WO2017114163A1 - 一种砜聚合物的组合物及其制备方法与应用 - Google Patents

一种砜聚合物的组合物及其制备方法与应用 Download PDF

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WO2017114163A1
WO2017114163A1 PCT/CN2016/109986 CN2016109986W WO2017114163A1 WO 2017114163 A1 WO2017114163 A1 WO 2017114163A1 CN 2016109986 W CN2016109986 W CN 2016109986W WO 2017114163 A1 WO2017114163 A1 WO 2017114163A1
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sulfone
composition
formula
sulfone polymer
group
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PCT/CN2016/109986
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French (fr)
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代惊奇
高红军
苏成晓
陈锐斌
曹民
姜苏俊
曾祥斌
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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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • 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
    • 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
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C08G65/4056—(I) or (II) containing sulfur

Definitions

  • the invention relates to the technical field of sulfone polymer compositions, in particular to a composition of a sulfone polymer and a preparation method and application thereof.
  • the polymer is a generic name used to describe any polymer comprising at least one ether group (-O-), at least one sulfone group (-SO2-), and at least one arylene group.
  • a group of commercially important poly(aryl ether sulfones) comprises a sulfone polymer designated herein as PESU, which has high mechanical strength, heat and oxidation resistance, hydrolysis resistance and resistance to many acids. / base and solvent are well known.
  • PESU is obtained by polycondensation of a reaction unit of dihalodiphenyl sulfone and dihydroxydiphenyl sulfone.
  • PESU is a high temperature, amorphous, engineered thermoplastic resin with a glass transition temperature of about 225 ° C and exhibits high strength and toughness from -40 ° C to 210 ° C. Because the polymer is completely amorphous, it also has outstanding light transmission, which has unique advantages in many end applications. Due to their excellent mechanical and thermal properties, as well as excellent hydrolytic stability and chemical resistance, they have been used in a wide variety of applications for a wide range of end-use temperatures, such as plumbing, food service items, medical trays.
  • EP2011053675 discloses the addition of hyperbranched polymers to improve the fluidity of sulfone polymers.
  • US 4,957,978 improves the flow by adding polymers with low glass transition temperatures.
  • US 4,855,388 utilizes sodium, lithium, alkaline earth or lanthanide metal salts as polyaryl ethers.
  • US5008364 discloses controlling the alkali metal salt content to not exceed 100 ppm to improve high temperature stability and to prepare thermoplastics with improved melt stability.
  • the above report does not address the effect of structural changes in the molecular chain itself on material properties.
  • the inventors have unexpectedly discovered that when a specific amount of ortho-etheroxy substituent isomer is present on the benzene ring structure of the composition of the sulfone polymer, the composition of the sulfone polymer can be rendered unpredictable performance improvement. , including improved processing fluidity, mechanical properties and color, while its transparency and heat resistance are significantly improved.
  • the composition of the sulfone polymer is applied to be blended with other high molecular polymers in any ratio, or applied to other blending modifications including dyeing, filling, and fiber reinforcement, and has good compatibility. .
  • Another object of the present invention is to provide a process for the preparation of a composition of the above sulfone polymer.
  • a further object of the invention is to provide the use of a composition of the above sulfone polymer.
  • n in the formula I is a positive integer greater than 0
  • x in the formula II is a positive integer greater than zero.
  • composition of the sulfone polymer has a ratio of m:n in the structural formula of the formula I of from 1:100,000 to 5:100, preferably from 1:2000 to 3:100.
  • a method for preparing a composition of the above sulfone polymer wherein the composition of the sulfone polymer is prepared by a solution method using a synthetic monomer comprising a dihalogen sulfone compound and a dihydroxy sulfone compound, and the specific steps are as follows:
  • 4,4'-dihalodiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfone, 2 were sequentially added in a three-necked flask equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a stirrer. 4-dihydroxydiphenyl sulfone, 2,4'-dihalodiphenyl sulfone, further added 490.3g solvent, stirred and heated to 100 ° C to dissolve the monomer until the solution is transparent, add 34.98g salt forming agent, then add 70mL two Toluene, heating is continued with stirring until the salt formation reaction begins.
