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 PDFInfo
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- 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
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- 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
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- 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
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- 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
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- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/309—Sulfur containing acids
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- 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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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
Description
Claims (2)
- 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。
- 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。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16872237.9A EP3323841B1 (en) | 2015-12-10 | 2016-10-21 | White carbon black/poly(itaconate-isoprene-glycidyl methacrylate) bio-based elastomer composite material free of silane coupling agent, and preparation method therefor |
JP2017559814A JP6628813B2 (ja) | 2015-12-10 | 2016-10-21 | シランカップリングを不要とするシリカ/ポリ(イタコナート−イソプレン−グリシジルメタクリレート)エラストマー複合材料及びその調製方法 |
US15/761,054 US10494514B2 (en) | 2015-12-10 | 2016-11-19 | Method of preparing bio-based elastomer composition comprising silica and polydibutyl itaconate-ter-isoprene-ter-glycidyl methacrylate |
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CN107189307A (zh) * | 2017-07-19 | 2017-09-22 | 盐城易宝路轮胎有限公司 | 一种轮胎用胎面胶及其制备 |
CN107141681A (zh) * | 2017-07-19 | 2017-09-08 | 盐城易宝路轮胎有限公司 | 一种三基体生物工程橡胶及其制备方法 |
CN109929159B (zh) * | 2017-12-15 | 2021-08-03 | 中国石油化工股份有限公司 | 用于车胎胎面的橡胶组合物和硫化橡胶及其制备方法和应用 |
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 |
CN113402674B (zh) * | 2021-06-30 | 2022-07-22 | 山西省应用化学研究所(有限公司) | 墙纸印刷用水性介质及其制备方法 |
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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