WO2017193478A1 - 砜聚合物组合物及其制备方法和由其组成的热塑性模塑组合物 - Google Patents

砜聚合物组合物及其制备方法和由其组成的热塑性模塑组合物 Download PDF

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WO2017193478A1
WO2017193478A1 PCT/CN2016/091708 CN2016091708W WO2017193478A1 WO 2017193478 A1 WO2017193478 A1 WO 2017193478A1 CN 2016091708 W CN2016091708 W CN 2016091708W WO 2017193478 A1 WO2017193478 A1 WO 2017193478A1
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sulfone
polymer composition
sulfone polymer
dichlorodiphenyl
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French (fr)
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代惊奇
高红军
吴浩滨
陈锐斌
孙学科
曹民
姜苏俊
李铭欣
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金发科技股份有限公司
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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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20—Polysulfones
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20—Polysulfones
    • C08G75/23—Polyethersulfones

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a sulfone polymer composition, a preparation method thereof and a thermoplastic molding composition composed thereof.
  • Sulfone polymer is a special high temperature resistant transparent thermoplastic engineering plastic with outstanding thermal properties, excellent chemical resistance, excellent high temperature creep resistance, excellent dimensional stability, extremely low smoke and toxic gas emissions, and superior heat resistance. Water and superheated steam, good electrical properties, mainly including polysulfone PSU, polyethersulfone PES and polyphenylsulfone PPSU. Since its development in the 1970s, it has experienced more than 50 years of development. With the development of sulfone polymer materials, its application range is becoming wider and wider.
  • Patent US6593445 discloses a method for improving the color of polyaryl ether sulfone by controlling the particle size of a single salt forming agent K 2 CO 3 in the range of 10-100 ⁇ m to obtain a light colored polyaryl ether sulfone product, but adding and varying the amount thereof. The effect of salt forming agents and mixed salt forming agents on color has not been clearly announced.
  • Patent EP2010061924 discloses a method for producing PPSU, using K 2 CO 3 as a salt forming agent, and controlling the content of the polymer end group chlorine by adding an aqueous solution of an alkali metal hydroxide in the late stage of polymerization to obtain a PPSU having a low chlorine content, which is light in color.
  • No. 4,176,222 discloses a method for preparing a sulfone polymer by mixing salts and a reactivity, that is, adding 0.1 to 20 moles of cerium salt or 0.05 to 10 moles of potassium salt per 100 moles of the sodium salt, the patent uses a mixed salt for the purpose of increasing the reaction rate.
  • the high molecular weight polymer is obtained, and the higher the reactivity, the easier the gel formation is, and the problem that the reaction is complete and the effect of the residual monomer content on color and transparency are not involved.
  • the present inventors have unexpectedly discovered that the content of 4,4'-dichlorodiphenyl sulfone in the sulfone polymer composition has a significant effect on the transparency and color of the resin, and the present invention will 4,4'-dichlorodiene in the sulfone polymer composition.
  • the weight content of phenylsulfone is controlled to less than 600 ppm
  • the sulfone polymer composition has a light transmittance of more than 85%, a haze of less than 4%, and a yellowness index of less than 5, and the transparency and color of the sulfone polymer composition can be remarkably improved.
  • the composition has significantly improved clarity and color levels.
  • Another object of the present invention is to provide a process for the preparation of the above sulfone polymer composition.
  • a sulfone polymer composition comprising:
  • weight content of 4,4'-dichlorodiphenyl sulfone is less than 600 ppm based on the total weight of the sulfone polymer composition.
  • the weight content of 4,4'-dichlorodiphenyl sulfone is less than 400 ppm, more preferably less than 300 ppm, based on the total weight of the sulfone polymer composition.
  • the aromatic sulfone polymer is polyethersulfone PES, polyphenylsulfone PPSU or a mixture thereof.
  • the present inventors have found through research that the content of 4,4'-dichlorodiphenyl sulfone in the sulfone polymer composition has a significant effect on the transparency and color of the resin.
  • the surprising discovery of the present invention is that the sulfone polymer composition is 4, 4'.
