WO2013097477A1 - 一种耐低温含氟弹性体及其制备方法 - Google Patents

一种耐低温含氟弹性体及其制备方法 Download PDF

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WO2013097477A1
WO2013097477A1 PCT/CN2012/080606 CN2012080606W WO2013097477A1 WO 2013097477 A1 WO2013097477 A1 WO 2013097477A1 CN 2012080606 W CN2012080606 W CN 2012080606W WO 2013097477 A1 WO2013097477 A1 WO 2013097477A1
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mol
perfluoro
bromo
monomer
vinyl ether
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PCT/CN2012/080606
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English (en)
French (fr)
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赵少春
兰军
张建新
刘斌
李斌
高家勇
王先荣
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中昊晨光化工研究院有限公司
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Priority to KR1020147013389A priority Critical patent/KR101648444B1/ko
Priority to JP2014546289A priority patent/JP5883157B2/ja
Priority to EP12862532.4A priority patent/EP2799457A4/en
Priority to US14/356,483 priority patent/US20140357821A1/en
Publication of WO2013097477A1 publication Critical patent/WO2013097477A1/zh

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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
    • 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
    • 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
    • C08F214/22—Vinylidene fluoride
    • C08F214/222—Vinylidene fluoride 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
    • 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
    • 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
    • C08F214/184—Monomers containing fluorine 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
    • 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
    • C08F214/22—Vinylidene fluoride
    • 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
    • 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
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/22—Coagulation
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/21—Rubbery or elastomeric properties
    • 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

Definitions

  • the present invention relates to a low temperature resistant fluorine-containing elastomer, and more particularly to a low temperature resistant fluorine-containing elastomer and a process for the preparation thereof. Background technique
  • the first low temperature fluororubber Viton GLT developed by DuPont Performance Elastomers is vinylidene fluoride-tetrafluoroethylene-perfluoromethyl vinyl ether (PMVE) and 4-bromo-3,3,4,4-tetrafluoro- A quaternary copolymer of 1-butene (BTFB) in which BTFB is a crosslinking point monomer, and copolymers having different fluorine contents are obtained by changing the copolymerization composition, thereby giving them different dielectric properties and low temperature resistance.
  • BTFB 4-bromo-3,3,4,4-tetrafluoro- A quaternary copolymer of 1-butene (BTFB) in which BTFB is a crosslinking point monomer, and copolymers having different fluorine contents are obtained by changing the copolymerization composition, thereby giving them different dielectric properties and low temperature resistance.
  • BTFB 4-bromo-3,3,4,4-tetrafluoro- A
  • Patent US 4,418,186 discloses a polymerization process of perfluoro(alkyl vinyl ether) and vinylidene fluoride and a third monomer in the presence of an ammonium persulfate initiator, an emulsifier.
  • the third monomer is perfluoro(2-bromoethyl vinyl ether) and the emulsifier is ammonium perfluorononanoate.
  • the obtained polymer was in the form of an emulsion, which was freeze-dried and dried to obtain a fluoroether rubber. Its glass transition temperature is -21 to -36 °C.
  • Patent WO0149758A1 discloses a fluoroether rubber obtained by radical polymerization of perfluoro(methyl vinyl ether) or perfluoro(propyl vinyl ether) and VDF, the initiator of which is a peroxide, a peroxidized lipid or an even Nitrogen compounds.
  • the obtained elastomer had a glass transition temperature Tg of -44 °C.
  • Patent No. 3,136,745 discloses a fluoroether rubber obtained by radical polymerization of perfluoro(methyl vinyl ether) or perfluoro(propyl vinyl ether) and VDF, the initiator of which is ammonium persulfate, and the obtained product has a low temperature back.
  • the shrinkage temperature TR-io is -28 ⁇ -24 °C. If a small amount of tetrafluoroethylene is added on this basis, the low temperature resistance is remarkably improved.
  • the low temperature resistant fluoroelastomer of the present invention is based on a large number of experiments to adjust each comonomer and
  • the content of the auxiliary agent improves the low temperature resistance of the product on the basis of ensuring good vulcanization properties and processing properties of the fluoroelastomer.
  • the low temperature retracting temperature of the product can reach TR-10 ⁇ -40 °C. Summary of the invention
  • the present invention provides a low temperature resistant fluoroelastomer which is polymerized from the following comonomer: 40 to 80 mol % 1,1-difluoroethylene, 2 to 10 mol % tetrafluoroethylene, 10 ⁇ 30 mol % perfluoro(alkyl vinyl ether), and 1 ⁇ 10 mol % of vulcanization point monomer.
  • the preferred comonomer content is:
  • the content of vinylidene fluoride of the present invention is selected to be 40 to 80 mol%, preferably 50 to 75 mol%; if the molar percentage of vinylidene fluoride is less than 40%, the polymerization rate is very slow. Moreover, the vulcanization effect is not good; if the molar percentage of vinylidene fluoride is more than 80%, the low-temperature resistance of the fluoroelastomer is lowered, the compression set is poor in permanent deformability, and the solvent resistance is low.
