate, dibutyl itaconate, itacon Diisobutyl acrylate, dipentyl itaconate, diisoamyl itaconate, dihexyl itaconate, diheptyl itaconate or dioctyl itaconate.
  • the emulsifier is one of the following substances or a mixture thereof: potassium oleate, sodium oleate, potassium disproportionate, sodium rosin, sodium dodecyl sulfate, dodecylbenzenesulfonic acid Sodium, sodium lauryl sulfate, CO436.
  • the reducing agent is ethylenediaminetetraacetic acid (EDTA) iron sodium salt or ferrous sulfate;
  • the secondary reducing agent is sodium formaldehyde sulfoxylate or polyvinyl polyamine
  • the chelating agent is disodium ethylenediaminetetraacetate (EDTA-2Na), tetrasodium ethylenediaminetetraacetate (EDTA-4Na) or B.
  • EDTA-Fe ⁇ Na Sodium iron diamine tetraacetate
  • the initiator is t-butyl hydroperoxide, cumene hydroperoxide or hydrogen peroxide to montan;
  • the flocculating agent is a calcium chloride aqueous solution having a mass concentration of 1 to 10%, an aqueous solution of 1 to 10% sodium chloride, a solution of 1 to 5% hydrochloric acid, a solution of 1 to 5% sulfuric acid, ethanol or methanol.
  • the white carbon black is a highly dispersed white carbon black, such as VN3, 833MP but is not limited to the above two;
  • the antioxidant is N-isopropyl-N'-phenyl-p-phenylenediamine (anti-4010NA), N-(1.3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (anti- 4020) but not limited to the above two;
  • the promoter is 2-nonyl benzothiazole (promoting M), N-cyclohexyl-2-benzothiazole sulfenamide (promoting CZ) but not limited to the above two;
  • the other fillers are paraffin wax, aromatic oil, but are not limited to the above two.
  • the white carbon black/poly(itaconate-isoprene-glycidyl methacrylate) bio-based elastomer composite of the present invention has no methyl group under the same formulation and process conditions. Compared with the glycidyl acrylate-functionalized silica/poly(itaconate-isoprene) bio-based elastomer composite, it has significantly improved dispersion and mechanical strength of silica, while reducing rubber products. The rolling resistance improves the wet skid resistance, avoids the introduction of silane coupling agent, and has a simple process. It is a promising bio-based "green tire” rubber material.
  • the obtained poly(ethylene itaconate-isoprene-glycidyl methacrylate) The flocculated gel was successively soaked and purified with ethanol and water, and dried in a blast oven at 60 ° C for 24 hours to obtain a poly(ethylene itaconate-isoprene-glycidyl methacrylate) biobased elastomer.
  • initiator hydrogen peroxide was added to the homopolymer to initiate polymerization, and the rotation speed was reduced to 200 rpm for 18 hours to obtain poly(dipropyl itaconate-isoprene-glycidyl methacrylate).
  • the ester was latex, and the latex was poured into calcium chloride having a mass fraction of 1% to carry out demulsification flocculation to obtain a poly(dipropyl itaconate-isoprene-glycidyl methacrylate) floc gel.
  • the obtained poly(dipropyl itaconate-isoprene-glycidyl methacrylate) floc gel was successively soaked and purified with ethanol and water, and dried in a blast oven at 60 ° C for 24 hours to obtain poly( Diethyl propyl itaconate-isoprene-glycidyl methacrylate) biobased elastomer.
  • the polymerization was initiated by adding 0.05 g of initiator t-butyl hydroperoxide, the rotation speed was reduced to 200 rpm, and the reaction was carried out for 12 hours to obtain poly(dibutyl itaconate-isoprene-methacrylic acid glycidol).
  • Ester) Latex the latex was poured into ethanol for demulsification flocculation to obtain a poly(dibutyl itaconate-isoprene-glycidyl methacrylate) floc gel.
  • the obtained poly(dibutyl itaconate-isoprene-glycidyl methacrylate) floc gel was successively soaked and purified with ethanol and water, and dried in a blast oven at 60 ° C for 24 hours to obtain poly( Dibutyl butylate-isoprene-glycidyl methacrylate) biobased elastomer.
  • the obtained poly(isoprenyl-isoprene-glycidyl methacrylate) floc gel was successively soaked and purified with ethanol and water, and dried in a blast oven at 60 ° C for 24 hours to obtain a poly (Diisoamyl itaconate-isoprene-glycidyl methacrylate) biobased elastomer.
  • the obtained poly(dihexyl-isoprene-glycidyl methacrylate) floc gel was successively soaked and purified with ethanol and water, and dried in a blast oven at 60 ° C for 24 hours to obtain poly( Dihexyl itaconate-isoprene-glycidyl methacrylate) biobased elastomer.
  • the obtained poly(ethylene itaconate-isoprene) floc gel was successively soaked and purified with ethanol and water, and dried in a blast oven at 60 ° C for 24 hours to obtain poly(ethylene itaconate- Isoprene) bio-based elastomer.
