WO2010017665A1 - 一种含氟聚醚过氧化物及其在含氟单体乳液聚合中的应用 - Google Patents

一种含氟聚醚过氧化物及其在含氟单体乳液聚合中的应用 Download PDF

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WO2010017665A1
WO2010017665A1 PCT/CN2008/001478 CN2008001478W WO2010017665A1 WO 2010017665 A1 WO2010017665 A1 WO 2010017665A1 CN 2008001478 W CN2008001478 W CN 2008001478W WO 2010017665 A1 WO2010017665 A1 WO 2010017665A1
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fluorine
surfactant
dispersion
weight
peroxide
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PCT/CN2008/001478
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English (en)
French (fr)
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谢学端
屈均
柏荣
张建新
杨旭仓
陈波
张金刚
张鸣
胡显权
程宇
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中昊晨光化工研究院
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Priority to KR1020117000238A priority Critical patent/KR101258616B1/ko
Priority to PCT/CN2008/001478 priority patent/WO2010017665A1/zh
Priority to JP2011510802A priority patent/JP5456769B2/ja
Priority to RU2010146212/04A priority patent/RU2458940C2/ru
Priority to US12/996,887 priority patent/US8536269B2/en
Priority to PL08800502T priority patent/PL2319879T3/pl
Priority to EP08800502.0A priority patent/EP2319879B1/en
Publication of WO2010017665A1 publication Critical patent/WO2010017665A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

Definitions

  • the invention belongs to the field of polymer chemistry, in particular to a kind of fluorine-containing polyether peroxide and its application as a surfactant in the polymerization of a fluorine-containing monomer, and polymerization of a fluorine-containing polyether peroxide as a surfactant.
  • the most common method for preparing a fluorine-containing dispersion is an emulsion polymerization method in which water, an initiator, a surfactant, a fluorine-containing monomer, and a necessary auxiliary agent are separately added in a pressure vessel.
  • reaction is carried out at 10 ° C to 150 ° C under a certain pressure to form a fluorine-containing aqueous dispersion.
  • perfluorooctanoic acid or a salt thereof is usually used as a surfactant.
  • the present invention provides a carboxylic acid or a salt thereof of a fluorine-containing polyether peroxide and a surfactant which is used as a surfactant for emulsion polymerization of a fluorine-containing monomer. Summary of the invention
  • the present invention provides a fluoropolyether peroxide-containing carboxylic acid or a salt thereof and use thereof as a surfactant.
  • the present invention also provides a dispersion of a fluoropolymer using a fluoropolyether peroxide-containing carboxylic acid or a salt thereof as a surfactant.
  • the fluoropolyether peroxide has a peroxy linkage -0-0- and an ether linkage in the main chain. From the perspective of bond energy and bond length, the C-F bond is very stable, and an appropriate amount of ether bond is introduced. The C-O-C chain is easy to rotate, curl and relax freely. The characteristics of the above structure make the fluorine-containing polyether excellent in high temperature resistance and chemical stability, and are very suitable as a surfactant.
  • the bond of the peroxygen bond is small, the bond is long, unstable and easy to decompose during the reaction, and the fluorine-containing polyether peroxide is used as a surfactant for producing an aqueous dispersion of the fluorine monomer, and synergistic with an auxiliary agent such as an initiator.
  • the action makes the reaction induction process proceed smoothly, which is beneficial to the polymerization control, and can reduce the amount of the initiator or shorten the reaction time.
  • the fluorine-containing polyether peroxide of the present invention has an average molecular weight of from 300 to 5,000 and has the following structure (see formula (I)):
  • G f is -CF 2 CF(CF 3 )- or -CF(CF 3 )CF 2 - ;
  • the terminal group A is -CF 3 , -COOM or -CF 2 COOM;
  • B is -COOM or -CF 2 COOM; wherein M is -H, -N or an alkali metal element;
  • the carboxylic acid or salt thereof of the fluorine-containing polyether peroxide according to the present invention is prepared by referring to Patent GB 1,104,482, and the main raw material is perfluoropropylene HFP, which is reacted under low temperature and ultraviolet lamp irradiation conditions, and then the obtained reactant is hydrolyzed.
  • the organic layer was taken and subjected to negative pressure fractionation to extract fractions of different boiling ranges (between 30 ° C and 18 °C) to obtain a fluorine-containing polyether peroxide having a certain range of acid value and/or peroxy value.
