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WO2002033003A1 - Fully cured thermoplastic elastomer, process for its manufacture and applications thereof - Google Patents

Fully cured thermoplastic elastomer, process for its manufacture and applications thereof Download PDF

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Publication number
WO2002033003A1
WO2002033003A1 PCT/CN2001/000972 CN0100972W WO0233003A1 WO 2002033003 A1 WO2002033003 A1 WO 2002033003A1 CN 0100972 W CN0100972 W CN 0100972W WO 0233003 A1 WO0233003 A1 WO 0233003A1
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WIPO (PCT)
Prior art keywords
rubber
fully vulcanized
thermoplastic elastomer
powder
fully
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/CN2001/000972
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English (en)
French (fr)
Inventor
Jinliang Qiao
Yiqun Liu
Xiaohong Zhang
Jianming Gao
Genshuan Wei
Shijun Zhang
Zhihai Song
Jiuqiang Li
Dechuan Zhuang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to AU2001295382A priority Critical patent/AU2001295382A1/en
Priority to US10/049,233 priority patent/US7491757B2/en
Priority to JP2002536377A priority patent/JP5420134B2/ja
Priority to EP01975972A priority patent/EP1279702A4/en
Publication of WO2002033003A1 publication Critical patent/WO2002033003A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers

Definitions

  • the present invention relates to a thermoplastic elastomer. Furthermore, the present invention relates to a fully vulcanized thermoplastic elastomer prepared by a blending method, and a preparation method and application of the fully vulcanized thermoplastic elastomer.
  • Fully vulcanized thermoplastic elastomer is a new material developed in the 1980s. It is prepared by mechanical blending of elastomer and rigid plastic under certain conditions. It has the characteristics of both plastic and rubber: it shows high elasticity of rubber at normal temperature, and can be plasticized at high temperature.
  • the fully vulcanized thermoplastic elastomer is in its phase state a fully crosslinked rubber phase dispersed in a plastic matrix. Because the rubber phase is already crosslinked, the strength, elasticity, heat resistance and compression set resistance of fully vulcanized thermoplastic elastomers are greatly improved compared to uncrosslinked thermoplastic elastomers. At the same time, the chemical resistance and processing stability have also been significantly improved, and the blending ratio of rubber and plastic can be changed within a wide range, giving the material more room for adjustment in performance.
  • thermoplastic elastomers are prepared by a dynamic vulcanization method.
  • Synthetic Rubber Industry No. 5 of 1986, pages 361 to 364, "Dynamic fully vulcanized ethylene-propylene rubber / polyolefin blend thermoplastic elastomer”; the scientific and technological journal “Progress in Chemical Industry”, No. 5 of 1987 Pages 16 to 19, “Development of Polyolefin Type Fully Vulcanized Thermoplastic Elastomers”; Zhu Yujun, eds. "Mechanical Modification of Elastomers", Beijing Science and Technology Press, pages 335 to 395 (1992).
  • the so-called dynamic vulcanization method refers to the process of vulcanization reaction by the use of cross-linking agents and strong shear stress when rubber and plastic are blended.
  • the key technology is that the vulcanization cannot be stopped before vulcanization is completed, and there must be sufficient vulcanizing agent. Dosage to ensure that the rubber can be completely cured.
  • the particle size of the rubber phase in the fully vulcanized thermoplastic elastomer prepared by the dynamic vulcanization method is mainly determined by the balance between mechanical blending shear and chemical crosslinking reaction, so the rubber phase particle size is difficult to be very small.
  • the average particle diameter of the rubber phase of the fully vulcanized thermoplastic elastomer prepared by the dynamic vulcanization method is 1 ⁇ to 2 ⁇ .
  • the object of the present invention is to provide a rubber phase with a particle size of 0.02 ⁇ ⁇ 1 ⁇ fully vulcanized thermoplastic elastomer.
  • Another object of the present invention is to provide a fully vulcanized thermoplastic elastomer having a rubber-like shape and a spherical shape.
  • This method uses general rubber-plastic blending equipment and a single process tube, and has good controllability of the particle size, particle size distribution, and degree of crosslinking of the rubber phase.
  • thermoplastic elastomer for preparing various shaped articles.
  • the dispersed phase of the fully vulcanized thermoplastic elastomer of the present invention that is, the rubber phase is flat.
  • the average particle diameter is generally 0.02 ⁇ to 1 ⁇ , preferably 0.05 ⁇ to 0.5 ⁇ , and more preferably 0.05 ⁇ to 0.2 ⁇ .
  • the outer shape of the rubber phase of the fully vulcanized thermoplastic elastomer of the present invention is a regular spherical shape.
  • the particle diameter of the rubber phase is from 0.02 ⁇ to 1 ⁇ , preferably from 0.05 ⁇ to 0.5 ⁇ , and more preferably from 0.05 ⁇ to 0.2 ⁇ .
  • the weight ratio of the rubber phase to the plastic body is preferably 30:70 to 75:25, and more preferably 50:50 to 75:25.
  • the gel content of the fully vulcanized thermoplastic elastomer rubber phase is 60% or more by weight ratio, and preferably 75% or more.
  • rubber of the rubber phase in the fully vulcanized thermoplastic elastomer of the present invention may be, for example, a fully vulcanized natural rubber, styrene-butadiene rubber, carboxyl styrene-butadiene rubber, nitrile rubber, carboxyl-nitrile rubber, neoprene, Polybutadiene, acrylate rubber, styrene butadiene rubber, isoprene rubber, butyl rubber, ethylene propylene rubber, polysulfide rubber, acrylate-butadiene rubber, silicone rubber, polyurethane rubber or fluoro rubber.
  • a fully vulcanized natural rubber styrene-butadiene rubber, carboxyl styrene-butadiene rubber, nitrile rubber, carboxyl-nitrile rubber, neoprene, Polybutadiene, acrylate rubber, styrene butadiene rubber, isopren
  • the main plastic of the fully vulcanized thermoplastic elastomer includes at least one of the following polymers and copolymers thereof: polyamide, polypropylene, polyethylene, polyvinyl chloride, polyurethane, polyester, polycarbonate, polyoxymethylene, polymer Styrene, polyphenylene ether, polyphenylene sulfide, polyimide, polysulfone, etc.
