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WO2018166413A1 - 一种由全氟烷基缩水甘油醚与多元环醚共聚的易溶侧链含氟共聚醚二醇 - Google Patents

一种由全氟烷基缩水甘油醚与多元环醚共聚的易溶侧链含氟共聚醚二醇 Download PDF

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WO2018166413A1
WO2018166413A1 PCT/CN2018/078672 CN2018078672W WO2018166413A1 WO 2018166413 A1 WO2018166413 A1 WO 2018166413A1 CN 2018078672 W CN2018078672 W CN 2018078672W WO 2018166413 A1 WO2018166413 A1 WO 2018166413A1
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glycidyl ether
fluorine
side chain
propylene oxide
ether
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PCT/CN2018/078672
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English (en)
French (fr)
Inventor
孔庆刚
施博文
王静
刘飞
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南京信息工程大学
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Publication of WO2018166413A1 publication Critical patent/WO2018166413A1/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
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • 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
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/20—Tetrahydrofuran
    • 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
    • C08G65/02—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
    • C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
    • C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine

Definitions

  • the invention belongs to the technical field of intermediates of polymer materials, and particularly relates to a readily soluble side chain fluorine-containing copolyether glycol copolymerized by a perfluoroalkyl glycidyl ether and a polycyclic ether.
  • 3,591,547 A describes a binary copolyol ether of the following structure C compound with glycerol and propylene oxide.
  • Patent CN201110049906.9 reports a binary copolyether glycol of the following structure D compound and tetrahydrofuran.
  • Patent CN201010022447.0 reports binary copolyether diols of the following structure E compounds and F compounds.
  • fluorine-containing homopolymers and binary copolymerized fluorine-containing side chain polyether polyols all exert a special effect of weather resistance, oxidation resistance and corrosion resistance of fluorine elements on the polymer chain.
  • the fluorine group has an extremely low surface free energy, and if it covers the surface of the polymer, it can impart excellent water repellency, oil repellency, abrasion resistance, low friction coefficient and stain repellency to the polymer.
  • the patent CN2013107367731 and the patent CN201310738875.7 report the multi-ring ring-opening copolymerization of four monomers having a length of a perfluoroalkyl-substituted three-membered cyclic ether and a four- or five-membered cyclic ether.
  • the object of the present invention is to overcome the deficiencies of the prior art and to provide a soluble side chain fluorine-containing copolyether glycol which is substituted by propylene oxide and a perfluoroalkyl group.
  • a ternary cationic copolymerization of a glyceryl ether and a four-membered cyclic oxetane or a five-membered cyclic tetrahydrofuran can obtain a side chain fluorine-containing copolyether diol having a desired fluorine content, and the side chain fluorine-containing copolyether
  • the diol has excellent solubility and is easily soluble in general-purpose, non-toxic or low-toxic solvents.
  • a side chain fluorine-containing copolyether glycol obtained by substituting propylene oxide, perfluoroalkyl glycidyl ether and oxetane or tetrahydrofuran to have a molecular structure as shown in Structural Formula I:
  • R is any one of hydrogen, a saturated alkyl group, a saturated alkoxy group, a phenoxy group, and a benzyloxy group.
  • the number average molecular weight is from 1000 to 10000 g/mol, and is a colorless or light yellow transparent viscous liquid.
  • the preparation method of the above copolyether diol is prepared by copolymerization of perfluoroalkyl glycidyl ether, substituted propylene oxide and oxetane or tetrahydrofuran, and the reaction formula is represented by the following formula:
  • R is any one of hydrogen, a saturated alkyl group, a saturated alkoxy group, a phenoxy group, and a benzyloxy group.
  • the perfluoroalkyl glycidyl ether is selected from any one of the following structural compounds:
  • the substituted propylene oxide is selected from any one of the following structural compounds:
  • L is any natural number from 0 to 10.
  • the above preparation method specifically includes the following steps:
  • step (2) adding a solvent, oxetane or tetrahydrofuran, a cationic initiator and a diol initiator in a waterless and oxygen-free reactor equipped with a stirrer, at a temperature of -10 ° C to 15 ° C, into the kettle
  • the substituted propylene oxide and perfluoroalkyl glycidyl ether solution in the above step (1) is slowly added dropwise, and then at -10 ° C to 15 ° C, the polymerization reaction is carried out for 5 to 15 hours, and then 3 to 10 times of diol is added.
  • the amount of the starting material is deionized water to terminate the reaction;
  • the organic solvent in the reaction vessel is distilled off and recovered, and then 1.5 to 2.5 volumes of distilled water of the mixture after distillation is added, using sodium carbonate, sodium hydrogencarbonate, ammonium carbonate, ammonium hydrogencarbonate or sodium hydroxide.