  • the perfluoro(alkyl vinyl ether) is preferably perfluoro(methyl vinyl ether) or perfluoro(n-propyl vinyl ether).
  • the perfluoro(alkyl vinyl ether) is contained in an amount of from 10 to 30 mol%, preferably from 15 to 30 mol%, which is used to provide an ether bond to the fluoroelastomer. Too little (alkyl vinyl ether) content will reduce its low temperature resistance; the higher the content, the better its low temperature resistance, but the content is too high, reducing its polymerization rate. And the cost is high.
  • the content of tetrafluoroethylene is 2-10 mol%, preferably 2-5 mol%, which may increase the fluorine content and also improve its low temperature resistance. Tetrafluoroethylene can improve the solvent resistance of the fluoroelastomer, tetrafluoroethylene A content higher than 10% will cause some polymers to crystallize to affect their low temperature compression set.
  • the present invention also provides a low temperature resistant fluoroelastomer preparation method, comprising the following steps: adding 0.01 ⁇ 5 parts by weight of emulsifier to the aqueous medium, and adjusting the pH value of 7 ⁇ 12;
  • the emulsifier in the step 1) is preferably a long-chain perfluorocarboxylic acid salt, such as ammonium perfluorooctanoate, sodium perfluorooctanoate or ammonium perfluorononanoate, preferably in an amount of 1 to 5 parts by weight of emulsified by adding 100 parts by weight of an aqueous medium. Agent.
  • the aqueous medium is deionized water, and deionized water having a conductivity of less than 1 ⁇ ⁇ ⁇ cm is preferred.
  • the pH adjustment in step 1) can be carried out by using a pH adjuster which is a hydrogen-oxygen step 2) wherein the mixed monomer is 40 to 80 mol% of 1,1-difluoroethylene, 2 to 10 mol%.
  • Tetrafluoroethylene 10 to 30 mol% of perfluoro(alkyl vinyl ether), and 1 to 10 mol% of a vulcanization point monomer, preferably 50 to 75% by mol of 1,1-difluoroethylene, 2 to 5 mol% of four Fluorine, 15 to 30 mol% of perfluoro(alkyl vinyl ether), and 2 to 6 mol% of vulcanization point monomers.
  • the initiator in step 3) is ammonium persulfate, potassium persulfate or sodium persulfate.
  • the amount of the initiator is from 0.001 to 5% by weight based on the total weight of the mixed monomers.
  • the polymerization temperature is preferably 40 to 100 ° C. If the temperature is lower than 40 ° C, the initiation efficiency of the initiator is affected, and the formed fluoroelastomer copolymer emulsion is easily broken, and is easily used in the polymerization reactor. Causing clogging, making it difficult to maintain emulsion stability during polymerization, above 100 ° C, triggering The rate of consumption of the agent is high, a large number of small molecules are formed, and it is difficult to form a dense cross-linking system by vulcanization.
  • the polymerization pressure is from 1 to 5 MPa, preferably from 1.2 to 4 MPa. The desired polymerization pressure is initially maintained by adjusting the amount of gaseous mixed monomer.
  • the polymerization pressure is set within the above range because if the pressure is lower than IMPa, the monomer concentration of the polymerization reaction system is too low to reach a satisfactory reaction rate. In addition, the molecular weight cannot be effectively increased. If the pressure is higher than 4 MPa, the amount of the monomer liquefied in the reactor is increased, thereby not only increasing the amount of the consumed monomer but also making the production efficiency poor. In addition, the pressure is higher than 4.0 MPa, which requires higher equipment, systems and pipelines, and increases production costs.
  • the polymerization reaction time is controlled within 2 to 10 hours.
  • the chain transfer agent is carbon tetrachloride, n-hexane, acetone, diethyl malonate, diethyl succinate or ethyl acetate, methylene iodide, perfluorobutyl iodide, 1,4-two Iodine perfluoro-butane.
  • the chain transfer agent functions to adjust the molecular weight of the polymer.
  • the amount of the chain transfer agent is 0.01 to 5% by weight of the mixed monomer, and is added in one portion after the initiation of the polymerization reaction.
  • the mixed monomer gas is continuously added during the polymerization to maintain the reaction constant pressure.
  • the bromine or iodine may be vulcanized during the polymerization by using an iodo or bromo chain transfer agent such as methylene iodide or 1,4-diiodo perfluoro-butane.
  • an iodo or bromo chain transfer agent such as methylene iodide or 1,4-diiodo perfluoro-butane.
  • the site is introduced into the end of the fluoroelastomer polymer chain to further improve the vulcanization properties of the rubber.
  • the presence of a brominated or iodo group allows the fluoroelastomer of the present invention to simultaneously possess the function of vulcanization of a hydroxy-vulcanizing agent such as bisphenol with an organic peroxide vulcanizing agent (double 2,5).
  • the present invention it is relatively easy for the present invention to maintain a constant pressure of the reactor throughout the polymerization reaction by controlling the flow rate of the mixed monomer.
