WO2023078040A1 - 一种耐高温全氟醚氟橡胶及其制备方法 - Google Patents

一种耐高温全氟醚氟橡胶及其制备方法 Download PDF

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WO2023078040A1
WO2023078040A1 PCT/CN2022/124635 CN2022124635W WO2023078040A1 WO 2023078040 A1 WO2023078040 A1 WO 2023078040A1 CN 2022124635 W CN2022124635 W CN 2022124635W WO 2023078040 A1 WO2023078040 A1 WO 2023078040A1
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perfluoroether
fluororubber
temperature
preparation
vinyl ether
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French (fr)
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刘波
余金龙
肖忠良
张廷健
钟子强
林周骏
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Zhonghao Chenguang Research Institute of Chemical Industry Co Ltd
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Zhonghao Chenguang Research Institute of Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • C08F14/26—Tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1408—Monomers containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a high-temperature-resistant perfluoroether fluororubber and a preparation method thereof.
  • High-temperature perfluoroether fluororubber mainly uses tetrafluoroethylene (TFE) and perfluoroalkyl vinyl ether (PAVE) as the main comonomers, and uses cyano-containing perfluoroolefins, bromine or iodine-containing olefins, and dienes as vulcanization materials. Copolymerization of point monomers, DuPont, Daikin, Solvay, 3M and other foreign companies have industrialized it.
  • the molar ratio of TFE/PAVE in high-temperature-resistant perfluoroether fluororubber is (55-75): (25-35).
  • the resulting product can withstand high temperatures of 300°C and more than 1,600 known organic or inorganic solvents, and is widely used in petrochemical industries. , Semiconductor industry and other industries. Its Tg is about -2°C to 0°C.
  • Patent CN110713564A reports a synthesis method of wide temperature range perfluoroether rubber and its perfluoroether rubber, which can only be used in a high temperature environment lower than 250°C, and cannot meet the high temperature environment.
  • Patents CN107868163A and CN1120343 report the preparation method of perfluoroether elastomer, but the prepared perfluoroether elastomer cannot meet the high temperature resistance performance.
  • USP 4487903 involves the use of perfluorovinyl ether of the following formula I to prepare fluorine-containing elastomeric copolymers. TFE and PAVE are used for copolymerization. Since the polymerization system adds PAVE monomers, the polymerization time is as long as 96 hours, which is very unfavorable for production.
  • the present invention provides a high-temperature-resistant perfluoroether fluororubber and a preparation method thereof.
  • the present invention provides a high temperature resistant perfluoroether fluororubber
  • the perfluoroether fluororubber is A-B segment distribution, wherein:
  • the segment A is formed by polymerizing tetrafluoroethylene and perfluoroalkyl vinyl ether (PAVE) in the first molar ratio (75-85): (15-25);
  • the segment B is formed by polymerizing tetrafluoroethylene and PAVE with a second molar ratio of (45-60):(40-55);
  • the molar weight of the chain segment B accounts for 35-45% of the total molar weight of the chain segment A and the chain segment B.
  • the present invention finds that by optimizing the molar ratio of segment A, segment B, and segment A to segment B, the high temperature resistance of perfluoroether fluororubber can be improved (it can withstand high temperatures of 300 ° C), and at the same time It has low hardness and pressure change, and good medium resistance and processing performance.
  • the perfluoroalkyl vinyl ether is selected from one or both of perfluoroethyl vinyl ether (PEVE) and perfluoropropyl vinyl ether (PPVE).
  • PEVE perfluoroethyl vinyl ether
  • PPVE perfluoropropyl vinyl ether
  • the present invention provides a method for preparing the above-mentioned high temperature resistant perfluoroether fluororubber, comprising the following steps:
  • Tetrafluoroethylene and perfluoroalkyl vinyl ether having the first molar ratio are subjected to the first polymerization reaction in the system of deionized water, emulsifier, initiator, vulcanization point monomer, and chain transfer agent, and then recovered Unreacted monomers: adding tetrafluoroethylene and perfluoroalkyl vinyl ether having the second molar ratio, performing a second polymerization reaction, recovering unreacted monomers, and preparing high temperature resistant perfluoroether fluororubber.
  • the temperature of the first polymerization reaction is 80-90°C, and the pressure is 2.0-3.0Mpa; the temperature of the second polymerization reaction is 80-90°C, and the pressure is 1.5-2.0Ma.