  • the azeotrope formed by the water and xylene produced in the system is blown out by the shielding gas to the condensation tube and condensed and dropped to the water separator for stratification, and the upper layer of xylene is refluxed to the same.
  • the water was boiled for 1 hour, filtered to remove water, and this was repeated 10 times until the filtrate was checked for turbidity by using silver nitrate, indicating that the by-product salt in the powder was washed away, and after filtration, the polymer was dried in a vacuum oven at 120 ° C to a constant weight, that is, A composition of a sulfone polymer is obtained.
  • the solvent is added in an amount of 10% by weight to 50% by weight based on the total mass of the composition of the sulfone polymer, and the amount of the salt forming agent is preferably not less than the molar amount of the dihydroxy sulfone compound, generally in the molar ratio of the salt forming agent.
  • the molar amount of the dihydroxy sulfone compound is preferably from 1 mol% to 15 mol%.
  • dihalosulfone compound is selected from the group consisting of 4,4'-dihalodiphenylsulfone of the formula VI and/or 2,4-dihalodiphenylsulfone of the formula V
  • dihydroxy sulfone compound is selected from the group consisting of 4,4'-dihydroxydiphenyl sulfone of the formula II and/or 2,4-dihydroxydiphenyl sulfone of the formula III;
  • X, X' are the same or different halogens, preferably Cl and/or F; the molar ratio of the synthetic monomers III and/or V to the synthetic monomers II and/or VI is from 1:100 to 5:100, preferably It is 1:2000-3:100. It has been found experimentally that if the etheroxy substituent isomer is absent, the fluidity and clarity of the composition of the sulfone polymer decreases, if the ortho-etheroxy substituent isomer content in the composition of the sulfone polymer Too high will affect the mechanical properties of the composition of the sulfone polymer, including a decrease in tensile modulus and/or flexural modulus.
  • the solvent is selected from the group consisting of diphenyl sulfone, sulfolane, dimethyl sulfone, N-methylpyrrolidone, dimethyl sulfoxide, N-methylformamide, N-methylacetamide, biphenyl benzene sulfin
  • the acyl groups preferably one or more of sulfolane, N-methylpyrrolidone, and dimethyl sulfoxide.
  • the salt forming agent is selected from one or more of a base, an alkali metal carbonate, and an alkali metal hydrogencarbonate; preferably KOH, NaOH, K 2 CO 3 , Na 2 CO 3 , KHCO 3 , NaHCO One or more of 3 .
  • the invention also discloses that the composition of the sulfone polymer obtained by the preparation method of the composition of the above sulfone polymer is applied to high temperature resistant and resistant to aerospace, medical and health, food safety, household appliances, electronic appliances, energy and chemical applications. Solvent and transparent conditions.
  • the invention also discloses the application of the sulfone polymer composition obtained by the preparation method of the composition of the sulfone polymer described above to be applied in any proportion with other high molecular polymers;
  • the other high molecular polymer is selected from the group of high temperature engineering plastics.
  • the high temperature engineering plastic is selected from one or more of PI, PAI, PEI, LCP, PEEK, PPS;
  • the general engineering plastic is selected from one of PA, PS, PC or Several.
  • the invention also discloses that the composition of the sulfone polymer obtained by the preparation method of the composition of the above sulfone polymer is applied to other Application in blending modification; the other blending modification is selected from one or more of dyeing, filling, fiber reinforcement; the dyeing is dyeing with organic and/or inorganic toner; Filling from the inorganic material; the fiber reinforcement is selected from the group consisting of glass fibers and/or carbon fibers for fiber reinforcement.
  • the present invention has the following beneficial effects:
  • the composition of the sulfone polymer can be obtained with unpredictable performance improvement, including improved processing fluidity. , mechanical properties and color, while its transparency and heat resistance are significantly improved.
  • the composition of the sulfone polymer is applied to be blended with other high molecular polymers in any ratio, or applied to other blending modifications including dyeing, filling, and fiber reinforcement, and has good compatibility. .