  • the alkaline compound was neutralized to a pH of 7, the mixture was stirred and washed, and the mixture was allowed to stand for separation.
  • the aqueous phase was separated, and the oil phase was washed once again with distilled water, and allowed to stand for stratification. After the oil phase is dehydrated and dried, the solvent is removed to obtain a side chain fluorine-containing copolyether glycol.
  • the substituted propylene oxide and perfluoroalkyl glycidyl ether solution in step (2) should be added dropwise within 1 to 6 hours.
  • the solvent for dissolving the substituted propylene oxide and the perfluoroalkyl glycidyl ether in the step (1) is selected from the group consisting of dichloromethane, 1,4-dioxane, diethyl ether, tetrahydrofuran, acetone, methyl ethyl ketone, dibutyl ether One of them.
  • the cationic initiator is selected from the group consisting of 20% by mass of fuming sulfuric acid, perchloric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, boron trifluoride etherate, trichloroacetic acid, phosphoric acid, trichlorination One of aluminum, titanium tetrachloride, tin tetrachloride, zinc chloride, and antimony pentachloride.
  • the diol initiator is selected from one of ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, and 1,4-butanediol.
  • the present invention employs a substituted propylene oxide and a perfluoro-substituted alkyl glycidyl ether to copolymerize with one of a four-membered cyclic ether or a five-membered cyclic ether, and has the beneficial effects of: (1) by changing the perfluoro group The ratio of the substituted alkyl glycidyl ether to the three raw materials of one of the substituted propylene oxide and the four-membered cyclic ether or the five-membered cyclic ether, to synthesize the desired side chain fluorine-containing copolyether glycol with different fluorine content, Make full use of expensive fluorine raw materials; (2) because a variety of structural groups can be substituted on propylene oxide, so that the raw material structure can be selected according to the next reaction with the side chain fluorine-containing copolyether diol, One step is to copolymerize the propylene oxide monomer with the same solubility parameter
  • the problem of severe phase separation and incompatibility (3)
  • the side chain fluorine-containing copolyether glycol is easily dissolved in a non-toxic or low-toxic solvent which is industrially versatile and inexpensive, which can be largely Low processing costs, reduce pollution processing environment.
  • the side chain fluorine-containing copolyether diols provided by the present invention are extremely convenient in various subsequent uses, and the space for the use of such polyether diols is also expanded to a considerable extent.
  • the reaction was quenched by the addition of 20 ml of deionized water, and the solvent was evaporated and neutralized to neutral with sodium carbonate. It was washed with 100 mL of deionized water for 20 minutes and allowed to stand for stratification. The oil phase was again washed once with distilled water and allowed to stand for stratification. The oil phase was passed through a rotary evaporator to remove the residual solvent to obtain a crude polyether diol having a side chain fluorine-containing phase. Then, it was vacuum dried at 120 ° C under a pressure of 5 mmHg to obtain a colorless viscous liquid of the product, and the yield was 73.5%, which was measured by a GPC analyzer. g/mol, The fluorine content was 6.8%, and the side chain fluorine-containing polyether glycol was numbered CFJM-1.
  • the reaction was maintained at 0 ° C for 10 hours, and the reaction was quenched by the addition of 50 ml of deionized water.
  • the solvent was evaporated and neutralized to neutral with aqueous amine carbonate.
  • the oil phase was vacuum dried at 120 ° C under a pressure of 5 mm Hg to obtain a colorless viscous liquid with a yield of 89%, which was determined by a GPC analyzer. g/mol,
  • the fluorine content was 24.7%
  • the side chain fluorine-containing polyether glycol was numbered CFJM-3.
  • the reaction was maintained at 5 ° C for 6 hours, the reaction was terminated by the addition of 30 ml of deionized water, the solvent was distilled off, and neutralized with a sodium carbonate solution. After adding 200 mL of deionized water and stirring for 20 minutes, the mixture was allowed to stand for stratification, and the oil phase was washed once again with distilled water, and allowed to stand for stratification. The oil phase was vacuum dried at 120 ° C under a pressure of 5 mm Hg to obtain a colorless viscous liquid in a yield of 72%, which was determined by a GPC analyzer. g/mol, The fluorine content was 38.8%, and the side chain fluorine-containing polyether glycol was numbered CFJM-4.
  • the reaction was maintained at 2 ° C for 5 hours, and the reaction was quenched by the addition of 50 ml of deionized water.
  • the solvent was evaporated and neutralized with sodium bicarbonate solution to neutral.
  • the mixture was allowed to stand for stratification, and the oil phase was again washed once with distilled water, and allowed to stand for stratification.
  • a crude polyether diol having a side chain fluorine-containing phase is obtained.
  • the oil phase was vacuum dried at 120 ° C under a pressure of 5 mm Hg to obtain a colorless viscous liquid with a yield of 79%, which was determined by a GPC analyzer. g/mol,
  • the fluorine content was 17.5%
  • the side chain fluorine-containing polyether glycol was numbered CFJM-5.
