CN103755857A - Low-temperature resistant fluorubber, and preparation method thereof - Google Patents

Low-temperature resistant fluorubber, and preparation method thereof Download PDF

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CN103755857A
CN103755857A CN 201310679947 CN201310679947A CN103755857A CN 103755857 A CN103755857 A CN 103755857A CN 201310679947 CN201310679947 CN 201310679947 CN 201310679947 A CN201310679947 A CN 201310679947A CN 103755857 A CN103755857 A CN 103755857A
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fluorine
low temperature
reaction
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containing
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CN103755857B (en )
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王昌尧
吴玉勋
钱厚琴
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江苏梅兰化工有限公司
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The invention relates to a low-temperature resistant fluorubber, and a preparation method thereof, and belongs to the field of fluorine chemical industry and high molecular material technology. The preparation method comprise following steps: 1) alcohols containing fluorine, such as tetrafluoro-1-Propanol, octafluoropentyl alcohol, and H,1H,7H-dodecafluoro-1-heptanol are taken as initial fluorine-containing materials, and are subjected to condensation with pentafluoro bromopropylene in the presence of a phase transfer catalyst so as to obtain a fluorine-containing ether containing carbon-carbon double bonds; 2) a monomer mixture is prepared from 1,1-difluoroethylene, hexafluoropropylene, and fluorine-containing alkyl pentafluoropropene ether according to a certain molar ratio, and is stored for further treatment; and 3) the monomer mixture is delivered into a polymerization vessel, and is subjected to emulsion polymerization in the presence of an emulsifier, an initiator, and a chain transferring agent, and latex obtained via polymerization is subjected to coacervation, washing, and drying, and is made into low-temperature resistant fluorubber sheets using a open mill. The preparation method is capable of improving low-temperature resistance of fluorubber effectively, so as to satisfy requirements on low-temperature sealing; the raw materials are easily available; preparation processes are easy to realize; and the preparation method is beneficial for popularization and application.

Description

一种耐低温氟橡胶及其制备方法 Low temperature resistance and preparation method fluororubber

技术领域 FIELD

[0001] 本发明涉及一种耐低温氟橡胶及其制备方法。 [0001] The present invention relates to a low temperature and a preparation method fluororubber.

背景技术 Background technique

[0002] 氟橡胶因具有耐油、耐高温、耐溶剂、耐强酸、耐强氧化剂、阻燃、耐老化等一系列优良的特性,所以在国防军工、航空航天、电子通信、车辆船舶、石油化工等尖端技术领域获得了广泛地应用。 [0002] The fluorine-containing rubber because oil resistance, high temperature resistance, solvent resistance, acid resistance, excellent characteristics series of strong oxidants, flame retardant, anti-aging, etc., so in the defense industry, aerospace, electronic communication, vehicles, ships, petrochemicals and other cutting-edge technology has been widely applied. 特别是近几年来,随着上述相关行业的高速发展和技术进步,氟橡胶作为一种不可替代的高性能弹性体,不仅在需求上大幅增加,在用途上也不断扩大。 Especially in recent years, with the rapid development and technological progress above related industries, fluorine rubber as an irreplaceable Performance Elastomers, not only a substantial increase in demand in the use also expanded. 但氟橡胶也有一个突出的缺点:其低温性能太差(一般Tg只有一20°C ),这远不能满足市场对其性能的要求,尤其在航空、航天方面,因其在高空中的高速飞行,使得工作部件的温度极低和极高,而且这些部件往往又都受到强腐蚀,更由于航空航天工业对安生性要求极高,故只有在氟橡胶方面寻找突破,也就是说要想办法使氟橡胶具有较低的脆性温度。 However, a fluororubber has a particular disadvantage: its poor low temperature properties (typically only one Tg 20 ° C), which can not meet its performance requirements of the market, especially in the aerospace aspect, because at high altitude high speed flight so that the working parts of the low and high temperature, and these parts are often strong and are subject to corrosion, but also because of the aerospace industry for extremely quiet requirements, it is only to find a breakthrough in terms of fluorine rubber, that is to find a way to make fluorine rubber having a low brittleness temperature. 当前生产耐低温氟橡胶普遍使用的方法是在VDF、TFE单体的基础上引入新单体一全氟甲基乙烯基醚(PMVE)进行共聚。 Current low temperature producing a rubber commonly used to introduce new monomer is a fluorine-perfluoromethyl vinyl ether (PMVE) on VDF, TFE based on the copolymerized monomers. 全氟甲基乙烯基醚能够明显地改善氟橡胶的低温柔性,有效地降低Tg。 Perfluoromethyl vinyl ether can significantly improve the low temperature flexibility fluororubber effectively reduce Tg. 但为了得到Tg较低的含氟弹性体,需要加入相当多的聚合单体PMVE,其用量通常在20%~40% (摩尔分数)之间。 However, in order to obtain a lower Tg fluoroelastomers, necessary to add a considerable amount of PMVE polymerizable monomers, generally in an amount between 20% to 40% (molar fraction). 在本发明作出之前,公开号为CN85109162,CN1152583A的中国发明专利中公开了几种能够改善橡胶低温性能的新型单体,但该技术方案所需的原材料价格昂贵,且在制备过程中有时使用含氟烷基碘,因此,加工工艺复杂。 Prior to the present invention, Publication No. CN85109162, Chinese patent CN1152583A disclosed invention, several low temperature properties of rubber can be improved novel monomers, prices of raw materials needed but this solution is expensive, and sometimes during preparation containing fluoroalkyl iodide, therefore, complicated processing.