  • 4,4'-dihydroxydiphenyl sulfone Commercial products can be ordered from the Aldrich website;
  • 2,4-dihydroxydiphenyl sulfone Commercial products can be ordered from the Aldrich website;
  • 2,4-dichlorodiphenyl sulfone Commercial products can be ordered from the Aldrich website;
  • 4,4'-dichlorodiphenyl sulfone Commercial products can be ordered from the Aldrich website;
  • 2,4-difluorodiphenyl sulfone Commercial products can be ordered from the Aldrich website;
  • 4,4-difluorodiphenyl sulfone Commercial products can be ordered from the Aldrich website;
  • Sulfolane Commercial products can be ordered from the Aldrich website;
  • Anhydrous sodium carbonate Commercial products can be ordered from the Aldrich website;
  • Weight average molecular weight Mw using DMF as a solvent, passing the GPC test;
  • Tensile modulus ISO 527-2, tensile rate 10 mm/min;
  • the azeotrope formed by the water and xylene produced in the system is blown out by the protective gas to the condensation tube and condensed and dropped to the water separator for stratification.
  • the upper layer of xylene It is also refluxed into the system; the temperature is maintained in the range of 200 ° C to 210 ° C.
  • the collected water volume is close to the theoretical value (5.4 g)
  • the reflux is continued for another 20 minutes, and no drops of water are observed, which proves that the salt is completely formed and then distilled.
  • the composition of the sulfone polymer the composition of the sulfone polymer; the weight average molecular weight, melt viscosity, tensile strength, tensile modulus, elongation at break, flexural strength, flexural modulus, and notch of the composition of the obtained sulfone polymer
  • performance indexes such as impact strength, light transmittance, yellowness index and haze are shown in Table 1.
  • Comparative example 1 Comparative example 2 4,4'-dichlorodiphenyl sulfone/mol 0.3045 2,4-dichlorodiphenyl sulfone / mol 4,4'-dihydroxydiphenyl sulfone/mol 0.3 0.3 2,4'-dihydroxydiphenyl sulfone/mol 4,4'-difluorodiphenyl sulfone/mol 0.3015 2,4-difluorodiphenyl sulfone/mol Molecular weight Mw/ ⁇ 10 4 5.15 5.47 Melt viscosity / P ⁇ s 281 289 Tensile strength / MPa 88.9 90.4 Tensile modulus / MPa 2690 2710 Elongation at break /% 16.2 11.5 Bending strength / MPa 125 124 Flexural modulus / MPa 2620 2620 Notched impact strength / kJ / m 2 11.5 14.2 Transmittance/% 79.3 78
  • the application of the composition of the sulfone polymer to the high temperature polymer can also significantly improve the processing fluidity, transparency, heat resistance and color of the final product; when the composition of the sulfone polymer is present on the benzene ring structure
  • the ortho-etheroxy group isomer content is less than 1:100,000, and as shown in Comparative Examples 1 and 2, the composition of the sulfone polymer is inferior in processing fluidity, transparency, and heat resistance.