  • the weight content of dichlorodiphenyl sulfone is controlled to be less than 600 ppm, the sulfone polymer composition has a light transmittance of more than 85%, a haze of less than 4%, a yellowness index of less than 5, and a sulfone polymer composition having remarkably improved transparency. And color.
  • the present invention provides a process for preparing the above sulfone polymer composition comprising the steps of using sulfolane as a solvent, 4,4'-dichlorodiphenyl sulfone and 4,4'-dihydroxydiphenyl sulfone or 4 4'-dihydroxybiphenyl is a reaction monomer, and a mixed salt of sodium carbonate and potassium carbonate is used as a salt forming agent, and polymerization is carried out by solution polymerization; wherein, 4,4'-dichlorodiphenyl sulfone is used.
  • the polymer When 4,4'-dihydroxydiphenyl sulfone is used as a reactive monomer, the polymer is obtained as polyethersulfone PES, and the molar ratio of the potassium carbonate to sodium carbonate is 0.1:100-3:100; if 4,4 When '-dichlorodiphenyl sulfone and 4,4'-dihydroxybiphenyl are the reactive monomers, the obtained polymer is polyphenylsulfone PPSU, and the molar ratio of the potassium carbonate to the sodium carbonate is 0.1:100-5:100. .
  • a mixture of sodium carbonate and a trace amount of potassium carbonate is added as a salt forming agent to the polymerization system, and the hydroxy group on the bisphenol monomer is first substituted with a phenolate group, that is, NaO- and KO-, by a nucleophilic substitution reaction, and then Reaction with another halogen-containing monomer (4,4'-dichlorodiphenyl sulfone) to form metal halides (NaCl and KCl), because K + activity is higher than Na + , then K + will Re-participating in the affinity substitution reaction, therefore, even a small amount of K + can play an overall role in increasing the reaction rate due to its cyclical participation in the reaction, thereby allowing the monomer to participate more fully in polymerization, and conversely, if K + When the content is too high, a large amount of active end groups participate in the reaction to form a cross-linking gel and other side reactions, such as US 4,176,222, while
  • the present invention also provides a thermoplastic molding composition comprising the above sulfone polymer composition.
  • the molding compositions of the invention may contain fillers, especially fibers, particularly preferably glass fibers. Any glass fiber known to those skilled in the art and suitable for use in thermoplastic molding compositions may be present in the thermoplastic molding compositions of the present invention.
  • the molding compositions of the invention may contain auxiliaries as further components, in particular processing aids, pigments, stabilizers, flame retardants, or mixtures of different additives.
  • auxiliaries as further components, in particular processing aids, pigments, stabilizers, flame retardants, or mixtures of different additives.
  • processing aids pigments, stabilizers, flame retardants, or mixtures of different additives.
  • Other examples of conventionally added materials are antioxidants, heat stabilizers, UV stabilizers, lubricants and mold release agents, and pigments.
  • Antioxidants and heat stabilizers may use hindered phenols, hydroquinones, substituted forms of the groups, secondary aromatic amines, or phosphite or phosphonite compounds, optionally with phosphorus-containing acids. Used in combination, or a salt thereof, or a mixture of the compounds.
  • UV stabilizers are various substituted resorcinols, salicylates, benzotriazoles, and benzophenones, and lubricants and mold release agents may be stearyl alcohol, alkyl stearates, stearic fats. Amides, as well as esters of pentaerythritol with long chain fatty acids, may also be used with dialkyl ketones such as distearyl.
  • the pigment may be a white pigment such as zinc oxide, zinc sulfide, white lead, zinc antimony white, antimony white and titanium dioxide.
  • Black pigments such as iron oxide black, spinel black, manganese black, cobalt black, and black, carbon black, and the like can also be used in accordance with the present invention.
  • thermoplastic molding compositions of the present invention can be prepared by methods known per se, such as extrusion.
  • the molding compositions of the invention can be prepared, for example, by mixing the starting components in a conventional mixing apparatus, such as a screw-based extruder, preferably a twin-screw extruder.