  • the dioxane solution was controlled to complete in 5 hours.
  • the reaction was maintained at 10 ° C for 15 hours, and the reaction was quenched by the addition of 60 ml of deionized water.
  • the solvent was evaporated and neutralized to neutral with sodium bicarbonate.
  • the oil phase was vacuum dried at 120 ° C under a pressure of 5 mm Hg to obtain a colorless viscous liquid with a yield of 79%, which was determined by a GPC analyzer. g/mol,
  • the fluorine content was 13.7%
  • the side chain fluorine-containing polyether glycol was numbered CFJM-6.
  • Comparative Example 7 is synthesized according to the embodiment of the granted patent ZL201310738875.7
  • Embodiment 8 effect embodiment
  • the present invention employs a substituted propylene oxide and a perfluoro-substituted alkyl glycidyl ether to copolymerize with one of a four-membered cyclic ether or a five-membered cyclic ether, and has the beneficial effects of: (1) by changing the perfluoro group The ratio of the substituted alkyl glycidyl ether to the three raw materials of one of the substituted propylene oxide and the four-membered cyclic ether or the five-membered cyclic ether, to synthesize the desired side chain fluorine-containing copolyether glycol with different fluorine content, Make full use of expensive fluorine raw materials; (2) because a variety of structural groups can be substituted on propylene oxide, so that the raw material structure can be selected according to the next reaction with the side chain fluorine-containing copolyether diol, One step is to copolymerize the propylene oxide monomer with the same solubility parameter
  • the problem of severe phase separation and incompatibility (3)
  • the side chain fluorine-containing copolyether glycol is easily dissolved in a non-toxic or low-toxic solvent which is industrially versatile and inexpensive, which can be largely Low processing costs, reduce pollution processing environment.