  • the composition unit and structure of the obtained substance are determined, and the peroxidation value of the obtained substance is determined by iodometric analysis.
  • the typical substance of the carboxylic acid or a salt thereof of the fluorine-containing polyether peroxide used in the present invention may be as follows The substance shown, but is not limited to this.
  • the present invention has an average molecular weight of 300-5000 as shown in formula (I).
  • a fluoropolyether peroxide carboxylic acid or a salt thereof used as a surfactant in aqueous polymerization of a fluorine-containing monomer the table
  • the surfactant may be a mixture of one or more of a class of compounds represented by the general formula (I).
  • the aqueous polymerization of the fluoromonomer generally comprises the following steps:
  • reaction medium water or other solvent
  • reaction temperature is from 10 ° C to 150 ° C
  • reaction time is generally from 0.5 h to 50 h. .
  • the auxiliary agent is a known pH adjuster, chain transfer agent or the like, and the initiator is a known organic peroxide, inorganic peroxide or redox system substance.
  • the surfactant fluoropolyether peroxide carboxylic acid or a salt thereof used in the present invention may be used in an amount of a usual surfactant such as ammonium perfluorooctanoate, generally based on the amount of water used in the polymerization, the surfactant
  • the amount added may be from 0.005% to 10% by weight, preferably from 0.05% by weight to 4% by weight, more preferably from 0.05% by weight to 0.4% by weight.
  • the carboxylic acid or a salt thereof of the surfactant fluorine-containing polyether peroxide used in the present invention is present in the reaction vessel during the polymerization, and the manner of addition thereof is not particularly limited and may be added before the start of the polymerization; or before the start of the polymerization Add a part first, and then add a part after the reaction starts.
  • the surfactant may be added to the reaction vessel alone or may be added to the reaction vessel together with other additives.
  • the fluorinated monomer which can be polymerized in the process of the present invention is not particularly limited and generally includes the following types:
  • Perfluoroolefins such as tetrafluoroethylene TFE, perfluoropropylene HFP, etc.;
  • Halogen-containing olefins such as vinylidene fluoride VDF, chlorotrifluoroethylene (CTFE), bromine or 3.
  • Fluorinated olefin ethers such as perfluoromethyl vinyl ether PPME;
  • a fluorine-free olefin or a double bond substance copolymerizable with a fluorine-containing olefin such as ethylene, propylene, or the like.
  • the fluorine-containing olefin may be polymerized separately to form a homopolymer dispersion, or may be polymerized with one or more other fluorine monomers or other fluorine-free monomers to form a copolymer; copolymerizable with the fluorine monomer.
  • the fluorine-free monomer generally includes ethylene and propylene.
  • homopolymers generally refer to polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE); the classification into homopolymers usually also refers to the addition of small amounts (generally no more than 3 wt%)
  • the polymer of the polymerizable monomer, the added polymerized monomer does not change the basic properties of the pure homopolymer.
  • Examples of the copolymer generally include copolymers of vinylidene fluoride VDF and/or tetrafluoroethylene TFE and/or perfluoropropylene HFP; as previously indicated, the comonomers are not limited to those listed herein.
  • the present invention also provides a carboxylic acid or a salt thereof in which the surfactant is a fluorine-containing polyether peroxide, and at least one fluorinated monomer is polymerized to obtain a fluoropolymer dispersion.
  • the surfactant is a fluorine-containing polyether peroxide, and at least one fluorinated monomer is polymerized to obtain a fluoropolymer dispersion.
  • the fluoropolymerized dispersion prepared by the process of the invention contains at least 15% by mass of solids based on the total mass of the dispersion; the average diameter of the particles in the dispersion does not exceed 300 nm;
  • the concentration of the surfactant is not more than 10% by weight, not less than 0.005% by weight, preferably from 0.05% by weight to 4% by weight, more preferably from 0.05% by weight to 0.4% by weight, based on the mass.
  • the fluoromonomer polymerized dispersion provided by the present invention generally has the following monomers:
  • Perfluoroolefins such as tetrafluoroethylene TFE, perfluoropropylene HFP, etc.;
  • Halogen-containing olefins such as vinylidene fluoride VDF, chlorotrifluoroethylene CTFE, bromine or iodine olefins;
  • Fluorinated olefin ethers such as perfluoromethyl vinyl ether PPME;
  • a fluorine-free olefin or a double bond substance copolymerizable with a fluorine-containing olefin such as ethylene, Propylene and the like.