  • the invention has the following beneficial effects:
  • the sulfone polymer composition of the present invention contains the compound 4,4'-dichlorodiphenyl sulfone in a weight content of less than 600 ppm, and the sulfone polymer composition has a light transmittance of more than 85% and a haze of less than 4%.
  • the yellowness index is less than 5 with significantly improved transparency and color levels.
  • the reactivity in the synthesis process can be improved, and the monomer can participate more fully in the reaction, shorten the polymerization time, and significantly reduce the
  • the content of the reactive monomer is such that the transparency and color of the sulfone polymer composition are remarkably improved, while the proportion of each component in the salt forming agent is strictly limited so that side reactions do not occur due to excessive activity.
  • Figure 1 is a graph showing the viscosity increase of a sulfone polymer prepared by mixing a salt-forming salt of Example 1.
  • Figure 2 is a graph showing the viscosity increase of a sulfone polymer prepared by the single salt former of Comparative Example 1.
  • Figure 3 is a headspace GC-MS spectrum of a sulfone polymer prepared by mixing a salt-forming salt of Example 1, wherein the mass spectrum peak at the position of 12.3 min is the residual monomer 4,4'-dichlorodiphenyl sulfone.
  • Figure 4 is a headspace GC-MS spectrum of a sulfone polymer prepared by the single salt former of Comparative Example 1, wherein the mass spectrum peak at the position of 12.3 min is the residual monomer 4,4'-dichlorodiphenyl sulfone.
  • Yellowness Index The yellowing index (YI) was measured by injection molding on a 2 mm thick test panel according to ASTM D1925.
  • melt viscosity growth melt viscosity can be monitored in real time by the German MARIMEX VS-4450 online viscometer.
  • the weight content of 4,4'-dichlorodiphenyl sulfone was determined by headspace gas chromatography and mass spectrometry.
  • the headspace equipment of the US CDS8000 dynamic headspace sample concentrator was equipped with the filling of Tenax-GC organic adsorption packing.
  • the upper layer of xylene is returned to the system; the temperature is maintained in the range of 200 ° C - 210 ° C.
  • the collected water volume is close to the theoretical value (540 g)
  • the reflux is continued for another 20 minutes, and no water drops are observed.
  • the salt formation is complete, and the xylene is further distilled and discharged, and the polymerization is gradually started to 230 ° C.
  • the viscosity starts to increase, and after 2.5 hours of constant temperature, the slope of the viscosity growth curve of the viscosity growth curve is substantially zero, and the viscosity growth curve is as follows. As shown in Figure 1, the viscosity of the system is completely constant, and the end is reversed.
  • the material is slowly poured into non-ionic water to cool into a white strip of solid, and then crushed into a powder by a pulverizer, boiled with ion-free water for 1 hour, filtered to remove water, and thus repeated 10 times until the filtrate
  • the turbidity was detected by using silver nitrate, indicating that the by-product salt in the powder was washed away.
  • the polymer was dried in a vacuum oven at 120 ° C to a constant weight to obtain polyethersulfone PES; 4,4'-dichlorodiphenyl sulfone.
  • the weight content was determined by headspace gas chromatography and mass spectrometry.
  • the detection chromatogram is shown in Figure 3.
  • the peak appearing at 12.8 min is the mass spectrum peak of the monomer 4,4'-dichlorodiphenyl sulfone.
  • the test results of the performance indexes such as the light transmittance, the yellowness index and the haze of the composition of the obtained sulfone polymer are shown in Table 1.
  • Example 1 3.498kg (33mol) salt-forming agent Na 2 CO 3 was added , and the rest was the same as in Example 1. After 4 hours of constant temperature, the slope of the viscosity growth curve slowed down.