  • the side chain fluorine-containing copolyether diols provided by the present invention are extremely convenient in various subsequent uses, and the space for the use of such polyether diols is also expanded to a considerable extent.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)

Abstract

本发明公开了一种由全氟烷基缩水甘油醚与多元环醚共聚的易溶侧链含氟共聚醚二醇，由全氟烷基缩水甘油醚、取代环氧丙烷和氧杂环丁烷或四氢呋喃进行共聚反应制备而成。本发明可通过改变原料比例合成出不同氟含量的侧链含氟共聚醚二醇，充分利用氟原料；同时可根据侧链含氟共聚醚二醇后续反应用途选择不同取代基的取代环氧丙烷，解决了有机氟化合物加工过程分相严重不便加工的缺陷；再者，该类侧链含氟共聚醚二醇易溶于工业上通用、价格便宜的无毒或低毒的溶剂，这可较大程度降低加工成本，减少加工环境污染。总之，本发明提供的侧链含氟共聚醚二醇在后续各种使用中极为方便，也在相当程度上拓展了该类聚醚二醇的使用空间。

Description

一种由全氟烷基缩水甘油醚与多元环醚共聚的易溶侧链含氟共聚醚二醇 技术领域
本发明属于高分子材料的中间体技术领域，具体涉及一种由全氟烷基缩水甘油醚与多元环醚共聚的易溶侧链含氟共聚醚二醇。
背景技术
双端羟基聚醚二醇作为合成聚酯和聚氨酯等聚合物的重要中间产物，在国民经济的诸多方面得到了许多重要的应用。而含氟侧基的引入则能把有机氟材料的许多优异性能带入到聚醚二醇中去，使得相关的材料在保留原有优异性能的基础上嫁接有有机氟材料的各种性能。许多文献和专利报道了这样的侧链含氟聚醚二醇的制备及其应用。美国专利US5654450和US647962381分别报道了如下述A和B两种结构的均聚以及两者分别与四氢呋喃共聚产物。专利US3591547A介绍了下述结构C化合物与丙三醇以及环氧丙烷的二元共聚多元醇醚。专利CN201110049906.9报道了下述结构D化合物与四氢呋喃的二元共聚醚二醇。专利CN201010022447.0则报道了下述结构E化合物与F类化合物的二元共聚醚二醇。
Figure PCTCN2018078672-appb-000001
这些含氟均聚物和二元共聚含氟侧链聚醚多元醇都很好的发挥了氟元素在聚合物链上的耐候性、抗氧化性和耐腐蚀性特殊作用。尤其是氟基团具有极低的表面自由能，如果其覆盖在聚合物的表面，可赋予聚合物以优异的拒水性、拒油性、耐磨性、低摩擦系数和拒污性能。专利CN2013107367731和专利CN201310738875.7报道了具有长短不一的全氟烷基取代的三元环醚与四元或五元环醚的四种单体的多元开环共聚。
上述的各种侧链含氟均聚、二元共聚或多种环醚单体的开环多元含氟共聚物，均不同程度地存在作两个方面的不足：(1)所制备的侧链含氟聚醚多元醇的氟含量控制有或多或少的困难；(2)所制备的侧链含氟聚醚多元醇不容易溶解在工业上通用、价格便宜的无毒或低毒的溶剂中。这两方面的因素导致了：1)价格昂贵的氟元素不能物尽其用，造成有效资源的浪费；2)这类含氟聚醚二醇在后加工时出现与其进一步反应或混合的原料混溶困难、对所要求 的溶剂苛刻，进而导致使用成本上升和带来加工环境的污染。
发明内容
本发明目的在于克服现有技术的不足，提供一种易溶的侧链含氟共聚醚二醇及其制备方法，该侧链含氟共聚醚二醇由取代环氧丙烷、全氟烷基缩水甘油醚及四元环醚氧杂环丁烷或五元环醚四氢呋喃进行三元阳离子共聚而成，可以获得预期不同氟含量的侧链含氟共聚醚二醇，且该侧链含氟共聚醚二醇溶解性出色，在通用、无毒或低毒溶剂中均易溶。
本发明的上述目的是通过下面的技术方案得以实现的：
一种取代环氧丙烷、全氟烷基缩水甘油醚和氧杂环丁烷或四氢呋喃共聚获得的侧链含氟的共聚醚二醇，具有如结构式I所示的分子结构：
Figure PCTCN2018078672-appb-000002
其中：
p为1或2中任一数；n为1或2中的任一数；m为4～13中任意一个自然数；q为0或3两者中任一数；x，y和z为1～100中的任意一个自然数；
y∶(x+z)在于5～1∶1范围内；x∶z在于20～1∶1范围内；
R是氢、饱和烷基、饱和烷氧基、苯氧基、苄氧基中的任意一种。
其数均分子量为1000～10000g/mol，为无色或淡黄色透明粘稠状液体。
上述共聚醚二醇的制备方法，由全氟烷基缩水甘油醚、取代环氧丙烷和氧杂环丁烷或四氢呋喃进行共聚反应制备而成，其反应式由下式表示：
