CN1059449C - Method for preparation of high-viscosity chloromethylated polysulfone - Google Patents

Method for preparation of high-viscosity chloromethylated polysulfone Download PDF

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CN1059449C
CN1059449C CN 96107032 CN96107032A CN1059449C CN 1059449 C CN1059449 C CN 1059449C CN 96107032 CN96107032 CN 96107032 CN 96107032 A CN96107032 A CN 96107032A CN 1059449 C CN1059449 C CN 1059449C
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method
preparation
high
viscosity
chloromethylated
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CN 96107032
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Chinese (zh)
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CN1139679A (en )
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吴光夏
张东华
王静荣
刘忠洲
张保成
刘福谅
韩式荆
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中国科学院生态环境研究中心
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Abstract

本发明属于用半透膜的分离方法及其设备的技术领域,公开了特性粘度为0.51-0.8的氯甲基化聚砜的制备方法。 The present invention belongs to the technical field separating method and apparatus of the semipermeable membrane, discloses a method for preparing an intrinsic viscosity of 0.51-0.8 chloromethylated polysulfone. 该方法的特点是控制聚砜、二氯乙烷、氯甲醚和氯化锌的配比及反应时间,并用自动控温仪控制反应温度。 Feature of the process is to control polysulfone, dichloroethane, chloromethyl ether and zinc chloride and the ratio of the reaction time and the reaction temperature is controlled by an automatic temperature controller. 出料采用反应釜体可升降而反应釜盖固定的出料装置,出料时釜体降下来,而进料时釜体升上去。 Discharging reactor using the reaction member may be a feeding device lid was fixed elevation, down when the kettle body material, while the kettle the feed going up. 本发明解决了用于制备中空纤维和无支撑体平板膜的高粘度氯甲基化聚砜的制备问题。 The present invention solves the problem of preparing a high viscosity and non-chlorine hollow fiber membranes used to prepare the support plates methylated polysulfone.

Description

高粘度氯甲基化聚砜的制备方法 High viscosity chloromethylated polysulfone preparation

本发明涉及用半透膜的分离方法及其设备,特别是涉及分离膜,即用于流体中不同分子量物质分离的材料的制备方法,属于物理或化学的方法及其设备的技术领域。 The present invention relates to a separating method and apparatus of the semipermeable membrane, and more particularly to a separation membrane, i.e., the fluid separation method of preparation of different molecular weight species material, belonging to the technical field of a physical or chemical method and apparatus.

聚砜经氯甲基化后成为氯甲基化聚砜,其化学结构为 Polysulfone After chloromethylation be chloromethylated polysulfone, having a chemical structure

氯甲基基团-CH2Cl很活泼,容易发生交联,形成分子量更大的分子,甚至交联成网络,成为不溶于溶剂的聚合物。 Chloromethyl groups -CH2Cl very lively, easy crosslinking, molecular weight form a larger molecule, or even a network crosslinked, become insoluble in the solvent of the polymer. 为了避免这种情况发生,通常聚合时采用特性粘度为η=0.5以下的聚砜。 To avoid this, use a normal polymerization intrinsic viscosity η = 0.5 or less polysulfone. 但这样制成的氯甲基化聚砜粘度低,只能制成带支撑体的膜,而不能纺制成中空纤维膜和其它不带支撑材料的膜。 But the low viscosity of the chloromethylated polysulfone thus prepared, a film formed with only the support, but not spun into hollow fiber membranes and other membrane without support material. 此外,通常的出料方法是在沸水中搅拌出料,但这种方法不适于高粘度聚砜氯甲基化后反应液的出料,因其不易被搅成碎片而极易粘附在搅拌棒上而很难取下。 In addition, the usual discharge method is stirring the material in boiling water, but this method is not suitable for the high viscosity polysulfone chloromethylation reaction liquid discharge, because of the difficult to be easily adhered debris churned stirring the rod is difficult to remove. 现有的背景技术经检索,有如下专利文献,未见报道有关用高粘度氯甲基化聚砜以制备无支撑体膜的方法及高粘度氯甲基化聚砜出料方法的技术。 BACKGROUND retrieved prior art, the following Patent Document, with no reports of high viscosity chloromethylated polysulfone support film to prepare a non-high viscosity method and chloromethylated polysulfone discharge method in the art. 有关文献如CN1036588A,JP04283208,SU999547,BE1005983,SU548984,R0365054,BE905179等。 The literature CN1036588A, JP04283208, SU999547, BE1005983, SU548984, R0365054, BE905179 and the like.