Abstract

本发明公开了一种砜聚合物的组合物，其中分子链结构以苯环为骨架，在苯环的对位以砜基和醚氧键相连，同时苯环上存在邻位的醚氧基取代基异构体，具有包括式I和式II的结构通式：其中，式I中的m为大于0的正整数，n为大于0的正整数；式II中的x为大于0的正整数。当砜聚合物的组合物的苯环结构上存在特定含量的邻位醚氧基取代基异构体时，能够使该砜聚合物的组合物获得难以预料的性能改善，包括改善的加工流动性、力学性能和颜色，同时其透明度和耐热性能有明显提高。同时，将该砜聚合物的组合物应用于与其它高分子聚合物任意比例共混改性、或应用于包括染色，填充，纤维增强的其它共混改性中而同样具有良好的相容性。

Description

一种砜聚合物的组合物及其制备方法与应用 技术领域
本发明涉及砜聚合物组合物技术领域，特别是涉及一种砜聚合物的组合物及其制备方法与应用。
背景技术
聚合物是一个用于描述包含至少一个醚基(-O-)、至少一个砜基(-SO2-)以及至少一个亚芳基的任何聚合物的属类名。一组商业上重要的聚(芳基醚砜)包含在此被指定为PESU的砜聚合物，该PESU的砜聚合物因机械强度高、耐热性和耐氧化性、耐水解以及耐许多酸/碱和溶剂而被众所周知。PESU通过二卤二苯砜与二羟基二苯砜的反应单元缩聚制得。PESU是一种耐高温无定型工程热塑性树脂，具有约225℃的玻璃化转变温度，并且从-40℃至210℃展示了高的强度以及韧性。因为该聚合物是完全无定型的，所以还具有突出的透光性，从而在许多最终应用中具有独特优势。由于它们优异的机械和热学性能，以及出色的水解稳定性和耐化学性，已经用于制备广泛范围的最终使用温度的各种各样应用中的产品，诸如管道物品、餐饮服务物品、医疗托盘、隔膜等等，包括要求与水、食品、药物和/或血液接触的那些应用要求使用满足被诸如食品与药品管理局(Food and Drug Administration)(FDA)、欧洲食品安全署和环境保护署(European Food Safety Agency and the Environmental Protection Agency)(EPA)的组织强制执行的某些要求的聚合材料。
随着市场对这类聚合物的应用领域的开拓和发展，一些苛刻条件下的应用越来越多，为此，对产品性能也提出了更高的要求，例如机械工业领域需要精密的部件或零件，要求更好的加工流动性；食品、医疗、水暖等领域的应用，要求更好的透明度、韧性、尺寸稳定性和耐热性能。针对上述改进要求，本领域技术人员也从各种角度进行技术开发，包括容易在工业规模上生产、成本适中、良好的或改进的机械性能(诸如值得注意的屈服伸长率)以及热性能。
国内外专利对改善砜聚合物的流动性、热稳定性、颜色和透明度的报道多有公布，如 EP2011053675公布了加入超支化聚合物以改善砜聚合物的流动性，US4957978通过加入低玻璃化转变温度的聚合物以改善流动性，US4855388利用钠、锂、碱土金属或镧系金属盐作为聚芳醚砜的稳定剂，抑制聚合物在氟离子存在下发生降解，以提高聚合物的热稳定性，US5008364公布了控制碱金属盐含量不超过100ppm以提高高温稳定，制备具有改善的熔融稳定性的热塑性模塑材料，US2003011501提到加入熔体稳定剂改善颜色和透明度，US6593445公布通过控制K2CO3的粒径来改善聚芳醚砜的颜色，获得浅色的聚芳醚砜产物。
以上报道未涉及分子链本身的结构变化对材料性能的影响问题。本发明人意外地发现，当砜聚合物的组合物的苯环结构上存在特定含量的邻位醚氧基取代基异构体时，能够使该砜聚合物的组合物获得难以预料的性能改善，包括改善的加工流动性、力学性能和颜色，同时其透明度和耐热性能有明显提高。同时，将该砜聚合物的组合物应用于与其它高分子聚合物任意比例共混改性、或应用于包括染色，填充，纤维增强的其它共混改性中而同样具有良好的相容性。
发明内容
为了克服现有技术的缺点与不足，本发明的首要目的在于提供一种具有改善的加工流动性、力学性能和颜色，同时其透明度和耐热性能有明显提高的砜聚合物的组合物。
本发明的另一目的是提供上述砜聚合物的组合物的制备方法。
本发明的再一目的是提供上述砜聚合物的组合物的用途。
本发明是通过如下技术方案实现的：