  • the preparation method of the fully vulcanized thermoplastic elastomer of the present invention is: a fully vulcanized thermoplastic elastomer is prepared by blending and granulating a fully vulcanized powder rubber and a plastic through a rubber-plastic blending device by using a common blending method in rubber and plastic processing.
  • the average particle diameter of the fully vulcanized powder rubber used therein depends on the particle diameter of the rubber phase in the fully vulcanized thermoplastic elastomer, and is generally 0.02 ⁇ to 1 ⁇ , preferably 0.05 ⁇ to 0.5 ⁇ , and more preferably 0.05 ⁇ to 0.2 ⁇ .
  • the weight ratio of the fully vulcanized powder rubber to the plastic is preferably 30:70 to 75:25, and more preferably 50:50 to 75:25.
  • powder rubber and plastic can be blended and extruded at one time, or a part of powder rubber and plastic can be blended to form a master batch, and then blended and extruded with the remaining powder rubber.
  • the host plastic may include at least one of the following polymers and copolymers thereof: polyamide, polypropylene, polyethylene, polyvinyl chloride, polyurethane, polyester, polycarbonate , Polyoxymethylene, polystyrene, polyphenylene ether, polyphenylene sulfide, polyimide or polysulfone, etc.
  • the fully vulcanized powder rubber in the method of the present invention may be a powder rubber prepared in accordance with Chinese patent 99125530.5 (the disclosure of which is incorporated herein in its entirety) filed by the inventor on December 3, 1999, and may include the following fully vulcanized powder rubbers: At least one: fully vulcanized powder natural rubber, fully vulcanized powder styrene-butadiene rubber, fully vulcanized powder styrene-butadiene rubber, fully vulcanized powder nitrile rubber, fully vulcanized powder carboxyl nitrile rubber, fully vulcanized powder polybutadiene rubber, Fully vulcanized powder neoprene, fully vulcanized powder silicone rubber, fully vulcanized powder acrylate rubber, fully vulcanized powder styrene-butadiene rubber, fully vulcanized powder isoprene rubber, fully vulcanized powder butyl rubber, fully vulcanized powder ethylene propylene rubber, Fully densified
  • the fully vulcanized powder rubber used in the method of the present invention is obtained by vulcanizing a corresponding rubber latex by irradiation.
  • a fully vulcanized powder rubber of the present invention can be prepared by using a commercially available or self-made rubber latex as a raw material, adding or not adding a crosslinking assistant, and irradiating it with high-energy rays to completely vulcanize it.
  • the high-energy ray source may be selected from a cobalt source, X-ray, ultraviolet, or high-energy electron accelerator, preferably a cobalt source.
  • the radiation dose is related to the type and formula of the latex.
  • the radiation dose should be such that the gel content of the fully vulcanized rubber obtained after vulcanization of the rubber latex reaches 60% by weight or more, preferably 75% by weight or more, and more preferably 90% by weight or more.
  • the irradiation dose may be from 0.1 to 30 Mrad, preferably from 0.5 to 20 Mrad.
  • the irradiated latex can be dried to obtain a fully vulcanized powder rubber having substantially the same size as the rubber particles in the latex.
  • the drying process can be performed by spray dryer or precipitation drying method. If it is performed by spray dryer, the inlet temperature can be controlled at 100 ⁇ 200C and the outlet temperature can be controlled. To control between 20 ⁇ 801 ;.
  • the rubber latex material used can be selected from natural rubber latex, styrene-butadiene rubber latex, carboxylated styrene-butadiene rubber latex, nitrile rubber latex, carboxylated nitrile rubber latex, and neoprene Latex, polybutadiene rubber latex, acrylic rubber latex, styrene-butadiene rubber latex, isoprene rubber latex, butyl rubber latex, ethylene-propylene rubber latex, polysulfide rubber latex, acrylate-butadiene rubber latex, Silicone rubber emulsion, polyurethane rubber latex or fluoro rubber latex.
  • the particle size of the rubber particles can vary depending on the application.
  • the cross-linking assistant used may be a mono-functional cross-linking assistant, a di-functional cross-linking assistant, a tri-functional cross-linking assistant, a tetra-functional cross-linking assistant or a multi-functional cross-linking assistant, and any combination thereof.
  • Examples of the monofunctional crosslinking assistant include, but are not limited to, (meth) octyl acrylate, (meth) isooctyl acrylate, (meth) glycidyl propionate; the difunctional group
  • Examples of the crosslinking assistant include, but are not limited to, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (methyl) ) Acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, divinylbenzene;
  • Examples of trifunctional cross-linking assistants include (but are not limited to) Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate; examples of the tetrafunctional crosslinking assistant include (but are not limited to) pentaerythrito
  • crosslinking auxiliaries can be used in any combination as long as they help the radiation dredging under irradiation.
  • the amount of these crosslinking auxiliaries varies with the type and formula of the rubber latex, and is generally 0.1 to 10% by weight of the weight of pure rubber, preferably 0.5 to 9% by weight. More preferably, it is 0.7 to 7% by weight.
  • the blending temperature of the materials is the blending temperature used in ordinary plastic processing, which can be determined according to the melting temperature of the basic plastic. It should be selected within the range that ensures that the base plastic is completely melted without decomposing the plastic. .
  • conventional additives and compatibilizers for plastics processing can be added to the blended materials in appropriate amounts.
  • the rubber blending equipment used in the method of the present invention may be an open mill, an internal mixer, a single screw extruder, a twin screw extruder, or the like.
  • the particle size of the rubber phase of the fully vulcanized thermoplastic elastomer of the present invention can be controlled than that of the rubber phase of the fully vulcanized thermoplastic elastomer prepared by the conventional dynamic vulcanization method, so the tensile strength and elongation at break are greatly improved. Good appearance and good processability.
