WO2018014746A1 - 砜聚合物组合物及由其组成的热塑性模塑组合物与应用 - Google Patents

砜聚合物组合物及由其组成的热塑性模塑组合物与应用 Download PDF

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WO2018014746A1
WO2018014746A1 PCT/CN2017/092328 CN2017092328W WO2018014746A1 WO 2018014746 A1 WO2018014746 A1 WO 2018014746A1 CN 2017092328 W CN2017092328 W CN 2017092328W WO 2018014746 A1 WO2018014746 A1 WO 2018014746A1
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sulfone polymer
polymer composition
total weight
sulfone
dimethylquinoline
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French (fr)
Inventor
高红军
代惊奇
吴浩滨
曾祥斌
曹民
姜苏俊
龙杰明
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ZHUHAI WANGO CHEMICAL CO Ltd
Kingfa Science and Technology Co Ltd
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ZHUHAI WANGO CHEMICAL CO Ltd
Kingfa Science and Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a sulfone polymer composition and a thermoplastic molding composition composed thereof and an application 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 polyphenylene sulfone PPSU.
  • polysulfone PSU polyethersulfone PES
  • polyphenylene sulfone PPSU polyphenylene sulfone
  • the patent US2002010307 realizes the preparation of the lighter PPSU by controlling the particle size of the salt forming agent sodium carbonate
  • the patent CN101479321 uses d/D.
  • US2003011501 prepares a light colored PSU by adding an antioxidant of phosphorous acid.
  • CN 104530431 discloses the addition of 3,4'-dihalobenzophenone.
  • the present inventors have unexpectedly discovered that a trace component having a specific structure has a significant influence on the color of a sulfone polymer resin, and the present invention controls a trace component having a specific structure in a sulfone polymer, and controls the weight content thereof to be less than or equal to At 1000 ppm, the resulting sulfone polymer composition has a yellowness index of less than 5, which can significantly improve the color of the sulfone polymer composition.
  • a sulfone polymer composition comprising:
  • V a sulfonic acid or a sulfate lactone
  • the total weight content of the trace component is less than or equal to 1000 ppm based on the total weight of the sulfone polymer composition.
  • the total weight content of the trace components is determined by headspace-gas chromatography-mass spectrometry, and is determined by headspace-gas chromatography-mass spectrometry: using the US CDS8000 dynamic headspace sample concentrator headspace equipment, A trap filled with Tenax-GC organic adsorption packing was placed, 0.3 g of the sulfone polymer composition to be tested was placed in a headspace injection chamber, and kept at 300 ° C for 1 h, and the collected gas phase was used with Agilent's 7890B-5977A MSD type.
  • GC-MS monitoring equipment was tested; chromatographic conditions: capillary column was HP-5MS (30m ⁇ 250 ⁇ m, 0.25m); temperature program was raised to 390 ° C at 15 ° C / min, inlet temperature was 390 ° C, carrier gas was He gas, flow rate is 0.8mL / min, split ratio is 50:1; mass spectrometry conditions are EI source, ionization voltage of 70eV, ion source temperature 250 °C, scanning range: 30-600m / z; total weight content of trace components Calculated by the external standard method.
  • the total weight content of the minor component is 800 ppm or less, more preferably 500 ppm or less, based on the total weight of the sulfone polymer composition, and the total weight content of the minor component is not 0.
  • the sulfolene is 2-sulfolene or 3-sulfolene;
  • the hydroxy-substituted, aliphatic branched-chain sulfolane or thiophene sulfone is 2-hydroxysulfolane, 3-hydroxysulfolane, 2- C / butyl / pentane / hexyl sulfolane, 3-propion / butyl / pentane / hexyl sulfolane or benzo sulfolane;
  • the dimethyl substituted quinoline is 2,3-dimethylquinoline, 2, 4 - dimethylquinoline, 2,5-dimethylquinoline, 2,6-dimethylquinoline, 2,7-dimethylquinoline or 2,8-dimethylquinoline;
  • the methyl substituted quinoline species is 2,4,8-trimethyl-1,2,3,4-tetrahydroquinoline or 2,2,4-trimethyl-1,2-dihydroquinoline.
