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WO2001040356A1 - Caoutchouc en poudre entierement vulcanise a diametre de particules regulable, son procede de preparation et des utilisations - Google Patents

Caoutchouc en poudre entierement vulcanise a diametre de particules regulable, son procede de preparation et des utilisations Download PDF

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Publication number
WO2001040356A1
WO2001040356A1 PCT/CN2000/000281 CN0000281W WO0140356A1 WO 2001040356 A1 WO2001040356 A1 WO 2001040356A1 CN 0000281 W CN0000281 W CN 0000281W WO 0140356 A1 WO0140356 A1 WO 0140356A1
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Prior art keywords
rubber
acrylate
latex
meth
powder
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PCT/CN2000/000281
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English (en)
French (fr)
Inventor
Jinliang Qiao
Genshuan Wei
Xiaohong Zhang
Shijun Zhang
Jianming Gao
Wei Zhang
Yiqun Liu
Jiuqiang Li
Fengru Zhang
Jingbo Shao
Renli Zhai
Kunkai Yan
Hua Yin
Original Assignee
China Petro-Chemical Corporation
Beijing Research Institute Of Chemical Industry, Sinopec
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Application filed by China Petro-Chemical Corporation, Beijing Research Institute Of Chemical Industry, Sinopec filed Critical China Petro-Chemical Corporation
Priority to BRPI0016302-3A priority Critical patent/BR0016302B1/pt
Priority to AU75031/00A priority patent/AU7503100A/en
Priority to DE60033321T priority patent/DE60033321T2/de
Priority to EP00963852A priority patent/EP1262510B1/en
Priority to CNB008164509A priority patent/CN1152082C/zh
Priority to CA2393311A priority patent/CA2393311C/en
Priority to JP2001541106A priority patent/JP2003515644A/ja
Publication of WO2001040356A1 publication Critical patent/WO2001040356A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/26—Crosslinking, e.g. vulcanising, of macromolecules of latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to powder rubber, and more particularly, the present invention relates to a fully vulcanized powder rubber having a controllable particle size (up to the nanometer level) and a powder rubber of this type. Preparation method and use.
  • rubber is generally block-shaped, rod-shaped, powdery, granular, or sheet-shaped, and powdered rubber is divided into unvulcanized (including slightly vulcanized) and vulcanized.
  • unvulcanized powder rubber except for the vulcanized powder silicone rubber prepared by the chemical crosslinking method, other vulcanized powder rubbers have not been reported in the literature.
  • US Patent No. 4743670 discloses a highly dispersed vulcanized powder silicone rubber and a method for preparing the vulcanized powder silicone rubber.
  • The; sulfur silicone rubber powder has average particle size and particle shape hook, a volume resistivity greater than 1013 ohm cm.
  • the preparation method of the vulcanized powder silicone rubber includes (1) preparing a heat-vulcanizable liquid silicone rubber dispersion liquid in the presence of a surfactant in water maintained at 0 ° C-25 ° C; (2) putting ( The dispersion prepared in 1) is dispersed in a liquid kept at least 5 ° C. to vulcanize the liquid silicone rubber composition into a powder and (3) separate the vulcanized powder silicone rubber.
  • U.S. Patent No. 4742142 (April 6, 1987) reports a method for preparing powdered silicone rubber. According to the method reported in this patent, a vulcanizable composition is heated at a temperature of (TC-25 ° C) in a liquid, The surfactant-containing water is emulsified into an emulsion, and the emulsion is sprayed into a water bath at a temperature of at least 25 ° C to fully vulcanize each component in the silicone rubber composition.
  • U.S. Patent No. 4749765 discloses a method for preparing powder silicone rubber with a uniform particle size.
  • the method includes (1) at a temperature of-60 ° C-+ 50 ° C, by The components are mixed together to prepare a liquid silicone rubber composition and maintained at the temperature; (2) combining the liquid silicone rubber prepared in (1) The material is sprayed into hot air at 80 ° C-200 ° C to form granules; (3) the granules prepared in (2) are vulcanized, and (4) the powdered silicone rubber prepared is recovered.
  • U.S. Patent No. 5837793 discloses a vulcanized powder silicone rubber and a preparation method thereof.
  • the powder silicone rubber has a high degree of hydrophilicity and softness, and the average particle diameter is less than 500 microns.
  • the preparation method is (1) vulcanizing a vulcanizable silicone composition containing a specific polyorganosiloxane to produce a vulcanized silicone rubber, and (2) The vulcanized silicone rubber produced by spray drying.
  • the alkylation reaction to produce vulcanized silicone rubber can be an addition reaction between an alkenyl group and silicon-bonded hydrogen, a condensation reaction between a silicon-bonded hydroxyl group and a silicon-bonded hydrogen, and an organic peroxide-induced reaction And UV-induced reactions.
  • the fully vulcanized powder rubber can be prepared by drying.
  • the particle size of this powder rubber is uniform and the particle size is controllable.
  • the particle size of powder rubber is basically the same as that of rubber particles in latex. It can be used to prepare toughened plastics and fully vulcanized thermoplastic elastomers, and has broad application prospects and great economic significance.
  • Another object of the present invention is to provide the use of the fully vulcanized powder rubber for toughening plastics and preparing thermoplastic elastomers.
  • the fully vulcanized powder rubber of the present invention is a kind of rubber particles having a gel content of 60% by weight or more and freely flowing without a release agent.
  • Gel content is a commonly used parameter in the art to characterize the degree of rubber cross-linking, and it can be determined according to methods well known in the art.
  • the gel content of the fully vulcanized powder rubber of the present invention is 60% by weight Amount or higher, preferably 75% by weight or higher, and most preferably 90% by weight or higher.