  • the rubber phase of the fully vulcanized thermoplastic body of the present invention has a regular spherical shape, which is advantageous for properties such as rheology and processing.
  • the fully vulcanized thermoplastic elastomer of the present invention does not need to be added with a vulcanizing agent during preparation, so it is easy to obtain a light-colored fully vulcanized thermoplastic elastomer product, and the fully vulcanized thermoplastic elastomer of the present invention is also easily made into various dyed products.
  • the method of the present invention uses ordinary rubber-plastic blending equipment and is prepared by a common blending extrusion method, so the process is simple, the equipment cost is low, the operation controllability is good, and it is suitable for the requirements of industrialized mass production.
  • the fully vulcanized thermoplastic elastomer of the present invention has excellent properties and can be used to prepare various molded products such as hoses, bellows, gaskets (pieces), joints, electrical products, auto parts, building materials, and sports equipment. After the flame retardant modification of this fully vulcanized thermoplastic elastomer, the flame retardant products will have larger application fields.
  • the particle size of the rubber phase in the fully vulcanized thermoplastic elastomer was measured using a conventional transmission electron microscope method.
  • FIG. 1 is a transmission electron microscope photograph of the sample obtained in Example 2.
  • a fully vulcanized styrene-butadiene powder rubber with an average particle size of about 0.1 ⁇ m (in the styrene-butadiene-50 emulsion provided by the Lanhua Latex Development Center) was added with a crosslinking assistant, trimethylol, at 3% of the dry mass of the styrene-butadiene emulsion.
  • the irradiation dose is 2.5Mrad, which is obtained after spray drying
  • polypropylene Yanshan Petrochemical, brand 1300
  • Irganox 1010 produced by Ciba-Geigy, Switzerland
  • a total weight of 0.5% of rubber and polypropylene was extruded and granulated with a ZSK-25 twin-screw extruder from WP, Germany.
  • the temperatures of the extruder sections were: 170 !, 190, 190 * C, 190 ° C, 190t !, and 195 ⁇ (head temperature).
  • the obtained pellets were analyzed, and the average particle diameter of the rubber phase in the thermoplastic elastomer was measured to be about 0.1 ⁇ m, and the shape was spherical.
  • thermoplastic elastomer has a whiteness value of 35.57 (GB 2913-88), which can be easily dyed into various colored products.
  • a fully vulcanized styrene-butadiene powder rubber (the same as in Example 1) with an average particle size of about 0.1 ⁇ m and polybenzyl ethylene (Yanshan Petrochemical, grade 666D) were mixed at a weight ratio of 70/30, and then based on the butadiene powder rubber And polybenzyl ethylene 0.5% antioxidant Irganox 1010, extruded and granulated by ZSK-25 twin-screw extruder of German WP company, the temperature of each section of the extruder is: 170 ° C, 185, 185 , 185 185 and (head temperature).
  • the obtained pellets were analyzed, and the average particle diameter of the rubber phase in the thermoplastic elastomer was measured to be about 0.1 ⁇ m, and the shape was spherical.
  • Example 2 The polyphenylenesulfonate in Example 2 was changed to high-impact polystyrene (Yanshan Petrochemical, grade 492J), and the rest were the same as in Example 2.
  • the obtained pellets were analyzed, and the average particle diameter of the rubber phase in the thermoplastic elastomer was measured to be about 0.1 ⁇ m, and the shape was spherical.
  • the results of the measured fully vulcanized styrene-butadiene rubber / high impact polystyrene thermoplastic elastomers are shown in Table 1.
  • Example 4 The results of the measured fully vulcanized styrene-butadiene rubber / high impact polystyrene thermoplastic elastomers are shown in Table 1.
  • Example 5 The polypropylene (brand 1300) in Example 1 was changed to polypropylene (Yanshan Petrochemical, brand 1740). The rest are the same as in Example 1. The obtained pellets were analyzed, and the average particle diameter of the rubber phase in the thermoplastic elastomer was measured to be about 0.1 ⁇ m, and the shape was spherical. The results of the measured fully vulcanized styrene-butadiene rubber / polypropylene thermoplastic elastomer are shown in Table 1.
  • Example 5 The results of the measured fully vulcanized styrene-butadiene rubber / polypropylene thermoplastic elastomer are shown in Table 1. Example 5
  • a fully vulcanized carboxylated styrene-butadiene powder rubber with an average particle size of about 0.15 ⁇ m (in the brand of XSBRL-54B1 carboxylated styrene-butadiene emulsion produced by Yanshan Petrochemical) was mixed into the crosslinking aid acrylic acid at 3% of the dry mass of the carboxylated styrene-butadiene emulsion
  • the irradiation dose is 2.5Mrad, which is obtained after spray drying
  • nylon 6 (1013B produced by Ube, Japan) is mixed at a weight ratio of 75/25, and then carboxylated styrene-butadiene powder rubber is added.
  • nylon 6 with 0.5% of total antioxidant Irganox 1010 extruded and granulated with ZSK-25 twin-screw extruder from WP, Germany.
  • the temperature of each section of the extruder is: 210 ° C, 225 ° C, 225, 225. 230 ° C and 225 "C (head temperature).
  • the obtained pellets were analyzed, and the average particle diameter of the rubber phase in the thermoplastic elastomer was measured to be about 0.15 ⁇ , and the shape was spherical.
  • Example 7 Except that the fully vulcanized carboxylated styrene-butadiene powder rubber and nylon 6 were mixed at a weight ratio of 50/50, the rest were the same as in Example 5. The obtained pellets were analyzed, and the average particle diameter of the rubber phase in the thermoplastic elastomer was measured to be about 0.15 ⁇ , and the shape was spherical. The measured results of the fully densified carboxylated butadiene rubber / nylon 6 thermoplastic elastomer are shown in Table 1.
  • Example 5 The same fully vulcanized styrene-butadiene powder rubber and nylon 6 as in Example 5 were mixed at a weight ratio of 70/30 and extruded and pelletized on a Brabender single-screw extruder.
  • the extruder temperature was 160, 190, 230 , 225 ° C.