  • the sulfonic acid or sulfate lactone is 1,3-propane sultone, 1,4-butane sultone, 1,5-pentane sultone, 1,6-hexane sulfonic acid Ester, propylene dilactone, butyrolactone sulfate, or glutaractone sulfate.
  • the sulfone polymer composition has a yellowness index of less than 5 as measured on a 2 mm thick injection molded panel according to ASTM D1925.
  • the aromatic sulfone polymer is polyphenylene sulfone PPSU, polyether sulfone PES or polysulfone PSU.
  • Sulfone polymers generally include polysulfone PSU, polyethersulfone PES and polyphenylenesulfone PPSU, all of which are amorphous transparent amber high temperature resistant polymers.
  • PSU is prepared by reacting 4,4'-dichlorodiphenyl sulfone (DCDPS) with a unit of bisphenol A (BPA) by making 4,4'-dichlorodiphenyl sulfone (DCDPS) with 4 , 4'-dihydroxydiphenyl sulfone (bisphenol S) unit reaction
  • PPSU is made by 4,4'-dichlorodiphenyl sulfone (DCDPS) and 4,4'-bisphenol (BP) unit reaction made.
  • the general solvent is mainly sulfolane or N-methylpyrrolidone.
  • the present inventors have found through research that a trace component having a specific structure has a significant influence on the color of the sulfone polymer resin, and the source of the minor component can be directly added to a specific structural trace component in the synthesis of the sulfone polymer.
  • the sulfone polymer composition contains at least one trace component selected from the group consisting of:
  • sulfolene including:
  • sulfolane or thiophene sulfone containing a hydroxy-substituted, aliphatic branched-chain substituent including:
  • dimethyl substituted quinoline including:
  • Trimethyl substituted quinoline species including:
  • V sulfonic acid or sulphate, including:
  • the unexpected discovery of the present invention is that in the sulfone polymer, by adding a trace component having a specific structure, and controlling the total weight content of the trace component to 1000 ppm or less, and the total weight content of the trace component is not 0, the obtained
  • the sulfone polymer composition has a yellowness index of less than 5 and the sulfone polymer composition has a significantly improved color level.
  • 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.
  • 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 can be present in the thermoplastic molding composition.
  • 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 above sulfone polymer composition of the present invention can be widely used in the fields of aerospace, medical and health, food safety, household appliances, electronic appliances or energy and chemical engineering.
  • the invention has the following beneficial effects:
  • the unexpected discovery of the present invention is that in the sulfone polymer, by adding a trace component having a specific structure, and controlling the total weight content of the trace component to 1000 ppm or less, and the total weight content of the trace component is not 0, the obtained sulfone is obtained.
  • the polymer composition has a yellowness index of less than 5 and has a significantly improved color level.
  • the raw materials used in this example were all commercially available.
  • the xylene is further distilled and discharged, and the temperature is gradually increased to 230 ° C to start the polymerization reaction. At this time, the viscosity is detected to increase, and the temperature is constant.
  • Yellowness index The yellowness index (YI) was measured by injection molding on a 2 mm thick test panel according to ASTM D1925.
  • the total weight content of the trace components was determined by headspace gas chromatography and mass spectrometry: using the US CDS8000 dynamic headspace sample concentrator headspace equipment with a trap filled with Tenax-GC organic adsorption packing, 0.3g
  • the sulfone polymer composition to be tested was placed in a headspace sample chamber at 300 ° C for 1 h, and the collected gas phase was tested with Agilent's Model 7890B-5977A MSD GC-MS monitoring device; chromatographic conditions: capillary column for HP -5MS (30m ⁇ 250 ⁇ m, 0.25m); the temperature program is raised to 390 ° C at 15 ° C / min, the inlet temperature is 390 ° C, the carrier gas is He gas, the flow rate is 0.8 mL / min, the split ratio is 50:1
  • Mass spectrometry conditions were EI source, ionization voltage of 70 eV, ion source temperature 250 ° C, scanning range: 30-600 m/z; total weight
  • the obtained sulfone polymer composition has a yellowness index of less than 5, and has a significantly improved color level
  • the total weight content of the trace components in the comparative example is more than 1000 ppm
  • the obtained sulfone polymer composition has a yellowness index of more than 5, and the color The level is significantly worse than the embodiment.