  • the fluoropolymerized dispersion prepared by the process of the present invention may be emulsion, plastic or gel after condensing by a known process technique; the fluoropolymer solid component may be a plastomer or an elastomer, which may be amorphous or partially crystalline. , thermoplastic or thermoset.
  • the fluorine-containing polyether peroxide of the invention is used as a surfactant for producing an aqueous dispersion of a fluorine-containing monomer, and synergistically acts with an auxiliary agent such as an initiator to induce a gentle reaction process, which is advantageous for polymerization control, shortening reaction time or reducing The amount of initiator used.
  • Standard specific gravity ASTM D-1457 method
  • Solid content concentration drying conditions: 150 ° C, 3 h;
  • an ultraviolet lamp (wavelength of 250 nm-400 nm) irradiation device with a power of 125 W is placed on a pressure-resistant steel reactor with a volume of 2000 ml and a reflow facility of -70 ° C.
  • the internal pressure in the vessel is lowered, and the TFE monomer is continuously added to maintain the internal pressure at 1.9 - 2.0 MPa until the solid concentration in the dispersion is about 30%. Then, the stirring is stopped, the pressure is released, and the reaction is terminated to obtain TFE.
  • the aqueous homopolymer dispersion; the reaction time is cumulatively 3.0 h; a subsequent unit process such as coagulation drying is a well-known process, and is not particularly limited.
  • Propylene (HFP) supplemental mixed monomer VDF: HFP 75: 25 (molar ratio) to the internal pressure of the vessel up to 2.3MPa, adding 5g of surfactant perfluorooctanoic acid ammonium, adding potassium persulfate 10g, perfluorooctanoic acid 40ml, malonic acid diethyl 80 ml of ester and 30 g of borax initiate the reaction.
  • VDF vinylidene fluoride
  • HFP hexafluoropropylene
  • VDF vinylidene fluoride
  • HFP hexafluoropropylene
  • a subsequent unit process such as coagulation drying is a well-known process, and is not particularly limited.
  • the reaction time of the reaction is 3.5 h