  • the viscosity growth curve is shown in Figure 2, indicating that the viscosity of the system is constant. Trend, end the reaction, the polymer is dried to obtain polyethersulfone PES, and the weight content of 4,4'-dichlorodiphenyl sulfone is determined by headspace gas chromatography and mass spectrometry. The chromatogram is shown in Figure 4, at 12.8. The peak appearing at the min position is the mass spectrum peak of the monomeric 4,4'-dichlorodiphenyl sulfone. The performance test results are shown in Table 1.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
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Abstract

一种砜聚合物组合物及其制备方法和由其组成的热塑性模塑组合物，包含：(A)至少一种芳族砜聚合物；(B)一种化合物4,4'-二氯二苯砜；其中，基于砜聚合物组合物的总重量，4,4'-二氯二苯砜的重量含量小于600ppm。其制备方法是以环丁砜为溶剂，以4,4'-二氯二苯砜和4,4'-二羟基二苯砜或4,4'-二羟基联苯为反应单体，以碳酸钠和碳酸钾的混合盐为成盐剂，采用溶液聚合技术进行聚合即得。该砜聚合物组合物的透光率大于85％，雾度小于4％，黄度指数小于5，具有改善的透明度和颜色水平。

Description

一种砜聚合物组合物及其制备方法和由其组成的热塑性模塑组合物 技术领域
本发明涉及高分子材料技术领域，具体涉及一种砜聚合物组合物及其制备方法和由其组成的热塑性模塑组合物。
背景技术
砜聚合物属特种耐高温透明热塑性工程塑料，具有突出的热性能，优良的耐化学性，出色的高温抗蠕变性，优异的尺寸稳定性极低的烟雾和有毒气体排放，优越的耐热水和过热蒸汽，良好的电性能，主要包括聚砜PSU，聚醚砜PES和聚苯砜PPSU三种类型。从上世纪70年代开发至今已经经历50多年的发展历程，随着砜聚合物材料开发的日趋完善，其应用范围也越来越广，如今在食品卫生，医疗器械，家用小电器，航空航天，电子电器等领域均有成熟应用，特别是在食品接触类用品方面，如婴儿奶瓶，不粘锅涂层，咖啡壶配件等等，因其透明性和耐热性，在近几年得到突出的应用，因此对材料有了更高的要求，包括透明度，颜色，小分子含量等，也成为开发研究人员研究的热点之一。
专利US6593445公布改善聚芳醚砜的颜色的方法是通过控制单一成盐剂K2CO3的粒径在10-100μm的范围，获得浅色的聚芳醚砜产物，但是对其添加量和不同成盐剂及混合成盐剂对颜色影响情况并未明确公布。专利EP2010061924公布的生产PPSU的方法，用K2CO3作成盐剂，在聚合后期通过添加碱金属氢氧化物的水溶液控制高分子端基氯的含量，得到氯含量较低的PPSU，颜色较浅，但未研究不同成盐剂对反应完全程度及残余单体的含量对颜色和透明度的影响。US4176222公布了混合盐制备砜聚合物的方法以及反应活性，即每100摩尔钠盐中加入0.1～20摩尔的铯盐或0.05～10摩尔的钾盐，该专利采用混合盐是为了提高反应速度而得到高分子量聚合物，反应活性越高，越易形成凝胶，并且未涉及反应是否完全的问题及残余单体的含量对颜色和透明度的影响。