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

一种砜聚合物组合物及由其组成的热塑性模塑组合物与应用，包含：(A)芳族砜聚合物；(B)至少一种选自如下结构的微量组分：I：环丁烯砜，II：含羟基取代、脂肪支链取代基的环丁砜或噻吩砜，III：二甲基取代的喹啉，IV：三甲基取代的喹啉类物质，V：磺酸或硫酸内酯类物质；其中，基于砜聚合物组合物的总重量，微量组分的总重量含量小于等于1000ppm，且微量组分的总重量含量不为0。在砜聚合物中通过添加具有特定结构微量组分，并控制微量组分的总重量含量，得到的砜聚合物组合物的黄度指数小于5，具有显著改善的颜色水平。

Description

一种砜聚合物组合物及由其组成的热塑性模塑组合物与应用 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由其组成的热塑性模塑组合物与应用。
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和聚亚苯基砜PPSU三种类型。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，在包括航空航天、医疗卫生，食品安全，家用电器，电子电器，能源化工应用领域均有适用性，特别是食品接触和医疗卫生方面，对材料的要求越来越高，其中一项最突出的要求就是作为可视视窗的浅色颜色和透明性，例如眼镜，咖啡机视窗，婴幼奶瓶等。
该领域技术人员对砜聚合物颜色的改善进行料多种角度的开发和尝试，如专利US2002010307通过控制成盐剂碳酸钠的粒径来实现制备出颜色较浅的PPSU，专利CN101479321使用d/D＞0.9且接近器壁的正传输搅拌器制备PSU和PES，US2003011501通过添加亚磷酸类的抗氧剂制备出浅色的PSU，CN 104530431公布了加入3,4’-二卤二苯甲酮为封端剂，应用低沸点溶剂及高压聚合法制备出低色泽的PSU的方法。
本发明意外地发现，具有特定结构的微量组分对砜聚合物树脂的颜色有显著影响，本发明通过在砜聚合物中添加具有特定结构的微量组分，并将其重量含量控制在小于等于1000ppm时，得到的砜聚合物组合物的黄度指数小于5，可以显著改善的砜聚合物组合物的颜色。
发明内容
本发明的目的在于提供一种含有特定结构的微量组分总重量含量小于等于1000ppm的砜聚合物组合物,该组合物具有显著改善的颜色水平。
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)至少一种选自如下结构的微量组分；
I：环丁烯砜；
II：含羟基取代、脂肪支链取代基的环丁砜或噻吩砜；
III：二甲基取代的喹啉；
IV：三甲基取代的喹啉类物质；
V：磺酸或硫酸内酯类物质；
其中，基于砜聚合物组合物的总重量，所述微量组分的总重量含量小于等于1000ppm，
且微量组分的总重量含量不为0。
所述微量组分的总重量含量采用顶空-气相色谱质谱联用的方法测定，顶空-气相色谱质谱联用的方法测定：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0.3g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；微量组分的总重量含量用外标法计算。
优选的，基于砜聚合物组合物的总重量，所述微量组分的总重量含量小于等于800ppm，更优选为小于等于500ppm，且微量组分的总重量含量不为0。
所述环丁烯砜为2-环丁烯砜或3-环丁烯砜；所述含羟基取代、脂肪支链取代基的环丁砜或噻吩砜为2-羟基环丁砜、3-羟基环丁砜、2-丙/丁/戊/己基环丁砜、3-丙/丁/戊/己基环丁砜或苯并八氢噻吩砜；所述二甲基取代的喹啉为2,3-二甲基喹啉、2,4-二甲基喹啉、2,5-二甲基喹啉、2,6-二甲基喹啉、2,7-二甲基喹啉或2,8-二甲基喹啉；所述三甲基取代的喹啉类物质为2,4,8-三甲基-1,2,3,4-四氢喹啉或2,2,4-三甲基-1,2-二氢喹啉；所述磺酸或硫酸内酯类物质为1,3-丙磺酸内酯、1,4-丁磺酸内酯、1,5-戊磺酸内酯、1,6-己磺酸内酯、硫酸丙二内酯、硫酸丁二内酯、或硫酸戊二内酯。