  • the swelling index is another commonly used parameter in the art to characterize the degree of rubber cross-linking, and it can be measured according to methods well known in the art.
  • the swelling index of the powdered rubber of the present invention is not more than 15, preferably not more than 13.
  • the fully vulcanized powder rubber of the present invention is a free-flowing rubber particle, and this free-flowing property can be achieved without using a release agent. Therefore, the fully vulcanized powder rubber of the present invention may not be added with a release agent. Of course, if necessary, a fully vulcanized powder rubber may also be added with a release agent to further improve its flowability and blocking resistance.
  • the fully vulcanized powder rubber of the present invention has a controllable particle diameter, and the average particle diameter is generally 20 to 2000 nm, preferably 30 to 1500 nm, and more preferably 50 to 500 nm.
  • the particle size is measured using a scanning electron microscope technique.
  • Each particle in the fully vulcanized powder rubber of the present invention is homogeneous, that is, the individual particles are homogeneous in composition, and no layering or equal unevenness is found in the particles under the observation of the existing microscopic technology. Phase phenomenon.
  • the kind of rubber of the fully vulcanized powder rubber of the present invention may be any kind of rubber other than the silicone rubber vulcanized by the chemical cross-linking method, such as a fully vulcanized natural rubber, a styrene-butadiene rubber, and a carboxyl butadiene rubber.
  • the fully vulcanized powder rubber 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 20 to 2000 nanometer 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, and a cobalt source is preferred.
  • the irradiation dose may be from 0.1 to 30 Mrad, preferably from 0.5 to 20 Mrad.
  • the irradiated latex is dried to obtain a fully vulcanized powder rubber having the same size as the rubber particles in the latex. Dry The 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 ⁇ 200 ° C, and the outlet temperature can be controlled at 20 ⁇ 8 (TC).
  • the rubber latex material used may be selected from natural rubber latex, styrene-butadiene rubber latex, carboxystyrene-butadiene rubber latex, nitrile rubber latex, carboxy-nitrile rubber latex, 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, polyurethane rubber latex, or fluoro rubber latex.
  • the particle size of the rubber particles can vary depending on the application. There is no particular limitation on the solid content of the rubber latex, but it is generally 20 to 70% by weight, preferably 30 to 60% by weight, and more preferably 40 to 50% by weight.
  • the fully vulcanized powder rubber of the present invention may be prepared without using a cross-linking aid, or with a cross-linking aid.
  • 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, (fluorenyl) glycidyl acrylate;
  • the difunctional crosslinking Examples of auxiliaries include, but are not limited to, 1,4-butanediol di (fluorenyl) acrylate, 1,6-hexanediol di (methyl) propionate, diethylene glycol bis (methyl) ) Propionate, triethylene glycol di (fluorenyl) acrylate, neopentyl glycol di (meth) acrylate, divinylbenzene;
  • examples of the trifunctional crosslinking assistant include (but not Limited to) trimethylolpropane tri (fluorenyl) acrylate, pentaerythritol tri (meth) acrylate;
  • examples of the tetrafunctional cross-linking assistants include (but
  • crosslinking auxiliaries can be used in any combination, as long as they help to irradiate Tu under irradiation.
  • the high-energy radiation source used for preparing the fully vulcanized powder rubber of the present invention is a general cobalt source, X-ray, ultraviolet or high-energy electron accelerator, and a cobalt source is preferably used.
  • the radiation dose may be from 0.1 to 30 Mrad, preferably from 0.5 to 20 Mard.
  • the radiation dose depends on the type and formulation of the latex. In general, the irradiation 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 higher, preferably 75% by weight or higher, and more preferably 90% by weight or higher.
  • the fully vulcanized powder rubber of the present invention is easily dispersed in a plastic matrix, so it can be mixed with various plastics to make various toughened plastics and thermoplastic elastomers.
  • the basic preparation method is to mix the fully vulcanized powder rubber and plastic of the present invention in a conventional mixing equipment and conventional process conditions at a certain ratio, and if necessary, add an appropriate amount of a processing aid and a compatibilizer.
  • the weight ratio of the fully vulcanized powder rubber to the plastic of the present invention is 0.5: 99. 5-50: 50, preferably 1: 99-30: 70.
  • the toughened plastic can be nylon, polypropylene, polyethylene, polyvinyl chloride, polyurethane, epoxy resin, polyester, polycarbonate, polyoxymethylene, polystyrene, polyphenylene ether (PP0), polyphenylene ether (PPS), polyimide, polysulfone and its copolymers and blends.
  • the weight ratio of the fully vulcanized powder rubber to the plastic is 30: 70-75: 25, preferably 50: 50-70: 30.
  • Available plastics are nylon, polypropylene, polyethylene, polyvinyl chloride, polyurethane, epoxy, polyester, polycarbonate, polyoxymethylene, polystyrene, polyphenylene ether (PP0), polyphenylene sulfide (PPS) , Polyimide, polysulfone and their copolymers and blends.
  • FIG. 1 is a scanning electron microscope photograph of a fully vulcanized styrene-butadiene rubber powder obtained in Example 4 at a magnification of 20,000 times;
  • Fig. 2 is an atomic force microscope photograph of a sample obtained in Example 14 at a magnification of 40,000 times.
  • the gel content was measured according to the following method: Weigh accurately about 0.1 g of powder rubber obtained by spray drying, wrap it with a universal lens paper, and then pack it into a 200-mesh copper mesh to accurately weigh it. It is then boiled in toluene, and the boiling time is based on the substantially constant quality of the copper mesh and its inclusions after being fully dried, generally 6 hours. After that, the fully boiled copper mesh and its inclusions are completely dried and accurately weighed. Calculate the gel content according to the following formula:
  • W Represents the weight of the powder rubber sample
  • ⁇ ⁇ Indicates the weight of the copper mesh and its inclusions before boiling; ⁇ ⁇ 2 indicates the weight of the copper mesh and its inclusions that are sufficiently dried after boiling.