  • the obtained pellets were analyzed, and the average particle diameter of the rubber phase in the thermoplastic elastomer was measured to be about 0.15 ⁇ , and the shape was spherical.
  • a fully vulcanized styrene-butadiene powder rubber having an average particle size of about 0.15 ⁇ (the same as that described in Example 5 except that the irradiation dose was 10 OMrad) and Nylon 6 (said by Ube Industries Ltd. 1013B) at 40/30 Weight ratio, and then add 0.7% antioxidant Irganox 1010 based on the total weight of carboxylated styrene-butadiene powder rubber and nylon 6, extruded and granulated on a Brabender single-screw extruder.
  • the extruder temperature is 160, 190, 230, 225t :.
  • the obtained pellets are mixed with the aforementioned carboxylated styrene-butadiene powder rubber at a weight ratio of 70/30, and the final weight ratio of the carboxylic styrene-butadiene powder rubber to nylon 6 is 70/30.
  • the obtained pellets were analyzed, and the rubber phase in the thermoplastic elastomer was measured. The average particle diameter is about 0.15 ⁇ , and the shape is spherical.
  • a cross-linking aid was added to a fully vulcanized carboxylated nitrile powder rubber having an average particle size of about 0.05 ⁇ (in a carboxylated butyronitrile emulsion of the brand XNBRL produced by the Blue Rubber Latex Research Center) at 3% of the dry mass of the carboxylated nitrile emulsion
  • the irradiation dose was lOMrad, obtained after spray drying) and nylon 6 (1013B produced by Ube, Japan) were mixed at a weight ratio of 70/30.
  • Carboxynitrile powder rubber and nylon 6 0.5% total weight Irganox 1010 were extruded and granulated by ZSK-25 type silent screw extruder from WP, Germany.
  • the temperature of each section of the extruder was 210 ° C. :, 225 ° C, 225 ° C ;, 225 ° C, 230 and 225 ° C (head temperature).
  • the obtained pellets were analyzed, and the average particle diameter of the rubber phase in the thermoplastic elastomer was measured to be about 0.05 m, and the shape was spherical.
  • the obtained sample was rolled into a roll mill (temperature: 160 ° C), and then pressed into a sample to perform various performance tests.
  • the measured results of the fully vulcanized natural rubber / polyethylene thermoplastic elastomer are shown in Table 1.

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Description