  • the obtained poly(i-propyl itaconate-isoprene) floc gel was successively soaked and purified with ethanol and water, and dried in a blast oven at 60 ° C for 24 hours to obtain poly(dipropyl itaconate- Isoprene) bio-based elastomer.
  • 100 g of the poly(ibutate-isoprene) bio-based elastomer obtained above was mixed with 50 g of highly disperse white carbon black VN3, 5 g of zinc oxide, 0.5 g of stearic acid, using an internal mixer.
  • 1 gram of anti-4010NA, 1 gram of CZ, 0.7 gram of M and 1 gram of sulphur are mixed uniformly to obtain a rubber compound, and the rubber compound is molded and vulcanized at 150 ° C to form white carbon black/poly (dibutyl itaconate-different) Pentadiene) composites.
  • the obtained poly(dihexate-isoprene) floc gel was successively soaked and purified with ethanol and water, and dried in a blast oven at 60 ° C for 24 hours to obtain poly(dihexyl citrate- Isoprene) bio-based elastomer.
  • Table 1 shows the performance test results of the composite materials prepared in the examples and comparative examples of the present invention.
  • the white carbon black/poly(itaconate-isoprene-glycidyl methacrylate) bio-based elastomer composite of the present invention has good mechanical properties, and Compared with the composite material in which glycidyl methacrylate is not added, the white carbon black/poly(itaconate-isoprene-glycidyl methacrylate) added with glycidyl methacrylate has a higher Tensile strength and modulus.
  • the tan ⁇ value of 0 °C can reflect the wet skid resistance of the tire to some extent, and the tan ⁇ value of 60 ° C can reflect the rolling resistance of the tire to some extent.
  • the introduction of glycidyl methacrylate improves the wet skid resistance of the composite and reduces the rolling resistance of the composite.
  • the preparation of the white carbon black/poly(itaconate-isoprene-glycidyl methacrylate) bio-based elastomer composite of the invention avoids the introduction of the silane coupling agent, the process is simple and no VOC is generated, A promising green bio-based "green tire” rubber material.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

本发明涉及一种无需硅烷偶联剂的白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料。白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)复合材料是一种环境友好型的复合材料，聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)与白炭黑皆来源于非石油基原料，不依赖石化资源。引入了甲基丙烯酸缩水甘油酯的复合材料与没有引入甲基丙烯酸缩水甘油酯的复合材料相比，白炭黑的分散改善，橡胶制品的力学性能提高，抗湿滑性提高，同时滚动阻力降低，避免了硅烷偶联剂的使用，从而简化了加工工艺，并避免了挥发性有机化合物(VOC)的产生，是一种很有应用前景的绿色的生物基"绿色轮胎"橡胶材料。