发明内容 SUMMARY

[0003] 本发明提供了一种耐低温氟橡胶及其制备方法,它可以有效地改善了氟橡胶的耐低温性能,以适应低温密封的要求;而且具有原材料易得,制备工艺易实现,有利于推广应用的优点。 [0003] The present invention provides a fluororubber low temperature and a preparation method, which can effectively improve the low temperature properties of fluorine rubber, to accommodate the requirements of low-temperature seal; and readily available raw material having a preparation process easy to implement, there conducive to the promotion of the advantages of the application.

[0004] 本发明采用了以下技术方案:一种耐低温氟橡胶,它具有如下结构: [0004] The present invention adopts the following technical solution: A low-temperature-resistant fluorine-containing rubber, which has the following structure:

Figure CN103755857AD00031

[0005] 本发明还公开了一种如权利要求1所述的耐低温氟橡胶的制备方法,它的制备步骤如下:步骤一,按重量比,将20~30份含氟醇、5~15份五氟溴丙烯和1份相转移催化剂溶于20份氯代烷烃类溶剂中,再滴加3~6份碱的7.5份水溶液,升温至45~50°C,待缩合反应完全后,冷却反应液,滤去不溶的盐,分出油层,以稀盐酸、蒸馏水洗涤至中性,经无水硫酸钠干燥后分馏得到产物含氟烷基全氟丙烯基醚;步骤二,将摩尔比为55~75:15~30:2~10的1,1- 二氟乙烯、六氟丙烯、含氟烷基全氟丙烯基醚组成单体混合物,备用;步骤三,向聚合釜中加入去离子水,经氮气置换和抽真空处理,至釜内氧含量合格后,将乳化剂、pH调节剂、链转移剂加入聚合釜,再将单体混合物通过压缩机加入反应釜内,使釜中的压力达到1.8~2.6Mpa,将反应混合物加热至75~95°C,加入引发剂开始反应,反 [0005] The present invention also discloses a method for preparing a low temperature fluororubber according to claim 1, which is prepared as follows: Step a, by weight, 20 to 30 parts of the fluorine-containing alcohol, 5 to 15 parts of propylene and 1-bromo-pentafluoropropene parts 7.5 parts aqueous phase transfer catalyst dissolved in 20 parts chlorinated alkane solvent, and then added dropwise 3 to 6 parts of a base, warmed to 45 ~ 50 ° C, after completion of the condensation reaction was cooled the reaction solution, the insoluble salts filtered off, separation of the oil with dilute hydrochloric acid, washed with distilled water until neutral, dried over anhydrous sodium sulfate the product was fractionated to give a fluorine-containing alkyl ether perfluoropropene; step two, the molar ratio 55 ~ 75: 15 ~ 30: 2 to 10 1,1-fluoride, hexafluoropropene, perfluoro fluorine-containing alkyl ether composition of the monomer mixture of propylene, standby; step three, the polymerization vessel was added to the deionized water, purged with nitrogen and vacuum treatment, the oxygen content of the autoclave to the qualified, the emulsifying agents, pH adjusting agents, chain transfer agent is added to the polymerization vessel, and then the monomer mixture was added to the reactor through a compressor, making kettle pressure reaches 1.8 ~ 2.6Mpa, the reaction mixture was heated to 75 ~ 95 ° C, the initiator is added to start the reaction, trans 过程中连续补加单体混合物将压力保持在1.8~2.6Mpa,同时保持300~600r/min的搅拌速率来保持反应速率;在反应2~5h后停止加入单体混合物,冷却后对未反应的混合单体进行回收;聚合所得乳胶经凝聚,洗涤,干燥脱水后由开炼机制成耐低温氟橡胶胶片。 During monomer mixture was continuously added to maintain the pressure at 1.8 ~ 2.6Mpa, while maintaining the stirring rate 300 ~ 600r / min to maintain the rate of the reaction; 2 ~ 5h after the reaction of the monomer mixture was stopped, after cooling of the unreacted recovering the monomer mixture; the resulting polymer latex coagulated, washed, dehydrated and dried by a mechanism into an open roll film fluororubber low temperature.