本发明意外地发现，砜聚合物组合物中4,4’-二氯二苯砜的含量对树脂透明度和颜色有显著影响，本发明将砜聚合物组合物中4,4’-二氯二苯砜的重量含量控制在小于600ppm时，砜聚合物组合物的透光率大于85％，雾度小于4％，黄度指数小于5，可以显著改善的砜聚合物组合物的透明度和颜色。
发明内容
本发明的目的在于提供一种含有4,4’-二氯二苯砜含量低于600ppm的砜聚合物组合 物,该组合物具有显著改善的透明度和颜色水平。
本发明的另一目的在于提供上述砜聚合物组合物的制备方法。
本发明是通过以下技术方案实现：
一种砜聚合物组合物，包含：
(A)芳族砜聚合物；
(B)4,4’-二氯二苯砜；
其中，基于砜聚合物组合物的总重量，4,4’-二氯二苯砜的重量含量小于600ppm。
优选的，基于砜聚合物组合物的总重量，4,4’-二氯二苯砜的重量含量小于400ppm，更优选小于300ppm。
所述芳族砜聚合物为聚醚砜PES、聚苯砜PPSU或其混合物。
本发明通过研究发现，砜聚合物组合物中4,4’-二氯二苯砜的含量对树脂透明度和颜色有显著影响，本发明意外的发现，将砜聚合物组合物中4,4’-二氯二苯砜的重量含量控制在小于600ppm时，砜聚合物组合物的透光率大于85％，雾度小于4％，黄度指数小于5，砜聚合物组合物具有显著改善的透明度和颜色。
本发明提供了了一种制备上述砜聚合物组合物的方法，包括如下步骤：以环丁砜为溶剂，以4,4’-二氯二苯砜和4,4’-二羟基二苯砜或4,4’-二羟基联苯为反应单体，以碳酸钠和碳酸钾的混合盐为成盐剂，采用溶液聚合技术进行聚合即得；其中，若以4,4’-二氯二苯砜和4,4’-二羟基二苯砜为反应单体时，得到聚合物为聚醚砜PES，所述碳酸钾和碳酸钠的摩尔比为0.1:100-3:100；若以4,4’-二氯二苯砜和4,4’-二羟基联苯为反应单体时，得到聚合物为聚苯砜PPSU，所述碳酸钾和碳酸钠的摩尔比为0.1:100-5:100。
本发明将碳酸钠和微量碳酸钾的混合物作为成盐剂加入聚合体系中，通过亲核取代反应，首先使双酚单体上的羟基被取代为酚盐基，即NaO-和KO-，然后与另一种含卤基的单体(4,4’-二氯二苯砜)反应生成金属卤化物(NaCl和KCl)，因为K+的活性比Na+的高，这时K+又会重新参与亲和取代反应，因此，即使是微量的K+，也能因其循环参与反应而起到总体提高反应速度的作用，从而使单体能够更完全地参与聚合，相反地，如果K+的含量过高时，会有大量活性端基参与反应而形成交联凝胶等副反应发生，如US4176222，同时能避免单体水解，如CN201310018193，所以，控制K+的含量尤为重要，本发明通过将碳酸钾和碳酸纳的摩尔比控制在0.1：100-5：100范围内，所制备的砜聚合物既能得到与现有单一成盐剂技术相当的分子链直链结构，又能获得更高反应速度的合成工艺，缩短聚合时间，最突出的技术特征是可以提高合成过程中的反应活性，进而使单体更充分地参与反应， 显著降低未反应单体的含量，从而显著改善砜聚合物组合物的透明度和颜色。
本发明还提供一种热塑性模塑组合物，其包含上述的砜聚合物组合物。
本发明的模塑组合物可以含有填料，尤其是纤维，特别优选玻璃纤维。在本发明的热塑性模塑组合物中可以存在本领域技术人员已知的和适用于热塑性模塑组合物中的任何玻璃纤维。
本发明的模塑组合物可以含有作为其它组分的助剂，尤其是加工助剂、颜料、稳定剂、阻燃剂，或不同添加剂的混合物。常规添加物质的其它例子是抗氧化剂、热稳定剂、UV稳定剂、润滑剂和脱模剂和颜料。
抗氧化剂和热稳定剂可以使用位阻酚、氢醌、所述基团的取代形式，芳族仲胺，或者亚磷酸酯或亚膦酸酯类化合物，也可以任选地与含磷的酸组合使用，或使用它们的盐，或所述化合物的混合。