  • the solid content of the dispersion is 32.1% (mass);
  • the average diameter of the primary particles is 185 nm; condensate
  • the invention provides a fluorine-containing polyether peroxide which can replace perfluorooctanoic acid or a salt thereof as a surfactant in the polymerization process of a fluorine-containing monomer, thereby reducing environmental damage and protecting the environment; and during the polymerization process
  • the fluorine-containing polyether peroxide can induce a gentle progress of the reaction process, thereby reducing the amount of the initiator or shortening the reaction time.
  • the present invention also provides a fluorine-containing dispersion obtained by polymerizing a fluorine-containing polyether peroxide as a surfactant to a fluorine-containing monomer, and the solid component thereof may be an amorphous or partially crystalline, thermoplastic or thermosetting plastomer or Elastomer, the fluorine-containing dispersion is subjected to condensate to prepare a final product such as an emulsion, a plastic or a rubber.

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  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Description

一种含氟聚醚过氧化物及其在含氟单体乳液聚合中的应用 技术领域
本发明属于高分子化学领域，特别涉及一类含氟聚醚过氧化物及 其作为表面活性剂在含氟单体聚合中的应用，以及将含氟聚醚过氧化 物作为表面活性剂聚合含氟单体得到的含氟分散体。 背景技术
制备含氟分散体最为常用的方法是乳液聚合法， 即在压力容器 中， 分别加入水、 引发剂、 表面活性剂、 含氟单体、 必要的助剂， 在
10°C ~ 150°C、 一定压力条件下反应生成含氟水性分散体。 在现有工 艺中， 通常釆用全氟辛酸或其盐作为表面活性剂。
近期研究发现，全氟辛酸或其盐在产品中的残留或生产过程中的 损失， 最终会进入生物圈。 调查结果表明： 地下水、 地面水和海水以 及所有野生动物和人类血液都存在全氟辛酸或其盐。 对人类而言， 它 可以通过脐带传输到婴儿体内积累。虽然目前没有确定的研究成果表 明对人类健康造成危害， 但全氟辛酸或其盐高度稳定，难以在环境中 降解， 目前还未发现它在环境中和生物体内的任何分解迹象， 而动物 实验表明高剂量的全氟辛酸铵会引发癌症、胚胎畸形等多种疾病， 因 而减少或消除该物质的使用或残留是具有现实意义的。
在含氟水性分散体的生产过程中，人们努力使用其它物质来代替 全氟辛酸或其盐作为表面活性剂。
美 国 Dupont 公 司 在 专 利 US 3,271,341 中 报 道 用 F-(CF2)m-0-[CF(X)-CF2-0]n-CF(X)-COOA 类物质做含氟烯烃乳液聚 合用的表面活性剂； 美国 3M公司在专利 WO 2007,011,631中介绍了 CF3 -0-(CF2)3-(0-CF(CF3)-CF2)z-0-L-Y 型聚醚物质在乳液聚合中的 应用； 比利时 Solvay公司在专利 US 6，878，772B2中描述了双官能团氟 聚醚表面活性剂的应用。 本发明提供一种含氟聚醚过氧化物的羧酸或其盐以及将其作为 含氟单体乳液聚合反应的表面活性剂的应用。 发明内容
本发明提供一种含氟聚醚过氧化物的羧酸或其盐及以其作为表 面活性剂的应用。
本发明还提供一种使用含氟聚醚过氧化物的羧酸或其盐为表面 活性剂的氟聚合物的分散体。