[0006] 所述的步骤一的相转移催化剂为四丁基溴化铵或十八烷基三甲基氯化铵。 [0006] The steps of a phase transfer catalyst is tetrabutylammonium bromide or octadecyl chloride. 所述的步骤一中碱为氢氧化钠或氢氧化钾。 A step in said base is sodium hydroxide or potassium hydroxide. 所述的步骤一种氯代烷烃类为二氯甲烷、二氯乙烷或四氯乙烷。 The steps of one of said chlorinated alkanes as dichloromethane, dichloroethane or tetrachloroethane. 所述的步骤三引发剂为过硫酸盐、过硫酸盐-亚硫酸氢盐、过氧化二碳酸二异丙酯、叔丁基过氧化氢或过氧化苯甲酰。 Step three said persulfate initiators, persulfate - bisulfite, peroxide, di isopropyl, t-butyl hydroperoxide or benzoyl peroxide. 所述的步骤三种乳化剂为全氟辛酸的钠盐、钾盐或铵盐、全氟辛基硫酸的锂盐。 The step of three kinds of perfluorooctanoic acid emulsifier is sodium, potassium or ammonium salt, a lithium salt of perfluorooctyl acid. 所述的步骤三种PH调节剂为碳酸氢钠、磷酸氢二钠、磷酸氢二钠或四硼酸钠。 The step of three kinds of PH adjusting agent is sodium bicarbonate, disodium hydrogen phosphate, disodium hydrogen phosphate or sodium tetraborate. 所述步骤三中链转移剂为丙酮、丙二酸二乙酯、异戊烷或醋酸乙酯。 Step III the chain transfer agent is acetone, diethyl malonate, ethyl acetate, or iso-pentane. 所述的组分的加入量以蒸馏水按100重量份计算,其余助剂分别为:引发剂0.05~0.2,乳化剂 The component is added in an amount to 100 parts by weight of distilled water, the remaining auxiliaries are: 0.05 to 0.2 initiator, emulsifier

0.04~0.8,pH调节剂0.02~0.6,链转移剂0.08~1.5。 0.04 ~ 0.8, pH adjusting agent, 0.02 to 0.6, the chain transfer agent is 0.08 to 1.5.

[0007] 本发明具有以下有益效果:采用了以上技术方案后,本发明的耐低温氟橡胶的制备方法,由含氟醇制备含碳碳双键的含氟醚单体,再将新型含氟醚单体和1,1- 二氟乙烯、六氟丙烯混合共聚制得耐低温氟橡胶,由于在氟橡胶分子中引入氟醚侧基,因此,改善了氟橡胶的低温性能,以适应低温密封的要求;且具有原材料易得,制备工艺易实现,有利于推广应用的优点。 [0007] The present invention has the following advantages: With the above technical solutions, low temperature method for preparing the fluororubber of the present invention, the fluorine-containing ether monomers prepared from fluorine-containing alcohol of the double bonds carbon-carbon, then the novel fluorine-containing ether monomers and vinylidene fluoride, hexafluoropropylene copolymer prepared by mixing the fluororubber low temperature, the introduction of side groups fluoroether fluororubber molecules, thus improving the low temperature properties of the fluororubber, to accommodate a low temperature seal requirement; and has the advantage of readily available materials, the preparation process easy to implement, is conducive to the application.

附图说明 BRIEF DESCRIPTION

[0008] 图1为本发明的工艺流程示意图。 [0008] FIG. 1 is a process flow schematic diagram of the invention.

具体实施方式 detailed description

[0009] 本发明提供了一种耐低温氟橡胶,它具有如下结构: [0009] The present invention provides a low-temperature-resistant fluorine-containing rubber, which has the following structure:

Figure CN103755857AD00041

其中:Rf= -(CF2CF2)nH, n=l ~6 的整数。 Wherein: Rf = - (CF2CF2) nH, n = an integer of l ~ 6.