  • the swelling index is measured according to the following method: Dry the radiation-cured rubber emulsion to form a film (if the film formation is difficult, use a dry powder directly). The exact weight will be W. 200 mesh copper mesh formed capsule soak into Yue benzene, placed slightly, then remove and quickly weighed referred weighed about 0.1 gram of film (or powder) is placed in a copper mesh W le capsule, the membrane Soak in copper with copper mesh, place in a cool place for swelling for 24 hours, carefully remove the copper mesh with the swollen gel, quickly remove the solvent on the gel surface, and then quickly weigh it. The weight is W 2 . The weighed copper mesh and gel were thoroughly dried to a constant weight, and the weight was recorded as W 3 . The swelling index is calculated according to the following formula:
  • the dried carboxybutyl styrene is collected in a cyclone separator.
  • the particle size of the powdered rubber was measured to be about 150 nm, the gel content was 92.6%, and the swelling index was 7.6.
  • Example 3 Except for the irradiation with a dose of OMrad, everything else was the same as in Example 1, and a free-flowing fully vulcanizable styrene-butadiene rubber powder sample 2 was obtained.
  • the particle size of the powdered rubber was measured to be about 150 nm, the gel content was 94.5%, and the swelling index was 5.4.
  • Example 3
  • Example 4 Except for diethylene glycol diacrylate used as a cross-linking auxiliary agent, all were the same as in Example 1 to obtain a free-flowing fully vulcanizable styrene-butadiene rubber powder sample 3.
  • the powder rubber was measured to have a particle diameter of about 150 nm, a gel content of 93.0%, and a swelling index of 7.3.
  • Example 5 5Kg of commercially available styrene-butadiene latex (produced by Lanhua, brand: styrene-butadiene-50) with a solid content of 45% by weight was placed in a container, and 67.5g of isooctyl acrylate was added dropwise under stirring.
  • Example 7 Except for trimethylolpropane triacrylate, which is used as a cross-linking auxiliary agent, it was the same as in Example 5, and a free-flowing fully vulcanizable styrene-butadiene rubber powder sample 2 was obtained.
  • the particle size of the powdered rubber was about 100 nm, the gel content was 90.4%, and the swelling index was 11.6.
  • Example 7
  • Example 7 Except for the trihydroxymethylpropane triacrylate for the cross-linking auxiliary agent, it was the same as in Example 7 to obtain a free-flowing fully vulcanizable carboxyl nitrile rubber powder sample 2.
  • the particle size of the powder rubber was measured to be about 50 nm, the gel content was 97.1%, and the swelling index was 6.7.
  • 5 Kg of commercially available butyl acrylate latex (produced by Beijing Dongfang Chemical Factory, brand BC-01) with a solid content of 48% by weight was placed in a container, and 72 g of isooctyl acrylate was added dropwise with stirring. After the dropwise addition was completed, Continue stirring for one hour.
  • the irradiated latex is spray-dried by a spray dryer.
  • the inlet temperature of the dryer is 14 (TC-160 ° C :, the outlet temperature is 40 ° C-50 ° C, and a free-flowing fully vulcanized butyl rubber powder is obtained.
  • the particle size of the powder rubber was about 100 nm, the gel content was 85.7%, and the swelling index was 12.2.
  • Example 9 Except for trimethylolpropane triacrylate, which is used as a cross-linking auxiliary agent, it was the same as in Example 9 to obtain a free-flowing fully vulcanizable butyl rubber powder sample 2.
  • the particle size of the powder rubber was measured to be about 100 nm, the gel content was 87.7%, and the swelling index was
  • Example 1 Using fully vulcanized styrene-butadiene rubber powder sample 1 (example 1) and nylon 6 (day Motobe Industries Co., Ltd. 1013B) was mixed at a ratio of 75/25, and was blended and pelletized with a ZSK-25 twin-screw extruder from WP, Germany. The temperature of each section of the extruder was set to: 210 ° C; 225 ° C, 225 ° C, 225 ° C, 230 ° C and 225. C (head temperature). The pellets were made into standard splines by tabletting and injection molding, and the properties of the fully vulcanized styrene-butadiene rubber / nylon 6 thermoplastic elastomer were tested and shown in Table 1.
  • Example 13 Example 13
  • a fully vulcanized natural rubber powder sample (Example 11) and a high-density polyethylene resin (produced by Beijing Auxiliary Chemical Factory No. J-1) were mixed at a ratio of 70/30, and blended with a Brabender kneader for 2 minutes.
  • the temperature of the oil bath is 160 ° C.
  • the obtained sample was formed into a sheet (temperature: 160 ° C) with a two-roll mill, and then pressed into a sheet to prepare a sample.
  • the properties of the fully vulcanized natural rubber / polyethylene thermoplastic elastomer were measured as shown in Table 1. Table 1
  • nylon 6 produced by Ube Industries, Japan, grade 1013B
  • 20% of a fully vulcanized styrene-butadiene rubber powder sample 1 (Example 1) and 0.6% of calcium stearate and 0.8% of ultrafine talc powder are added at a high speed. (1500 rpm) mixing for 3 minutes, and then using WP company ZSK-25 twin-screw extruder to blend and pelletize, the temperature of each section of the extruder is set to: 230 ° C 235 ° C, 240 ° C, 245 ° (:, 240. (, 235 ° C, pellets are dried after injection molding into a standard spline, and the properties of super tough nylon 6 measured according to ASTM standards are shown in Table 2.