含氟聚醚过氧化物的主链上有过氧键 -0-0-和醚键。 从键能和键 长的角度分析， C-F键非常稳定， 引入适量醚键， C-O-C链易于自由 旋转、卷曲和松弛。 上述结构的特点使含氟聚醚具有杰出的耐高温性 能和化学稳定性， 非常适合用作表面活性剂。 过氧键的键能小、 键长 长， 在反应过程中不稳定、 易分解， 采用含氟聚醚过氧化物作为生产 氟单体水性分散体的表面活性剂， 与引发剂等助剂协同作用，使反应 诱导过程平缓进行， 利于聚合控制， 可降低引发剂用量或缩短反应时 间。
本发明涉及的含氟聚醚过氧化物的平均分子量为 300-5000， 具有 如下结构 （见式 (I) ):
A-0-(GrO)m(GrO-0)n-(CF20)p-(CF200)q-(CF(CF3)0)r-B (I) 其中： Gf是 -CF2CF(CF3)- 或 -CF(CF3)CF2- ；
端基 A 是 -CF3、 -COOM 或 -CF2COOM; B 是 -COOM 或 -CF2COOM; 其中， M是 -H、 -N 或碱金属元素；
m、 n、 p、 q、 r满足以下条件：
( 1 ) m、 n、 p、 q、 r均是不小于零的整数；
( 2 ) n+q > 1 ;
( 3 ) n+q < m+p+r;
( 4 ) m > n+p+q+r
( 5 ) 满足分子量范围要求 酸值： 20-120 mgNaOH/g;
过氧值： 0.5% ~ 10.0% ( wt )。
本发明涉及的含氟聚醚过氧化物的羧酸或其盐参照专利 GB 1,104,482制备， 主要原料为全氟丙烯 HFP， 在低温和紫外灯照射条 件下反应， 然后将制得的反应物水解， 取有机物层， 进行负压分馏截 取不同沸程的馏分（30°C-18(TC之间）， 得到一定范围内酸值和 /或过 氧值的含氟聚醚过氧化物。 用 19FNMR (核磁共振）确定所得物质的 组成单元及结构， 用碘量法分析确定所得物质的过氧值。 本发明中使用的含氟聚醚过氧化物的羧酸或其盐的典型物质可 以是如下所示物质， 但不限于此。
CF30(CF2CF(CF3)0) (CF200) (C(CF3)FO)COONH4
CF30(CF2CF(CF3)0) (CF200) (C(CF3)FO)COOH
CF30(CF2CF(CF3)0) (CF200) (C(CF3)FO)COOK
CF30(CF2CF(CF3)0)3(CF2CF(CF3)00)(CF20) (C(CF3)FO)CF2COONH4 CF30(CF2CF(CF3)0)3(CF2CF(CF3)00)(CF20) (C(CF3)FO)CF2COOH
CF30(CF2CF(CF3)0)3(CF2CF(CF3)00)(CF20) (C(CF3)FO)CF2COOK
CF30(CF2CF(CF3)0)4(CF2CF(CF3)OOXCF2OXCF200)(C(CF3)FO)CF2COONH4 C F30(CF2CF(CF3)0)4(CF2CF(CF3)00)(CF20)(CF200)(C(CF3)FO)CF2COOH C F30(CF2CF(CF3)0)4(CF2CF(CF3)00)(CF20)(CF200)(C(CF3)FO)CF2COO NH4OOCO(CF2CF(CF3)0)3(CF2CF(CF3)00) (C(CF3)FO)2CF2COONH4 HOOCO(CF2CF(CF3)0)3(CF2CF(CF3)00) (C(CF3)FO)2CF2COOH
OOCO(CF2CF(CF3)0)3(CF2CF(CF3)00) (C(CF3)FO)2CF2COOK
CF30(CF2CF(CF3)0)(CF2CF(CF3)00) (C(CF3)FO)COONH4
CF30(CF2CF(CF3)0)(CF2CF(CF3)00) (C(CF3)FO)COOH
CF30(CF2CF(CF3)0)(CF2CF(CF3)00) (C(CF3)FO)COOK 本发明将式 （I )所示的平均分子量为 300-5000的含氟聚醚过氧 化物的羧酸或其盐用作含氟单体水性聚合反应中的表面活性剂，该表 面活性剂可以是由通式 （I )所示的一类化合物中的一种或多种的混 合物。
含氟单体水性聚合反应一般包括以下步骤：
(1)向反应容器中加入反应媒介（水或其它溶剂）， 通过加入 N2 或反应气体的置换来除去反应容器中的氧， 一般控制氧含量 20ppm;
(2)加入含氟聚醚过氧化物作为表面活性剂， 再加入含氟单体， 使反应体系的压力控制在 0.5MPa ~ 12MPa;
(3)在反应体系中加入助剂， 引发剂， 进行含氟单体聚合反应， 得到含氟单体聚合分散体，反应温度在 10°C-150°C ,反应时间一般为 0.5h ~ 50h。
其中所述助剂为公知的 pH调节剂、 链转移剂等， 所述引发剂为 公知的有机过氧化物、 无机过氧化物或氧化还原体系类物质。
本发明使用的表面活性剂含氟聚醚过氧化物的羧酸或其盐可以 以通常表面活性剂如全氟辛酸铵的量使用，一般来说以聚合中使用的 水量为基准， 该表面活性剂的加入量可以是 0.005% ~ 10wt%， 优选 0.05wt% ~ 4wt%, 更优选 0.05 wt% ~ 0.4wt%。