UV稳定剂的例子是各种取代的间苯二酚、水杨酸盐、苯并三唑以及苯甲酮，润滑剂和脱模剂可以是硬脂醇、硬脂酸烷基酯、硬脂酰胺，以及季戊四醇与长链脂肪酸形成的酯，也可以使用二烷基酮，例如二硬脂基。
颜料可以是白色颜料，例如氧化锌、硫化锌、白铅、锌钡白、锑白和二氧化钛。也可以根据本发明使用黑色颜料，比如氧化铁黑，尖晶石黑，锰黑，钴黑，以及锑黑，炭黑等。
本发明的热塑性模塑组合物可以通过本身公知的方法制备，例如挤出。本发明的模塑组合物可以例如通过将起始组分在常规混合设备中混合来制备，例如基于螺杆的挤出机，优选双螺杆挤出机。
本发明与现有技术相比，具有如下有益效果：
(1)本发明的砜聚合物组合物中含有重量含量小于600ppm的化合物4,4’-二氯二苯砜，该砜聚合物组合物的透光率大于85％，雾度小于4％，黄度指数小于5，具有显著改善的透明度和颜色水平。
(2)本发明制备工艺中通过将碳酸钠和微量碳酸钾的混合盐作为成盐剂，可以提高合成过程中的反应活性，进而使单体更充分地参与反应，缩短聚合时间，显著降低未反应单体的含量，从而显著改善砜聚合物组合物的透明度和颜色，同时严格限定成盐剂中各成分的比例不至于因活性过高而发生副反应。
附图说明
图1为实施例1混合盐成盐剂制备的砜聚合物的粘度增长曲线。
图2为对比例1单一成盐剂制备的砜聚合物的粘度增长曲线。
图3为实施例1混合盐成盐剂制备的砜聚合物的顶空GC-MS谱图，其中在12.3min位置处的质谱峰即为残留单体4,4’-二氯二苯砜。
图4为对比例1单一成盐剂制备的砜聚合物的顶空GC-MS谱图，其中在12.3min位置处的质谱峰即为残留单体4,4’-二氯二苯砜。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。
性能测试方法：
透光率和雾度：通过根据ASTM D1003-07在厚度为2mm的注塑板上检测(％)。
黄度指数：通过根据ASTM D1925在厚度为2mm的注塑板上检测黄变指数(YI)。
聚合熔体粘度增长情况：熔体粘度可用德国MARIMEX公司VS-4450型在线粘度计实时监测。
4,4’-二氯二苯砜的重量含量采用顶空气相色谱与质谱联用法测定：采用美国CDS8000型动态顶空进样浓缩器顶空设备，内附填充Tenax-GC有机吸附填料的捕集阱，将0.2g待测聚合物置于顶空进样腔中，300℃保持1h，将收集到的气相用Agilent公司的7890B-5977A MSD型的GC-MS监测设备进行测试；色谱条件：毛细管柱为HP-5MS(30m×250μm，0.25m)；升温程序以15℃/min升到390℃，进样口温度为390℃，载气为He气，流速为0.8mL/min，分流比为50:1；质谱条件以EI源，70eV的电离电压，离子源温度250℃，扫描范围：30-600m/z。用内标法可以得到标准曲线用来定量单体4，4’-二氯二苯砜的含量。
实施例1
在装有温度计、通氮气管、冷凝分水器、搅拌器的50L聚合釜中依次加入7.508kg(30mol)的4,4’-二羟基二苯砜，8.787kg(30.6mol)的4,4’-二氯二苯砜、再加入32.62kg的环丁砜，搅拌并升温至100℃溶解单体至溶液透明，3.396kg(32.039mol)成盐剂Na2CO3和132.6g(0.961mol)成盐剂K2CO3，随后加入2L二甲苯，继续搅拌下升温至成盐反应开始，体系中生产的水与二甲苯生成的共沸物被保护气吹出至冷凝管中冷凝滴下至分水器中分层，上层的二甲苯又回流至体系中；维持温度在200℃-210℃的范围，当收集水量接近理论值(540g)时，再继续回流20分钟，观察不到有水珠落下，证明成盐完全，再蒸馏并放出二甲苯，逐渐升温至230℃开始聚合反应，此时检测到粘度开始增大，恒温2.5小时 后，粘度增长曲线斜率粘度增长曲线斜率基本为零，粘度增长曲线如图1所示，说明体系粘度完全恒定，结束反应；停止搅拌和加热，把物料缓慢倒入无离子水中冷却成白色条状固体，再用粉碎机破碎成粉末状，用无离子水煮沸1小时，过滤去水分，如此重复10次，直至滤液用硝酸银检测不变浑浊，说明粉末中副产物盐洗除干净，过滤后把聚合物用真空烘箱120℃干燥至恒重，即得聚醚砜PES；4,4’-二氯二苯砜的重量含量采用顶空气相色谱与质谱联用法测定，检测色谱图如图3所示，在12.8min位置出现的峰是单体4，4’-二氯二苯砜的质谱峰。制备得到的砜聚合物的组合物的透光率、黄度指数和雾度等性能指标测试结果如表1所示。