Figure PCTCN2018078672-appb-000003
其中：
p为1或2中任一数；n为1或2中的任一数；m为4～13中任意一个自然数；q为0或3两者中任一数；x，y和z为1～100中的任意一个自然数；
y∶(x+z)在于5～1∶1范围内；x∶z在于20～1∶1范围内；
R是氢、饱和烷基、饱和烷氧基、苯氧基、苄氧基中的任意一种。
优选地，所述全氟烷基缩水甘油醚选自如下结构化合物中的任意一种：
Figure PCTCN2018078672-appb-000004
其中，n为1或2中的任一数；m为4～13中任意一个自然数。
优选地，所述取代环氧丙烷选自如下结构化合物中的任意一种：
Figure PCTCN2018078672-appb-000005
其中，L为0到10中任一自然数。
上述制备方法具体包括下列步骤：
(1)原料准备：取代环氧丙烷和全氟烷基缩水甘油醚，两者的摩尔数之和与氧杂环丁烷或四氢呋喃其中之一的摩尔数之比为1∶5～1范围内，其中取代环氧丙烷和全氟烷基缩水甘油醚摩尔比为20～1∶1，阳离子引发剂所释放出阳离子物质的量占总单体总物质的量的2％～7％，二醇起始剂占总单体物质的量的2.5％～7％；将取代环氧丙烷和全氟烷基缩水甘油醚溶解到溶剂中，溶液中溶质浓度为1～20摩尔/升；
(2)在无水无氧装有搅拌器的反应釜中加入溶剂、氧杂环丁烷或四氢呋喃、阳离子引发剂和二醇起始剂，在-10℃～15℃温度下，向釜中同时缓慢滴加上述步骤(1)中取代环氧丙烷和全氟烷基缩水甘油醚溶液，然后在-10℃～15℃下，聚合反应5～15小时后，加入3～10倍二醇起始剂物质的量的去离子水终止反应；
(3)终止反应后，蒸出并回收反应釜中的有机溶剂，然后加入蒸馏后混合物的1.5～2.5倍体积的蒸馏水，用碳酸钠、碳酸氢钠、碳酸铵、碳酸氢胺或氢氧化钠等碱性化合物中和pH值到7，搅拌洗涤、静置分层，分出水相，油相再次用蒸馏水洗涤一次，静置分层。油相脱 水干燥后，经除去溶剂即得侧链含氟的共聚醚二醇。
优选地，步骤(2)中取代环氧丙烷和全氟烷基缩水甘油醚溶液应在1～6小时内滴加完成。
优选地，步骤(1)溶解取代环氧丙烷和全氟烷基缩水甘油醚的溶剂选自二氯甲烷、1，4-二氧六环、乙醚、四氢呋喃、丙酮、丁酮、二丁基醚中的一种。
优选地，所述阳离子引发剂选自质量分数20％的发烟硫酸、高氯酸、三氟乙酸、三氟甲基磺酸、三氟化硼乙醚、三氯代乙酸、磷酸、三氯化铝、四氯化钛、四氯化锡、氯化锌、五氯化锑中的一种。
优选地，二醇起始剂选自乙二醇、1，2-丙二醇、1，3-丙二醇、1，4-丁二醇中的一种。
本发明的有益效果：
本发明采用取代环氧丙烷和全氟取代的烷基缩水甘油醚与四元环醚或五元环醚其中之一进行共聚，具有这样几个方面的有益效果：(1)可以通过改变全氟取代的烷基缩水甘油醚与取代环氧丙烷和四元环醚或五元环醚其中之一的三者原料比例，合成出预期的不同氟含量的侧链含氟共聚醚二醇，最大限度的充分利用价格昂贵的氟原料；(2)由于多种结构基团可以取代在环氧丙烷上，这样可以根据与侧链含氟共聚醚二醇进行下一步反应的原料结构，选择具有与下一步参与反应原料溶度参数相同或相近取代基团的环氧丙烷单体进行共聚，这样当所合成的侧链含氟聚醚二醇与下一步原料反应时，就可以轻松解决了有机氟化合物加工中严重分相、互不相溶的问题；(3)该类侧链含氟共聚醚二醇在工业上通用、价格便宜的无毒或低毒的溶剂中易于溶解，这可较大程度的降低加工成本，减少加工环境的污染。总之，本发明提供的侧链含氟共聚醚二醇在后续各种使用中极为方便，也在相当程度上拓展了该类聚醚二醇的使用空间。
具体实施方式
下面结合实施例具体介绍本发明的实质性内容，但并不以此限定本发明的保护范围。实验中未详述的试验操作均为本领域技术人员所熟知的常规试验操作。
实施例1
将2-(二十七氟十三烷基)乙基缩水甘油醚0.05摩尔和2-甲基苯基缩水甘油醚0.95摩尔一起溶于用100mL二氯甲烷，形成的二氯甲烷溶液。
然后，向1000mL釜中，用纯氮气置换釜中空气后，降温到-10℃，加入5摩尔的氧杂环丁烷、50mL二氯甲烷、0.15摩尔98％浓硫酸和0.18摩尔乙二醇，降温到-10℃搅拌20分钟后并维持此温度，滴加2-(二十七氟十三烷基)乙基缩水甘油醚0.05摩尔和2-甲基苯基缩水甘油醚0.95摩尔的二氯甲烷溶液，控制在2小时内滴完。维持在-10℃，反应10小时。加入20ml去离子水终止反应，蒸出溶剂，用碳酸钠溶液中和到中性。加入100mL去离子水水 洗20分钟，静置分层。油相再次用蒸馏水洗涤一次，静置分层。油相经旋转蒸发仪除去残留的溶剂，得到侧链含氟的粗聚醚二醇。再在120℃下、5mm汞柱压力下真空干燥，得到产物无色粘稠状液体，产率为73.5％，经GPC分析仪测定，