Description

一种无需硅烷偶联剂的白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料及其制备方法 技术领域
本发明涉及一种白炭黑/生物基弹性体复合材料及其制备方法，特别是涉及一种无需硅烷偶联剂就可以改善白炭黑的分散，提高橡胶制品的力学性能，提高抗湿滑性并降低滚动阻力，且在制备过程中无VOC气体生成的绿色环保橡胶复合材料的制备方法。
背景技术
橡胶作为重要的基础产业之一，在国民经济中占有举足轻重的作用。传统的橡胶可以划分为天然橡胶和合成橡胶。但是目前而言，天然橡胶面临着可种植区域小、生长条件苛刻等问题；而合成橡胶大多来源于石化资源，而石化资源面临着资源紧缺、环境污染等问题。因此，寻求一种既能满足传统橡胶优异的性能，又能解决其面临着的问题的新型橡胶，是目前橡胶领域的一个重要发展方向。生物基工程弹性体(Bio-based Engineering Elastomer)正是在这种背景下由北京化工大学张立群课题组提出的。生物基工程弹性体的原材料不依赖于石油化工资源，并可通过传统的橡胶加工工艺进行加工，所制得的制品具有良好的环境稳定性。
橡胶的分子结构导致了其虽然具有高弹性但力学强度较差，一般需用填料对其进行增强才可以充分发挥其使用价值。橡胶领域中使用最多的补强填料为炭黑和白炭黑。其中，白炭黑的生产不依赖于石化资源，而且与炭黑相比，白炭黑填充的橡胶具有较好的抗湿滑性和较低的滚动阻力。但是白炭黑表面具有大量羟基，很容易产生填料聚集，而较差的分散影响了白炭黑填充橡胶制品的性能的发挥。目前工业上大多使用硅烷偶联剂，通过偶联白炭黑与橡胶，来改善白炭黑的分散及其与橡胶之间的界面作用力。但是一般来说加入了硅烷偶联剂的橡胶需要热处理，不但增加了制备成本，而且使橡胶加工工艺变得较为繁琐。此外，在橡胶复合材料加工过程中，通常会有VOC气体生成，如甲醇、乙醇等，对环境造成一定的污染。
聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)是一种新型的环境友好型的生物基弹性体，其原材料衣康酸、醇及异戊二烯都可以通过生物发酵法制得。聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)分子中含有大量的酯基和一部分环氧官能团，酯基能够通过与白炭黑表面形成氢键来改善白炭黑的分散，而环氧官能团能够与白炭黑表面的羟基发生开环交联，从而极大程度地改善了白炭黑在橡胶基体中的分散及其白炭黑与橡胶基体之间的界面作用力，进而提高了绿色橡胶制品的力学性能及抗湿滑性，降低了制品的滚动阻力，并避免 了硅烷偶联剂的使用，简化了加工工艺，并避免了VOC气体的产生。因此，白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料是一种很有应用前景的绿色生物基“绿色轮胎”橡胶材料。
发明内容
本发明的目的是提供一种白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料的其制备方法。甲基丙烯酸缩水甘油酯的加入提高了白炭黑的分散、提高了橡胶制品的力学性能及抗湿滑性能，并降低了橡胶制品的滚动阻力，省去了硅烷偶联剂的引入，简化了橡胶加工工艺并避免了VOC气体的产生。
本发明提供了一种甲基丙烯酸缩水甘油酯官能化的生物基弹性体聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)的制备方法，并将此生物基弹性体与白炭黑进行混炼复合，制备白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料。该复合材料的制备过程中无需硅烷偶联剂的引入。
具体制备条件和步骤如下：
A：聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体的制备
首先，将30～90wt.％的衣康酸酯、10～70wt.％的异戊二烯和0.5～20wt.％的甲基丙烯酸缩水甘油酯进行混合(衣康酸酯、异戊二烯及甲基丙烯酸缩水甘油酯为单体，三者总和的百分比为100％)，加入单体总质量50～500％的去离子水做分散剂，0.5～10％的乳化剂，0～5％的螯合剂，0.01～5％的还原剂和0.01～5％的二次还原剂，0.01～5％的引发剂，在5～30℃的条件下，反应6～72小时，得到聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)胶乳，用絮凝剂破乳干燥后得到聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)絮凝胶，聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)絮凝胶依次用乙醇及水进行浸泡提纯，并在60℃鼓风烘箱中干燥24小时，得到聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体；