本发明使用的表面活性剂含氟聚醚过氧化物的羧酸或其盐在聚 合期间存在于反应容器中， 其加入方式没有特别的限定， 可以在聚合 开始前加入； 也可以在聚合开始前先加入一部分， 反应开始后再加入 一部分。该表面活性剂可以单独加入到反应容器中， 也可以与其它添 加物一起加入到反应容器中。
本发明工艺中可以聚合的氟化单体没有特别限定，一般包括如下 几类：
1. 全氟烯烃类， 如四氟乙烯 TFE、 全氟丙烯 HFP等；
2. 含卤烯烃类， 如偏氟乙烯 VDF、 三氟氯乙烯 CTFE、 含溴或 3. 含氟烯烃醚类， 如全氟甲基乙烯基醚 PPME等；
4. 含氟杂环双键物质，全氟 -2,2-二甲基 -1,3-二氧杂环戊烯 PDD等;
5. 可与含氟烯烃共聚的不含氟的烯烃或双键类物质， 如乙烯、 丙炼等。
含氟烯烃可以单独聚合而生成一种均聚物分散体，也可以与一种 或多种其他氟单体或者其它不含氟的单体一起聚合生成共聚物；能够 与氟单体一起共聚的不含氟的单体一般包括乙烯和丙烯。均聚物的实 例通常指聚四氟乙烯（PTFE )、 聚偏氟乙烯（PVDF )、 聚三氟氯乙烯 ( PCTFE ); 归入均聚物的通常还指有加入少量（一般不超过 3wt% ) 可聚合单体的聚合物，加入的聚合单体不至于改变纯均聚物的基本性 能。 共聚物的实例通常包括偏氟乙烯 VDF和 /或四氟乙烯 TFE和 /或 全氟丙烯 HFP的共聚物； 如前所涉指， 共聚单体不仅仅是这里所罗 列的这些。
本发明还提供表面活性剂是含氟聚醚过氧化物的羧酸或其盐，至 少一种氟化单体聚合而得到氟聚合物分散体。
用本发明工艺制备的氟聚合分散体含有至少 15% (质量）的固体 (以分散体总质量为基准）； 所述分散体中微粒的平均直径不超过 300nm; 以所述分散体中水的质量为基准， 表面活性剂的浓度不大于 10wt% , 不少于 0.005 wt%， 优选量为 0.05 wt% ~ 4wt%， 更优选 0.05wt% ~ 0.4wt%。 本发明提供的含氟单体聚合的分散体， 其单体一 般是如下几类：
1. 全氟烯烃类， 如四氟乙烯 TFE、 全氟丙烯 HFP等；
2. 含卤烯烃类， 如偏氟乙烯 VDF、 三氟氯乙烯 CTFE、 含溴或 碘烯烃等；
3. 含氟烯烃醚类， 如全氟甲基乙烯基醚 PPME等；
4. 含氟杂环双键物质，全氟 -2,2-二甲基 -1，3-二氧杂环戊烯 PDD等;
5. 可与含氟烯烃共聚的不含氟的烯烃或双键类物质， 如乙烯、 丙烯等。
用本发明工艺制备的氟聚合分散体经公知的工艺技术凝析后可 以是乳液状、 塑料状或胶状； 氟聚合物固体成份可以是塑性体或弹性 体， 其可以是无定型或部分结晶的、 可热塑或热固成型。
釆用本发明的含氟聚醚过氧化物作为生产含氟单体水性分散体 的表面活性剂， 与引发剂等助剂协同作用， 诱导反应过程平缓进行， 利于聚合控制， 缩短反应时间或降低引发剂的用量。
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 例中涉及的基本分析检测方法如下：
1. 微粒的平均直径： 光散射法；
2. 标准比重： ASTM D-1457方法；
3. 固体成分浓度： 烘燥条件： 150°C , 3h;
4. 分子量分布： 凝胶色谱法；
5. 门尼黏度： GB/T 1232 (中国国家标准）;
6. 密度： GB/T 533 (中国国家标准）;
7. 过氧值： 碘量法。 实施例 1 含氟聚醚过氧化物的制备
参照专利 GB 1,104,482 ( 1968 ) 的制备方法， 在容积为 2000ml 的带 -70°C的回流设施的耐压钢制反应器上安置功率为 125W 的紫外 灯（波长为 250nm-400nm )照射装置， 预冷反应器和原料， 然后向已 经预冷的反应器里加入经预冷至 -45°C的全氟丙烯 HFP 2000g;向反应 器底部以 20L/h的速度通入氧气（ 02， 以标态计量）和 C2F3C1 2.5L/h (以标态计量） 的混合气， 保持反应温度为 -45 ， 反应 8h; 然后停 止紫外灯照射， 停止反应； 停止冷冻， 回收 HFP。 将釜底反应产物取 出， 放在有搅拌的容器内， 加适量 90°C的热水水解 16h， 停止搅拌， 静置分层， 取油层， 得 665g水解产物； 将该水解产物负压分馏截取 不同沸程的馏分（30°C-18(TC之间）， 得到一定范围的酸值和 /或过氧 值的含氟聚醚过氧化物羧酸共计 604g。 用碘量法分析各馏分段物质 的过氧值； 用 19FNMR确定物质的组成单元及结构。 比较例 1