实施例2
其中，加入3.446kg(32.512mol)成盐剂Na2CO3和67.4g(0.488mol)成盐剂K2CO3，其余同实施例1，恒温3小时后，体系粘度完全恒定。聚合物干燥后得到聚醚砜PES，性能测试结果见表1。
实施例3
其中，然后加入3.412kg(32.195mol)成盐剂Na2CO3和111.242g(0.805mol)成盐剂K2CO3，其余同实施例1，恒温3.5小时后，体系粘度完全恒定。聚合物干燥后得到聚醚砜PES，性能测试结果见表1。
实施例4
其中，然后加入3.429kg(32.353mol)成盐剂Na2CO3和89.294g(0.6470mol)成盐剂K2CO3，其余同实施例1，恒温3.5小时后，体系粘度完全恒定。聚合物干燥后得到聚醚砜PES，性能测试结果见表1。
实施例5
其中，然后加入3.463kg(32.673mol)成盐剂Na2CO3和45.158g(0.327mol)成盐剂K2CO3，其余同实施例1，恒温3.5小时后，体系粘度完全恒定。聚合物干燥后得到聚醚砜PES，性能测试结果见表1。
实施例6
其中，然后加入3.470kg(32.738mol)成盐剂Na2CO3和36.198g(0.262mol)成盐剂K2CO3，其余同实施例1，恒温3.5小时后，体系粘度完全恒定。聚合物干燥后得到聚醚砜PES，性能测试结果见表1。
实施例7
其中，然后加入3.480kg(32.836mol)成盐剂Na2CO3和22.69g(0.164mol)成盐剂 K2CO3，其余同实施例1，恒温3.5小时后，体系粘度完全恒定。聚合物干燥后得到聚醚砜PES，性能测试结果见表1。
实施例8
其中，然后加入3.494kg(32.967mol)成盐剂Na2CO3和4.56g(0.0329mol)成盐剂K2CO3，其余同实施例1，恒温3.5小时后，体系粘度完全恒定。聚合物干燥后得到聚醚砜PES，性能测试结果见表1。
实施例9
在装有温度计、通氮气管、冷凝分水器、搅拌器的50L聚合釜中依次加入5.586kg(30mol)的4,4’-二羟基联苯，8.787kg(30.6mol)的4,4’-二氯二苯砜、再加入28.14kg的环丁砜，搅拌并升温至溶解，然后加入3.331kg(31.428mol)成盐剂Na2CO3和0.217kg(1.571mol)成盐剂K2CO3，其余同实施例1，恒温3小时后，体系粘度完全恒定。聚合物干燥后得到聚苯砜PPSU，性能测试结果如表1所示。
实施例10
其中，加入3.429kg(32.353mol)成盐剂Na2CO3和893g(0.647mol)成盐剂K2CO3，其余同实施例9，恒温3.5小时后，体系粘度完全恒定。聚合物干燥后得到聚苯砜PPSU，性能测试结果如表1所示。
实施例11
其中，加入3.495kg(32.967mol)成盐剂Na2CO3和4.55g(0.0329mol)成盐剂K2CO3，其余同实施例9，恒温4小时后体系粘度完全恒定。聚合物干燥后得到聚苯砜PPSU，性能测试结果如表1所示。
对比例1
其中，加入3.498kg(33mol)成盐剂Na2CO3，其余同实施例1，恒温4小时后，粘度增长曲线斜率有放缓趋势，粘度增长曲线如图2所示，说明体系粘度有恒定趋势，结束反应，聚合物干燥后得到聚醚砜PES，4,4’-二氯二苯砜的重量含量采用顶空气相色谱与质谱联用法测定，检测色谱图如图4所示，在12.8min位置出现的峰是单体4，4’-二氯二苯砜的质谱峰。性能测试结果见表1。