  • the emulsifier is perfluorooctanoate, and its salts are ammonium salts, sodium salts or potassium salts; the amount of the emulsifier is 0.01-5% of the total mass of monomers fed.
  • the initiator is selected from ammonium persulfate and/or potassium persulfate; the amount of the initiator is 0.01-8% of the total mass of monomers fed.
  • the chain transfer agent is a perfluoroiodoalkane, preferably 1,2-diiodoperfluoroethane and/or 1,4-diiodoperfluorobutane; the amount of the chain transfer agent is 0.01-5% of the total feeding mass.
  • the vulcanization point monomer is perfluoromethylene diene; the amount of the vulcanization point monomer is 0.3% to 5% of the total mass of monomers fed.
  • the present invention further found that the above vulcanization point monomer enables the perfluoroether elastomer to be cross-linked and vulcanized by using a peroxide vulcanization system. Vulcanization of peroxides. Moreover, the above vulcanization point monomer is beneficial to improve the processing fluidity of perfluoroether fluororubber.
  • the preparation method of the high temperature resistant perfluoroether fluororubber comprises the following steps:
  • the agglomeration, washing and drying of the present invention are carried out using conventional processes in the art.
  • the perfluoroether fluororubber provided by the present invention is A-B chain segment distribution, and the polymerization process is divided into two stages: the high temperature resistant segment (segment A) of perfluoroether fluororubber is prepared in the first stage, and the molecular chain of segment A has a higher content of TFE monomer, so that perfluoroether rubber has high temperature resistance, the second stage prepares the rubber segment (segment B) of perfluoroether fluororubber, and the obtained high temperature resistant perfluoroether fluororubber emulsion is coagulated, washed, Drying, high temperature resistant perfluoroether fluororubber products can withstand high temperature of 300 °C, low hardness and pressure change, good medium resistance and processing performance.
  • This embodiment provides a preparation method of high temperature resistant perfluoroether fluororubber, comprising the following steps:
  • the molar ratio of segment A to segment B is 64:36, Mooney viscosity is 82, fluorine content is 72.6%, tensile strength is 28.6MPa, elongation is 120%, hardness is 82Ha, compression deformation is 18%, resistance to 310°C ⁇ After 70h, the strength is 27.5MPa and the elongation is 110%.
  • This embodiment provides a preparation method of high temperature resistant perfluoroether fluororubber, comprising the following steps:
  • the molar ratio of segment A to segment B is 60:40, the Mooney viscosity is 65, the fluorine content is 72.2%, the tensile strength is 29.2MPa, the elongation is 130%, the hardness is 80Ha, the compression deformation is 20%, and the resistance is 310°C ⁇ After 70h, the strength is 27.5.7MPa and the elongation is 130%.
  • This embodiment provides a preparation method of high temperature resistant perfluoroether fluororubber, comprising the following steps:
  • the molar ratio of segment A to segment B is 58:42, the Mooney viscosity is 52, the fluorine content is 72.6%, the tensile strength is 30.7MPa, the elongation is 110%, the hardness is 78Ha, the compression deformation is 17%, and the resistance is 310°C ⁇ After 70h, the strength is 29.5.7MPa and the elongation is 110%.
  • the molar ratio of segment A to segment B of the obtained product is 45:55, the Mooney viscosity is 81, the fluorine content is 72.5%, the tensile strength is 27.5MPa, the elongation is 130%, the hardness is 80Ha, the compression deformation is 18%, and the resistance After 310°C ⁇ 70h, the strength is 16.2.MPa and the elongation is 90%.
  • This comparative example provides a preparation method of perfluoroether fluororubber.
  • the difference between it and Example 1 is that the amount of mixed monomers added in step 2) is 4.8 kg, and the amount of mixed monomers added in step 3) is 5.3 kg. .
  • the molar ratio of segment A to segment B of the obtained product is 43:47, the Mooney viscosity is 65, the fluorine content is 72.6%, the tensile strength is 25.0MPa, the elongation is 130%, the hardness is 78Ha, the compression deformation is 19%, and the resistance After 310°C ⁇ 70h, the strength is 15.8MPa and the elongation is 80%.
  • the invention provides a high temperature resistant perfluoroether fluororubber and a preparation method thereof.