向容积为 50升的带有搅拌的耐压不锈钢容器中加入 32L去离子 水、 2000g石腊、 50g表面活性剂全氟辛酸铵； 先用氮气置换容器内 的氧， 再用四氟乙烯（TFE )单体置换， 使容器内氧含量低于 20ppm; 在 72°C下通入 TFE单体至容器内压达 2.0MPa， 进而加入 0.05% (质 量） 的过硫酸铵（APS )水溶液 500g， 丁二酸 8g， 引发反应。 随反 应进行， 容器中内压降低， 连续补加 TFE单体， 使内压维持在 1.9 - 2.0 MPa, 直至分散液中固体成分浓度约 30%; 然后停止搅拌， 释放 压力，结束反应，得到 TFE均聚物水性分散体；反应时间累计为 3.0h; 凝析干燥等后续单元过程是公知工艺， 没有特别限定。
取样分析， 该分散体的固体含量为 29.3% (质量）； 初级粒子平 均直径 230nm; 凝析物的标准比重 （ SSG )为 2.184。 实施例 2
在比较例 1中， 只是改变表面活性剂的种类， 加入含氟聚醚过氧 化物的羧酸盐 [CF30(CF2CF(CF3)0) (CF200) (C(CF3)FO)COONH4, 酸 值 70.1mgNaOH/g， 过氧值 5%] 50g， 制得含氟单体聚合分散体。 其 中该反应的反应时间为 2.3h; 分散体的固体含量为 29.1% (质量）； 初级粒子平均直径 240nm; 凝析物的标准比重 （SSG )为 2.182。 实施例 3
在比较例 1中， 只是改变表面活性剂的种类， 加入含氟聚醚过氧 化物的羧酸盐 [CF30(CF2CF(CF3)0)3(CF2CF(CF3)00)(CF20)(C(CF3)F 0)CF2COONH4, 酸值 43mg NaOH/g， 过氧值 2.8%] 50g, 制得含氟 单体聚合分散体。其中该反应的反应时间为 2.4h; 分散体的固体含量 为 30.5% (质量）； 初级粒子平均直径 235nm; 凝析物的标准比重（S SG )为 2.180。 将实施例 2， 3与比较例 1 比较， 可见： 使用本发明提供的含氟 聚醚过氧化物作表面活性剂， 四氟乙烯的聚合反应时间明显缩短。 比较例 2
向容积为 50升的带有搅拌的耐压不锈钢容器中加入 30L去离子 水； 先用氮气置换容器内的氧， 使容器内氧含量低于 20ppm; 先加入 3kg初始混合单体：偏氟乙烯（VDF )和六氟丙烯（HFP )，其中 VDF: HFP=55: 45 (摩尔比）； 进而开启搅拌并调节温度， 在容器内温 90°C 时通入偏氟乙烯 （VDF ) 和六氟丙烯 （HFP ) 补加混合单体 VDF: HFP=75: 25 (摩尔比） 至容器内压达 2.3MPa, 加入 5g表面活性剂 全氟辛酸铵、加入过硫酸钾 10g，全氟辛酸 40ml，丙二酸二乙酯 80ml、 硼砂 30 g， 引发反应。 随反应进行， 容器内压降低， 连续补加偏氟乙 烯 （VDF ) 和六氟丙烯 （HFP ) 补加混合单体（VDF: HFP=75: 25 (摩尔比））， 使内压维持在 2.2 - 2.3 MPa。 加入混合单体使分散液中 固体成分浓度约 32%; 然后停止搅拌， 释放内压， 结束反应， 得到偏 氟乙烯（VDF )和六氟丙烯（HFP ) 的共聚物水性分散体； 反应时间 累计为 4h; 凝析干燥等后续单元过程是公知工艺， 没有特别限定。
取样分析， 该分散体的固体含量为 31.4% (质量）； 初级粒子平 均直径 190nm;凝析物的门尼黏度值为 M ^°=42; 密度为 1.811g/cm3; 分子量分布值 2.40。
实施例 4
在比较例 2中， 只改变表面活性剂的种类和引发剂加入量， 加入 含氟聚醚过氧化物 的羧酸盐 [CF30(CF2CF(CF3)0) (CF200) (C(CF3)FO)COONH4, 酸值 70.1mgNaOH/g, 过氧值 5%] 5g， 过硫酸 钾 8g。 制得氟单体聚合分散体。 其中该反应的反应时间 3.5h， 分散 体的固体含量为 32.1% (质量）； 初级粒子平均直径 185nm; 凝析物 的门尼黏度值为^+2;°=42； 密度为 1.812g/cm3; 分子量分布值 2.67。 实施例 5
在比较例 2中， 只是改变表面活性剂的种类和引发剂加入量， 加 入含氟聚醚过氧化物的羧酸盐 [CF30(CF2CF(CF3)0)3(CF2CF(CF3)00) (CF20)(C(CF3)FO)CF2COONH4 , 酸值 43mgNaOH/g， 过氧值 2.8%] 5g， 过硫酸钾 8g。 制得氟单体聚合分散体。 其中该反应的反应时间 为 3.5h， 所得分散体的固体含量为 31.6% (质量）； 初级粒子平均直 径 182nm; 凝析物的门尼黏度值为 M ^ =43; 密度为 1.816g/cm3; 分 子量分布值 2.56。 将实施例 4， 5与比较例 2比较， 可见该含氟聚醚过氧化物作为 表面活性剂可以减少引发剂的用量。 工业实用性
本发明提供了一种含氟聚醚过氧化物，它可以替代全氟辛酸或其 盐，在含氟单体聚合过程中用作表面活性剂，从而减轻对环境的危害， 保护环境； 且在聚合过程中， 作为表面活性剂， 该含氟聚醚过氧化物 可诱导反应过程平缓进行，从而降低引发剂的用量，或缩短反应时间。
本发明还提供将该含氟聚醚过氧化物作为表面活性剂聚合含氟 单体得到的含氟分散体， 其固体成份可以是无定型或部分结晶的、 热 塑或热固的塑性体或弹性体， 该含氟分散体经过凝析后可制备乳液、 塑料或橡胶等最终产品。