所述的衣康酸酯包括但不仅限于：衣康酸二甲酯、衣康酸二乙酯、衣康酸二丙酯、衣康酸二异丙酯、衣康酸二丁酯、衣康酸二异丁酯、衣康酸二戊酯、衣康酸二异戊酯、衣康酸二己酯、衣康酸二庚酯或衣康酸二辛酯。
所述的乳化剂为下列物质中的一种或他们的混合物：油酸钾、油酸钠、歧化松香酸钾、企划松香酸钠、十二烷基磺酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、CO436。
所述的还原剂为乙二胺四乙酸(EDTA)铁钠盐或硫酸亚铁；
所述的二次还原剂为甲醛次硫酸钠或多乙烯基多胺；
所述的螯合剂为乙二胺四乙酸二钠(EDTA-2Na)、乙二胺四乙酸四钠(EDTA-4Na)或乙 二胺四乙酸铁钠(EDTA-Fe·Na)；
所述的引发剂为叔丁基过氧化氢、过氧化氢异丙苯或过氧化氢对孟烷；
所述的絮凝剂采用质量浓度1～10％的氯化钙水溶液、1～10％的氯化钠水溶液、1～5％的盐酸溶液、1～5％的硫酸溶液、乙醇或甲醇。
B：白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料的制备
取上述聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体100质量份，与10份以上白炭黑、0.5～3.0份硫磺、0.5～3份防老剂、0.5～10份氧化锌、0.5～5份硬脂酸、0.5～5份促进剂、0～30份其他填充剂通过开炼机或密炼机共混，在130～170℃下模压硫化制成白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料。
所述的白炭黑为高分散白炭黑，如VN3、833MP但不限于以上两种；
所述的防老剂为N-异丙基-N’-苯基对苯二胺(防4010NA)、N-(1.3-二甲基丁基)-N'-苯基-对苯二胺(防4020)但不限于以上两种；
所述的促进剂为2-巯醇基苯并噻唑(促M)、N-环已基-2-苯并噻唑次磺酰胺(促CZ)但不限于以上两种；
所述的其他填充剂为石蜡、芳烃油但不限于以上两种。
本发明的效果：在同样的配方和工艺条件下，本发明的白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料与没有甲基丙烯酸缩水甘油酯官能化的白炭黑/聚(衣康酸酯-异戊二烯)生物基弹性体复合材料相比，具有明显改善的白炭黑的分散及力学强度，同时降低了橡胶制品的滚动阻力，提高了其抗湿滑性，避免了硅烷偶联剂的引入，工艺简单，是一种很有应用前景的生物基“绿色轮胎”橡胶材料。
具体实施方式
实施例1
5℃下，在装有机械搅拌、氮气出入口、温度计和冷凝管的装置中，在氮气保护下，加入150克去离子水，5克油酸钾，0.5克硫酸亚铁，0.1克乙二胺四乙酸四钠，2克甲醛次硫酸钠，60克衣康酸二乙酯，30克异戊二烯，10克甲基丙烯酸缩水甘油酯，以400转/分的转速进行搅拌。1小时之后，加入0.1克引发剂过氧化氢异丙苯引发聚合，转速降为200转/分，反应10小时，得到聚(衣康酸二乙酯-异戊二烯-甲基丙烯酸缩水甘油酯)胶乳，将胶乳倒入质量分数为2％的氯化钠中进行破乳絮凝，得到聚(衣康酸二乙酯-异戊二烯-甲基丙烯酸缩水甘油酯)絮凝胶。将得到的聚(衣康酸二乙酯-异戊二烯-甲基丙烯酸缩水甘油酯) 絮凝胶依次用乙醇及水进行浸泡提纯，并在60℃鼓风烘箱中干燥24小时，得到聚(衣康酸二乙酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体。
用双辊开炼机，将100克上述得到的聚(衣康酸二乙酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体与50克高分散白炭黑833MP、1克石蜡、3克氧化锌、1克硬脂酸、2克防4010NA、2克促CZ、1克促M及1.5克硫磺混合均匀得到混炼胶，混炼胶在150℃下模压硫化制成白炭黑/聚(衣康酸二乙酯-异戊二烯-甲基丙烯酸缩水甘油酯)复合材料。
实施例2
10℃下，在装有机械搅拌、氮气出入口、温度计和冷凝管的装置中，在氮气保护下，加入300克去离子水，3.5克歧化松香酸钾，1.5克油酸钾，0.05克硫酸亚铁，0.1克乙二胺四乙酸四钠，0.2克甲醛次硫酸钠，78克衣康酸二丙酯，20克异戊二烯，2克甲基丙烯酸缩水甘油酯，以400转/分的转速进行搅拌。1小时之后，加入0.07克引发剂过氧化氢对孟烷引发聚合，转速降为200转/分，反应18小时，得到聚(衣康酸二丙酯-异戊二烯-甲基丙烯酸缩水甘油酯)胶乳，将胶乳倒入质量分数为1％的氯化钙中进行破乳絮凝，得到聚(衣康酸二丙酯-异戊二烯-甲基丙烯酸缩水甘油酯)絮凝胶。将得到的聚(衣康酸二丙酯-异戊二烯-甲基丙烯酸缩水甘油酯)絮凝胶依次用乙醇及水进行浸泡提纯，并在60℃鼓风烘箱中干燥24小时，得到聚(衣康酸二丙酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体。
用双辊开炼机，将100克上述得到的聚(衣康酸二丙酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体与40克高分散白炭黑VN3、5克氧化锌、1克硬脂酸、1.5克防4020、1克促CZ、1克促M及1.5克硫磺混合均匀得到混炼胶，混炼胶在150℃下模压硫化制成白炭黑/聚(衣康酸二丙酯-异戊二烯-甲基丙烯酸缩水甘油酯)复合材料。
实施例3