一种全硫化热塑性弹性体及其制备方法和应用 本发明涉及热塑性弹性体。 更进一步地说， 本发明涉及利用 共混法制得的一种全硫化热塑性弹性体和这种全硫化热塑性弹性 体的制备方法和应用。
全硫化热塑性弹性体是八十年代开发的新型材料， 是由弹性 体与刚性塑料在一定的条件下， 通过机械共混的方法来制备的。 它兼有塑料和橡胶特性： 在常温下显示橡胶的高弹性， 高温下又 能塑化成型。 全硫化热塑性弹性体在相态上是完全交联了的橡胶 相分散在塑料基质中。 由于橡胶相已经交联， 所以全硫化热塑性 弹性体的强度、 弹性、 耐热性及抗压缩永久变形性都比未交联的 热塑性弹性体要有很大的提高。 同时， 耐化学品性以及加工稳定 性也有明显改善， 而且橡塑共混比可在较大范围内变化， 使材料 在性能上有更大的调节余地。
在现有技术中全硫化热塑性弹性体是用动态硫化法来制备 的。 如文献： 科技期刊 《合成橡胶工业》 ， 1986年第 5期 361 ~ 364页， "动态全硫化乙丙橡胶 /聚烯烃共混热塑性弹性体" ； 科 技期刊 《化工进展》 ， 1987年第 5期 16 ~ 19页， "聚烯烃型全 硫化热塑性弹性体的发展"；朱玉俊编箸， "弹性体的力学改性"， 北京科学技术出版社， 335 ~ 395页（ 1992年）。 所谓动态硫化法 是指橡胶与塑料共混时， 借助交联剂和强烈的剪切应力作用进行 硫化反应的过程， 其技术关键是在硫化尚未结束之前不能停止混 合， 并且要有足够的硫化剂用量以保证橡胶能够完全硫化。
由于传统的动态硫化法是在共混的过程中对橡胶相进行完全 硫化， 对交联剂、 共混温度、 剪切速率、 共混时间及相互间的配 合等都有很高的要求， 而且还需要特殊的共混设备， 所以该法的 生产成本很高， 生产工艺比较复杂， 难于控制橡胶相的平均粒径 及疏化程度。 在制备饱和橡胶（如丙烯酸酯橡胶、 硅橡胶） 型全 硫化热塑性弹性体方面存在困难， 且对设备要求较高。 对于全硫 化热塑性弹性体来说， 橡胶相粒径对其物性影响极大， 橡胶相粒 径越小， 材料的拉伸强度越高及断裂伸长 越高， 其加工性能也 越好。 动态硫化法制备的全硫化热塑性弹性体中橡胶相的粒径大 小主要依靠机械共混剪切与化学交联反应之间的平衡来决定， 所 以橡胶相粒径难以做到很小。 如 Coran A.Y.等人的 Rubb. Chem. TechnoL, 53 (1)， 141 (1980)所述，动态硫化法制备的全硫化热塑性 弹性体的橡胶相平均粒径为 1μ ~ 2μ。 此外， 由于传统的全硫化热 塑性弹性体是在动态硫化法的熔融剪切及硫化的过程中完成橡胶 的相反转， 使大量的橡胶分散在塑料基体中。 因此其橡胶相的外 形为不规则形状， 这对于全疏化热塑性弹性体的流变及加工性不 利。 并且， 由于动态硫化法中使用硫化剂使橡胶相进行硫化， 所 以现有的全琉化热塑性弹性体的制品颜色较深， 不易得到浅色制 本发明的目的是提供一种橡胶相粒径为 0.02μ ~ 1μ的全硫化 热塑性弹性体。
本发明的另一目的是提供一种橡胶相的外形为类球形的全硫 化热塑性弹性体。
本发明的再一目的是提供一种橡胶相的粒径可控、 且外形为 类球形的全硫化热塑性弹性体。
本发明的再一个目的是提供所述全硫化热塑性弹性体的制备 方法。 该方法使用通用的橡塑共混设备， 工艺筒单， 对于橡胶相 的粒径及粒径分布和交联度可控性好。
本发明的再一目的是提供该热塑性弹性体用于制备各种成型 制品的应用。
一方面， 本发明的全硫化热塑性弹性体的分散相即橡胶相平 均粒径一般为 0.02μ ~ Ιμ,优选为 0.05μ ~ 0.5μ, 更优选为 0.05μ ~ 0.2μ。
另一方面， 本发明的全硫化热塑性弹性体的橡胶相的外形为 规整的类球形。 在此方面的优选实施方案中， 橡胶相的粒径为 0.02μ - 1μ, 优选为 0.05μ ~ 0.5μ, 更优选为 0.05μ ~ 0.2μ。
在本发明全硫化热塑性弹性体中， 橡胶相与塑料主体的重量 比优选为 30:70 75:25, 更优选为 50:50 ~ 75:25。 该全硫化热塑 性彈性体橡胶相的凝胶含量以重量比计达 60 %以上，优选 75 %以 上。
对本发明的全硫化热塑性弹性体中橡胶相的橡胶种类没有任 何限制， 它例如可以是全硫化的天然橡胶、 丁苯橡胶、 羧基丁苯 橡胶、 丁腈橡胶、 羧基丁腈橡胶、 氯丁橡胶、 聚丁二烯、 丙烯酸 酯类橡胶、 丁苯吡橡胶、 异戊橡胶、 丁基橡胶、 乙丙橡胶、 聚硫 橡胶、 丙烯酸酯-丁二烯橡胶、 硅橡胶、 聚氨酯橡胶或氟橡胶。
该种全硫化热塑性弹性体的主体塑料包括以下聚合物及其共 聚物中的至少一种： 聚酰胺、 聚丙烯、 聚乙烯、 聚氯乙烯、 聚氨 酯、 聚酯、 聚碳酸酯、 聚甲醛、 聚苯乙烯、 聚苯醚、 聚苯硫醚、 聚酰亚胺、 聚砜等。
本发明全硫化热塑性弹性体的制备方法是： 利用橡塑加工中 常用的共混法， 将全硫化粉末橡胶与塑料通过橡塑共混设备共混 造粒而制得全硫化热塑性弹性体。 其中所用全硫化粉末橡胶的平 均粒径根据全硫化热塑性弹性体中橡胶相的粒径而定， 一般为 0.02μ ~ 1μ, 优选为 0.05μ ~ 0.5μ, 更优选为 0.05μ ~ 0.2μ。 全硫化 粉末橡胶与塑料的重量比优选为 30:70 ~ 75:25,更优选为 50:50 ~ 75:25。 在共混过程中可以将粉末橡胶和塑料一次性共混挤出， 也 可以将一部分粉末橡胶与塑料共混制成母粒， 然后再与剩下的粉 末橡胶进行二次共混挤出。 在制备本发明的全硫化热塑性彈性体时， 主体塑料可以包括 以下聚合物及其共聚物中的至少一种： 聚酰胺、 聚丙婦、 聚乙烯、 聚氯乙烯、 聚氨酯、 聚酯、 聚碳酸酯、 聚甲醛、 聚苯乙烯、 聚苯 醚、 聚苯硫醚、 聚酰亚胺或聚砜等。