[0010] 在图1中,本发明还公开了一种耐低温氟橡胶的制备方法,它的制备步骤如下:步骤一,准备物料:按重量比,将20~30份含氟醇、5~15份五氟溴丙烯和1份相转移催化剂溶于20份氯代烷烃类溶剂中,再滴加3~6份碱的7.5份水溶液,升温至45~50V,待缩合反应完全后,冷却反应液,滤去不溶的盐,分出油层,以稀盐酸、蒸馏水洗涤至中性,经无水硫酸钠干燥后分馏得到产物含氟烷基全氟丙烯基醚,相转移催化剂为四丁基溴化铵或十八烷基三甲基氯化铵,碱为氢氧化钠或氢氧化钾,氯代烷烃类为二氯甲烷、二氯乙烷或四氯乙烷;步骤二,将摩尔比为55~75:15~30:2~10的1,1- 二氟乙烯、六氟丙烯、含氟烷基全氟丙烯基醚组成单体混合物,备用;步骤三,向聚合釜中加入去离子水,经氮气置换和抽真空处理,至釜内氧含量合格后,将乳化剂、PH调节剂、链转移剂加入聚 [0010] In FIG 1, the present invention also discloses a method for preparing the fluororubber low temperature, it was prepared as follows: Step one, material preparation: weight ratio, 20 to 30 parts of the fluorine-containing alcohol, 5 ~ after 15 parts of propylene and 1-bromo-pentafluoropropene parts of an aqueous solution of 7.5 parts of phase transfer catalyst dissolved in 20 parts chlorinated alkane solvent, and then added dropwise 3 to 6 parts of a base, warmed to 45 ~ 50V, until the condensation reaction was complete, the reaction was cooled solution, the insoluble salts filtered off, separation of the oil with dilute hydrochloric acid, washed with distilled water until neutral, dried over anhydrous sodium sulfate to give the product fractionation fluorinated alkyl perfluoropropylene ether, a phase transfer catalyst is tetrabutylphosphonium ammonium or octadecyl trimethyl ammonium chloride, the base is sodium hydroxide or potassium hydroxide, chlorinated alkanes as dichloromethane, dichloroethane or tetrachloroethane; step two, the molar ratio 55 ~ 75: 15 ~ 30: 2 to 10 1,1-fluoride, hexafluoropropene, perfluoro fluorine-containing alkyl ether composition of the monomer mixture of propylene, standby; step three, the polymerization vessel was added to the deionized water, purged with nitrogen and vacuum treatment, the oxygen content of the autoclave to the qualified, an emulsifier, PH adjusting agents, chain transfer agent, the addition of polyethylene 釜,乳化剂为全氟辛酸的钠盐、钾盐或铵盐、全氟辛基硫酸的锂盐,PH调节剂为碳酸氢钠、磷酸氢二钠、磷酸氢二钠或四硼酸钠,链转移剂为丙酮、丙二酸二乙酯、异戊烷或醋酸乙酯,再将单体混合物通过压缩机加入反应釜内,使釜中的压力达到1.8~2.6Mpa,将反应混合物加热至75~95°C,加入引发剂开始反应,引发剂为过硫酸盐、过硫酸盐-亚硫酸氢盐、过氧化二碳酸二异丙酯、叔丁基过氧化氢或过氧化苯甲酰,反应过程中连续补加单体混合物将压力保持在 Kettle, perfluorooctanoic acid emulsifier is sodium, potassium or ammonium salts, the lithium salt of perfluorooctyl acid, PH adjusting agent is sodium bicarbonate, disodium hydrogen phosphate, disodium hydrogen phosphate or sodium tetraborate, chain transfer agent was added to the reactor as acetone, diethyl malonate, ethyl acetate, or isopentane, and then a monomer mixture through the compressor, the pressure in the autoclave reached 1.8 ~ 2.6Mpa, the reaction mixture was heated to 75 to 95 ° C, the reaction initiator is added initiator, a persulfate initiator, persulfate - bisulfite, peroxide, di isopropyl, t-butyl hydroperoxide or benzoyl peroxide, the reaction process the monomer mixture was continuously added to maintain the pressure

1.8~2.6Mpa,同时保持300~600r/min的搅拌速率来保持反应速率;在反应2~5h后停止加入单体混合物,冷却后对未反应的混合单体进行回收;聚合所得乳胶经凝聚,洗涤,干燥脱水后由开炼机制成耐低温氟橡胶胶片,本发明的所添加物料的组分的加入量以蒸馏水按100重量份计算,其余助剂分别为:引发剂0.05~0.2,乳化剂0.04~0.8,pH调节剂 1.8 ~ 2.6Mpa, while maintaining 300 ~ 600r / min agitation rate to maintain the reaction rate; 2 ~ 5h after the reaction of the monomer mixture was stopped, the unreacted monomer mixed recovery after cooling; the resulting polymeric latex by coagulation, after washing, dehydration by a mechanism into an open roll film fluororubber low temperature, addition of the added amount of component materials of the present invention with distilled water calculated on 100 parts by weight, the remaining auxiliaries are: 0.05 to 0.2 initiator, emulsifier 0.04 ~ 0.8, pH adjusting agents

0.02~0.6,链转移剂0.08~1.5。 0.02 to 0.6, the chain transfer agent is 0.08 to 1.5.

[0011] 下面通过实施例进一步说明本发明的技术方案: [0011] The following aspect of the invention is further illustrated by way of example:

实施例一: Example One:

本实施例以四氟丙醇为原料,先经缩合反应制备四氟丙基五氟丙烯基醚: In this embodiment, as the raw material tetrafluoropropanol, pentafluoropropene tetrafluoropropyl ether is first prepared by condensation reaction of:

在配有搅拌、温度计、冷凝器的反应器中,以重量计,将24份四氟丙醇、8份五氟溴丙烯和1份四丁基溴化铵溶于20份CH2Cl2中,滴加5份NaOH的7.5份水溶液,升温至50°C反应24h后,冷却反应液,滤去不溶的盐,分出油层,以4%的盐酸酸洗I次,蒸馏水洗涤3次至中性,无水硫酸钠干燥后分馏得到产物四氟丙基五氟丙烯基醚,收率83.5%。 It equipped with a stirrer, a thermometer, a condenser reactor, by weight, 24 parts of tetrafluoropropanol, 8 parts of propylene and 1-bromo-pentafluoropropene parts of tetrabutylammonium bromide were dissolved in 20 parts of CH2Cl2 was added dropwise 5 parts of aqueous solution of 7.5 parts of NaOH, the reaction was warmed to 50 ° C after 24h, the reaction solution was cooled, the insoluble salts filtered off, separation of the oil, 4% hydrochloric acid I times, washed three times with distilled water to neutral, without after the product was fractionated and dried over anhydrous sodium sulfate pentafluoropropene tetrafluoropropyl ether, a yield of 83.5%.

[0012] 再合成支链含四氟丙基五氟丙烯基醚的氟橡胶: [0012] resynthesis fluororubber containing branched pentafluoropropene tetrafluoropropyl ether:

向3m3聚合釜中加入1500Kg去离子水,经氮气置换和抽真空处理,至釜内氧含量合格后,将3.0Kg全氟辛酸铵、7.5Kg磷酸氢二钠、1.2Kg丙二酸二乙酯加入聚合釜,再将1,1- 二氟乙烯、六氟丙烯、四氟丙基五`氟丙烯基醚以70:25:5的摩尔比组成的单体混合物通过压缩机加入反应釜内,使釜中的压力达到2.4Mpa,将反应混合物加热至90°C,加入2.3Kg过硫酸钾开始反应,反应过程中连续补加单体混合物将压力保持在2.4Mpa,同时保持450r/min的搅拌速率来保持反应速率;在反应3h后停止加入单体混合物,冷却后对未反应的混合单体进行回收;聚合所得乳胶经凝聚,洗涤,干燥脱水后由开炼机制得本发明的耐低温氟橡胶生胶。 3m3 was added to the polymerization vessel 1500Kg deionized water, purged with nitrogen and vacuum treatment, the oxygen content of the autoclave to the qualified, the ammonium perfluorooctanoate 3.0Kg, 7.5Kg of disodium hydrogen phosphate, diethyl malonate was added 1.2Kg polymerization autoclave, and then vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene hexafluoropropylene `pentamethyl ether to 70: 25: 5 molar ratio of monomer mixture composition by the compressor to the kettle, the kettle was the pressure reaches 2.4Mpa, the reaction mixture was heated to 90 ° C, potassium persulfate was added 2.3Kg start of the reaction, during the reaction of the monomer mixture was continuously added to keep the pressure 2.4Mpa, while maintaining the stirring rate 450r / min to maintaining the reaction rate; 3h the reaction was stopped after the monomer mixture, mixing the unreacted monomer is recovered after cooling; the resulting polymeric latex coagulated, washed, dehydrated and dried to give the open roll mechanism of the present invention low temperature raw fluororubber glue. 以此生胶为基体制备的硫化胶经测定,玻璃化温度为_26°C。 Vulcanizates was determined for the gum base in this preparation, the glass transition temperature of _26 ° C.

[0013] 实施例二: [0013] Example II:

本实施例以八氟戊醇为原料,按实施例1的制备方法,先经缩合反应制备八氟戊基五氟丙烯基醚,收率76.4%。 In this embodiment, octafluoropentanol as starting material, prepared by the method of Example 1, is first reacted pentafluoropropene octafluoropentyl ether prepared by condensation, yield 76.4%.

[0014] 再合成支链含八氟戊基五氟丙烯基醚的氟橡胶: [0014] resynthesis branched fluorine-containing rubber octafluoropentyl pentafluoropropene ether:

向3m3聚合釜中加入1500Kg去离子水,经氮气置换和抽真空处理,至釜内氧含量合格后,将0.9Kg全氟辛酸铵、1.5Kg磷酸氢二钠、7.5Kg丙二酸二乙酯加入聚合釜,再将1,1- 二氟乙烯、六氟丙烯、八氟戊基五氟丙烯基醚以75:22:3的摩尔比组成的单体混合物通过压缩机加入反应釜内,使釜中的压力达到2.0Mpa,将反应混合物加热至85°C,加入0.9Kg过硫酸钾开始反应,反应过程中连续补加单体混合物将压力保持在2.0Mpa,同时保持550r/min的搅拌速率来保持反应速率;在反应4h后停止加入单体混合物,冷却后对未反应的混合单体进行回收;聚合所得乳胶经凝聚,洗涤,干燥脱水后由开炼机制得本发明的耐低温氟橡胶生胶。 3m3 was added to the polymerization vessel 1500Kg deionized water, purged with nitrogen and vacuum treatment, the oxygen content of the autoclave to the qualified, the ammonium perfluorooctanoate 0.9Kg, 1.5Kg of disodium hydrogen phosphate, diethyl malonate was added 7.5Kg polymerization autoclave, and then vinylidene fluoride, hexafluoropropylene, octafluoropentyl pentafluoropropene ether 75: 22: 3 molar ratio by the addition of the monomer mixture of a compressor in the reaction kettle, the kettle was pressure reaches 2.0Mpa, the reaction mixture was heated to 85 ° C, potassium persulfate was added 0.9Kg start of the reaction, during the reaction of the monomer mixture was continuously added to keep the pressure 2.0Mpa, while maintaining the stirring rate 550r / min to maintain reaction rate; stopped after 4h the reaction mixture was added to the monomer, mixing the unreacted monomer is recovered after cooling; the resulting polymeric latex coagulated, washed, and dried to give the present invention an open roll mechanism by dehydration and low temperature fluororubber gum . 以此生胶为基体制备的硫化胶经测定,玻璃化温度为_32°C。 Vulcanizates was determined for the gum base in this preparation, the glass transition temperature of _32 ° C.