20℃下，在装有机械搅拌、氮气出入口、温度计和冷凝管的装置中，在氮气保护下，加入250克去离子水，2.5克十二烷基苯磺酸钠，0.04克乙二胺四乙酸铁钠盐，0.2克甲醛次硫酸钠，65克衣康酸二丁酯，30克异戊二烯，5克甲基丙烯酸缩水甘油酯，以400转/分的转速进行搅拌。1小时之后，加入0.05克引发剂叔丁基过氧化氢引发聚合，转速降为200转/分，反应12小时，得到聚(衣康酸二丁酯-异戊二烯-甲基丙烯酸缩水甘油酯)胶乳，将胶乳倒入乙醇中进行破乳絮凝，得到聚(衣康酸二丁酯-异戊二烯-甲基丙烯酸缩水甘油酯)絮凝胶。将得到的聚(衣康酸二丁酯-异戊二烯-甲基丙烯酸缩水甘油酯)絮凝胶依次用乙醇及水进行浸泡提纯，并在60℃鼓风烘箱中干燥24小时，得到聚(衣康酸二丁酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体。
用密炼机，将100克上述得到的聚(衣康酸二丁酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体与50克高分散白炭黑VN3、5克氧化锌、0.5克硬脂酸、1克防4010NA、1克促CZ、0.7克促M及1克硫磺混合均匀得到混炼胶，混炼胶在150℃下模压硫化制成白炭黑/聚(衣康酸二丁酯-异戊二烯-甲基丙烯酸缩水甘油酯)复合材料。
实施例4
25℃下，在装有机械搅拌、氮气出入口、温度计和冷凝管的装置中，在氮气保护下，加入400克去离子水，5克十二烷基磺酸钠，0.05克乙二胺四乙酸铁钠盐，0.2克甲醛次硫酸钠，67克衣康酸二异戊酯，30克异戊二烯，3克甲基丙烯酸缩水甘油酯，以400转/分的转速进行搅拌。1小时之后，加入0.05克引发剂叔丁基过氧化氢引发聚合，转速降为200转/分，反应24小时，得到聚(衣康酸二异戊酯-异戊二烯-甲基丙烯酸缩水甘油酯)胶乳，将胶乳倒入甲醇中进行破乳絮凝，得到聚(衣康酸二异戊酯-异戊二烯-甲基丙烯酸缩水甘油酯)絮凝胶。将得到的聚(衣康酸二异戊酯-异戊二烯-甲基丙烯酸缩水甘油酯)絮凝胶依次用乙醇及水进行浸泡提纯，并在60℃鼓风烘箱中干燥24小时，得到聚(衣康酸二异戊酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体。
用密炼机，将100克上述得到的聚(衣康酸二异戊酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体与70克高分散白炭黑833MP、5克氧化锌、1克硬脂酸、2克防4020、1克促CZ、1克促M及1克硫磺混合均匀得到混炼胶，混炼胶在150℃下模压硫化制成白炭黑/聚(衣康酸二异戊酯-异戊二烯-甲基丙烯酸缩水甘油酯)复合材料。
实施例5
30℃下，在装有机械搅拌、氮气出入口、温度计和冷凝管的装置中，在氮气保护下，加入300克去离子水，2克十二烷基苯磺酸钠，2克CO436，0.1克乙二胺四乙酸铁钠盐，0.5克甲醛次硫酸钠，55克衣康酸二己酯，40克异戊二烯，5克甲基丙烯酸缩水甘油酯，以400转/分的转速进行搅拌。1小时之后，加入0.1克引发剂过氧化氢异丙苯引发聚合，转速降为200转/分，反应20小时，得到聚(衣康酸二己酯-异戊二烯-甲基丙烯酸缩水甘油酯)胶乳，将胶乳倒入质量分数为1％的盐酸溶液中进行破乳絮凝，得到聚(衣康酸二己酯-异戊二烯-甲基丙烯酸缩水甘油酯)絮凝胶。将得到的聚(衣康酸二己酯-异戊二烯-甲基丙烯酸缩水甘油酯)絮凝胶依次用乙醇及水进行浸泡提纯，并在60℃鼓风烘箱中干燥24小时，得到聚(衣康酸二己酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体。
用双辊开炼机，将100克上述得到的聚(衣康酸二己酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体与70克高分散白炭黑833MP、6克氧化锌、1克硬脂酸、0.5克防4010NA、 2克促CZ、1克促M及1.5克硫磺混合均匀得到混炼胶，混炼胶在150℃下模压硫化制成白炭黑/聚(衣康酸二己酯-异戊二烯-甲基丙烯酸缩水甘油酯)复合材料。
对比例1
5℃下，在装有机械搅拌、氮气出入口、温度计和冷凝管的装置中，在氮气保护下，加入150克去离子水，5克油酸钾，0.5克硫酸亚铁，0.1克乙二胺四乙酸四钠，2克甲醛次硫酸钠，70克衣康酸二乙酯，30克异戊二烯，以400转/分的转速进行搅拌。1小时之后，加入0.1克引发剂过氧化氢异丙苯引发聚合，转速降为200转/分，反应10小时，得到聚(衣康酸二乙酯-异戊二烯)胶乳，将胶乳倒入质量分数为2％的氯化钠中进行破乳絮凝，得到聚(衣康酸二乙酯-异戊二烯)絮凝胶。将得到的聚(衣康酸二乙酯-异戊二烯)絮凝胶依次用乙醇及水进行浸泡提纯，并在60℃鼓风烘箱中干燥24小时，得到聚(衣康酸二乙酯-异戊二烯)生物基弹性体。
用双辊开炼机，将100克上述得到的聚(衣康酸二乙酯-异戊二烯)生物基弹性体与50克高分散白炭黑833MP、1克石蜡、3克氧化锌、1克硬脂酸、2克防4010NA、2克促CZ、1克促M及1.5克硫磺混合均匀得到混炼胶，混炼胶在150℃下模压硫化制成白炭黑/聚(衣康酸二乙酯-异戊二烯)复合材料。
对比例2
10℃下，在装有机械搅拌、氮气出入口、温度计和冷凝管的装置中，在氮气保护下，加入300克去离子水，3.5克歧化松香酸钾，1.5克油酸钾，0.05克硫酸亚铁，0.1克乙二胺四乙酸四钠，0.2克甲醛次硫酸钠，80克衣康酸二丙酯，20克异戊二烯，以400转/分的转速进行搅拌。1小时之后，加入0.07克引发剂过氧化氢对孟烷引发聚合，转速降为200转/分，反应18小时，得到聚(衣康酸二丙酯-异戊二烯)胶乳，将胶乳倒入质量分数为1％的氯化钙中进行破乳絮凝，得到聚(衣康酸二丙酯-异戊二烯)絮凝胶。将得到的聚(衣康酸二丙酯-异戊二烯)絮凝胶依次用乙醇及水进行浸泡提纯，并在60℃鼓风烘箱中干燥24小时，得到聚(衣康酸二丙酯-异戊二烯)生物基弹性体。