一种砜聚合物的组合物，其中分子链结构以苯环为骨架，在苯环的对位以砜基和醚氧键相连，同时苯环上存在邻位的醚氧基取代基异构体，具有包括式I和式II的结构通式：
Figure PCTCN2016109986-appb-000001
Figure PCTCN2016109986-appb-000002
其中，式I中的m为大于0的正整数，n为大于0的正整数；式II中的x为大于0的正整数。
其中，所述砜聚合物的组合物式I的结构通式中m：n的比例为1：100000-5：100，优选为1：2000-3：100。
一种上述砜聚合物的组合物的制备方法，所述砜聚合物的组合物采用合成单体包括二卤基砜化合物和二羟基砜化合物通过溶液法缩聚制备得到，具体步骤如下：
在装有温度计、通氮气管、冷凝分水器、搅拌器的三口烧瓶中按照配比依次加入4,4’-二卤基二苯砜、4,4’-二羟基二苯砜、2,4-二羟基二苯砜、2,4’-二卤基二苯砜，再加入490.3g溶剂，搅拌并升温至100℃溶解单体至溶液透明，加入34.98g成盐剂，随后加入70mL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(5.4g)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，恒温3小时，直至搅拌电机扭矩不变，说明体系粘度基本恒定；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，即得砜聚合物的组合物。
其中溶剂添加量占该砜聚合物的组合物总质量的10wt％-50wt％，成盐剂的添加量以不低于二羟基砜化合物的摩尔量为宜，一般以成盐剂的摩尔量比二羟基砜化合物的摩尔量多1mol％-15mol％为宜。
其中，所述二卤基砜化合物选自结构通式为VI的4,4’-二卤基二苯砜和/或结构通式为V的2,4-二卤基二苯砜，所述二羟基砜化合物选自结构通式为II的4,4’-二羟基二苯砜和/或结构通式为III的2,4-二羟基二苯砜；
Figure PCTCN2016109986-appb-000003
Figure PCTCN2016109986-appb-000004
其中，X，X'为相同或不同的卤素，优选Cl和/或F；合成单体III和/或V与合成单体II和/或VI的摩尔比例为1：100000-5：100，优选为1：2000-3：100。实验发现，如果不存在醚氧基取代基异构体，则该砜聚合物的组合物的流动性和透明度下降，如果砜聚合物的组合物中邻位的醚氧基取代基异构体含量过高则会影响该砜聚合物的组合物的力学性能，包括拉伸模量和/或弯曲模量下降。
其中，所述溶剂选自二苯砜、环丁砜、二甲基砜、N-甲基吡咯烷酮、二甲基亚砜、N-甲基甲酰胺、N-甲基乙酰胺、联苯基苯亚磺酰中的一种或多种；优选为环丁砜、N-甲基吡咯烷酮、二甲基亚砜中的一种或多种。
其中，所述成盐剂选自碱、碱金属碳酸盐、碱金属碳酸氢盐中的一种或多种；优选为KOH、NaOH、K2CO3、Na2CO3、KHCO3、NaHCO3中的一种或多种。
本发明还公开了上述砜聚合物的组合物的制备方法得到的砜聚合物的组合物应用于包括航空航天、医疗卫生，食品安全，家用电器，电子电器，能源化工应用领域的耐高温，耐溶剂和透明条件。
本发明还公开了上述砜聚合物的组合物的制备方法得到的砜聚合物的组合物应用于与其它高分子聚合物任意比例共混的应用；所述其它高分子聚合物选自高温工程塑料和/或通用工程塑料；所述高温工程塑料选自PI、PAI、PEI、LCP、PEEK、PPS中的一种或几种；所述通用工程塑料选自PA、PS、PC中的一种或几种。
本发明还公开了上述砜聚合物的组合物的制备方法得到的砜聚合物的组合物应用于其它 共混改性中的应用；所述其它共混改性选自染色、填充、纤维增强中的一种或几种；所述染色为采用有机和/或无机色粉进行染色；所述填充选自无机物进行填充；所述纤维增强选自玻璃纤维和/或碳纤维进行纤维增强。
与现有技术相比，本发明具有如下有益效果：