[0015] 实施例三: [0015] Example III:

向3m3聚合釜中加入1500Kg去离子水,经氮气置换和抽真空处理,至釜内氧含量合格后,将12Kg全氟辛酸铵、6Kg磷酸氢二钠、3Kg丙二酸二乙酯加入聚合釜,再将1,1- 二氟乙烯、六氟丙烯、四氟丙基五氟丙烯基醚以78:12:10的摩尔比组成的单体混合物通过压缩机加入反应釜内,使釜中的压力达到2.4Mpa,将反应混合物加热至75°C,加入1.5Kg过硫酸钾开始反应,反应过程中连续补加单体混合物将压力保持在2.6Mpa,同时保持500r/min的搅拌速率来保持反应速率;在反应5h后停止加入单体混合物,冷却后对未反应的混合单体进行回收;聚合所得乳胶经凝聚,洗涤,干燥脱水后由开炼机制得本发明的耐低温氟橡胶生胶。 3m3 was added to the polymerization vessel 1500Kg deionized water, purged with nitrogen and vacuum treatment, the oxygen content of the autoclave to the qualified, the ammonium perfluorooctanoate 12Kg, 6Kg disodium hydrogen phosphate, was added diethyl malonate 3Kg polymerization vessel, and then the vinylidene fluoride, hexafluoropropylene, pentafluoropropene, tetrafluoroethylene propyl ether is added by a compressor 78:12:10 molar ratio of the monomer in the reaction mixture of the autoclave, the pressure in the autoclave reached 2.4MPa, the reaction mixture was heated to 75 ° C, potassium persulfate was added 1.5Kg start of the reaction, during the reaction of the monomer mixture was continuously added to maintain the pressure at 2.6 mPa, while maintaining the stirring rate 500r / min to maintain the reaction rate; after 5h the reaction was stopped monomer mixture, mixing the unreacted monomer is recovered after cooling; the resulting polymer latex coagulated, washed, dehydrated and dried to obtain low temperature fluoro rubber adhesive of the present invention by an open roll mechanism. 以此生胶为基体制备的硫化胶经测定,玻璃化温度为_31°C。 Vulcanizates was determined for the gum base in this preparation, the glass transition temperature of _31 ° C.

[0016] 实施例四: [0016] Example IV:

向3m3聚合釜中加入1500Kg去离子水,经氮气置换和抽真空处理,至釜内氧含量合格后,将6Kg全氟辛酸铵、12Kg磷酸氢二钠、15Kg丙二酸二乙酯加入聚合釜,再将1,1- 二氟乙烯、六氟丙烯、八氟戊基五氟丙烯基醚以74:18:8的摩尔比组成的单体混合物通过压缩机加入反应釜内,使釜中的压力达到2.0Mpa,将反应混合物加热至85°C,加入3Kg过硫酸钾开始反应,反应过程中连续补加单体混合物将压力保持在1.8Mpa,同时保持300r/min的搅拌速率来保持反应速率;在反应2h后停止加入单体混合物,冷却后对未反应的混合单体进行回收;聚合所得乳胶经凝聚,洗涤,干燥脱水后由开炼机制得本发明的耐低温氟橡胶生胶。 3m3 was added to the polymerization vessel 1500Kg deionized water, purged with nitrogen and vacuum treatment, the oxygen content of the autoclave until after passing the 6Kg ammonium perfluorooctanoate, disodium hydrogen phosphate 12Kg, 15Kg added diethyl malonate polymerization vessel, and then the vinylidene fluoride, hexafluoropropylene, octafluoropentyl pentafluoropropene ether 74: 18: 8 molar ratio by the addition of the monomer mixture of the compressor in the reaction vessel, the pressure in the autoclave reached 2.0Mpa, the reaction mixture was heated to 85 ° C, potassium persulfate was added 3Kg start of the reaction, during the reaction of the monomer mixture was continuously added to keep the pressure 1.8Mpa, while maintaining the stirring rate 300r / min to maintain the reaction rate; in the reaction was stopped after 2h monomer mixture, mixing the unreacted monomer is recovered after cooling; the resulting polymeric latex coagulated, washed, dehydrated and dried to give the open roll mechanism of the present invention low temperature fluoro rubber adhesive. 以此生胶为基体制备的硫化胶经测定,玻璃化温度为_37°C。 Vulcanizates was determined for the gum base in this preparation, the glass transition temperature of _37 ° C.