Figure PCTCN2018078672-appb-000006
克/摩尔，
Figure PCTCN2018078672-appb-000007
含氟量6.8％，该侧链含氟聚醚二醇编号为CFJM-1。
实施例2
将2-(十七氟辛烷基)乙基缩水甘油醚0.1摩尔和苄基缩水甘油醚0.5摩尔一起溶于用200mL乙醚，形成的乙醚溶液。
在装有搅拌器的1000mL的釜中，用纯氮气置换釜中空气后，降温到-5℃，加入100mL乙醚作为溶剂，加入氧杂环丁烷1.8摩尔、高氯酸0.072摩尔和0.12摩尔丁二醇。滴加上述由2-(十七氟辛烷基)乙基缩水甘油醚0.1摩尔和苄基缩水甘油醚0.5摩尔溶解与200mL乙醚所形成三元的乙醚溶液，控制滴加在3小时内完成。保持-5℃，反应8小时，加入30mL去离子水终止反应，蒸出溶剂，用碳酸氢钠溶液中和到中性。加入200mL去离子水搅拌水洗20分钟，静置分层，油相再次用蒸馏水洗涤一次，静置分层。油相经旋转蒸发仪除去溶剂，得到侧链含氟的粗聚醚二醇。再在120℃下、5mm汞柱压力下真空干燥，得到产物无色粘稠状液体，产率为82％，经GPC分析仪测定，
Figure PCTCN2018078672-appb-000008
克/摩尔，
Figure PCTCN2018078672-appb-000009
含氟量16.6％，该侧链含氟聚醚二醇编号为CFJM-2。
实施例3
将1-(九氟丁基)甲基缩水甘油醚0.15摩尔和苄基缩水甘油醚0.3摩尔一起溶于用250mL丙酮，形成三的丙酮溶液。
在装有搅拌器的1000mL的釜中，用纯氮气置换釜中空气后，降温到-0℃加入100mL丙酮作为溶剂，加入四氢呋喃0.45摩尔、高氯酸0.0225摩尔和0.027摩尔丁二醇。滴加上述由1-(九氟丁基)甲基缩水甘油醚0.15摩尔和苄基缩水甘油醚0.3摩尔溶解于250mL丙酮所形成的丙酮溶液，控制滴加在3小时内完成。保持0℃，反应10小时，加入50ml去离子水终止反应，蒸出溶剂，用碳酸胺水溶液中和到中性。加入200mL去离子水水洗20分钟，静置分层，油相再次用蒸馏水洗涤一次，静置分层。油相再在120℃下、5mm汞柱压力下真空干燥，得到产物无色粘稠状液体，产率为89％，经GPC分析仪测定，
Figure PCTCN2018078672-appb-000010
克/摩尔，
Figure PCTCN2018078672-appb-000011
含氟量24.7％，该侧链含氟聚醚二醇编号为CFJM-3。
实施例4
将2-(十五氟庚基)乙基缩水甘油醚0.1摩尔和丁基缩水甘油醚0.2摩尔一起溶于用200mL四氢呋喃，形成的四氢呋喃溶液。
在装有搅拌器的1000mL的釜中，用纯氮气置换釜中空气后，降温到5℃加入氧杂环丁烷 0.9摩尔、三氟代乙酸0.024摩尔和0.072摩尔1，2-丙二醇。滴加上述由2-(十五氟庚基)乙基缩水甘油醚0.1摩尔和丁基缩水甘油醚0.2摩尔一起溶于用200mL四氢呋喃所形成的溶液，控制滴加在2小时内完成。保持5℃，反应6小时，加入30ml去离子水终止反应，蒸出溶剂，用碳酸钠溶液中和到中性。加入200mL去离子水搅拌水洗20分钟，静置分层，油相再次用蒸馏水洗涤一次，静置分层。油相再在120℃下、5mm汞柱压力下真空干燥，得到产物无色粘稠状液体，产率为72％，经GPC分析仪测定，
Figure PCTCN2018078672-appb-000012
克/摩尔，
Figure PCTCN2018078672-appb-000013
含氟量38.8％，该侧链含氟聚醚二醇编号为CFJM-4。
实施例5
将2-(十七氟辛基)乙基缩水甘油醚0.25摩尔和丁基缩水甘油醚1摩尔一起溶于用150mL四氢呋喃，形成的四氢呋喃溶液。
在装有搅拌器的1000mL的釜中，用纯氮气置换釜中空气后，降温到2℃加入四氢呋喃1.9摩尔、三氟化硼乙醚0.25摩尔和0.25摩尔1，2-丙二醇。滴加上述由2-(十七氟辛基)乙基缩水甘油醚0.25摩尔和丁基缩水甘油醚1摩尔溶于用150mL四氢呋喃所形成的溶液，控制滴加在3小时内完成。保持2℃，反应5小时，加入50ml去离子水终止反应，蒸出溶剂，用碳酸氢钠溶液中和到中性。加入250mL去离子水搅拌水洗20分钟，静置分层，油相再次用蒸馏水洗涤一次，静置分层。得到侧链含氟的粗聚醚二醇。油相再在120℃下、5mm汞柱压力下真空干燥，得到产物无色粘稠状液体，产率为79％，经GPC分析仪测定，
Figure PCTCN2018078672-appb-000014
克/摩尔，
Figure PCTCN2018078672-appb-000015