  • the particle distribution chart measured with an atomic force microscope is shown in Figure 2 (The particle diameter of the dispersed phase rubber particles is about 150 nm). Comparative Example 1
  • Example 15 The nylon 6 used in Example 14 was directly injection molded into a standard spline. The test results are shown in Table 2.
  • Example 15 The nylon 6 used in Example 14 was directly injection molded into a standard spline. The test results are shown in Table 2.
  • Example 2 To polymethene (manufactured by Asahi Kasei, brand 4520) was added 28% of a fully vulcanized styrene-butadiene rubber powder sample 1 (Example 1), and 1.2% of calcium stearate, 0.6% of ultrafine talc powder, 0.3 % Polyethylene wax and 0.4% antioxidant IRGAN0X 1010 (purchased from Ciba-Geigy), mixed at high speed (1500 rpm) for 3 minutes, then blended with WP company ZSK-25 twin-screw extruder to pelletize, extruder The temperature of each section is set to: 175 ° (:, 180 ° C, 1851 :, 185 ° C, 180 ° C, 175 ° C. The pellets are dried and injection molded into standard splines. Toughened polymers are measured according to ASTM standards. The properties of formaldehyde are shown in Table 2. Comparative Example 2
  • Example 15 The polyacetal used in Example 15 was directly injection molded into a standard spline. The test results are shown in Table 2. Table 2

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Description

全硫化可控粒径粉末橡胶及其制备方法和用途 本发明涉及粉末橡胶， 更具体地说， 本发明涉及具有可控粒 径 （可达纳米级） 的全硫化粉末橡胶和这种粉末橡胶的制备方法 及用途。
众所周知， 橡胶一般为块状、 棒状、 粉状、 粒状或片状等， 粉末橡胶又有未硫化 （包括轻微硫化） 和硫化之分。 在硫化粉末 橡胶中， 除通过化学交联法制备的硫化粉末硅橡胶外， 其它的硫 化粉末橡胶未见文献报道。
对硫化粉末硅橡胶及其制备方法报道的文献较多， 例如美国 专利 No. 4743670 ( 1988年 5月 10 日 ）公开了一种高度分散的硫 化粉末硅橡胶和该硫化粉末硅橡胶的制备方法。 该；琉化粉末硅橡 胶有均勾颗粒形状和粒径， 体积电阻率大于 1 013欧姆 ·厘米。 该 硫化粉末硅橡胶的制备方法包括（ 1 )在表面活性剂存在下， 在保 持 0 °C - 25 °C的水中， 制备加热可硫化的液体硅橡胶组合物的分 散液； （2 )把（1 ) 中制备的分散液分散在至少保持在 5 (TC的液 体中， 使液体硅橡胶组合物硫化成粉末和（ 3 )分离硫化的粉末硅 橡胶。
美国专利 No. 4742142 ( 1987年 4月 6 日 ）报导了一种粉末硅 橡胶的制备方法， 按照该专利报导的方法， 用液体于 （TC - 25 °C 加热可硫化的组合物， 将其在含表面活性剂的水中乳化成乳液， 然后将该乳液喷入至少为 25 °C温度的水浴中， 充分硫化硅橡胶组 合物中的各组分。
美国专利 No. 4749765 ( 1988年 6月 7 日 ）揭示了一种均匀 粒径的粉末硅橡胶的制备方法， 该方法包括（ 1 )在- 60 °C - + 50 °C的温度下， 通过将各组分混合在一起， 制备一种液体硅橡胶组 合物并保持在该温度下； （ 2 )把（ 1 ) 中制备的液体硅橡胶组合 物喷入 80 °C - 200 °C的热空气中， 生成粒状物； （3 )硫化 （2 ) 中制备的粒状物， 和 （4 ) 回收制备的粉末硅橡胶。
美国专利 No. 5837793 ( 1998年 11月 17 日 ）公开了一种硫 化粉末硅橡胶及其制备方法。 该粉末硅橡胶具有高度的亲水性和 柔软感， 平均粒径小于 500微米， 其制备方法是（1 )硫化包含特 定聚有机硅氧烷的可硫化硅酮组合物， 生成硫化硅橡胶， 和 （2 ) 喷雾干燥所生成的硫化硅橡胶。 生成硫化硅橡胶的 ^化反应可以 是链烯基与硅键合的氢之间的加成反应、 硅键合的羟基与硅键合 的氢之间的缩合反应、 有机过氧化物诱导的反应和紫外线诱导的 反应。
虽然现有技术报导了用化学交联法硫化的粉末硅橡胶及其制 备方法， 但对其它全硫化粉末橡胶尚无报道。
本发明人经过长期深入的研究后发现， 橡胶胶乳辐照后， 经 干燥就可制成全硫化粉末橡胶。 这种粉末橡胶粒度均勾， 粒径可 控， 粉末橡胶的粒径与胶乳中橡胶粒子的粒径基本相同。 可用于 制备增韧塑料和全硫化热塑弹性体， 具有广阔的应用前景和重大 的经济意义。