[0017] 实施例五: [0017] Example Five:

向3m3聚合釜中加入1500Kg去离子水,经氮气置换和抽真空处理,至釜内氧含量合格后,将0.6Kg全氟辛酸铵、0.6Kg磷酸氢二钠、1.5Kg丙二酸二乙酯加入聚合釜,再将1,1_ 二氟乙烯、六氟丙烯、四氟丙基五氟丙烯基醚以64:30:6的摩尔比组成的单体混合物通过压缩机加入反应釜内,使釜中的压力达到2.2Mpa,将反应混合物加热至95°C,加入0.75Kg过硫酸钾开始反应,反应过程中连续补加单体混合物将压力保持在2.2Mpa,同时保持500r/min的搅拌速率来保持反应速率;在反应4h后停止加入单体混合物,冷却后对未反应的混合单体进行回收;聚合所得乳胶经凝聚,洗涤,干燥脱水后由开炼机制得本发明的耐低温氟橡胶生胶。 3m3 was added to the polymerization vessel 1500Kg deionized water, purged with nitrogen and vacuum treatment, the oxygen content of the autoclave to the qualified, the ammonium perfluorooctanoate 0.6Kg, 0.6Kg of disodium hydrogen phosphate, diethyl malonate was added 1.5Kg polymerization autoclave, then 1,1_ vinylidene fluoride, hexafluoropropylene, pentafluoropropene, tetrafluoroethylene propyl ether in 64: 30: 6 molar ratio of monomer mixture composition was added to the reactor through a compressor, making kettle pressure reached 2.2MPa, the reaction mixture was heated to 95 ° C, 0.75Kg of potassium persulfate was added to start the reaction, during the reaction of the monomer mixture was continuously added to maintain the pressure at 2.2MPa, while maintaining the stirring rate 500r / min to maintain the reaction rate; after 4h the reaction was stopped monomer mixture, mixing the unreacted monomer is recovered after cooling; the resulting polymer latex coagulated, washed, dehydrated and dried to obtain low temperature fluoro rubber adhesive of the present invention by an open roll mechanism. 以此生胶为基体制备的硫化胶经测定,玻璃化温度为_29°C。 Vulcanizates was determined for the gum base in this preparation, the glass transition temperature of _29 ° C.

Claims (10)