  • the pressure of the polymerization reactor drops very slowly, and the gas mixture is simple.
  • the stage feed increment is very small to maintain a constant pressure in the reactor.
  • the polymerization rate is increased, the polymerization reactor pressure drops rapidly, and the flow rate of the gaseous mixed monomer entering the reactor can be increased to maintain the constant pressure of the reactor, and a flow meter and a constant pressure device are required between the reactor and the mixed monomer source. , to accurately control the flow, and thus maintain the constant pressure of the reactor.
  • the agglomeration in the step 4) is carried out by adding MgCl 2 or potassium aluminum sulfate or the like in an amount of 1 to 2% by weight based on the weight of the emulsion.
  • the washing and drying are carried out by techniques well known in the art, and the washing is repeated with ion-free water until the residual water conductivity in the elastomer is less than S s . cm , the washing is stopped, and the degree of vacuum is -O. lMPa vacuum oven at 120 ° C, dried for 18 h.
  • the performance indexes of the low-temperature resistant fluoroelastomer of the present invention are shown in Table 1.
  • the researcher of the present invention has made a lot of experimental research and selected to reduce the content of tetrafluoroethylene, increase the content of vinylidene fluoride, increase the amount of monomer in the vulcanization point, and adjust the content of the fluoroelastomer comonomer to improve.
  • the crystallinity of the fluoroelastomer increases the elasticity of the fluoroelastomer, increases the vulcanization point ratio of the fluoroelastomer, increases the crosslink density of the elastomer after vulcanization, and significantly improves the low temperature resistance, and the low temperature retraction temperature reaches TR. -10 ⁇ -40 ° C; and the volume change rate of the fluoroelastomer in methanol is small, oil resistance and solvent resistance are improved, and oil resistance and solvent resistance of the fluoroelastomer are improved.
  • VDF 65 mol% l,l-difluoroethylene
  • TFE mixed monomer storage tank
  • PMVE perfluoro(methyl vinyl ether)
  • CF 2 CFOCF 2 CF 2 CF 2 OCF 2 Br
  • the reaction was started by adding 3 g of potassium persulfate. After the polymerization was carried out, 5 ml of diethyl malonate was added, and the mixed monomer disposed in the mixed monomer tank was continuously added to maintain the constant pressure of the reactor to maintain the absolute pressure in the reactor. Between 3.75 ⁇ 0.02 MPa, the reaction time is 5h, the solid content of the emulsion reaches 30% (mass percentage), the polymerization reaction is terminated, the reaction monomer is recovered, and the emulsion is discharged to the coagulation barrel.
  • VDF 1,1-difluoroethylene
  • TFE tetrafluoroethylene
  • PMVE perfluoro(methyl vinyl ether)
  • VDF 1,1-difluoroethylene
  • TFE tetrafluoroethylene
  • PMVE perfluoro(methyl vinyl ether)
  • 4 mol% of CF 2 were placed in the mixed monomer storage tank.
  • the reaction was started by adding 3 g of potassium persulfate. After the polymerization was carried out, 5 ml of diethyl malonate was added, and the mixed monomer disposed in the mixed monomer tank was continuously added to maintain the constant pressure of the reactor to maintain the absolute pressure in the reactor.
  • Example 4 diethyl malonate was replaced with 1,4-diiodoperfluoro-butane in an amount of 6 g, and the monomer ratio and process were the same as in Example 2. See Table 3 for performance characteristics.
  • Example 5 On the basis of Example 5, the coagulant was changed to potassium aluminum sulfate, and the monomer ratio and process were the same as in Example 5. See Table 3 for performance characteristics.
  • the molecular weight regulator diethyl malonate is replaced by 1,4-diiodoperfluoro-butane, and the rheology of the product is more excellent.
  • VDF l-difluoroethylene
  • TFE tetrafluoroethylene
  • perfluoro(n-propyl vinyl ether) 10 mol% of 3-bromine
  • a mixed monomer of fluorine (propyl vinyl) ether is used.
  • the reaction was started by adding 2 g of sodium persulfate, and after the polymerization was carried out, 1,4-diiodoperfluoro-butane was added.
  • the invention provides a low temperature resistant fluorine-containing elastomer and a preparation method thereof, which are obtained by polymerizing the following comonomer: 40 ⁇ 80 mol % 1,1-difluoroethylene, 2 ⁇ 10 mol % tetrafluoroethylene, 10 ⁇ 30 mol % perfluoro(alkyl vinyl ether), and 1 to 10 mol % of vulcanization point monomer.