因此， 本发明的目的是提供一种全硫化的粉末橡胶。
本发明的另一目的是提供所述全硫化粉末橡胶的制备方法。 本发明的另一目的是提供可用于制备增韧塑料和热塑性弹性 体的组合物， 它含有本发明的全硫化粉末橡胶和塑料。
本发明还有一个目的是提供所述全硫化粉末橡胶用于增韧塑 料和制备热塑性弹性体的应用。
本发明的全硫化粉末橡胶是一种凝胶含量为 60 %重量或更 高、 无需隔离剂即可自由流动的橡胶微粒。 凝胶含量是本领域中 用于表征橡胶交联程度的一种常用参数， 它可以按照本领域熟知 的方法进行测定。 本发明的全硫化粉末橡胶的凝胶含量为 60 %重 量或更高，优选 75 %重量或更高，最优选 90 %重量或更高。此外， 溶胀指数是本领域中用于表征橡胶交联程度的另一种常用参数， 它可以按照本领域熟知的方法进行测定。 本发明的全 化粉末橡 胶的溶胀指数不大于 15 , 优选不大于 13。 此外， 本发明的全硫化 粉末橡胶是一种可自由流动的橡胶微粒， 并且这种可自由流动性 无需借助隔离剂即可达到。 因此， 本发明的全硫化粉末橡胶可以 不加入隔离剂， 当然， 如需要， 本发明的全硫化粉末橡胶中也可 以加入隔离剂， 以进一步提高其可流动性和抗粘连性。
本发明的全硫化粉末橡胶具有可控的粒径， 平均粒径一般为 20 ~ 2000nm , 优选为 30 - 1500nm , 更优选为 50 - 500nm。 在本发 明中， 粒径是采用扫描电镜技术测定的。
本发明的全硫化粉末橡胶中的每个微粒都是均相的， 即单个 微粒在组成上都是均质的 , 在现有显微技术的观察下微粒内没有 发现分层、 分相等不均相的现象。
' 对本发明的全硫化粉末橡胶对橡胶的种类没有任何限制， 它 可以是除通过化学交联法硫化的硅橡胶之外的任何种类的橡胶， 例如全硫化的天然橡胶、 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、 聚氨酯橡胶或氟橡胶。
本发明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 20 - 2000纳米的橡胶胶 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。 辐照的剂量 可以为 0. 1 - 30Mrad， 优选 0.5 - 20Mrad。 将辐照后的胶乳经干燥 就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 ~ 200°C， 出口温度可以 控制在 20 ~ 8 (TC。
在制备本发明的全硫化粉末橡胶时， 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、 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。 对橡胶胶乳的固含量没有 特别限制， 一般为 20-70%重量、 优选 30-60%重量、 更优选 40 - 50%重量。
制备本发明的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、 (曱基） 丙烯酸缩水甘油酯； 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 （曱基） 丙烯酸酯、 1, 6 -己二 醇二 （甲基） 丙浠酸酯、 二乙二醇二 （甲基） 丙埽酸酯、 三乙二 醇二 （曱基） 丙烯酸酯、 新戊二醇二 （甲基） 丙烯酸酯， 二乙烯 基苯； 所述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 （曱基） 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^ Tu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， 一般为純橡胶重量的 0. 1 - 10%重量， 优选为 0. 5 - 9%重量， 更优选为 0. 7 一 7%重量。
制备本发明的全硫化粉末橡胶所使用的高能射线源为通用的 钴源、 X-射线、 紫外线或高能电子加速器， 优选用钴源。 辐照的 剂量可以为 0. 1 - 30Mrad， 优选 0.5 - 20Mard。 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 9 0 %重量或更高。
本发明的全硫化粉末橡胶极易分散在塑料母体中， 因此可以 与各种塑料混合， 制成各种增韧塑料和热塑性弹性体。 基本制备 方法是将本发明的全硫化粉末橡胶与塑料按一定比例在常规混合 设备中和常规工艺条件下混合， 如果需要， 适量加入加工助剂和 增容剂。
在制备增韧塑料时， 本发明的全硫化粉末橡胶与塑料的重量 比为 0.5: 99. 5 - 50: 50 , 优选为 1: 99 - 30: 70。 被增韧的塑料可以 是尼龙、 聚丙烯、 聚乙烯、 聚氯乙烯、 聚氨酯、 环氧树脂、 聚酯、 聚碳酸酯、 聚甲醛、 聚苯乙烯、 聚苯醚（PP0 )、 聚苯 ^醚（ PPS ) 、 聚酰亚胺、 聚砜及其共聚物和共混物。
在制备热塑性弹性体时， 全硫化粉末橡胶与塑料的重量比为 30: 70 - 75: 25 , 优选为 50: 50 - 70: 30。 可用的塑料是尼龙、 聚丙 烯、 聚乙烯、 聚氯乙烯、 聚氨酯、 环氧树脂、 聚酯、 聚碳酸酯、 聚甲醛、 聚苯乙烯、 聚苯醚（PP0 ) 、 聚苯硫醚（PPS ) 、 聚酰亚 胺、 聚砜及其共聚物和共混物。 下面用实施例结合附图进一步描述本发明， 但本发明的范围 不受这些实施例的限制。本发明的范围由后附的权利要求书确定。
附图 1为实施例 4所得的全硫化羧基丁苯橡胶粉末的放大倍 数为 2万倍的扫描电镜照片；
附图 2为实施例 14所得样品的放大倍数为 4万倍的原子力显 微镜照片。