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。
所述芳族砜聚合物为聚亚苯基砜PPSU、聚醚砜PES或聚砜PSU。
砜聚合物通常包括聚砜PSU，聚醚砜PES和聚亚苯基砜PPSU三类，均属非晶形透明琥珀色耐高温聚合物。PSU是通过使4,4’-二氯二苯砜(DCDPS)与双酚A(BPA)的单元反应制成的，PES是通过使4,4’-二氯二苯砜(DCDPS)与4,4’-二羟基二苯砜(双酚S)的单元反应制成的，PPSU是通过使4,4’-二氯二苯砜(DCDPS)与4,4’-双酚 (BP)的单元反应制成的。尽管合成单体有所差别，但均是通过溶液聚合法制备，通用的溶剂主要为环丁砜或N-甲基吡咯烷酮。
本发明通过研究发现，具有特定结构的微量组分对砜聚合物树脂的颜色有显著影响，微量组分的来源可以通过在砜聚合物合成过程中直接添加具有特定结构微量组分。其中，砜聚合物组合物中至少含有一种选自如下结构的微量组分：
I：环丁烯砜，包括：
Figure PCTCN2017092328-appb-000001
(2-环丁烯砜)，(3-环丁烯砜)
II：含羟基取代、脂肪支链取代基的环丁砜或噻吩砜，包括：
(2-羟基环丁砜)，
Figure PCTCN2017092328-appb-000002
(3-羟基环丁砜)，
(n＝0～3)(2-丙/丁/戊/己基环丁砜),(n＝0～3)(3-丙/丁/戊/己基环丁砜)，
Figure PCTCN2017092328-appb-000003
(苯并八氢噻吩砜)，
III：二甲基取代的喹啉，包括：
Figure PCTCN2017092328-appb-000004
(2,3-二甲基喹啉)，
Figure PCTCN2017092328-appb-000005
(2,4-二甲基喹啉)，(2,5-二甲基喹啉)，
Figure PCTCN2017092328-appb-000006
(2,6-二甲基喹啉)，(2,7-二甲基喹啉)，(2,8-二甲基喹啉)
IV：三甲基取代的喹啉类物质，包括：
Figure PCTCN2017092328-appb-000007
(2,4,8-三甲基-1,2,3,4-四氢喹啉)，
Figure PCTCN2017092328-appb-000008
(2,2,4-三甲基-1,2-二氢喹啉)
V：磺酸或硫酸内酯类物质，包括：
(n＝0～3)(1,3-丙磺酸内酯、1,4-丁磺酸内酯、1,5-戊磺酸内酯、1,6-己磺酸内酯),
(n＝0～2)(硫酸丙二内酯、硫酸丁二内酯、硫酸戊二内酯)。
本发明意外的发现，在砜聚合物中通过添加具有特定结构微量组分，并将微量组分的总重量含量控制在小于等于1000ppm时，且微量组分的总重量含量不为0，得到的砜聚合物组合物的黄度指数小于5，砜聚合物组合物具有显著改善的颜色水平。
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。
本发明的上述砜聚合物组合物可以广泛应用在航空航天、医疗卫生、食品安全、家用电器、电子电器或能源化工领域中。
本发明与现有技术相比，具有如下有益效果：
本发明意外的发现，在砜聚合物中通过添加具有特定结构微量组分，并将微量组分的总重量含量控制在小于等于1000ppm，且微量组分的总重量含量不为0，得到的砜聚合物组合物的黄度指数小于5，具有显著改善的颜色水平。
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。
本实施例所用原料均为市购。
实施例1-6、实施例11-12及对比例1-2：
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4,4’-二羟基二苯砜，4,4’-二氯二苯砜，再加入环丁砜溶剂，搅拌并升温至100℃溶解单体至溶液透明，然后加入成盐剂Na2CO3，随后加入环丁烯砜、含羟基取代、脂肪支链取代基的环丁砜或噻吩 砜、二甲基取代的喹啉、三甲基取代的喹啉类物质或磺酸或硫酸内酯类物质中的一种或几种，并加入二甲苯，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3小时后，粘度增长恒定，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。黄度指数测试结果列于表1。