  • the invention adjusts fluoroelasticity
  • the content of the comonomer is such that its low temperature resistance is significantly improved, and its low temperature retraction temperature

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Polymerisation Methods In General (AREA)

Abstract

本发明提供了一种耐低温含氟弹性体，其由如下共聚单体聚合而成：40~80mol%1，1-二氟乙烯，2~10mol%四氟乙烯，10~30mol%全氟（烷基乙烯基醚），和1~10mol%的硫化点单体。本发明还提供了该含氟弹性体的制备方法。本发明是在大量实验的基础上调整含氟弹性体共聚单体的含量组成，使其耐低温性能显著提高，其低温回缩温度TR-10<-40°C。且此氟弹性体在甲醇中的体积变化率变小，耐油性、耐溶剂性得到了提高，从而提高含氟弹性体的耐油性、耐溶剂性能。

Description

一种耐低温含氟弹性体及其制备方法 技术领域
本发明涉及一种耐低温含氟弹性体， 具体地说， 涉及一种耐低温含氟弹 性体及其制备方法。 背景技术
DuPont Performance Elastomers公司最先研制的而†低温氟橡胶 Viton GLT 是偏氟乙烯-四氟乙烯 -全氟甲基乙烯基醚（PMVE ) 和 4-溴 -3,3,4,4-四氟 -1-丁 烯（BTFB ) 的四元共聚物， 其中 BTFB是交联点单体， 通过改变共聚组成得 到不同氟含量的共聚物， 从而使其具有不同的耐介质性能和耐低温性能。 相 比通常的氟橡胶， 其具有更好的耐低温性能， 且兼顾了优异的物理性能和加 工性能。 广泛应用在各种工厂的化学反应装置密封， 化学管线衬里及配件， 半导体行业密封件， 以及汽车工业， 石化工业和航天工业中的特种零件。
专利 US4418186公开了全氟（烷基乙烯基醚）和偏氟乙烯和第三单体在 过硫酸铵引发剂， 乳化剂存在的下的聚合方法。 其中第三单体为全氟 （2-溴 乙基乙烯基醚），乳化剂为全氟壬酸铵。得到的聚合物为乳液形式，经过冷冻， 洗涤干燥， 得到氟醚橡胶。 其玻璃化转变温度为 -21〜 - 36°C。
专利 WO0149758A1 公开了全氟 (甲基乙烯基醚）或者全氟 （丙基乙烯 基醚）和 VDF通过自由基聚合方式得到的氟醚橡胶， 其引发剂为过氧化物、 过氧化脂类或者偶氮化合物。 得到的弹性体的玻璃转变温度 Tg为 -44°C。
专利 US3136745公开了全氟 (甲基乙烯基醚 )或者全氟 (丙基乙烯基醚 ) 和 VDF 通过自由基聚合方式得到的氟醚橡胶， 其引发剂为过硫酸铵， 得到 的产品其低温回缩温度 TR-io为 -28 ~ -24°C。 如果在此基础上加入微量的四 氟乙烯， 其耐低温性能显著提高。
1966年美国宇航局公布了一份资料显示： 在高压下（p>1000atm ), 釆用 引发剂 AIBN ( 2-2'-偶氮二异丁氰） 引发 VDF 和通式为 CF2=CFOCnF2n+1 ( n= 1,2,3 ) 的单体聚合， 得到的弹性体的玻璃转变温度 Tg为 -25〜 - 20°C。
本发明所述耐低温的氟弹性体是在大量实验的基础上调整各共聚单体和 助剂的含量组成， 在保证氟弹性体具有良好的硫化性能及加工性能基础上， 提高了产品的耐低温性能， 产品的低温回缩温度可达 TR- 10<-40 °C。 发明内容
本发明的目的在于克服现有技术的不足， 提供一种耐低温含氟弹性体。 本发明的另一目的是提供该耐低温含氟弹性体的制备方法。
为了实现本发明目的， 本发明提供一种耐低温含氟弹性体， 其由如下共 聚单体聚合而成： 40 ~ 80 mol % 1,1-二氟乙烯， 2 ~ 10 mol %四氟乙烯， 10 ~ 30 mol %全氟 （烷基乙烯基醚）， 和 1 ~ 10 mol %的硫化点单体。