含氟量17.5％，该侧链含氟聚醚二醇编号为CFJM-5。
实施例6
将1-(十三氟庚烷基)甲基缩水甘油醚0.1摩尔和1，2-环氧环己烷0.5摩尔一起溶于用200mL1，4-二氧六环，形成的1，4-二氧六环溶液。
在装有搅拌器的1000mL的釜中，用纯氮气置换釜中空气后，降温到10℃，加入1，4-二氧六环100mL做溶剂，加入氧杂环丁烷2.4摩尔、三氟化硼乙醚0.09摩尔和0.165摩尔乙二醇。滴加上述由1-(十三氟庚烷基)甲基缩水甘油醚0.1摩尔和1，2-环氧环己烷0.5摩尔溶解与200mL1，4-二氧六环所形成的1，4-二氧六环溶液，控制滴加在5小时内完成。保持10℃，反应15小时，加入60ml去离子水终止反应，蒸出溶剂，用碳酸氢钠溶液中和到中性。加入200mL去离子水搅拌水洗20分钟，静置分层，油相再次用蒸馏水洗涤一次，静置分层，得到侧链含氟的粗聚醚二醇。油相再在120℃下、5mm汞柱压力下真空干燥，得到产物无色粘稠状液体，产率为79％，经GPC分析仪测定，
Figure PCTCN2018078672-appb-000016
克/摩尔，
Figure PCTCN2018078672-appb-000017
含氟量13.7％，该侧链含氟聚醚二醇编号为CFJM-6。
对比实施例7根据授权专利ZL201310738875.7实施例合成
在装有搅拌的500mL的压力釜中加入150mL二氯甲烷作为溶剂，用纯氮气置换釜中空气20分钟。然后按照四氢呋喃∶2-(七氟正丙基)甲基缩水甘油醚∶2-(十一氟正戊基)甲基缩水甘油醚∶2-(十五氟正庚基)甲基缩水甘油醚∶三氟化硼乙醚络合物∶1，4-丁二醇的摩尔比为0.35∶0.15∶0.2∶0.3∶0.07∶0.07比例准备好各种反应物。分别称取0.35摩尔四氢呋喃、0.15摩尔2-(七氟正丙基)甲基缩水甘油醚、0.2摩尔2-(十一氟正戊基)甲基缩水甘油醚和0.3摩尔2-(十五氟正庚基)甲基缩水甘油醚。将后三者一起用70mL二氯甲烷溶解备用。在控制反应釜中温度为5℃时，向釜中加入三氟化硼乙醚络合物和1，4-丁二醇，并一次性加入0.35摩尔四氢呋喃，搅拌20分钟。然后滴加三种含氟甲基缩水甘油醚的二氯甲烷溶液，在三小时内滴加完成。升温到回流温度反应24小时。加入20ml去离子水终止反应。降低反应体系的温度到环境温度。加入100mL去离子水搅拌20分钟，静置分层，油相再次用蒸馏水洗涤一次，静置分层。油相再在120℃2、2mm汞柱压强下除去杂质，得到侧链含有不同全氟取代烷基的聚醚二醇。产率78％，GPC分析仪测定，
Figure PCTCN2018078672-appb-000018
克/摩尔，
Figure PCTCN2018078672-appb-000019
含氟量43.2％。该侧链含氟聚醚二醇编号为CFJM-7。
实施例8效果实施例
对实施例1-7合成的侧链含氟共聚醚二醇进行不同溶剂溶解实验，具体的实验方法为：取八个50mL的单口烧瓶，分别在八个烧瓶中加入40mL乙醚、40mL二丁基醚、40mL丙酮、40mL丁酮、40mL环己酮、40mL二氯甲烷、40mL乙酸乙酯、40mL乙酸丁酯和40mL四氢呋喃，然后在称取10克上面实施例的侧链含氟共聚醚二醇加入到每一个溶剂瓶中，加入磁子搅拌30分钟，再经过超声分散10分钟，放置24小时，观察各样品烧瓶中的溶解状况。实验结果如表1。
表1 各实施例样品在常用溶剂中的溶解结果表
Figure PCTCN2018078672-appb-000020
Figure PCTCN2018078672-appb-000021
本发明采用取代环氧丙烷和全氟取代的烷基缩水甘油醚与四元环醚或五元环醚其中之一进行共聚，具有这样几个方面的有益效果：(1)可以通过改变全氟取代的烷基缩水甘油醚与取代环氧丙烷和四元环醚或五元环醚其中之一的三者原料比例，合成出预期的不同氟含量的侧链含氟共聚醚二醇，最大限度的充分利用价格昂贵的氟原料；(2)由于多种结构基团可以取代在环氧丙烷上，这样可以根据与侧链含氟共聚醚二醇进行下一步反应的原料结构，选择具有与下一步参与反应原料溶度参数相同或相近取代基团的环氧丙烷单体进行共聚，这样当所合成的侧链含氟聚醚二醇与下一步原料反应时，就可以轻松解决了有机氟化合物加工中严重分相、互不相溶的问题；(3)该类侧链含氟共聚醚二醇在工业上通用、价格便宜的无毒或低毒的溶剂中易于溶解，这可较大程度的降低加工成本，减少加工环境的污染。总之，本发明提供的侧链含氟共聚醚二醇在后续各种使用中极为方便，也在相当程度上拓展了该类聚醚二醇的使用空间。
上述实施例的作用在于具体介绍本发明的实质性内容，但本领域技术人员应当知道，不应将本发明的保护范围局限于该具体实施例。

Claims (10)