本发明方法中全硫化粉末橡胶可以是按照本发明人于 1999 年 12月 3日申请的中国专利 99125530.5(其公开内容全部并入本 文） 所制备的粉末橡胶， 可包括以下全硫化粉末橡胶中的至少一 种： 全硫化粉末天然橡胶、 全硫化粉末丁苯橡胶、 全硫化粉末羧 基丁苯橡胶、 全疏化粉末丁腈橡胶、 全硫化粉末羧基丁腈橡胶、 全硫化粉末聚丁二烯橡胶、 全硫化粉末氯丁橡胶、 全硫化粉末硅 橡胶、 全硫化粉末丙烯酸酯类橡胶、 全硫化粉末丁苯吡橡胶、 全 硫化粉末异戊橡胶、 全硫化粉末丁基橡胶、 全硫化粉末乙丙橡胶、 全疏化粉末聚硫橡胶、 全硫化粉末丙烯酸酯-丁二烯橡胶、 全硫 化粉末聚氨酯橡胶或全硫化粉末氟橡胶等。 此种全硫化粉末橡胶 的凝胶含量以重量比计达 60 %以上， 更优为 75 %以上。
用于本发明方法中的全硫化粉末橡胶是通过用辐照法将相应 的橡胶胶乳硫化得到的。 例如， 可以用市售或自制的橡胶胶乳为 原料， 加入或不加入交联助剂， 用高能射线照射， 使其完全硫化， 以制备本发明的全硫化粉末橡胶。 高能射线源可以选自钴源、 X- 射线、 紫外线或高能电子加速器， 优选钴源。 辐照剂量与胶乳的 种类和配方有关。 在一般情况下， 辐照剂量应使得橡胶胶乳辐照 硫化后得到的全硫化橡胶的凝胶含量达到 60 %重量或更高， 优选 75 %重量或更高， 更优选 90 %重量或更高。辐照的剂量可以为 0.1 - 30Mrad, 优选 0.5 - 20Mrad。 如有必要， 可以将辐照后的胶乳 干燥得到与胶乳中橡胶粒子大小基本相同的全硫化粉末橡胶。 干 燥过程可以用喷雾干燥器进行也可以用沉淀干燥法进行， 如果用 喷雾干燥器进行， 进口温度可以控制在 100 ~ 200C 出口温度可 以控制在 20 ~ 801；。
在制备全硫化粉末橡胶时， 对所用的橡胶胶乳原料没有任何 限制， 可以选自天然橡胶胶乳、 丁苯橡胶胶乳、 羧基丁苯橡胶胶 乳、 丁腈橡胶胶乳、 羧基丁腈橡胶胶乳、 氯丁橡胶胶乳、 聚丁二 烯橡胶胶乳、 丙烯酸酯类橡胶胶乳、 丁苯吡橡胶胶乳、 异戊橡胶 胶乳、 丁基橡胶胶乳、 乙丙橡胶胶乳、 聚硫橡胶胶乳、 丙烯酸酯- 丁二烯橡胶胶乳、 硅橡胶乳液、 聚氨酯橡胶胶乳或氟橡胶胶乳。 橡胶微粒的粒径可以根据不同的应用而不同。
制备全硫化粉末橡胶时可以不使用交联助剂， 也可以使用交 联助剂。 所用的交联助剂可以是单官能团交联助剂、 二官能团交 联助剂、 三官能团交联助剂、 四官能团交联助剂或多官能团交联 助剂及其任意组合。 所述的单官能团交联助剂的实例包括（但不 限于） （甲基） 丙烯酸辛酯、 （甲基） 丙烯酸异辛酯、 （甲基） 丙埽酸缩水甘油酯； 所述的二官能团交联助剂的实例包括（但不 限于） 1，4 -丁二醇二（甲基） 丙烯酸酯、 1, 6 -己二醇二（甲基） 丙烯酸酯、 二乙二醇二（甲基） 丙烯酸酯、 三乙二醇二（甲基） 丙烯酸酯、 新戊二醇二（甲基） 丙烯酸酯， 二乙烯基苯； 所迷的 三官能团交联助剂的实例包括（但不限于） 三羟甲基丙烷三（甲 基） 丙烯酸酯、 季戊四醇三（甲基） 丙烯酸酯； 所述的四官能团 交联助剂的实例包括（但不限于）季戊四醇四（甲基） 丙烯酸酯、 乙氧化季戊四醇四 （甲基） 丙烯酸酯； 所述的多官能团交联助剂 的实例包括（但不限于） 二季戊四醇五（甲基） 丙烯酸酯。 在本 文中， " （甲基） 丙烯酸酯" 指丙烯酸酯或甲基丙烯酸酯。
这些交联助剂可以任意组合方式使用， 只要它们在辐照下有 助于辐照疏化即可。
这些交联助剂的加入量随橡胶胶乳的种类和配方不同而变 化， 一般为纯橡胶重量的 0.1 - 10%重量， 优选为 0.5 - 9%重量， 更优选为 0.7 - 7%重量。
在制备过程中， 物料的共混温度即为普通塑料加工中所用的 共混温度， 可根据基本塑料的熔融温度而定， 应该在既保证基体 塑料完全熔融又不会使塑料分解的范围内选择。 此外， 根据加工 需要， 可在共混物料中适量加入塑料加工的常规助剂和增容剂。
本发明方法中所使用的橡胶共混设备可以是开炼机、密炼机， 单螺杆挤出机或双螺杆挤出机等。
本发明的全硫化热塑性弹性体的橡胶相粒径比传统动态硫化 方法所制得的全硫化热塑性弹性体的橡胶相粒径可以控制， 故其 拉伸强度及断裂伸长率得到很大提高， 外观好且具有良好的加工 性。 并且， 本发明的全硫化热塑性体的橡胶相外形为规整的类球 形， 利于流变及加工等性能。 此外， 本发明全硫化热塑性弹性体 在制备时无需加入硫化剂， 因此易于制得浅色的全硫化热塑性弹 性体制品， 本发明的全硫化热塑性弹性体也易于制成各种染色制 品。 本发明方法使用普通的橡塑共混设备， 利用通常的共混挤出 法制备， 所以工艺简单、 设备成本低、 操作可控性好， 适用于工 业化大批量生产的要求。
本发明的全硫化热塑性弹性体性能优异， 可用于制备软管、 波紋管、 垫圈 （片） 、 接头、 电器制品、 汽车零配件以及建筑材 料和运动器材等各种成型制品。 将该种全硫化热塑性弹性体进行 阻燃改性后， 其阻燃制品将会有更大的应用领域。
在以下实施例中， 全硫化热塑性弹性体中橡胶相的粒径是采 用常规的透射电镜法测量的。
下面结合实施例进一步描述本发明。 本发明的范围不受这些 实施例的限制， 本发明的范围在权利要求书中给出。
附图 1为实施例 2所得样品的透射电镜照片。 实施例 1