其中， 所述硫化点单体为含卤素的硫化点单体， 包括但不限于卤代三氟 乙烯、溴代烷基乙烯基醚、氯代异丁烯、 CF2=CFOCF2CF2CF2OCF2Br、 1-溴 -2, 2-二氟乙烯、 溴代三氟乙烯、 4-溴 -1,1,2-三氟丁烯 -1、 2-溴全氟（乙基乙烯基） 醚、 3-溴全氟 （丙基乙烯基） 醚和 1-溴 -3,3,4,4-四氟丁烯等； 优选的为 CF2=CFOCF2CF2CF2OCF2Br、 1-溴 -2, 2-二氟乙烯、 溴代三氟乙烯、 4-溴 -1,1,2- 三氟丁烯 -1、 2-溴全氟（乙基乙烯基）醚、 3-溴全氟（丙基乙烯基）醚、 1-溴 -3,3,4,4-四氟丁烯， 最优选的为 CF2=CFOCF2CF2CF2OCF2Br、 3-溴全氟（丙基 乙烯基） 醚、 1-溴 -3,3,4,4-四氟丁烯。
其中， 优选的共聚单体含量为：
50 ~ 75mol% 1,1-二氟乙烯， 2 ~ 5 mol %四氟乙烯， 15 ~ 30 mol %全氟 (烷基乙烯基醚）， 和 2〜6 mol %的硫化点单体。
本发明的 1,1-二氟乙烯的含量选择在 40 ~ 80 mol %, 优选 50 ~ 75mol%; 如果 1,1-二氟乙烯摩尔百分含量少于 40%时， 则聚合速率很慢， 且硫化效果 不好； 如果 1,1-二氟乙烯摩尔百分含量高于 80%时， 会导致含氟弹性体的耐 低温性能降低， 抗压缩性永久变形性差和耐溶剂性能低。
所述全氟 （烷基乙烯基醚）优选为全氟 （甲基乙烯基醚）或全氟 （正丙 基乙烯基醚）。
所述全氟（烷基乙烯基醚） 的含量为 10 ~ 30 mol %, 优选 15 ~ 30mol%, 其用于给含氟弹性体提供醚键。 全氟 （烷基乙烯基醚）含量太少， 会降低其 耐低温性能； 含量越高其耐低温性能越好， 但是含量太高， 降低其聚合速度， 且成本很高。
四氟乙烯的含量为 2~ 10mol%,优选 2~5mol%,其既可能增加氟含量， 也同时可以提高其耐低温性能， 四氟乙烯能改进含氟弹性体的耐溶剂性， 四 氟乙烯含量高于 10%, 会导致一些聚合物结晶， 以影响其低温压缩永久变形。
本发明还提供了一种耐低温含氟弹性体的制备方法， 包括如下步骤： 份水介质中加入 0.01 ~ 5重量份乳化剂， 并调节 pH值为 7~ 12；
2)加入 1,1-二氟乙烯， 四氟乙烯， 全氟 （烷基乙烯基醚）和硫化点单体 的混合单体， 按配比混合形成乳液， 每 100重量份水介质中加入 30 ~ 150重 量份的混合单体；
3)加入引发剂， 在 0~ 110°C, l ~5MPa下进行聚合反应， 在聚合反应 过程中， 加入链转移剂， 并维持反应恒压；
4) 最后将聚合后的乳液凝聚， 洗涤和干燥而成。
其中， 步骤 1 ) 中所述乳化剂优选为长链全氟羧酸盐， 比如全氟辛酸铵、 全氟辛酸钠或者全氟壬酸铵，优选的浓度为 100重量份水介质中加入 1 ~5重 量份乳化剂。
所述水介质为去离子水， 选择电导率小于 1 μδ · cm 的去离子水为佳。 步骤 1 ) 中调节 pH值可以釆用 pH调节剂进行， 所述 pH调节剂为氢氧 步骤 2) 中所述混合单体为 40 ~ 80 mol% 1,1-二氟乙烯， 2~ 10mol%四 氟乙烯， 10~30mol%全氟（烷基乙烯基醚）， 和 1 ~ 10mol%的硫化点单体， 优选为 50〜75%mol% 1,1-二氟乙烯， 2~5mol%四氟乙烯， 15~30mol%全氟 (烷基乙烯基醚）， 和 2~6mol%的硫化点单体。
步骤 3) 中所述引发剂为过硫酸铵、 过硫酸钾或过硫酸钠。 引发剂的量 为混合单体总重量的 0.001 ~5%。
所述聚合反应温度优选为 40~ 100°C, 如果温度低于 40°C, 会影响引发 剂的引发效率， 且所形成的含氟弹性体共聚物乳液易破乳， 易于在聚合反应 器中引起堵塞， 使聚合反应期间难以维持乳液的稳定性， 高于 100°C, 引发 剂消耗速率高， 形成大量的小分子， 不易通过硫化形成致密的交联体系。 聚合反应压力为 l ~ 5MPa, 优选 1.2 ~ 4MPa。 所需的聚合压力开始是通 过调节气态混合单体的量来维持的。 聚合压力设定在上述范围内， 因为如果 压力低于 IMPa,则聚合反应体系的单体浓度太低，不能达到满意的反应速率。 此外分子量也不能有效增加。如果压力高于 4MPa, 则在反应器中液化的单体 量增加， 由此不仅增加了被消耗的单体量， 而且使生产效率差。 此外压力高 于 4.0MPa, 对设备及系统、 管线的要求较高， 增加了生产成本。
所述聚合反应时间控制在 2 ~ 10小时。
所述链转移剂为四氯化碳、 正己烷、 丙酮、 丙二酸二乙脂、 丁二酸二乙 脂或者乙酸乙脂， 亚甲基碘， 全氟丁基碘， 1,4-二碘全氟-丁烷。 所述链转移 剂的作用是调节聚合物分子量的大小。 链转移剂的量为混合单体重量的 0.01 ~ 5%, 在聚合反应开始后一次性加入。