用双辊开炼机，将100克上述得到的聚(衣康酸二丙酯-异戊二烯)生物基弹性体与40克高分散白炭黑VN3、5克氧化锌、1克硬脂酸、1.5克防4020、1克促CZ、1克促M及1.5克硫磺混合均匀得到混炼胶，混炼胶在150℃下模压硫化制成白炭黑/聚(衣康酸二丙酯-异戊二烯)复合材料。
对比例3
20℃下，在装有机械搅拌、氮气出入口、温度计和冷凝管的装置中，在氮气保护下，加 入250克去离子水，2.5克十二烷基苯磺酸钠，0.04克乙二胺四乙酸铁钠盐，0.2克甲醛次硫酸钠，70克衣康酸二丁酯，30克异戊二烯，以400转/分的转速进行搅拌。1小时之后，加入0.05克引发剂叔丁基过氧化氢引发聚合，转速降为200转/分，反应12小时，得到聚(衣康酸二丁酯-异戊二烯)胶乳，将胶乳倒入乙醇中进行破乳絮凝，得到聚(衣康酸二丁酯-异戊二烯)絮凝胶。将得到的聚(衣康酸二丁酯-异戊二烯)絮凝胶依次用乙醇及水进行浸泡提纯，并在60℃鼓风烘箱中干燥24小时，得到聚(衣康酸二丁酯-异戊二烯)生物基弹性体。
用密炼机，将100克上述得到的聚(衣康酸二丁酯-异戊二烯)生物基弹性体与50克高分散白炭黑VN3、5克氧化锌、0.5克硬脂酸、1克防4010NA、1克促CZ、0.7克促M及1克硫磺混合均匀得到混炼胶，混炼胶在150℃下模压硫化制成白炭黑/聚(衣康酸二丁酯-异戊二烯)复合材料。
对比例4
25℃下，在装有机械搅拌、氮气出入口、温度计和冷凝管的装置中，在氮气保护下，加入400克去离子水，5克十二烷基磺酸钠，0.05克乙二胺四乙酸铁钠盐，0.2克甲醛次硫酸钠，70克衣康酸二异戊酯，30克异戊二烯，以400转/分的转速进行搅拌。1小时之后，加入0.05克引发剂叔丁基过氧化氢引发聚合，转速降为200转/分，反应24小时，得到聚(衣康酸二异戊酯-异戊二烯)胶乳，将胶乳倒入甲醇中进行破乳絮凝，得到聚(衣康酸二异戊酯-异戊二烯)絮凝胶。将得到的聚(衣康酸二异戊酯-异戊二烯)絮凝胶依次用乙醇及水进行浸泡提纯，并在60℃鼓风烘箱中干燥24小时，得到聚(衣康酸二异戊酯-异戊二烯)生物基弹性体。
用密炼机，将100克上述得到的聚(衣康酸二异戊酯-异戊二烯)生物基弹性体与70克高分散白炭黑833MP、5克氧化锌、1克硬脂酸、2克防4020、1克促CZ、1克促M及1克硫磺混合均匀得到混炼胶，混炼胶在150℃下模压硫化制成白炭黑/聚(衣康酸二异戊酯-异戊二烯)复合材料。
对比例5
30℃下，在装有机械搅拌、氮气出入口、温度计和冷凝管的装置中，在氮气保护下，加入300克去离子水，2克十二烷基苯磺酸钠，2克CO436，0.1克乙二胺四乙酸铁钠盐，0.5克甲醛次硫酸钠，60克衣康酸二己酯，40克异戊二烯，以400转/分的转速进行搅拌。1小时之后，加入0.1克引发剂过氧化氢异丙苯引发聚合，转速降为200转/分，反应20小时，得到聚(衣康酸二己酯-异戊二烯)胶乳，将胶乳倒入质量分数为1％的盐酸溶液中进行破乳 絮凝，得到聚(衣康酸二己酯-异戊二烯)絮凝胶。将得到的聚(衣康酸二己酯-异戊二烯)絮凝胶依次用乙醇及水进行浸泡提纯，并在60℃鼓风烘箱中干燥24小时，得到聚(衣康酸二己酯-异戊二烯)生物基弹性体。
用双辊开炼机，将100克上述得到的聚(衣康酸二己酯-异戊二烯)生物基弹性体与70克高分散白炭黑833MP、6克氧化锌、1克硬脂酸、0.5克防4010NA、2克促CZ、1克促M及1.5克硫磺混合均匀得到混炼胶，混炼胶在150℃下模压硫化制成白炭黑/聚(衣康酸二己酯-异戊二烯)复合材料。
对比例6
20℃下，在装有机械搅拌、氮气出入口、温度计和冷凝管的装置中，在氮气保护下，加入250克去离子水，2.5克十二烷基苯磺酸钠，0.04克乙二胺四乙酸铁钠盐，0.2克甲醛次硫酸钠，70克衣康酸二丁酯，30克异戊二烯，以400转/分的转速进行搅拌。1小时之后，加入0.05克引发剂叔丁基过氧化氢引发聚合，转速降为200转/分，反应12小时，得到聚(衣康酸二丁酯-异戊二烯)胶乳，将胶乳倒入乙醇中进行破乳絮凝，得到聚(衣康酸二丁酯-异戊二烯)絮凝胶。将得到的聚(衣康酸二丁酯-异戊二烯)絮凝胶依次用乙醇及水进行浸泡提纯，并在60℃鼓风烘箱中干燥24小时，得到聚(衣康酸二丁酯-异戊二烯)生物基弹性体。
用密炼机，将100克上述得到的聚(衣康酸二丁酯-异戊二烯)生物基弹性体与50克高分散白炭黑VN3、5克硅烷偶联剂TESPT、5克氧化锌、0.5克硬脂酸、1克防4010NA、1克促CZ、0.7克促M及1克硫磺混合均匀得到混炼胶，混炼胶在150℃下模压硫化制得橡胶制品。
表1为本发明实施例与对比例制备的复合材料的性能测试结果。
Figure PCTCN2016102900-appb-000001
Figure PCTCN2016102900-appb-000002
(注：表中数据均采用常规的国家标准测试方法获得)
从表1的对比数据可以看出，本发明白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料具有较好的机械性能，而且与没有加入甲基丙烯酸缩水甘油酯的复合材料相比，加入了甲基丙烯酸缩水甘油酯的白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)具有较高的拉伸强度及模量。在橡胶领域，普遍认为0℃的tanδ数值可以在一定程度上反映轮胎的抗湿滑性能，而60℃的tanδ数值可以在一定程度上反映轮胎的滚动阻力。甲基丙烯酸缩水甘油酯的引入，提高了复合材料的抗湿滑性，降低了复合材料的滚动阻力。本发明白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料的制备避免了硅烷偶联剂的引入，工艺简单且无VOC生成，是一种很有应用前景的绿色生物基“绿色轮胎”橡胶材料。