  1. 一种取代环氧丙烷、全氟烷基缩水甘油醚和氧杂环丁烷或四氢呋喃共聚获得的侧链含氟的共聚醚二醇，其特征在于，具有如结构式I所示的分子结构：
    Figure PCTCN2018078672-appb-100001
    其中：
    p为1或2中任一数；n为1或2中的任一数；m为4～13中任意一个自然数；q为0或3两者中任一数；x，y和z为1～100中的任意一个自然数；
    y∶(x+z)在于5～1∶1范围内；x∶z在于20～1∶1范围内；
    R是氢、饱和烷基、饱和烷氧基、苯氧基、苄氧基中的任意一种。
  2. 根据权利要求1所述的共聚醚二醇，其特征在于：其数均分子量为1000～10000g/mol。
  3. 权利要求1或2所述共聚醚二醇的制备方法，其特征在于，由全氟烷基缩水甘油醚、取代环氧丙烷和氧杂环丁烷或四氢呋喃进行共聚反应制备而成，其反应式由下式表示：
    Figure PCTCN2018078672-appb-100002
    其中：
    p为1或2中任一数；n为1或2中的任一数；m为4～13中任意一个自然数；q为0或3两者中任一数；x，y和z为1～100中的任意一个自然数；
    y∶(x+z)在于5～1∶1范围内；x∶z在于20～1∶1范围内；
    R是氢、饱和烷基、饱和烷氧基、苯氧基、苄氧基中的任意一种。
  4. 根据权利要求3所述的制备方法，其特征在于，所述全氟烷基缩水甘油醚选自如下结 构化合物中的任意一种：
    Figure PCTCN2018078672-appb-100003
    其中，n为1或2中的任一数；m为4～13中任意一个自然数。
  5. 根据权利要求3所述的制备方法，其特征在于，所述取代环氧丙烷选自如下结构化合物中的任意一种：
    Figure PCTCN2018078672-appb-100004
    其中，L为0到10中任一自然数。
  6. 根据权利要求3所述的制备方法，其特征在于，包括下列步骤：
    (1)原料准备：取代环氧丙烷和全氟烷基缩水甘油醚，两者的摩尔数之和与氧杂环丁烷或四氢呋喃其中之一的摩尔数之比为1∶5～1范围内，其中取代环氧丙烷和全氟烷基缩水甘油醚摩尔比为20～1∶1，阳离子引发剂所释放出阳离子物质的量占总单体总物质的量的2％～7％，二醇起始剂占总单体物质的量的2.5％～7％；将取代环氧丙烷和全氟烷基缩水甘油醚溶解到溶剂中，溶液中溶质浓度为1～20摩尔/升；
    (2)在无水无氧装有搅拌器的反应釜中加入溶剂、氧杂环丁烷或四氢呋喃、阳离子引发剂和二醇起始剂，在-10℃～15℃温度下，向釜中同时缓慢滴加上述步骤(1)中取代环氧丙烷和全氟烷基缩水甘油醚溶液，然后在-10℃～15℃下，聚合反应5～15小时后，加入3～10倍二醇起始剂物质的量的去离子水终止反应；
    (3)终止反应后，蒸出并回收反应釜中的有机溶剂，然后加入蒸馏后混合物的1.5～2.5倍体积的蒸馏水，用碱性化合物中和pH值到7，搅拌洗涤、静置分层，分出水相，油相再次用蒸馏水洗涤一次，静置分层，油相脱水干燥后，经除去溶剂即得侧链含氟的共聚醚二醇。
  7. 根据权利要求6所述的制备方法，其特征在于：步骤(2)中的取代环氧丙烷和全氟烷基缩水甘油醚溶液应在1～6小时内滴加完成。
  8. 根据权利要求6所述的制备方法，其特征在于：步骤(1)溶解取代环氧丙烷和全氟烷基缩水甘油醚的溶剂选自二氯甲烷、1，4-二氧六环、乙醚、四氢呋喃、丙酮、丁酮、二丁基醚中的一种或多种。
  9. 根据权利要求6所述的制备方法，其特征在于：所述阳离子引发剂选自质量分数20％的发烟硫酸、高氯酸、三氟乙酸、三氟甲基磺酸、三氟化硼乙醚、三氯代乙酸、磷酸、三氯化铝、四氯化钛、四氯化锡、氯化锌、五氯化锑中的一种；步骤(3)所述碱性化合物选自碳酸钠、碳酸氢钠、碳酸铵、碳酸氢胺或氢氧化钠。
  10. 根据权利要求6所述的制备方法，其特征在于：所述二醇起始剂选自乙二醇、1，2-丙二醇、1，3-丙二醇、1，4-丁二醇中的一种。
PCT/CN2018/078672 2017-03-16 2018-03-12 一种由全氟烷基缩水甘油醚与多元环醚共聚的易溶侧链含氟共聚醚二醇 WO2018166413A1 (zh)

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CN109337063A (zh) * 2018-10-13 2019-02-15 郑州博物馆 一种用于文物粘接剂的端羟基聚醚合成方法
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