本发明的目的在于克服已有技术的缺陷,提出适合于制备中空纤维膜和其它无支撑体膜的高粘度氯甲基化聚砜的制备方法及简便易行的出料方法。 Object of the present invention to overcome deficiencies of the prior art, the proposed method and simple method of preparing the material of high viscosity chloromethylated polysulfone suitable for preparing a hollow fiber membrane and the other unsupported film.

本发明是这样实现的:把特性粘度为0.51至0.8的聚砜在60℃至90℃的真空烘箱中烘20至40小时;氯化锌在110℃至140℃的真空烘箱中烘24至48小时。 The present invention is achieved: the intrinsic viscosity of 0.51 to 0.8 polysulfone in a vacuum drying 60 ℃ oven to 90 deg.] C in 20 to 40 hours; chloride drying in a vacuum oven at 24 to 48 deg.] C to 110 deg.] C in 140 hour.

聚砜、二氯乙烷、氯甲醚、氯化锌的重量比为:聚砜∶二氯乙烷∶氯甲醚∶氯化锌=(0.8~1.2)∶(10~15)∶(0.8~1.2)∶(0.06~0.08)在装有自动控温仪传感器,冷凝管和搅拦器的可加温反应釜中,按上述配比,先放入0.51至0.8特性粘度的聚砜和二氯乙烷,室温搅拦2-3小时使聚砜完全溶解,然后放入氯甲醚和氯化锌。 Polysulfone, dichloroethane, chloromethyl ether, a weight ratio of zinc chloride: Polysulfone: dichloroethane: chloromethyl ether: zinc = (0.8 to 1.2): (10 ~ 15): (0.8 ~ 1.2): (0.06 to 0.08) equipped with automatic temperature control gauge sensor, a condenser and a stir bar is heated reactor, the above ratio, to put an intrinsic viscosity of 0.51 to 0.8 and two polysulfone ethyl chloride, stirred at room temperature for 2-3 hours bar polysulfone was completely dissolved, then add chloromethyl ether and zinc chloride. 反应温度由自动控温仪控制在50℃至60℃,反应4至10小时。 The reaction temperature is controlled by an automatic temperature controller at 50 deg.] C to 60 ℃, reaction from 4 to 10 hours. 反应完毕使其自然冷却。 After the reaction allowed to cool naturally.

本发明提供一幅附图,即图1为氯甲基化聚砜出料装置图。 The present invention provides one of the figures, i.e. FIG. 1 is a chloromethylated polysulfone discharge means in FIG.

以下结合附图说明制备氯甲基化聚砜中的出料工艺过程。 BRIEF DESCRIPTION The following discharging process for preparing a chloromethylated polysulfone. 出料装置如图1所示,该装置主要包括:升降台1,以带加热金属膜的陶瓷加热锅为反应釜2,带有三个口的釜盖3,釜盖3上的一个口4内装有控温仪传感器5并加以固定,釜盖3上的另一个口7作为溶剂和其它化学组分的出口,釜盖3上的第三个口8装有温度计9并作为投料口,冷凝管10和溶剂收集瓶11。 Discharge means shown in Figure 1, the apparatus includes: a lifting platform, with heated metal film to the ceramic heating pot for the reactor 2, the reactor lid 3 with three ports, a port kettle cover 4 contains the 3 temperature controller has to be fixed and the sensor 5, the vessel cover 3 as an outlet port 7 of the other solvents and other chemical components, the kettle cover the third port 3 equipped with a thermometer 8 and 9 as a feeding port, condenser 10 collected and the solvent bottle 11. 釜盖3的空间位置是用铁架子和卡子6固定的,而反应釜2放置在升降台1上可上下移位。 Kettle lid 3 is fixed spatial position of the shelf and the clip 6 with iron, and the kettle 2 is placed on the lifting table 1 may be displaced up and down.