将平均粒径约为 Ο.ΐμ的全硫化丁苯粉末橡胶（在兰化胶乳研 制中心提供的丁苯- 50乳液中， 按丁苯乳液干胶质量的 3 %加入 交联助剂三羟甲基丙烷三丙烯酸酯后， 进行辐照硫化， 辐照剂量 为 2.5Mrad,经喷雾干燥后得到）和聚丙烯（燕山石化，牌号 1300 ) 以 70/30 的重量比混合， 再加入基于丁苯粉末橡胶和聚丙烯总重 量 0.5 %的抗氧剂 Irganox 1010 (瑞士 Ciba一 Geigy生产）， 用德 国 WP公司的 ZSK - 25型双螺杆挤出机挤出造粒，挤出机各段温 度分别为： 170 !、 190 、 190 *C、 190 °C、 190t!和 195Ό (机头 温度） 。 对所得粒料进行分析， 测得该热塑性弹性体中橡胶相的 平均粒径为约 Ο.ΐμ, 外形为类球形。
将粒料用注塑法制成标准样条， 进行各项性能测试， 测得的 全硫化丁苯橡胶 /聚丙烯热塑性弹性体结果列于表 1中。 该热塑性 弹性体的白度值为 35.57 ( GB 2913 - 88 ) , 可以方便地染成各种 有色制品。 实施例 2
将平均粒径约为 Ο.ΐμ的全硫化丁苯粉末橡胶（与实施例 1中 相同）和聚笨乙烯（燕山石化， 牌号 666D )以 70/30重量比混合， 再加入基于丁笨粉末橡胶和聚笨乙烯总重量 0.5 %的抗氧剂 Irganox 1010, 用德国 WP公司的 ZSK- 25型双螺杆挤出机挤出 造粒， 挤出机各段温度分别为： 170°C、 185 、 185 、 185 185 和 (机头温度） 。 对所得粒料进行分析， 测得该热塑 性弹性体中橡胶相的平均粒径为约 Ο.ΐμ, 外形为类球形。
将粒料用注塑法制成标准样条， 进行各项性能测试， 测得的 全疏化丁苯橡胶 /聚苯乙蹄热塑性弹性体结果列于表 1中。 实施例 3
将实施例 2中的聚苯乙埽改为高抗冲聚苯乙烯（燕山石化， 牌号 492J ) , 其余均与实施例 2相同。 对所得粒料进行分析， 测 得该热塑性弹性体中橡胶相的平均粒径为约 Ο.ΐμ,外形为类球形。 测得的全硫化丁苯橡胶 /高抗冲聚苯乙烯热塑性弹性体结果列于 表 1中。 实施例 4
将实施例 1中的聚丙烯（牌号 1300 )改为聚丙烯（燕山石化， 牌号 1740 ) , 其余均与实施例 1相同。 对所得粒料进行分析， 测 得该热塑性弹性体中橡胶相的平均粒径为约 Ο.ΐμ,外形为类球形。 测得的全硫化丁苯橡胶 /聚丙烯热塑性弹性体结果列于表 1中。 实施例 5
将平均粒径约为 0.15μ的全硫化羧基丁苯粉末橡胶 (在燕山石 化生产的牌号为 XSBRL - 54B1羧基丁苯乳液中， 按羧基丁苯乳 液干胶质量的 3 %混入交联助剂丙烯酸异辛酯后， 进行辐照硫化， 辐照剂量为 2.5Mrad, 经喷雾干燥后得到） 和尼龙 6 ( 日本宇部 兴产 1013B ) 以 75/25的重量比混合， 再加入基于羧基丁苯粉末 橡胶和尼龙 6总重量 0.5%的抗氧剂 Irganox 1010,用德国 WP公 司的 ZSK - 25 型双螺杆挤出机挤出造粒， 挤出机各段温度分别 为： 210°C、 225°C、 225 、 225 . 230°C和 225"C (机头温度）。 对所得粒料进行分析， 测得该热塑性弹性体中橡胶相的平均粒径 为约 0.15μ， 外形为类球形。
将粒料分别用压片法和注塑法制成标准样条， 进行各项性能 测试， 测得的全硫化羧基丁苯橡胶 /尼龙 6热塑性弹性体结果列于 表 1中。 实施例 6
除全硫化羧基丁苯粉末橡胶与尼龙 6按 50/50的重量比混合 外， 其余均与实施例 5相同。 对所得粒料进行分析， 测得该热塑 性弹性体中橡胶相的平均粒径为约 0.15μ， 外形为类球形。 测得的 全疏化羧基丁笨橡胶 /尼龙 6热塑性弹性体结果列于表 1中。 实施例 7
采用与实施例 5中相同的全硫化羧基丁苯粉末橡胶与尼龙 6, 按 70/30的重量比混合， 在 Brabender单螺杆挤出机上挤出造粒， 挤出机温度为 160、 190、 230、 225°C。 对所得粒料进行分析， 测 得该热塑性弹性体中橡胶相的平均粒径为约 0.15μ, 外形为类球 形。
将粒料用注塑法制成标准样条， 进行各项性能测试， 测得的 全硫化羧基丁苯橡胶 /尼龙 6热塑性弹性体结果列于表 1中。 实施例 8
将平均粒径约为 0.15μ的全硫化羧基丁苯粉末橡胶（除辐照剂 量为 lOMrad外， 其它与实施例 5 中所述相同） 和尼龙 6 ( 曰本 宇部兴产 1013B ) 以 40/30的重量比混合， 再加入基于羧基丁苯 粉末橡胶和尼龙 6 总重量 0.7 %的抗氧剂 Irganox 1010, 在 Brabender单螺杆挤出机上挤出造粒， 挤出机温度为 160、 190、 230、 225t：。 然后再将所得粒料与前述羧基丁笨粉末橡胶以 70/30 的重量比混合，最终羧基丁苯粉末橡胶与尼龙 6的重量比为 70/30。 用德国 WP公司的 ZSK - 25型双螺杆挤出机挤出造粒，挤出机各 段温度分别为： 210"C、 225" 、 225 ；、 225 230°C和 225"C (机 头温度） 。 对所得粒料进行分析， 测得该热塑性弹性体中橡胶相 的平均粒径为约 0.15μ， 外形为类球形。
再将最后所得粒料用注塑法制成标准样条， 进行各项性能测 试， 测得的全硫化羧基丁苯橡胶 /尼龙 6热塑性弹性体结果列于表 1中。 实施例 9
将平均粒径约为 0.05μ的全硫化羧基丁腈粉末橡胶（在兰化胶 乳研制中心生产的牌号为 XNBRL的羧基丁腈乳液中， 按羧基丁 腈乳液干胶质量的 3 %加入交联助剂三羟甲基丙烷三丙烯酸酯后， 进行辐照硫化， 辐照剂量为 lOMrad, 经喷雾干燥后得到） 和尼 龙 6 ( 日本宇部兴产 1013B ) 以 70/30的重量比混合， 再加入基于 羧基丁腈粉末橡胶和尼龙 6总重量 0.5 %的抗氧剂 Irganox 1010, 用德国 WP公司的 ZSK - 25型默螺杆挤出机挤出造粒，挤出机各 段温度分别为： 210°C：、 225°C、 225°C；、 225 °C , 230 和 225°C (机 头温度） 。 对所得粒料进行分析， 测得该热塑性弹性体中橡胶相 的平均粒径为约 0.05μ, 外形为类球形。