对比例2
其中，加入3.498kg(33mol)成盐剂Na2CO3，其余同实施例9，恒温4.5小时后，体系粘度有恒定趋势，结束反应。聚合物干燥后得到聚苯砜PPSU，性能测试结果如表1所示。
对比例3
其中，加入3.496kg(32.984mol)成盐剂Na2CO3和2.28g(0.0165mol)成盐剂K2CO3，恒温4.5小时后，其余同实施例1，聚合物干燥后得到聚醚砜PES，性能测试结果见表1。
对比例4
其中，加入3.180kg(33.0mol)成盐剂Na2CO3和414.63g(3mol)成盐剂K2CO3，恒温2.5小时后，其余同实施例1，聚合物干燥后得到聚醚砜PES，性能测试结果见表1。
表1实施例和对比例砜聚合物组合物的性能测试结果
Figure PCTCN2016091708-appb-000001
续表1
Figure PCTCN2016091708-appb-000002

Claims (9)

  1. 一种砜聚合物组合物，包含：
    (A)芳族砜聚合物；
    (B)4,4’-二氯二苯砜；
    其中，基于砜聚合物组合物的总重量，4,4’-二氯二苯砜的重量含量小于600ppm。
  2. 根据权利要求1所述的砜聚合物组合物，其特征在于：所述4,4’-二氯二苯砜的重量含量采用顶空气相色谱与质谱联用法测定：采用美国CDS8000型动态顶空进样浓缩器顶空设备，内附填充Tenax-GC有机吸附填料的捕集阱，将0.2g待测砜聚合物组合物置于顶空进样腔中，300℃保持1h，将收集到的气相用Agilent公司的7890B-5977A MSD型的GC-MS监测设备进行测试；色谱条件：毛细管柱为HP-5MS,30m×250μm，0.25m；升温程序以15℃/min升到390℃，进样口温度为390℃，载气为He气，流速为0.8mL/min，分流比为50:1；质谱条件以EI源，70eV的电离电压，离子源温度250℃，扫描范围：30-600m/z。
  3. 根据权利要求1所述的砜聚合物组合物，其特征在于：基于砜聚合物组合物的总重量，4,4’-二氯二苯砜的重量含量小于400ppm。
  4. 根据权利要求3所述的砜聚合物组合物，其特征在于：基于砜聚合物组合物的总重量，4,4’-二氯二苯砜的重量含量小于300ppm。
  5. 根据权利要求1-4任一项所述的砜聚合物组合物，其特征在于：所述砜聚合物组合物通过根据ASTM D1003-07在厚度为2mm的注塑板上检测的透光率大于85％，雾度小于4％。
  6. 根据权利要求1-4任一项所述的砜聚合物组合物，其特征在于：所述砜聚合物组合物通过根据ASTM D1925在厚度为2mm的注塑板上检测的黄度指数小于5。
  7. 根据权利要求1-4任一项所述的砜聚合物组合物，其特征在于：所述芳族砜聚合物为聚醚砜、聚苯砜或其混合物。
  8. 一种制备权利要求1-7任一项所述的砜聚合物组合物的方法，其特征在于，包括如下步骤：以环丁砜为溶剂，以4,4’-二氯二苯砜和4,4’-二羟基二苯砜或4,4’-二羟基联苯为反应单体，以碳酸钠和碳酸钾的混合盐为成盐剂，采用溶液聚合技术进行聚合即得；其中，若以4,4’-二氯二苯砜和4,4’-二羟基二苯砜为反应单体时，得到聚合物为聚醚砜PES，所述碳酸钾和碳酸钠的摩尔比为0.1:100-3:100；若以4,4’-二氯二苯砜和4,4’-二羟基联苯为反应单体时，得到聚合物为聚苯砜PPSU，所述碳酸钾和碳酸钠的摩尔比为0.1:100-5:100。
  9. 一种热塑性模塑组合物，其包含权利要求1-7任一项所述的砜聚合物组合物。
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