在反应釜2内注入2/3去离子水,水温由控温仪控制温度在80℃至98℃之间。 2 implanted in the reactor 2/3 deionized water, the water temperature is controlled by a temperature control device a temperature between 80 deg.] C to 98 ℃. 把反应釜2由升降台1上升至与釜盖3紧密扣合。 The reactor 2 lifts up from 1 to 3 and the lid was tightly engaging. 当水温达到要求值时,从投料口8徐徐投入氯甲基化聚砜反应液。 When the water temperature reaches the desired value, from the doghouse 8 slowly into chloromethylated polysulfone reaction solution. 此时,二氯乙烷、氯甲醚和少量水变成气态挥发出来并在冷凝管10凝结成液态,流入溶剂收集瓶11中。 At this time, dichloroethane, ether and a small amount of water into chlorine volatilized gas condenser 10 and condensed into liquid, the solvent flows into the collection bottle 11. 氯甲基化聚砜因不溶于水而被析出。 Chloromethylated polysulfone is insoluble in water due to precipitation. 过6-10分钟后收集瓶中不再有液体滴入。 Over 6-10 minutes after no more liquid collected flask dropwise. 转动升降台旋钮使反应釜降下来,把氯甲基化聚砜取出,然后把釜体升上去,再投入氯甲基化聚砜反应液,循序进行。 Rotation of knob to the lift down reactor, the chloromethylated polysulfone removed, then the kettle ascend again into chloromethylated polysulfone reaction solution sequentially performed.

把块状氯甲基化聚砜剪成碎片,用去离子水浸泡、冲洗,置于甩干机中甩干,然后自然风干,再用真空烘箱于20℃-40℃烘干,装于带封口的塑料袋中备用。 The chloromethylated polysulfone block cut into pieces, soaked with deionized water, washing, drying in the dryer is placed, followed by natural drying, and then dried in a vacuum oven at -40 ℃ 20 ℃, mounted to the tape sealed plastic bags until use.

以下提供一实施例。 The following provides an embodiment.

聚砜粘度0.63,80℃烘24小时。 Polysulfone viscosity 0.63,80 ℃ bake for 24 hours. 各原料组分的重量比为:聚砜∶二氯乙烷∶氯甲醚∶氯化锌=1∶12∶0.9∶0.07 The weight ratio of each raw material component is: Polysulfone: dichloroethane: chloromethyl ether: zinc = 1:12:0.9:0.07

反应温度56℃,反应8小时。 The reaction temperature is 56 ℃, reacted for 8 hours. 反应釜2内水温由自动控温仪控制在95℃,每釜出料时间为8分钟。 2 reactor temperature is controlled by an automatic temperature controller at 95 ℃, each reactor discharge time of 8 minutes. 氯甲基化聚砜烘料温度控制在30℃,采用上述条件可制备适合于纺制中空纤维和制备无支撑体平板膜的氯甲基化聚砜。 Chloromethylated polysulfone material drying temperature was controlled at 30 ℃, may be prepared using the above-described conditions suitable for spinning hollow fiber and flat membrane prepared without the support chloromethylated polysulfone.

Claims (3)