  • the perfluoroether fluororubber has an A-B segment distribution, wherein: the segment A is polymerized from tetrafluoroethylene and perfluoroalkyl vinyl ether in the first molar ratio (75-85): (15-25) into; the chain segment B is polymerized from tetrafluoroethylene and perfluoroalkyl vinyl ether with a second molar ratio of (45-60):(40-55); the chain segment B accounts for the chain 35-45% of the total molar weight of segment A and segment B.
  • the perfluoroether fluorororubber of the invention can withstand a high temperature of 300°C, has low hardness and pressure change, good medium resistance and processing performance, and has good economic value and application prospect.

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Abstract

本发明提供一种耐高温全氟醚氟橡胶及其制备方法。所述全氟醚氟橡胶为A-B链段分布，其中：所述链段A由第一摩尔比(75～85):(15～25)的四氟乙烯与全氟烷基乙烯基醚聚合而成；所述链段B由第二摩尔比为(45～60):(40～55)的四氟乙烯与全氟烷基乙烯基醚聚合而成；所述链段B的占所述链段A和链段B的总摩尔量的35～45％。本发明的全氟醚氟橡胶可耐300℃高温、硬度和压变较低，耐介质性能和加工性能良好。

Description

一种耐高温全氟醚氟橡胶及其制备方法
交叉引用
本申请要求2021年11月4日提交的专利名称为“一种耐高温全氟醚氟橡胶及其制备方法”的第202111302034.2号中国专利申请的优先权，其全部公开内容通过引用整体并入本文。
技术领域
本发明涉及高分子材料技术领域，尤其涉及一种耐高温全氟醚氟橡胶及其制备方法。
背景技术
高温全氟醚氟橡胶主要采用四氟乙烯(TFE)与全氟烷基乙烯基醚(PAVE)为主要共聚单体，使用含氰基全氟烯烃、含溴或碘烯烃、含二烯烃为硫化点单体进行共聚合，目前国外杜邦、大金、苏威、3M等公司已工业化。耐高温全氟醚氟橡胶中TFE/PAVE摩尔比为(55～75)：(25～35)，所得产品可耐300℃高温、并耐已知1600多种有机或无机溶剂，备受石油化工、半导体工业等行业青睐。其Tg约为-2℃～0℃。
专利CN110713564A报道了一种宽温域全氟醚橡胶的合成方法及其全氟醚橡胶，只能在低于250℃的高温环境中使用，不能满足太高的高温环境。
专利CN107868163A、CN1120343报道了全氟醚弹性体的制备方法，所制备的全氟醚弹性体不能满足耐高温性能。
USP 4487903涉及使用下I式的全氟乙烯基醚制备含氟弹性体共聚物，采用TFE与PAVE进行共聚，由于聚合体系加入了PAVE单体，聚合时间长达96h，非常不利于生产。
I式：CF 2＝CF-(O-CF 2) n-CF 3(n＝3～5)
发明内容
为此，本发明提供一种耐高温全氟醚氟橡胶及其制备方法。
具体而言，本发明提供一种耐高温全氟醚氟橡胶，所述全氟醚氟橡胶为A-B链段分布，其中：
所述链段A由第一摩尔比(75～85):(15～25)的四氟乙烯与全氟烷基乙烯基醚(PAVE)聚合而成；
所述链段B由第二摩尔比为(45～60):(40～55)的四氟乙烯与PAVE聚合而成；