在聚合过程中连续补加混合单体气体， 以保持反应恒压。
在使用硫化点单体（CSM ) 的同时， 可以通过釆用碘代或溴代链转移剂 如亚甲基碘或 1,4-二碘全氟-丁烷在聚合过程中将溴或碘硫化部位引入到含氟 弹性体聚合物链末端， 进一步提高橡胶的硫化性能。 溴代或碘代基团的存在 使本发明的含氟弹性体可同时具备羟基硫化剂如双酚与有机过氧化物硫化剂 (双 2,5 )硫化的功能。
本发明通过控制混合单体的流量来保持反应器在整个聚合反应期间的恒 定压力是较容易的， 在聚合反应早期阶段， 当聚合速率较低时， 聚合反应器 压力下降很慢， 气态混合单体的阶段进料增量非常小， 以保持反应器的恒定 压力。 当聚合速率增加时， 聚合反应器压力下降很快， 可以增加进入反应器 气态混合单体的流量以维持反应器恒定压力， 在反应器和混合单体源之间需 要流量计量器和恒压器， 以准确控制流量， 并由此保持反应器的恒压。
步骤 4 ) 中所述凝聚， 釆用加入 MgCl2或硫酸铝钾等进行， 用量为所述 乳液重量的 1〜2%。
所述洗涤、 干燥釆用本领域熟知的技术进行， 釆用无离子水反复洗涤， 直至弹性体中残留水电导率小于 S s . cm , 停止洗涤， 通过在真空度为 -O. lMPa真空烘箱中 120°C , 18h干燥。
经检测， 本发明所述耐低温含氟弹性体的性能指标如表 1。
表 1 含氟弹性体相关特性表征数据
Figure imgf000006_0001
本发明研究人员经过大量实验研究， 选择釆用降低四氟乙烯含量， 提高 1,1-二氟乙烯含量，增加硫化点单体用量， 来调整含氟弹性体共聚单体的含量 组成， 得以改善含氟弹性体的结晶度， 提高含氟弹性体的弹性， 增加含氟弹 性体的硫化点比例， 提高弹性体硫化后的交联密度， 使其耐低温性能显著提 高， 低温回缩温度达 TR-10<-40°C ; 且此氟弹性体在甲醇中的体积变化率变 小， 耐油性、 耐溶剂性得到了提高， 从而提高含氟弹性体的耐油性、 耐溶剂 性能。 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 1
在混合单体贮槽中配置 65mol%l,l-二氟乙烯 （VDF ), 3mol%四氟乙烯 ( TFE ) , 29.5mol%全氟（甲基乙烯基醚） （ PMVE ) 和 2.5mol%的 CF2=CFOCF2CF2CF2OCF2Br的混合单体待用。
在 10L的立式不锈钢反应釜中，加入 6L去离子水， 20g全氟辛酸铵溶液， 5g磷酸氢二钠，聚合体系 pH为 8。反应器应进行抽空处理，待其氧含量≤20ppm 时， 将反应器中的内容物加热到 55°C。 用混合单体槽内配置好的单体通过隔 膜压缩机加入反应釜至压力 3.75MPa。 开始以 120r/min速率进行搅拌， 反应 器压力控制在 3.75±0.02 MPa内。
加入过硫酸钾 3g开始反应， 聚合反应进行后， 加入丙二酸二乙酯 5ml, 通过连续补加混合单体槽配置好的混合单体， 维持反应釜恒压， 使反应器内 绝对压力维持在 3.75±0.02 MPa之间，反应时间 5h,乳液固含量达到 30% (质 量百分数）， 结束聚合反应， 回收为反应单体， 放乳液至凝聚桶。 加入 30g的 MgCl2 (乳液量的 1% )凝聚。 釆用去离子水反复洗涤， 直至弹性体中残留水 电导率小于 5 μ δ . cm , 停止洗涤， 通过在真空度为 -O. lMPa真空烘箱中 120 °C , 18h干燥。 产生聚合物 1.8Kg, 该氟弹性体的性能特性指标见表 2。
实施例 2
如实施例 1 ,在混合单体贮槽中配置 65mol%l,l-二氟乙烯（ VDF ), 5mol% 四氟乙烯 （TFE ), 27.5mol%全氟（甲基乙烯基醚） （ PMVE ) 和 2.5mol%的 CF2=CFOCF2CF2CF2OCF2Br的混合单体待用。
聚合及凝聚、 洗涤同实施例 1 , 得 1.9kg聚合物， 性能指标见表 2。
实施例 3
如实施例 1 ,在混合单体贮槽中配置 70mol%l,l-二氟乙烯（ VDF ), 5mol% 四氟乙烯 （TFE ), 22.5mol%全氟（甲基乙烯基醚） （PMVE ) 和 2.5mol%的 CF2=CFOCF2CF2CF2OCF2Br的混合单体待用。 聚合及凝聚、 洗涤同实施例 1 , 得 1.9kg聚合物， 性能指标见表 2。
相关特性表征数据
数据