  1. 1.一种耐低温氟橡胶,其特征是它具有如下结构: A low temperature fluororubber, characterized in that it has the following structure:
    Figure CN103755857AC00021
    其中:Rf= -(CF2CF2)nH, n=l ~6 的整数。 Wherein: Rf = - (CF2CF2) nH, n = an integer of l ~ 6.
  2. 2.一种如权利要求1所述的耐低温氟橡胶的制备方法,它的制备步骤如下: 步骤一,按重量比,将20~30份含氟醇、5~15份五氟溴丙烯和1份相转移催化剂溶于20份氯代烷烃类溶剂中,再滴加3~6份碱的7.5份水溶液,升温至45~50°C,待缩合反应完全后,冷却反应液,滤去不溶的盐,分出油层,以稀盐酸、蒸馏水洗涤至中性,经无水硫酸钠干燥后分馏得到产物含氟烷基全氟丙烯基醚; 步骤二,将摩尔比为55~75:15~30:2~10的1,1- 二氟乙烯、六氟丙烯、含氟烷基全氟丙烯基醚组成单体混合物,备用; 步骤三,向聚合釜中加入去离子水,经氮气置换和抽真空处理,至釜内氧含量合格后,将乳化剂、PH调节剂、链转移剂加入聚合釜,再将单体混合物通过压缩机加入反应釜内,使釜中的压力达到1.8~2.6Mpa,将反应混合物加热至75~95°C,加入引发剂开始反应,反应过程中连续补加 2. A low temperature method of preparing the fluorine-containing rubber as claimed in claim 1, which is prepared as follows: Step a, by weight, 20 to 30 parts of the fluorine-containing alcohol, 5 to 15 parts of allyl bromide and pentafluoropropene 1 parts 7.5 parts aqueous phase transfer catalyst dissolved in 20 parts chlorinated alkane solvent, and then added dropwise 3 to 6 parts of a base, warmed to 45 ~ 50 ° C, after completion of the condensation reaction, the reaction solution was cooled, insolubles were filtered off salt, separation of the oil with dilute hydrochloric acid, washed with distilled water until neutral, dried over anhydrous sodium sulfate the product was fractionated to give a fluorine-containing alkyl ether perfluoropropene; two step, a molar ratio of 55 ~ 75: 15 ~ 30: 2 to 10 1,1-fluoride, hexafluoropropene, a fluorine-containing monomer mixture consisting of perfluorinated alkyl propenyl ether, standby; step three, deionized water was added to the polymerization reactor, purged with nitrogen and vacuuming, until the oxygen content of the autoclave qualified, an emulsifier, PH adjusting agents, chain transfer agent is added to the polymerization vessel, and then the monomer mixture was added to the reactor through a compressor, the pressure in the autoclave reached 1.8 ~ 2.6Mpa the reaction mixture was heated to 75 ~ 95 ° C, the initiator is added to start the reaction, during the reaction was continuously added 单体混合物将压力保持在1.8~2.6Mpa,同时保持300~600r/min的搅拌速率来保持反应速率;在反应2~5h后停止加入单体混合物,冷却后对未反应的混合单体进行回收;聚合所得乳胶经凝聚,洗涤,干燥脱水后由开炼机制成耐低温氟橡胶胶片。 The monomer mixture pressure was maintained at 1.8 ~ 2.6Mpa, while maintaining the stirring rate 300 ~ 600r / min to maintain the rate of the reaction; 2 ~ 5h after the reaction of the monomer mixture was stopped, the unreacted monomer mixed recovered after cooling ; the resulting polymer latex coagulated, washed, dehydrated and dried by a mechanism into an open roll film fluororubber low temperature.
  3. 3.根据权利要求2所述的耐低温氟橡胶的制备方法,其特征是所述的步骤一的相转移催化剂为四丁基溴化铵或十八烷基三甲基氯化铵。 3. The low temperature method of preparing the fluorine-containing rubber according to claim 2, wherein said step of a phase transfer catalyst is tetrabutylammonium bromide or octadecyl chloride.
  4. 4.根据权利要求2所述的耐低温氟橡胶的制备方法,其特征是所述的步骤一中碱为氢氧化钠或氢氧化钾。 4. The low temperature method of preparing the fluorine-containing rubber according to claim 2, wherein in said step a base is sodium hydroxide or potassium hydroxide.
  5. 5.根据权利要求2所述的耐低温氟橡胶的制备方法,其特征是所述的步骤一种氯代烷烃类为二氯甲烷、二氯乙烷或四氯乙烷。 The low temperature method of preparing the fluorine-containing rubber according to claim 2, wherein said steps of one chlorinated alkanes as dichloromethane, dichloroethane or tetrachloroethane.
  6. 6.根据权利要求2所述的耐低温氟橡胶的制备方法,其特征是所述的步骤三引发剂为过硫酸盐、过硫酸盐-亚硫酸氢盐、过氧化二碳酸二异丙酯、叔丁基过氧化氢或过氧化苯甲酰。 6. A low temperature method of preparing the fluorine-containing rubber according to claim 2, wherein said step of three initiators are persulfates, persulfate - bisulfite, peroxydicarbonate diisopropyl t-butyl hydroperoxide or benzoyl peroxide.
  7. 7.根据权利要求2所述的耐低温氟橡胶的制备方法,其特征是所述的步骤三种乳化剂为全氟辛酸的钠盐、钾盐或铵盐、全氟辛基硫酸的锂盐。 7. A low temperature method of preparing the fluorine-containing rubber according to claim 2, wherein said step of three kinds of perfluorooctanoic acid emulsifier is sodium, potassium or ammonium salts, the lithium salt of perfluorooctyl acid.
  8. 8.根据权利要求2所述的耐低温氟橡胶的制备方法,其特征是所述的步骤三种pH调节剂为碳酸氢钠、磷酸氢二钠、磷酸氢二钠或四硼酸钠。 8. A low temperature method of preparing the fluorine-containing rubber according to claim 2, wherein said step of three kinds of pH adjusting agent is sodium bicarbonate, disodium hydrogen phosphate, disodium hydrogen phosphate or sodium tetraborate.
  9. 9.根据权利要求2所述的耐低温氟橡胶的制备方法,其特征是所述步骤三中链转移剂为丙酮、丙二酸二乙酯、异戊烷或醋酸乙酯。 9. A low temperature method of preparing the fluorine-containing rubber according to claim 2, wherein said step 3 chain transfer agent is acetone, diethyl malonate, ethyl acetate, or iso-pentane.
  10. 10.根据权利要求2所述的耐低温氟橡胶的制备方法,其特征是所述的组分的加入量以蒸馏水按100重量份计算,其余助剂分别为:引发剂0.05~0.2,乳化剂0.04~0.8,pH调节剂0.02~0.6,链转移剂0.08~1.5。 10. A low temperature method of preparing the fluorine-containing rubber according to claim 2, characterized in that said component is added in an amount calculated to 100 parts by weight of distilled water, the remaining auxiliaries are: 0.05 to 0.2 initiator, emulsifier 0.04 ~ 0.8, pH adjusting agent, 0.02 to 0.6, the chain transfer agent is 0.08 to 1.5.
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