Claims

权 利 要 求 书
1、 一种含氟聚醚过氧化物， 其平均分子量为 300 - 5000， 并具有 下式所示的结构：
A-0-(GrO)m(GrO-0)n-(CF20)p-(CF200)q-(CF(CF3)0)r-B (I) 其中： Gf是 -CF2CF(CF3)- 或 -CF(CF3)CF2- ；
端基 A 是 -CF3、 -COOM 或 -CF2COOM; B 是 -COOM 或 -CF2COOM; 其中， M是 -H、 -NH4或碱金属元素；
m、 n、 p、 q、 r满足以下条件：
( 1 ) m、 n、 p、 q、 r均是不小于零的整数；
( 2 ) n+q > 1；
( 3 ) n+q < m+p+r;
( 4 ) m > n+p+q+r
( 5 ) 满足分子量范围要求。
2、 如权利要求 1所述的含氟聚醚过氧化物， 其特征在于其酸值 为 20-120mgNaOH/g; 过氧值为 0.5wt% ~ 10.0wt%。
3、 一种含氟单体聚合分散体， 其特征在于含有权利要求 1或 2 所述的含氟聚醚过氧化物作为表面活性剂。
4、 如权利要求 3所述的分散体， 其特征在于其中固体含量大于等 于 15wt%, 所述分散体中微粒的平均直径不超过 300nm。
5、 如权利要求 3所述的分散体， 其特征在于所述表面活性剂的 浓度不大于 10wt%。
6、 如权利要求 5所述的分散体， 其特征在于所述表面活性剂的 加入量为 0.05 wt% ~ 4wt%。
7、 如权利要求 5所述的分散体， 其特征在于所述表面活性剂的 加入量为 0.05 wt% ~ 0.4wt%。
8、 如权利要求 5所述的分散体， 其特征在于所述含氟单体包括: ( 1 ) 四氟乙烯、 全氟丙烯的全氟烯烃类； (2)偏氟乙烯、 三氟氯乙烯、 含溴或碘烯烃的含卤烯烃类；
(3)全氟甲基乙烯基醚的含氟烯烃醚类；
(4)全氟 -2, 2-二甲基 -1, 3-二氧杂环戊烯的含氟杂环双键物质;
(5) 乙烯、 丙烯的可与含氟烯烃共聚的不含氟的烯烃或双键类 物质。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012058793A1 (zh) * 2010-11-02 2012-05-10 中昊晨光化工研究院 含氟微乳的制备方法及应用
CN102464730A (zh) * 2010-11-02 2012-05-23 中昊晨光化工研究院 含氟微乳的制备方法及应用
US20130213270A1 (en) * 2010-11-02 2013-08-22 Zhonghao Chenguang Research Institute Of Chemical Industry Co., Ltd. Preparation method and use for fluorine-containing microemulsion
JP2013540869A (ja) * 2010-11-02 2013-11-07 チョンハオ チェングァン リサーチ インスティテュート オブ ケミカル インダストリー 含フッ素マイクロエマルションの製造方法及び応用
US9101892B2 (en) 2010-11-02 2015-08-11 Zhonghao Chenguang Research Institute Of Chemical Industry Co., Ltd Preparation method and use for fluorine-containing microemulsion
KR101572556B1 (ko) 2010-11-02 2015-11-27 중호우 천광 리서치 인스티튜트 오브 케미컬 인더스트리 컴퍼니 리미티드 불소 함유 마이크로 에멀션의 제조방법 및 응용

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KR101258616B1 (ko) 2013-04-26
EP2319879A4 (en) 2015-03-11
US8536269B2 (en) 2013-09-17
RU2010146212A (ru) 2012-06-27
US20110207880A1 (en) 2011-08-25
KR20110028340A (ko) 2011-03-17
PL2319879T3 (pl) 2016-04-29
JP2011523946A (ja) 2011-08-25
RU2458940C2 (ru) 2012-08-20
JP5456769B2 (ja) 2014-04-02
EP2319879A1 (en) 2011-05-11
EP2319879B1 (en) 2015-11-18

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