所述链段B的摩尔量占所述链段A和链段B的总摩尔量的35～45％。
本发明发现，通过对链段A、链段B，以及链段A与链段B的摩尔比进行上述优化后，可以提高全氟醚氟橡胶的耐高温性(可耐300℃高温)，同时具有较低的硬度和压变，以及耐介质性能和加工性能良好。
优选的，所述全氟烷基乙烯基醚选自全氟乙基乙烯基醚(PEVE)、全氟丙基乙烯基醚(PPVE)中的一种或两种。
本发明提供一种上述的耐高温全氟醚氟橡胶的制备方法，包括如下步骤：
具有所述第一摩尔比的四氟乙烯与全氟烷基乙烯基醚在去离子水、乳化剂、引发剂、硫化点单体、链转移剂的体系中，进行第一聚合反应，而后回收未反应单体；加入具有所述第二摩尔比的四氟乙烯与全氟烷基乙烯基醚，进行第二聚合反应，回收未反应单体，制得耐高温全氟醚氟橡胶。
优选地，所述第一聚合反应的温度为80～90℃，压力为2.0～3.0Mpa；所述第二聚合反应的温度为80～90℃，压力为1.5～2.0Ma。
优选的，所述乳化剂为全氟辛酸盐，其盐类为铵盐、钠盐或钾盐；所述乳化剂的用量为单体总投料质量的0.01～5％。
优选的，所述引发剂选自过硫酸铵和/或过硫酸钾；所述引发剂的用量为单体总投料质量的0.01～8％。
优选的，所述链转移剂为全氟碘代烷烃，优选1,2-二碘全氟乙烷和/或1,4-二碘全氟丁烷；所述链转移剂的用量为单体总投料质量的0.01～5％。
优选的，所述硫化点单体为全氟亚甲基二烯烃；所述硫化点单体的用 量为单体总投料质量的0.3～5％。
优选的，所述全氟亚甲基二烯烃为CH 2＝CH-(CF 2) n-CH＝CH 2，其中n为2～6的整数。本发明进一步发现，上述硫化点单体使全氟醚弹性体可采用过氧化物硫化体系进行交联硫化，同时，橡胶端点的碘原子在自由基的作用下非常容易脱除，进而有利于促进过氧化物的硫化。并且，上述硫化点单体有利于提高全氟醚氟橡胶的加工流动性能。
在一些具体的实施例中，所述耐高温全氟醚氟橡胶的制备方法包括如下步骤：
1)向反应釜中加入去离子水，去除反应釜内的空气，向反应釜中加入乳化剂后升温至80～90℃，而后加入具有所述第一摩尔比的四氟乙烯与全氟烷基乙烯基醚的第一混合单体至釜内压力2.0～3.0Mpa，加入引发剂、硫化点单体和链转移剂进行聚合反应，持续加入所述第一混合单体，保持釜内温度为80～90℃，压力为2.0～3.0Mpa，当所述第一混合单体的加入量为投料总量的55～65％时结束反应，回收未反应单体；
2)而后加入具有所述第二摩尔比的四氟乙烯与全氟烷基乙烯基醚的第二混合单体至釜内压力为1.5～2.0Mpa，当所述第二混合单体的加入量为投料总量的35～45％时结束反应，回收未反应单体，得到乳液；
3)对所述乳液进行电解质凝聚后洗涤、干燥，制得耐高温全氟醚氟橡胶。
作为优选，本发明的凝聚、洗涤和干燥采用本领域常规工艺进行。
基于上述方案，本发明的有益效果如下：
本发明提供的全氟醚氟橡胶为A-B链段分布，聚合过程分两个阶段：第一阶段制备全氟醚氟橡胶的耐高温段(链段A)，链段A分子链中具有较高含量的TFE单体，使全氟醚橡胶具有耐高温性能，第二阶段制备全氟醚氟橡胶的橡胶段(链段B)，制得的耐高温全氟醚氟橡胶乳液经凝聚、洗涤、干燥，得耐高温全氟醚氟橡胶产品可耐300℃高温、硬度和压变较低，耐介质性能和加工性能良好。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的范围。
实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件，或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可通过正规渠道商购买得到的常规产品。
实施例1
本实施例提供一种耐高温全氟醚氟橡胶的制备方法，包括如下步骤：
1)在50L的反应釜中加入30L去离子水，反应釜进行抽空处理，至氧含量≤30ppm；
2)向反应釜加入全氟辛酸铵35g，升温至90℃后，加入TFE/PEVE＝80/20(摩尔比)的混合单体，将反应釜内的压力升至2.8MPa，加入15g过硫酸钾、25g 1,2-二碘全氟乙烷和60g CH 2＝CH-(CF 2) 6-CH＝CH 2，进行聚合反应，待混合单体加入量为6.4kg时，结束反应；