Figure PCTCN2016102900-appb-000003
图1.白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料透射电镜照片

Claims (2)

  1. 一种无需硅烷偶联剂的白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料的制备方法，其特征在于步骤如下：
    A：聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体的制备
    首先，将30～90wt.％的衣康酸酯、10～70wt.％的异戊二烯和0.5～20wt.％的甲基丙烯酸缩水甘油酯进行混合(衣康酸酯、异戊二烯及甲基丙烯酸缩水甘油酯为单体，三者总和的百分比为100％)，加入单体总质量50～500％的去离子水做分散剂，0.5～10％的乳化剂，0～5％的螯合剂，0.01～5％的还原剂和0.01～5％的二次还原剂，0.01～5％的引发剂，在5～30℃的条件下，反应6～72小时，得到聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)胶乳，用絮凝剂破乳干燥后得到聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)絮凝胶，聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)絮凝胶依次用乙醇和水进行浸泡提纯，并在60℃鼓风烘箱中干燥24小时，得到聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体；
    所述的乳化剂为下列物质中的一种或他们的混合物：油酸钾、油酸钠、歧化松香酸钾、企划松香酸钠、十二烷基磺酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、乙氧基化烷基酚硫酸铵(CO436)；
    所述的还原剂为乙二胺四乙酸(EDTA)铁钠盐或硫酸亚铁；
    所述的二次还原剂为甲醛次硫酸钠或多乙烯基多胺；
    所述的螯合剂为乙二胺四乙酸二钠(EDTA-2Na)、乙二胺四乙酸四钠(EDTA-4Na)或乙二胺四乙酸铁钠(EDTA-Fe·Na)；
    所述的引发剂为叔丁基过氧化氢、过氧化异丙苯或过氧化氢对孟烷；
    所述的絮凝剂采用质量浓度1～10％的氯化钙水溶液、1～10％的氯化钠水溶液、1～5％的盐酸溶液、1～5％的硫酸溶液、乙醇或甲醇。
    B：白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料的制备
    取上述聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体100质量份，与10份以上白炭黑、0.5～3.0份硫磺、0.5～3份防老剂、0.5～10份氧化锌、0.5～5份硬脂酸、0.5～5份促进剂、0～30份其他填充剂通过开炼机或密炼机共混，在130～170℃下模压硫化制成白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料；
    所述的白炭黑为高分散白炭黑，如VN3、833MP但不限于以上两种；
    所述的防老剂为N-异丙基-N’-苯基对苯二胺(防4010NA)、N-(1.3-二甲基丁基)-N'-苯基- 对苯二胺(防4020)但不限于以上两种；
    所述的促进剂为2-巯醇基苯并噻唑(促M)、N-环已基-2-苯并噻唑次磺酰胺(促CZ)但不限于以上两种。
    所述的其它填充剂为石蜡、芳烃油但不限于以上两种。
  2. 根据权利要求1所述的一种无需硅烷偶联剂的白炭黑/聚(衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯)生物基弹性体复合材料，衣康酸酯包括但不仅限于：衣康酸二甲酯、衣康酸二乙酯、衣康酸二丙酯、衣康酸二异丙酯、衣康酸二丁酯、衣康酸二异丁酯、衣康酸二戊酯、衣康酸二异戊酯、衣康酸二己酯、衣康酸二庚酯或衣康酸二辛酯。
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CN109320658B (zh) * 2018-07-17 2021-05-25 湖北大学 一种衣康酸酯生物基耐热油弹性体及其制备方法
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03277602A (ja) * 1990-03-28 1991-12-09 Japan Synthetic Rubber Co Ltd 共重合体ラテックスの製造方法
CN1665870A (zh) * 2002-07-05 2005-09-07 埃克森美孚化学专利公司 官能化的弹性体纳米复合材料
EP1874864A1 (en) * 2005-04-12 2008-01-09 General Electric Company Process for making a thermoplastic vulcanizate composition