在以下实施例中， 凝胶含量是按照以下方法测量的： 准确称 取喷雾干燥得到的粉末橡胶约 0.1 克， 用通用的镜头纸包好， 再 包入 200 目的铜网中， 准确称量， 然后将其在甲苯中煮沸， 煮沸 时间以铜网及其包裹物在充分干燥后的质量基本恒定为准， 一般 为 6小时。 之后将充分煮沸过的铜网及其包裹物完全干燥， 准确 称量。 按照以下公式计算凝胶含量：
凝胶含量 （％) = [W0-(W1-W2)]AV0xlOO%
式中： W。表示粉末橡胶样品的重量；
\^表示煮沸前铜网及其包裹物的重量； \¥2表示煮沸后经充分干燥的铜网及其包裹物的重量。 溶胀指数是按照以下方法测量的： 将辐射硫化后的橡胶乳液 干燥成膜 （如成膜困难则直接用干燥的粉末） 。 将精确称量重量 为 W。的 200 目铜网制成的小盒泡入曱苯中，稍微放置， 然后捞出 迅速称重记为 Wl e称取约 0.1克的膜（或粉末）放入铜网小盒中， 将膜和铜网一起泡入曱苯中，放置于阴凉处溶胀 24小时后， 将铜 网连同溶胀的凝胶小心撈出， 快速吸去凝胶表面的溶剂， 然后迅 速称重， 重量记为 W2。 将称重后的铜网及凝胶彻底干燥至恒重， 重量记为 W3。 溶胀指数根据下式计算：
溶胀指数= ( W2-Wi ) /(W3-Wo) 实施例 1
将固含量 50重量％的市售羧基丁苯胶乳（燕山石化生产，牌 号： XSBRL - 5 1 ) 5Kg置于一容器中， 在搅拌下滴加丙烯酸异辛 酯 75g， 滴加完成后， 继续搅拌一' 时。 之后用钴源辐照， 剂量 为 2. 5Mrad， 剂量率为 50Gy/min。 辐照后的胶乳通过喷雾干燥器 喷雾干燥， 喷雾干燥器的进口温度为 140 °C - 160 °C， 出口温度为 40 °C - 60 °C , 于旋风分离器中收集干燥后的羧基丁苯橡胶粉末， 得到可自由流动的全硫化羧基丁苯橡胶粉末样品 1。 测得粉末橡 胶的粒径约为 150nm， 凝胶含量为 92. 6%，溶胀指数为 7.6。 实施例 2
除用 l OMrad剂量辐照外， 其它均与实施例 1中的相同，得到 可自由流动的全硫化羧基丁苯橡胶粉末样品 2。 测得粉末橡胶的 粒径约为 150nm， 凝胶含量为 94. 5%，溶胀指数为 5.4。 实施例 3
除交联助剂用二乙二醇二丙烯酸酯外， 其它均与实施例 1相 同， 得到可自由流动的全硫化羧基丁苯橡胶粉末样品 3。 测得粉 末橡胶粒径约为 150nm , 凝胶含量为 93. 0%，溶胀指数为 7.3。 实施例 4
除交联助剂用三羟甲基丙烷三丙烯酸酯外， 其它均与实施例 1相同， 得到可自由流动的全硫化羧基丁苯橡胶粉末样品 4。 测得 粉末橡胶的粒径约为 150nm (见附图 1 ) ， 凝胶含量为 93. 3%，溶 胀指数为 5.8。 实施例 5 将固含量为 45%重量的市售丁苯胶乳 （兰化生产， 牌号： 丁 苯- 50) 5Kg置于容器中， 在搅拌下滴加丙烯酸异辛酯 67.5g， 滴 加完成后， 继续搅拌一'■!、时。 之后用钴源辐照， 剂量为 2.5Mrad， 剂量率为 50Gy/min。 辐射后的胶乳通过喷雾干燥器喷雾干燥， 干 燥器的进口温度为 140°C - 160°C， 出口温度为 40°C -60°C, 得到 可自由流动的全硫化丁苯橡胶粉末样品 1。 测得粉末橡胶的粒径 约为 100nm， 凝胶含量为 90.0%,溶胀指数为 12.9。 实施例 6
除交联助剂用三羟甲基丙烷三丙烯酸酯外， 其它均与实施例 5相同， 得到可自由流动的全硫化丁苯橡胶粉末样品 2。 测得粉末 橡胶的粒径约为 100nm， 凝胶含量为 90.4%,溶胀指数为 11.6。 实施例 7
将固含量为 45重量％的市售羧基丁腈胶乳（兰化生产， 牌号 为 XNBRL) 5Kg置于容器中， 在搅拌下滴加丙烯酸异辛酯 67.5g， 在滴加完成后， 继续搅拌一小时。 之后用钴源辐照， 剂量为 2.5Mrad, 剂量率为 50Gy/min。 辐照后的胶乳通过喷雾干燥器喷 雾干燥， 干燥器进口温度为 140。C -160°C, 出口温度为 40°C -60 °C, 得到可自由流动的全硫化羧基丁腈粉末橡胶样品 1。 测得粉 末橡胶的粒径约为 50nm， 凝胶含量为 96.1°/。，溶胀指数为 7.5。 实施例 8
除交联助剂用三羟曱基丙烷三丙烯酸酯外， 其它均与实施例 7相同， 得到可自由流动的全硫化羧基丁腈橡胶粉末样品 2。 测得 粉末橡胶的粒径约为 50nm， 凝胶含量为 97.1%，溶胀指数为 6.7。 将固含量为 48重量％市售的丙烯酸丁酯胶乳（北京东方化工 厂生产， 牌号为 BC- 01) 5Kg置于容器中， 在搅拌下滴加丙烯酸 异辛酯 72g， 在滴加完成后， 继续搅拌一小时。 之后用钴源辐照， 剂量为 2.5Mrad， 剂量率为 50Gy/min。 辐照后的胶乳通过喷雾干 燥器喷雾干燥， 干燥器的进口温度为 14(TC - 160°C：， 出口温度为 40°C - 50°C, 得到可自由流动的全硫化丙烯酸丁酯橡胶粉末样品
I。 测得粉末橡胶的粒径约为 lOOnm, 凝胶含量为 85.7%，溶胀指数 为 12.2。 实施例 10
除交联助剂用三羟甲基丙烷三丙烯酸酯外， 其它均与实施例 9相同， 得到可自由流动的全硫化丙烯酸丁酯橡胶粉末样品 2。 测 得粉末橡胶的粒径约为 100nm， 凝胶含量为 87.7%，溶胀指数为
II.0。 实施例 11
将固含量为 60重量％的天然橡胶胶乳（北京乳胶厂提供）5Kg 置于容器中， 在搅拌下滴加三羟甲基丙烷三丙烯酸酯 150g， 在滴 加完成后， 继续搅拌一'』、时。 之后用钴源辐照， 剂量为 15Mrad， 剂量率为 50Gy/min。 辐照后的胶乳通过喷雾干燥器喷雾干燥， 干 燥器的进口温度为 140°C - 160°C， 出口温度为 40°C - 50°C，得到 可自由流动的全硫化天然橡胶粉末样品 1。 测得粉末橡胶的平均 粒径约为 500nm， 凝胶含量为 94.1%，溶胀指数为 12.8。 实施例 12
采用全硫化羧基丁苯橡胶粉末样品 1(实施例 1 )和尼龙 6(日 本宇部兴产 1013B) 以 75/25的比例混合， 用德国 WP公司的 ZSK - 25 双螺杆挤出机共混造粒， 挤出机各段温度分别设定为： 210 °C；、 225°C、 225°C、 225°C、 230°C和 225。C (机头温度） 。 将粒 料分别用压片法和注塑法制成标准样条， 经测试得到此全硫化羧 基丁苯橡胶 /尼龙 6热塑性弹性体的性能如表 1所示。 实施例 13