将粒料用注塑法制成标准样条， 进行各项性能测试， 测得的 全疏化羧基丁腈橡胶 /尼龙 6热塑性弹性体结果列于表 1中。 实施例 10
将平均粒径约为 0.5μ的全硫化天然橡胶粉末（在北京乳胶厂 提供的天然橡胶乳液中， 按天然橡胶乳液干胶质量的 5 %混入交 联剂三羟甲基丙烷三丙烯酸酯后， 进行辐照硫化， 辐照剂量为 15Mrad, 经喷雾干燥后得到）和高密度聚乙烯树脂（北京助剂二 厂生产， 牌号为 J - 1 ) 以 70/30的重量比混合， 再加入基于天然 橡胶粉末和高密度聚乙烯树脂总重量 0.5 %的抗氧剂 Irganox
1010, 用 Brabender捏合机共混 2分钟， 捏合机油浴温度为 160 °C。 对所得样品进行分析， 测得该热塑性弹性体中橡胶相的平均 粒径为约 0.5μ, 外形为类球形。
所得样品用 辊开炼机成片（温度： 160°C ) , 然后压片制样， 进行各项性能测试， 测得的全硫化天然橡胶 /聚乙烯热塑性弹性体 结果列于表 1中。
Figure imgf000012_0001

Claims

权 利 要 求
1. 一种全硫化热塑性弹性体， 其特征在于该全硫化热塑性弹 性体中的橡胶相平均粒径为 0.02μ ~ 1μ。
2. 一种全硫化热塑性弹性体， 其特征在于该全硫化热塑性弹 性体中橡胶相的外形为类球形。
3. 根据权利要求 2 的所述的全硫化热塑性弹性体， 其特征在 于该全硫化热塑性弹性体中橡胶相的平均粒径为 0.02μ ~ 1μ。
4. 根据权利要求 1 - 3中任一项所迷的全硫化热塑性弹性体， 其特征在于所述橡胶相平均粒径为 0.05μ ~ 0.5μ, 更优选为 0·05μ ~ 0·2μ。
5. 根据权利要求 1― 4中任一项所述的全硫化热塑性弹性体， 其特征在于橡胶相与塑料的重量比为 30: 70 - 75： 25,优选为 50: 50 - 75： 25。
6. 根据权利要求 1 - 5中任一项所迷的全硫化热塑性弹性体， 其特征在于所述橡胶相的凝胶含量以重量比计≥60 % , 优选 > 75
% 。
7. 根据权利要求 1 - 6中任一项所迷的全硫化热塑性弹性体， 其特征在于所述全硫化热塑性弹性体的主体塑料包括以下聚合物 及其共聚物中的至少一种： 聚酰胺、 聚丙烯、 聚乙烯、 聚氯乙烯、 聚氨酯、 聚酯、 聚碳酸酯、 聚甲醛、 聚苯乙烯、 聚苯醚、 聚苯硫 醚、 聚酰亚胺、 聚砜。
8. 根据权利要求 1 - 7中任一项所迷的全硫化热塑性弹性体， 其特征在于所述全硫化热塑性弹性体的橡胶相包括以下橡胶的至 少一种： 天然橡胶、 丁苯橡胶、 羧基丁苯橡胶、 丁腈橡胶、 羧基 丁腈橡胶、 聚丁二烯橡胶、 氯丁橡胶、 硅橡胶、 丙烯酸酯类橡胶、 丁苯吡橡胶、 异戊橡胶、 丁基橡胶、 乙丙橡胶、 聚硫橡胶、 丙烯 酸酯-丁二烯橡胶、 聚氨酯橡胶或氟橡胶。
9. 一种制备全硫化热塑性弹性体的方法， 它包括将全硫化粉 末橡胶与塑料共混的步骤。
10. 根据权利要求 9所述的方法， 其特征在于全硫化粉末橡胶 与塑料的重量比为 30: 70 - 75： 25, 优选 50: 50 - 75： 25。
11. 根据权利要求 9所述的方法， 其特征在于所述全硫化粉末 橡胶的平均粒径为 0.02μ ~ 1μ。
12. 根据权利要求 9所述的方法， 其特征在于所述全硫化粉末 橡胶的外形为类球形。
13. 根据权利要求 12所述的方法， 其特征在于所迷全硫化粉 末橡胶的平均粒径为 0.02μ ~ 1μ。
14. 根据权利要求 9 - 13中任一项所述的方法， 其特征在于所 述全疏化粉末橡胶的平均粒径为 0.05μ ~ 0.5μ, 优选为 0.05μ ~ 0·2μ。
15. 根据权利要求 9 - 14中任一项所述的方法， 其特征在于所 述全硫化粉末橡胶包括下列橡胶中的至少一种： 全硫化粉末天然 橡胶、 全硫化粉末丁笨橡胶、 全硫化粉末羧基丁苯橡胶、 全硫化 粉末丁腈橡胶、 全硫化粉末羧基丁腈橡胶、 全硫化粉末聚丁二浠 橡胶、 全硫化粉末氯丁橡胶、 全硫化粉末硅橡胶、 全硫化粉末丙 烯酸酯类橡胶、 全硫化粉末丁笨吡橡胶、 全硫化粉末异戊橡胶、 全硫化粉末丁基橡胶、 全硫化粉末乙丙橡胶、 全硫化粉末聚硫橡 胶、 全硫化粉末丙烯酸酯-丁二烯橡胶、 全硫化粉末聚氨酯橡胶 或全硫化粉末氟橡胶。
16. 根据权利要求 9 - 15中任一项所述的方法， 其特征在于， 所述塑料包括以下聚合物及其共聚物中的至少一种： 聚酰胺、 聚 丙烯、 聚乙烯、 聚氯乙烯、 聚氨酯、 聚酯、 聚碳酸酯、 聚甲醛、 聚笨乙烯、 聚苯醚、 聚笨硫醚、 聚酰亚胺、 聚砜。
17. 权利要求 1-8中任一项的或权利要求 9-16中任一项的 方法制备的全硫化热塑性弹性体用于制备成型制品的应用。
PCT/CN2001/000972 2000-06-15 2001-06-15 Fully cured thermoplastic elastomer, process for its manufacture and applications thereof Ceased WO2002033003A1 (en)

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