实施例7-8及对比例3：
将4,4’-二氯二苯砜与4,4’-双酚作为反应单体，其余同实施例1，得到聚亚苯基砜PPSU。黄度指数测试结果列于表1。
实施例9-10及对比例4：
将4,4’-二氯二苯砜与双酚A作为反应单体，其余同实施例1，得到聚砜PSU。黄度指数测试结果列于表1。
性能测试方法：
黄度指数：通过根据ASTM D1925在厚度为2mm的注塑板上检测黄度指数(YI)。
微量组分的总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0.3g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；微量组分的总重量含量用外标法计算。
表1实施例和对比例砜聚合物组合物的性能测试结果
Figure PCTCN2017092328-appb-000009
续表1：
Figure PCTCN2017092328-appb-000010
由表1可以看出，实施例中通过在砜聚合物中添加具有特定结构微量组分，并将微量组分的总重量含量控制在小于等于1000ppm，且微量组分的总重量含量不为0，得到的砜聚合物组合物的黄度指数小于5，具有显著改善的颜色水平，对比例中微量组分的总重量含量大于1000ppm，得到的砜聚合物组合物的黄度指数大于5，颜色水平明显差于实施例。

Claims (8)

  1. 一种砜聚合物组合物，包含：
    (A)芳族砜聚合物；
    (B)至少一种选自如下结构的微量组分；
    I：环丁烯砜；
    II：含羟基取代、脂肪支链取代基的环丁砜或噻吩砜；
    III：二甲基取代的喹啉；
    IV：三甲基取代的喹啉类物质；
    V：磺酸或硫酸内酯类物质；
    其中，基于砜聚合物组合物的总重量，所述微量组分的总重量含量小于等于1000ppm，且微量组分的总重量含量不为0。
  2. 根据权利要求1所述的砜聚合物组合物，其特征在于：所述微量组分的总重量含量采用顶空-气相色谱质谱联用的方法测定：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0.3g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；微量组分的总重量含量用外标法计算。
  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，所述微量组分的总重量含量小于等于800ppm，优选小于等于500ppm，且微量组分的总重量含量不为0。
  4. 根据权利要求1-3任一项所述的砜聚合物组合物，其特征在于：所述环丁烯砜为2-环丁烯砜或3-环丁烯砜；所述含羟基取代、脂肪支链取代基的环丁砜或噻吩砜为2-羟基环丁砜、3-羟基环丁砜、2-丙/丁/戊/己基环丁砜、3-丙/丁/戊/己基环丁砜或苯并八氢噻吩砜；所述二甲基取代的喹啉为2,3-二甲基喹啉、2,4-二甲基喹啉、2,5-二甲基喹啉、2,6-二甲基喹啉、2,7-二甲基喹啉或2,8-二甲基喹啉；所述三甲基取代的喹啉类物质为2,4,8-三甲基-1,2,3,4-四氢喹啉或2,2,4-三甲基-1,2-二氢喹啉；所述磺酸或硫酸内酯类物质为1,3-丙磺酸内酯、1,4-丁磺酸内酯、1,5-戊磺酸内酯、1,6-己磺酸内酯、硫酸丙二内酯、硫酸丁二内酯、或硫酸戊二内酯。
  5. 根据权利要求1-3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。
  6. 根据权利要求1-3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亚苯基砜PPSU、聚醚砜PES或聚砜PSU。
  7. 权利要求1-6任一项所述的砜聚合物组合物在航空航天、医疗卫生、食品安全、家用电器、电子电器或能源化工领域中的应用。
  8. 一种热塑性模塑组合物，其包含权利要求1-6任一项所述的砜聚合物组合物。
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