CN102558578A (zh) * 2011-12-26 2012-07-11 北京化工大学 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
US20120282836A1 (en) * 2011-05-03 2012-11-08 Tesa Se Adhesive tape for jacketing elongate material such as especially cable looms and jacketing method
CN103224632A (zh) * 2013-03-22 2013-07-31 北京化工大学 一种聚(衣康酸酯/异戊二烯)生物基弹性体/层状硅酸盐纳米复合材料制备方法
CN104725756A (zh) * 2014-09-06 2015-06-24 北京化工大学 一种衣康酸酯/异戊二烯共聚物型生物基弹性体胎面胶及制备方法
CN105622841A (zh) * 2015-12-10 2016-06-01 北京化工大学 白炭黑/聚（衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯）生物基弹性体复合材料的制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4094831A (en) * 1976-10-22 1978-06-13 The Goodyear Tire & Rubber Company Green strength of elastomers
JP3674954B2 (ja) * 1993-03-02 2005-07-27 Ｊｓｒ株式会社 回路基板形成用アルカリ現像型液状フォトレジスト組成物
JP5457054B2 (ja) * 2009-03-13 2014-04-02 株式会社ブリヂストン ゴム組成物、セメント組成物、ゴム組成物同士の接着方法及びタイヤ
CN102558437B (zh) * 2011-12-26 2013-11-13 北京化工大学 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
WO2015075971A1 (ja) * 2013-11-19 2015-05-28 住友ゴム工業株式会社 ゴム組成物及び該ゴム組成物を用いて作製したトレッドを有する空気入りタイヤ
CN103937057A (zh) * 2014-04-28 2014-07-23 北京化工大学 一种淀粉改性白炭黑/橡胶复合填料的制备方法
CN103951924A (zh) * 2014-05-14 2014-07-30 北京化工大学 一种衣康酸酯基生物工程橡胶阻尼材料及其制备方法
CN104945817B (zh) * 2015-06-15 2017-12-29 北京化工大学 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

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03277602A (ja) * 1990-03-28 1991-12-09 Japan Synthetic Rubber Co Ltd 共重合体ラテックスの製造方法
CN1665870A (zh) * 2002-07-05 2005-09-07 埃克森美孚化学专利公司 官能化的弹性体纳米复合材料
EP1874864A1 (en) * 2005-04-12 2008-01-09 General Electric Company Process for making a thermoplastic vulcanizate composition
US20120282836A1 (en) * 2011-05-03 2012-11-08 Tesa Se Adhesive tape for jacketing elongate material such as especially cable looms and jacketing method
CN102558578A (zh) * 2011-12-26 2012-07-11 北京化工大学 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
CN103224632A (zh) * 2013-03-22 2013-07-31 北京化工大学 一种聚(衣康酸酯/异戊二烯)生物基弹性体/层状硅酸盐纳米复合材料制备方法
CN104725756A (zh) * 2014-09-06 2015-06-24 北京化工大学 一种衣康酸酯/异戊二烯共聚物型生物基弹性体胎面胶及制备方法
CN105622841A (zh) * 2015-12-10 2016-06-01 北京化工大学 白炭黑/聚（衣康酸酯-异戊二烯-甲基丙烯酸缩水甘油酯）生物基弹性体复合材料的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3323841A4 *

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US10494514B2 (en) 2019-12-03
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