3)快速回收未反应单体，直至釜内表压为0KPa，向反应釜中加入TFE/PEVE＝45/55(摩尔比)的混合单体，将反应釜内的压力升至1.6MPa，待反应单体加入量为3.6kg时，结束反应；
4)回收未反应单体，得到耐高温全氟醚氟橡胶乳液，加入硝酸凝聚，去离子水洗涤，在温度110℃、真空度-85Kpa条件下干燥10h，得到耐高温全氟醚氟橡胶产品10.0Kg。
对所制备的耐高温全氟醚氟橡胶的性能进行检测，结果如下：
链段A与链段B的摩尔比为64：36，门尼粘度82，氟含量72.6％，拉伸强度28.6MPa，伸长率为120％，硬度82Ha，压缩变形18％，耐310℃×70h后，强度27.5MPa，伸长率为110％。
实施例2
本实施例提供一种耐高温全氟醚氟橡胶的制备方法，包括如下步骤：
1)在50L的反应釜中加入30L去离子水，反应釜进行抽空处理，至氧含量≤30ppm；
2)向反应釜加入全氟辛酸铵35g，升温至85℃后，加入TFE/PPVE＝76/24(摩尔比)的混合单体，将反应釜内的压力升至2.5MPa，加入36g过硫酸钾、30g 1,2-二碘全氟丁烷和80g CH 2＝CH-(CF 2) 6-CH＝CH 2，进行聚合反应，待混合单体加入量为6.8kg时，结束反应；
3)快速回收未反应单体，直至釜内表压为0KPa，向反应釜中加入TFE/PPVE＝45/55(摩尔比)的混合单体，将反应釜内的压力升至1.8MPa，待反应单体加入量为4.0kg时，结束反应；
4)回收未反应单体，得到耐高温全氟醚氟橡胶乳液，加入硝酸凝聚，去离子水洗涤，在温度110℃、真空度-85Kpa条件下干燥10h，得到耐高温全氟醚氟橡胶产品10.2Kg。
对所制备的耐高温全氟醚氟橡胶的性能进行检测，结果如下：
链段A与链段B的摩尔比为60：40，门尼粘度65，氟含量72.2％，拉伸强度29.2MPa，伸长率为130％，硬度80Ha，压缩变形20％，耐310℃×70h后，强度27.5.7MPa，伸长率为130％。
实施例3
本实施例提供一种耐高温全氟醚氟橡胶的制备方法，包括如下步骤：
1)在50L的反应釜中加入30L去离子水，反应釜进行抽空处理，至氧含量≤30ppm；
2)向反应釜加入全氟辛酸铵35g，升温至82℃后，加入TFE/PPVE＝82/18(摩尔比)的混合单体，将反应釜内的压力升至2.0MPa，加入55g过硫酸钾、45g 1,2-二碘全氟丁烷和100g CH 2＝CH-(CF 2) 6-CH＝CH 2，进行聚合反应，待混合单体加入量为7.0kg时，结束反应；
3)快速回收未反应单体，直至釜内表压为0KPa，向反应釜中加入TFE/PPVE＝58/42(摩尔比)的混合单体，将反应釜内的压力升至1.6MPa，待反应单体加入量为3.8kg时，结束反应；
4)回收未反应单体，得到耐高温全氟醚氟橡胶乳液，加入硝酸凝聚， 去离子水洗涤，在温度110℃、真空度-85Kpa条件下干燥10h，得到耐高温全氟醚氟橡胶产品10.5Kg。
对所制备的耐高温全氟醚氟橡胶的性能进行检测，结果如下：
链段A与链段B的摩尔比为58：42，门尼粘度52，氟含量72.6％，拉伸强度30.7MPa，伸长率为110％，硬度78Ha，压缩变形17％，耐310℃×70h后，强度29.5.7MPa，伸长率为110％。
对比例1
本对比例提供一种全氟醚氟橡胶的制备方法，其与实施例1的区别仅在于，步骤2)中，向反应釜中加入TFE/PEVE＝65/35(摩尔比)的混合单体。
所得产品的链段A与链段B的摩尔比为45：55，门尼粘度81，氟含量72.5％，拉伸强度27.5MPa，伸长率为130％，硬度80Ha，压缩变形18％，耐310℃×70h后，强度16.2.MPa，伸长率为90％。
对比例2
本对比例提供一种全氟醚氟橡胶的制备方法，其与实施例1的区别仅在于，对步骤2)混合单体加入量为4.8kg、步骤3)的混合单体的添加量5.3kg。