采用全硫化天然橡胶粉末样品（实施例 11 )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的比例混合， 用 Brabender捏合机共混 2分钟， 捏合机油浴温度为 160°C。 所 得样品用双辊开炼机成片 （温度： 160°C ) , 然后压片制样， 测得 全硫化天然橡胶 /聚乙烯热塑性弹性体的性能如表 1所示。 表 1
拉伸断裂 拉伸永 100%定 维卡软 拉伸强度
伸长率 久变形 伸强度 邵氏 化温度 (MPa)
样品 (%) (%) (MPa) O
ASTM ASTM ASTM ASTM ASTM D2240 - ASTM D412 D412 D412 D412 95 D1525 压片
17.0 175 61 11.8
实施 制样
例 12 注射 40
16.4 216 101 10.5 164.8 制样 (邵氏 ¾¾D) 实施 压片 86
15.0 438 122
例 13 制样 (邵氏 ¾¾A) 实施例 14
在尼龙 6 (日本宇部兴产生产， 牌号 1013B) 中加入 20%的 全硫化羧基丁苯橡胶粉末样品 1 (实施例 1 )和 0.6 %的硬脂酸钙 及 0.8%的超细滑石粉， 高速（ 1500rpm)混合 3分钟， 然后用 WP 公司 ZSK- 25双螺杆挤出机共混造粒， 挤出机各段温度设定为： 230°C 235°C、 240°C, 245° (：、 240。 ( 、 235°C, 粒料烘干后注塑 成标准样条， 按 ASTM标准测得超韧尼龙 6的性能如表 2所示。 用 原子力显微镜测得的粒子分布图如附图 2所示 （分散相橡胶粒子 的粒径约为 150nm) 。 比较例 1
将实施例 14中所用的尼龙 6直接注塑成标准样条，测试结果 如表 2所示。 实施例 15
在聚甲窿（旭化成生产， 牌号 4520 )中加入 28%的全硫化羧 基丁苯橡胶粉末样品 1 (实施例 1 ) ， 并加入 1.2 %的硬脂酸钙、 0.6 %的超细滑石粉、 0.3%的聚乙烯蜡和 0.4 %的抗氧剂 IRGAN0X 1010(购自 Ciba-Geigy)， 高速（ 1500rpm) 混合 3 分钟， 然后用 WP公司 ZSK - 25双螺杆挤出机共混造粒，挤出机各段温度设定为： 175° (：、 180°C、 1851：、 185°C、 180°C、 175°C , 粒料烘干后注塑 成标准样条， 按 ASTM标准测得增韧聚甲醛的性能如表 2所示。 比较例 2
将实施例 15中所用的聚曱醛直接注塑成标准样条，测试结果 如表 2所示。 表 2
测试方法 比较例 1 实施例 14 比较例 2 实施例 15 拉伸强度 ASTM D638 72 51.5 62.2 47.2
(MPa )
断裂伸长率 ASTM D638 60 175 30 215 ( % )
弯曲强度 ASTM D790 80.5 56.6 82.5 56.7 (MPa)
弯曲模量 ASTM D790 2.2 1.72 2.34 1.65 (GPa)
Izod 缺口冲击 ASTM D256 45 665 42 562 强度 (J/m)
HDT 1.82MPa ASTM D648 68.5 61.8
CO 0.46MPa 161.5 142.8

Claims

权 利 要 求
1. 一种除通过化学交联法制备的硫化粉末硅橡胶以外的全硫 化粉末橡胶。
2. 按权利要求 1所述的全硫化粉末橡胶，其特征是，所述粉末 橡胶的粒径为 20― 2000nm,优选 30― 1500nm,更优选 50 - 500nm。
3. 按权利要求 1所述的全硫化粉末橡胶，其特征是，所述粉末 橡胶的凝胶含量为 75 %重量或更多， 优选 9 0 %重量或更多。
4. 按权利要求 1所述的全硫化粉末橡胶，其特征是，所述粉末 橡胶的微粒是均相的。
5. 按权利要求 1 - 4之任一项所述的全硫化粉末橡胶，其特征 是， 所述橡胶选自天然橡胶、 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、 聚氨酯橡胶和氟橡胶。
6， 制备权利要求 1 - 5 之任一项所述的全硫化粉末橡胶的方 法， 它包括用辐照法将相应的橡胶胶乳硫化。
7. 按权利要求 6所述的方法， 其特征是， 所述辐照采用高能 射线源进行， 橡胶胶乳中加入或不加入交联助剂， 辐照后再经干 燥， 得到全硫化粉末橡胶。
8. 按权利要求 6所述的方法， 其特征是， 所述高能射线源选 自钴源、 X-射线、 紫外线和高能电子加速器， 优选钴源。
9. 按权利要求 6'所述的方法， 其特征是， 所述橡胶胶乳选自 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、 聚丁二埽橡胶胶乳、 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、 聚氨酯橡 胶胶乳和氟橡胶胶乳。
10. 按权利要求 6所述的方法，其特征是，在辐照时在橡胶胶 乳中加入交联助剂， 所述交联助剂选自单官能团交联助剂、 二官 能团交联助剂、 三官能团交联助剂、 四官能团交联助剂、 多官能 团交联助剂及其任意组合。
11. 按权利要求 10所述的方法， 其特征是， 所述交联助剂选 自 （甲基） 丙烯酸辛酯、 （甲基） 丙烯酸异辛酯、 （甲基） 丙烯 酸缩水甘油酯、 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、 三羟甲基丙烷三 （曱基） 丙烯酸酯、 季戊四醇三 （甲基） 丙烯酸酯、 季戊四醇四（甲基）丙烯酸酯、 乙氧化季戊四醇四（甲 基） 丙浠酸酯或二季戊四醇五 （甲基） 丙烯酸酯及其任意组合。
12. 按权利要求 6所述的方法，其特征是， 所述干燥用喷雾干 燥器进行喷雾干燥或者通过用沉淀干燥法进行， 优选喷雾干燥。
13. 按权利要求 6所述的方法， 其特征是， 辐照的剂量为 0.1 - 30Mrad, 优选 0.5 - 20Mrad。
14. 按权利要求 10所述的方法， 其特征是， 所述交联助剂的 加入量为纯橡胶重量的 0.1 - 10%， 优选 0.5 - 9%， 更优选 0.7