检测条件 单位 实施例 1 实施例 2 实施例 3 批次
门尼粘度 121 °C , 1+lOmin 75 73 80 密度 ASTM D792 g/cm3 1.780 1.796 1.790
。c
Tg DSC -42.0 -41.2 -41.7
MH N · m 2.381 2.060 2.520
ML 硫化仪 N · m 0.669 0.610 0.600
T90 177°C 6min min 2-46 3-45 2-10
TS2 min 0-58 1-28 0-48 拉伸强度 MPa 10.4 13.7 13.8 断裂伸长率 GB/T 528-1988 % 300 310 270 硬度 HA 75 77 78
。c
TRIO -41.2 -40.5 -40.3 结论： 1.在偏氟乙烯单体用量一定的条件下， 通过提高全氟甲基乙烯基 单体用量可以提高氟弹性体的耐低温性能。
2.在四氟乙烯用量一定的条件下， 提高偏氟乙烯单体用量， 降低全氟甲 基乙烯基醚单体用量， 低温性能下降。
实施例 4
在混合单体贮槽中配置 70mol%l,l-二氟乙烯 （VDF ), 5mol%四氟乙烯 ( TFE ) , 21mol%全氟（甲基乙烯基醚） ( PMVE ) 和 4mol%的 CF2=CFOCF2CF2CF2OCF2Br的混合单体待用。
在 10L的立式不锈钢反应釜中，加入 6L去离子水， 20g全氟辛酸铵溶液， 3g磷酸氢二钠， 0.2gNaOH聚合体系 pH为 9。 反应器应进行抽空处理， 待其 氧含量≤20ppm 时， 将反应器中的内容物加热到 80°C。 用混合单体槽内配置 好的单体通过隔膜压缩机加入反应釜至压力 3.8MPa。开始以 120r/min速率进 行搅拌， 反应器压力控制在 3.8±0.02 MPa内。
加入过硫酸钾 3g开始反应， 聚合反应进行后， 加入丙二酸二乙酯 5ml, 通过连续补加混合单体槽配置好的混合单体， 维持反应釜恒压， 使反应器内 绝对压力维持在 3.8±0.02 MPa之间， 反应时间 4h, 乳液固含量达到 32% (质 量百分数）， 结束聚合反应， 回收为反应单体， 放乳液至凝聚桶， 加入 35g的 MgCl2凝聚（乳液量的 2% )。 釆用去离子水反复洗涤， 直至弹性体中残留水 电导率小于 5 μ δ . cm , 停止洗涤， 通过在真空度为 -O. lMPa真空烘箱中 120 °C , 18h干燥。 产生聚合物 2Kg, 该氟弹性体的性能特性指标见表 3。
实施例 5
在实施例 4基础上将丙二酸二乙酯换用 1,4-二碘全氟-丁烷,使用量为 6g, 单体配比及工艺同实施例 2。 性能特性指标见表 3。
实施例 6
在实施例 5基础上将凝聚剂换为硫酸铝钾， 单体配比及工艺同实施例 5。 性能特性指标见表 3。
Figure imgf000009_0001
结论： 1.适当增加硫化点单体用量，可以提高耐低温氟弹性体的硫变性能， 进而提高产品的加工性能。
2.将分子量调节剂丙二酸二乙酯换作 1,4-二碘全氟-丁烷， 产品的流变性 能更优异。
3.后处理絮凝剂釆用硫酸铝钾在硫化性能方面优于使用氯化镁。 实施例 7
在混合单体贮槽中配置 50mol%l,l-二氟乙烯 （VDF ), 10mol%四氟乙烯 ( TFE ), 30mol%全氟 (正丙基乙烯基醚)和 10mol%的 3-溴全氟（丙基乙烯基） 醚的混合单体待用。
在 10L的立式不锈钢反应釜中，加入 6L去离子水， 20g全氟辛酸钠溶液，
3g磷酸氢二钠， 0.5gNaOH聚合体系 pH为 10。 反应器应进行抽空处理， 待 其氧含量≤2(^ 111 时， 将反应器中的内容物加热到 90°C。 用混合单体槽内配 置好的单体通过隔膜压缩机加入反应釜至压力 1.5MPa。开始以 120r/min速率 进行搅拌， 反应器压力控制在 ±0.02 MPa内。
加入过硫酸钠 2g开始反应， 聚合反应进行后， 加入 1,4-二碘全氟 -丁烷
4ml, 通过连续补加混合单体槽配置好的混合单体， 维持反应釜恒压， 使反应 器内绝对压力维持在 1.5±0.02 MPa之间，反应时间 10h,乳液固含量达到 30% (质量百分数）， 结束聚合反应， 回收为反应单体， 放乳液至凝聚桶， 加入 10g的 MgCl2凝聚（乳液量的 1.5% )。 釆用去离子水反复洗涤， 直至弹性体中 残留水电导率小于 5 s•cm , 停止洗涤， 通过在真空度为 -O.lMPa真空烘箱 中 120°C , 18h干燥。 在 120°C条件下真空干燥 18h。 产生聚合物 1.8Kg。