所得产品的链段A与链段B的摩尔比为43：47，门尼粘度65，氟含量72.6％，拉伸强度25.0MPa，伸长率为130％，硬度78Ha，压缩变形19％，耐310℃×70h后，强度15.8MPa，伸长率为80％。
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
工业实用性
本发明提供一种耐高温全氟醚氟橡胶及其制备方法。所述全氟醚氟橡 胶为A-B链段分布，其中：所述链段A由第一摩尔比(75～85):(15～25)的四氟乙烯与全氟烷基乙烯基醚聚合而成；所述链段B由第二摩尔比为(45～60):(40～55)的四氟乙烯与全氟烷基乙烯基醚聚合而成；所述链段B的占所述链段A和链段B的总摩尔量的35～45％。本发明的全氟醚氟橡胶可耐300℃高温、硬度和压变较低，耐介质性能和加工性能良好，具有较好的经济价值和应用前景。

Claims (10)

  1. 一种耐高温全氟醚氟橡胶，其特征在于，所述全氟醚氟橡胶为A-B链段分布，其中：
    所述链段A由第一摩尔比(75～85):(15～25)的四氟乙烯与全氟烷基乙烯基醚聚合而成；
    所述链段B由第二摩尔比为(45～60):(40～55)的四氟乙烯与全氟烷基乙烯基醚聚合而成；
    所述链段B的摩尔量占所述链段A和链段B的总摩尔量的35～45％。
  2. 根据权利要求1所述的耐高温全氟醚氟橡胶，其特征在于，所述全氟烷基乙烯基醚选自全氟乙基乙烯基醚、全氟丙基乙烯基醚中的一种或两种。
  3. 一种权利要求1或2所述的耐高温全氟醚氟橡胶的制备方法，其特征在于，包括如下步骤：
    具有所述第一摩尔比的四氟乙烯与全氟烷基乙烯基醚在去离子水、乳化剂、引发剂、硫化点单体、链转移剂的体系中，进行第一聚合反应，而后回收未反应单体；加入具有所述第二摩尔比的四氟乙烯与全氟烷基乙烯基醚，进行第二聚合反应，回收未反应单体，制得耐高温全氟醚氟橡胶。
  4. 根据权利要求3所述的制备方法，其特征在于，所述第一聚合反应的温度为80～90℃，压力为2.0～3.0Mpa；所述第二聚合反应的温度为80～90℃，压力为1.5～2.0Ma。
  5. 根据权利要求3或4所述的制备方法，其特征在于，所述乳化剂为全氟辛酸盐，其盐类为铵盐、钠盐或钾盐；所述乳化剂的用量为单体总投料质量的0.01～5％。
  6. 根据权利要求3-5任一项所述的制备方法，其特征在于，所述引发剂选自过硫酸铵和/或过硫酸钾；所述引发剂的用量为单体总投料质量的0.01～8％。
  7. 根据权利要求3-6任一项所述的制备方法，其特征在于，所述链 转移剂为全氟碘代烷烃，优选1,2-二碘全氟乙烷和/或1,4-二碘全氟丁烷；所述链转移剂的用量为单体总投料质量的0.01～5％。
  8. 根据权利要求3-7任一项所述的制备方法，其特征在于，所述硫化点单体为全氟亚甲基二烯烃；所述硫化点单体的用量为单体总投料质量的0.3～5％。
  9. 根据权利要求8所述的制备方法，其特征在于，所述全氟亚甲基二烯烃为CH 2＝CH-(CF 2) n-CH＝CH 2，其中n为2～6的整数。
  10. 根据权利要求3-9任一项所述的制备方法，其特征在于，包括以下步骤：
    1)向反应釜中加入去离子水，去除反应釜内的空气，向反应釜中加入乳化剂后升温至80～90℃，而后加入具有所述第一摩尔比的四氟乙烯与全氟烷基乙烯基醚的第一混合单体至釜内压力为2.0～3.0Mpa，加入引发剂、硫化点单体和链转移剂进行聚合反应，持续加入所述第一混合单体，保持釜内温度为80～90℃，压力为2.0～3.0Mpa，当所述第一混合单体的加入量为投料总量的55～65％时结束反应，回收未反应单体；
    2)而后加入具有所述第二摩尔比的四氟乙烯与全氟烷基乙烯基醚的第二混合单体至釜内压力为1.5～2.0Mpa，当所述第二混合单体的加入量为投料总量的35～45％时结束反应，回收未反应单体，得到乳液；
    3)对所述乳液进行电解质凝聚后洗涤、干燥，制得耐高温全氟醚氟橡胶。
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