- 7 %。
15. 按权利要求 12所述的方法， 其特征是， 所述喷雾干燥器 的进口温度为 100'C - 200°C， 出口温度为 20°C - 80°C。
16. —种可用于制备增韧塑料或热塑弹性体的组合物 ,其特征 是， 它含有权利要求 1 - 5 之任一项所述的全硫化粉末橡胶和塑 料。
17. 权利要求 1 - 5之任一项所述的全硫化粉末橡胶用于增韧 塑料或制备热塑性弹性体的应用。
PCT/CN2000/000281 1999-12-03 2000-09-18 Caoutchouc en poudre entierement vulcanise a diametre de particules regulable, son procede de preparation et des utilisations WO2001040356A1 (fr)

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AU75031/00A AU7503100A (en) 1999-12-03 2000-09-18 Full vulcanized powdered rubber with controllable particle diameter, preparing method and uses thereof
DE60033321T DE60033321T2 (de) 1999-12-03 2000-09-18 Voll vulkanisiertes kautschukpulver mit kontrollierbarem partikeldurchmesser sowie herstellungsverfahren und verwendung dafür
EP00963852A EP1262510B1 (en) 1999-12-03 2000-09-18 Full vulcanized powdered rubber with controllable particle diameter, preparing method and uses thereof
CNB008164509A CN1152082C (zh) 1999-12-03 2000-09-18 全硫化可控粒径粉末橡胶及其制备方法和用途
CA2393311A CA2393311C (en) 1999-12-03 2000-09-18 Fully vulcanized powdery rubber with controllable particle diameter, preparing method and uses thereof
JP2001541106A JP2003515644A (ja) 1999-12-03 2000-09-18 制御可能な粒度を有する全硫化粉末ゴム，その調製方法及び用途

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WO2013060290A1 (zh) 2011-10-26 2013-05-02 中国石油化工股份有限公司 一种橡胶组合物及其制备方法和其硫化胶
CN103070165B (zh) * 2011-10-26 2014-08-06 中国石油化工股份有限公司 一种粉末橡胶负载的抗菌剂及其制备方法
CN103070165A (zh) * 2011-10-26 2013-05-01 中国石油化工股份有限公司 一种粉末橡胶负载的抗菌剂及其制备方法
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US9944883B2 (en) 2015-04-20 2018-04-17 China Petroleum & Chemical Corporation Lubricant composition, and preparation method and use thereof
CN108976446A (zh) * 2017-05-31 2018-12-11 中国石油化工股份有限公司 粉末丁苯橡胶的制备方法
CN108976446B (zh) * 2017-05-31 2021-04-13 中国石油化工股份有限公司 粉末丁苯橡胶的制备方法
WO2019007217A1 (zh) 2017-07-01 2019-01-10 中国石油化工股份有限公司 类蜘蛛丝的聚合物纤维、其制备方法及其用途
US11572638B2 (en) 2017-07-01 2023-02-07 China Petroleum & Chemical Corporation Spider-silk-like polymer fiber, preparation method therefor and use thereof

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DE60033321T2 (de) 2007-10-25
BR0016302A (pt) 2002-11-05
US6423760B1 (en) 2002-07-23
CA2393311A1 (en) 2001-06-07
ES2280244T3 (es) 2007-09-16
EP1262510A4 (en) 2004-11-24
JP2003515644A (ja) 2003-05-07
JP5069407B2 (ja) 2012-11-07
DE60033321D1 (de) 2007-03-22
BR0016302B1 (pt) 2011-02-22
EP1262510B1 (en) 2007-02-07
AU7503100A (en) 2001-06-12
EP1262510A1 (en) 2002-12-04
ATE353349T1 (de) 2007-02-15
CA2393311C (en) 2010-11-23
JP2005325370A (ja) 2005-11-24

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