  1. 1.一种高粘度氯甲基化聚砜的制备方法,其特征在于按如下重量比准备反应材料:特性粘度为0.51至0.8的聚砜∶二氯乙烷∶氯甲醚∶氯化锌=(0.8-1.2)∶(10-15)∶(0.8-1.2)∶(0.06-0.08);把聚砜在60℃至90℃的真空烘箱中烘20至40小时,氯化锌在110℃至140℃的真空烘箱中烘24至48小时;向装备有自动控温仪传感器(5)、冷凝管(10)和搅拌器的可加温反应釜(2)中先放入聚砜和二氯乙烷,在室温下搅拌2-3小时使聚砜完全溶解,然后放入氯甲醇和氯化锌进行反应,由自动控温仪控制反应温度在50℃至60℃,反应4至10小时,反应完毕使其自然冷却;采用包括升降台(1)和反应釜(2)的出料装置出料,出料后用甩干机甩干,再用真空烘箱烘干,装于带封口的塑料袋中备用。 1. A method for preparing a high viscosity chloromethylated polysulfone, wherein the weight ratio of the following reaction to prepare the material: an intrinsic viscosity of 0.51 to 0.8 polysulfone: dichloroethane: chloromethyl ether: zinc = (0.8-1.2): (10-15): (0.8-1.2): (0.06-0.08); the polysulfone 20-40 hours drying in vacuo 60 ℃ oven to 90 deg.] C, the zinc chloride deg.] C to 110 vacuum drying oven at 140 deg.] C in 24 to 48 hours; automatic temperature control apparatus equipped with a sensor (5), a condenser (10) and can be heated reactor agitator (2) is first placed polysulfones and dichloro ethane, stirred at room temperature for 2-3 hours to completely dissolve polysulfone, then placed chloride and zinc chloride in methanol is reacted, the reaction is controlled by the automatic temperature control device at a temperature of 50 deg.] C to 60 ℃, reaction from 4 to 10 hours, after the reaction allowed to cool naturally; comprises using lifting platform (1) and reactor (2) discharge of the discharge device, after drying machine drying with the material, and then vacuum oven dried, mounted on a plastic seal band bag aside.
  2. 2.根据权利要求1所述的方法,其特征在于该出料装置包括:升降台(1),带加热金属膜的陶瓷加热锅反应釜(2),带有三个口的釜盖(3),其中,在釜盖(3)上的一个口(4)内装备并固定有控温仪传感器(5),釜盖(3)上的另一个口(7)做为溶剂和其他化学组分的出口,釜盖(3)上的第3个口(8)装有温度计(9)并作为投料口,冷凝管(10)和溶剂收集瓶(11),釜盖(3)的空间位置是用铁架子和卡子(6)固定的,而反应釜(2)放置在升降台(1)上,可上下移动。 2. The method according to claim 1, characterized in that the discharge apparatus comprising: a lifting platform (1), a ceramic heating pot with a heating kettle metal film (2), with three ports kettle lid (3) wherein, one port (4) on the tank lid (3) is equipped with a temperature controller and a fixed sensor (5), the other port kettle cover (7) (3) as a solvent, and other chemical components an outlet, the third port kettle cover (8) (3) fitted with a thermometer (9) and as a feed port, a condenser (10) and a solvent collection bottle (11), the kettle lid (3) is the spatial position iron shelf and the clip (6) is fixed, while the reactor (2) is placed on the lifting platform (1), movable up and down.
  3. 3.根据权利要求1、2所述的方法,其特征在于反应结束后向反应釜(2)内注入2/3体积的去离子水,由控温仪控制水温在80℃至90℃,用升降台(1)把反应釜(2)抬升至与釜盖(3)紧密扣合;从投料口(8)徐徐投入氯甲基化聚砜反应液,过6-10分钟后,当收集瓶(11)中不再有液体滴入时,用升降台(1)使反应釜(2)降下来,把析出的氯甲基化聚砜取出,然后把釜体升上去,再投入氯甲基化聚砜反应液,循序进行;把收获的块状氯甲基化聚砜剪成碎片,用去离子水浸泡、冲洗,置于甩干机中甩干,然后自然风干,再用真空烘箱于20℃-40℃烘干,装于带封口的塑料袋中备用。 3. The method according to claim 1, characterized in that the injection volume of 2/3 (2) After completion of the reaction the reactor deionized water, the water temperature is controlled by the temperature controller at 80 deg.] C to 90 ℃, with lifting platform (1) the reactor (2) raised to the tank lid (3) snap fit; the feeding port (8) slowly into the reaction chloromethylated polysulfone solution, over 6-10 minutes, when the collection flask when (11) no more liquid dripped, (1) using the lift reactor (2) down, the precipitated chloromethylated polysulfone removed, and the reactor body is going up, then put chloromethyl polysulfone reaction solution sequentially performed; the harvest chloromethylated polysulfone block cut into pieces, soaked with deionized water, washing, drying in the dryer is placed, followed by natural drying, and then in a vacuum oven 20 ℃ -40 ℃ drying belt installed in sealed plastic bags until use.
CN 96107032 1996-07-08 1996-07-08 Method for preparation of high-viscosity chloromethylated polysulfone CN1059449C (en)

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CN101875723B (en) 2009-04-30 2012-06-20 比亚迪股份有限公司 Resin and preparation method thereof, and catalyst used for preparing biodiesel and preparation method thereof
CN104479146B (en) * 2014-12-04 2017-06-23 杭州水处理技术研究开发中心有限公司 Chloromethylated polysulfone one kind of post-processing method

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US4634742A (en) * 1984-11-08 1987-01-06 The B. F. Goodrich Company Polyarylene polyethers with pendant vinyl groups and process for preparation thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4634742A (en) * 1984-11-08 1987-01-06 The B. F. Goodrich Company Polyarylene polyethers with pendant vinyl groups and process for preparation thereof

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