实施例 8
同实施例 7, 提高聚合压力至 3.0MPa, 聚合时间为 2.5h。
由此可以判断， 在耐低温氟弹性体聚合过程中， 通过提高聚合压力， 可 以改变单体竟聚率， 提高聚合速度。
虽然， 上文中已经用一般性说明及具体实施方案对本发明作了详尽的描 述， 但在本发明基础上， 可以对之作一些修改或改进， 这对本领域技术人员 而言是显而易见的。 因此， 在不偏离本发明精神的基础上所做的这些修改或 改进， 均属于本发明要求保护的范围。 工业实用性
本发明提供一种耐低温含氟弹性体及其制备方法， 其由如下共聚单体聚 合而成： 40 ~ 80 mol % 1,1-二氟乙烯， 2 ~ 10 mol %四氟乙烯， 10 ~ 30 mol % 全氟 （烷基乙烯基醚）， 和 l ~ 10 mol %的硫化点单体。 本发明调整含氟弹性 体共聚单体的含量组成， 使其耐低温性能显著提高， 其低温回缩温度
TR-10<-40°C。 且此氟弹性体在甲醇中的体积变化率变小， 耐油性、 耐溶剂性 得到了提高， 从而提高含氟弹性体的耐油性、 耐溶剂性能。 具有工业实用性。

Claims

权 利 要 求 书
1. 一种耐低温含氟弹性体， 其特征在于， 其由如下共聚单体聚合而成：： 40~80mol% 1,1-二氟乙烯， 2 ~ 10 mol %四氟乙烯， 10 ~ 30 mol %全氟 （烷 基乙烯基醚），和 l〜10mol%的硫化点单体； 所述硫化点单体包括卤代三氟乙 烯、 溴代烷基乙烯基醚、 氯代异丁烯、 CF2=CFOCF2CF2CF2OCF2Br、 1-溴 -2, 2-二氟乙烯、 溴代三氟乙烯、 4-溴 -1,1,2-三氟丁烯 -1、 2-溴全氟（乙基乙烯基） 醚、 3-溴全氟 （丙基乙烯基）醚或 1-溴 -3,3,4,4-四氟丁烯。
2. 根据权利要求 1所述的耐低温含氟弹性体， 其特征在于， 所述共聚单 体含量为： 50~75mol% 1,1-二氟乙烯， 2~5mol%四氟乙烯， 15 ~ 30 mol % 全氟 （烷基乙烯基醚）， 和 2〜6mol%的硫化点单体。
3. 根据权利要求 1或 2所述的耐低温含氟弹性体， 其特征在于， 所述硫 化点单体为 CF2=CFOCF2CF2CF2OCF2Br、 1-溴 -2, 2-二氟乙烯、溴代三氟乙烯、 4-溴 -1,1,2-三氟丁烯 -1、 2-溴全氟 (乙基乙烯基）醚、 3-溴全氟（丙基乙烯基） 醚或 1-溴 -3,3,4,4-四氟丁烯， 最优选的为 CF2=CFOCF2CF2CF2OCF2Br、 3-溴全 氟 （丙基乙烯基） 醚或 1-溴 -3,3,4,4-四氟丁烯。
4. 根据权利要求 1-3任意一项所述的耐低温含氟弹性体， 其特征在于， 所述全氟 （烷基乙烯基醚） 为全氟 （甲基乙烯基醚）或全氟 （正丙基乙烯基 醚）。
5. 制备权利要求 1-4任意一项所述的耐低温含氟弹性体的方法， 其特征 在于， 包括如下步骤： 份水介质中加入 0.01 ~ 5重量份乳化剂， 并调节 pH值为 7~12；
2)加入 1,1-二氟乙烯， 四氟乙烯， 全氟 （烷基乙烯基醚）和硫化点单体 的混合单体， 按配比混合形成乳液， 每 100重量份水介质中加入 30 ~ 150重 量份的混合单体；
3)加入引发剂， 在 0~110°C, l~5MPa下进行聚合反应， 在聚合反应 过程中， 加入链转移剂， 并维持反应恒压； 4 ) 最后将聚合后的乳液凝聚， 洗涤和干燥而成。
6. 根据权利要求 5所述的方法， 其特征在于， 步骤 1 ) 中所述乳化剂为
7. 根据权利要求 5或 6所述的方法， 其特征在于， 所述引发剂为过硫酸 铵、 过硫酸钾或过硫酸钠； 引发剂的量为混合单体重量的 0.001 ~ 5%；
8. 根据权利要求 5-7任意一项所述的方法， 其特征在于， 所述聚合反应 温度为 40 ~ 100°C。
9. 根据权利要求 5-8任意一项所述的方法， 其特征在于， 所述链转移剂 为四氯化碳、 正己烷、 丙酮、 丙二酸二乙脂、 丁二酸二乙脂或者乙酸乙脂， 亚甲基碘， 全氟丁基碘， 1,4-二碘全氟-丁烷， 所述链转移剂的量为混合单体 重量的 0.01 ~ 5%。
10. 根据权利要求 5-9任意一项所述的方法， 其特征在于， 保持恒压釆用 补加混合单体， 反应压力控制在 1.2 ~ 4MPa。
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