当砜聚合物的组合物的苯环结构上存在特定含量的邻位醚氧基取代基异构体时，能够使该砜聚合物的组合物获得难以预料的性能改善，包括改善的加工流动性、力学性能和颜色，同时其透明度和耐热性能有明显提高。同时，将该砜聚合物的组合物应用于与其它高分子聚合物任意比例共混改性、或应用于包括染色，填充，纤维增强的其它共混改性中而同样具有良好的相容性。
附图说明
图1为砜聚合物的组合物的苯环结构上存在邻位醚氧基取代基异构体的核磁共振NMR的13C谱图；δ＝121.25，129.74，139.29的化学位移证明存在邻位的醚氧基取代基异构体；
图2为实施例1、5、8和对比例1的热稳定性变化图。
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。
本发明的实施例及对比例采用如下原料，但不仅限于这些原料：
4,4’-二羟基二苯砜：可从Aldrich网站订购商业化产品；
2,4-二羟基二苯砜：可从Aldrich网站订购商业化产品；
2,4-二氯二苯砜：可从Aldrich网站订购商业化产品；
4,4’-二氯二苯砜：可从Aldrich网站订购商业化产品；
2,4-二氟二苯砜：可从Aldrich网站订购商业化产品；
4,4-二氟二苯砜：可从Aldrich网站订购商业化产品；
环丁砜：可从Aldrich网站订购商业化产品；
无水碳酸钠：可从Aldrich网站订购商业化产品；
各性能的测试标准或方法：
重均分子量Mw：采用DMF为溶剂，通过GPC测试；
熔体粘度：ISO 1133，360℃，剪切速率1000-1；
拉伸强度：ISO 527-2，拉伸速率10mm/min；
拉伸模量：ISO 527-2，拉伸速率10mm/min；
断裂伸长率：ISO 527-2，拉伸速率10mm/min；
弯曲强度：ISO 178，弯曲速率2mm/min；
弯曲模量：(ISO 178，弯曲速率2mm/min；
缺口冲击强度：ISO 180/1A；
透光率：ASTM D-1003；
黄度指数：ASTM D-1925；
雾度：ASTM D-1003。
实施例1-10及对比例1-2：砜聚合物的组合物的制备
在装有温度计、通氮气管、冷凝分水器、搅拌器的三口烧瓶中按照表1的配比依次加入4,4’-二卤基二苯砜、4,4’-二羟基二苯砜、2,4-二羟基二苯砜、2,4’-二卤基二苯砜，再加入490.3g溶剂，搅拌并升温至100℃溶解单体至溶液透明，加入34.98g成盐剂，随后加入70mL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(5.4g)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，恒温3小时，直至搅拌电机扭矩不变，说明体系粘度基本恒定；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，即得砜聚合物的组合物；制备得到的砜聚合物的组合物的重均分子量、熔体粘度、拉伸强度、拉伸模量、断裂伸长率、弯曲强度、弯曲模量、缺口冲击强度、透光率、黄度指数和雾度等性能指标测试结果如表1所示。
表1实施例1-10及对比例1-2的合成单体配比及各性能指标测试结果
Figure PCTCN2016109986-appb-000005
续表1
  对比例1 对比例2
4,4’-二氯二苯砜/mol 0.3045  
2,4-二氯二苯砜/mol    
4,4’-二羟基二苯砜/mol 0.3 0.3
2,4’-二羟基二苯砜/mol    
4,4’-二氟二苯砜/mol   0.3015
2,4-二氟二苯砜/mol    
分子量Mw/×104 5.15 5.47
熔体粘度/P·s 281 289
拉伸强度/MPa 88.9 90.4
拉伸模量/MPa 2690 2710
断裂伸长率/％ 16.2 11.5
弯曲强度/MPa 125 124
弯曲模量/MPa 2620 2620
缺口冲击强度/kJ/m2 11.5 14.2
透光率/％ 79.3 78.6
黄度指数 17.32 18.65
雾度/％ 8.57 8.98
从表1的实施例1-10及对比例1-2的比较可以看出：当砜聚合物的组合物的苯环结构上存在特定含量的邻位醚氧基取代基异构体时，能够使该砜聚合物的组合物获得难以预料的性能改善，包括改善的加工流动性、力学性能和颜色，同时其透明度和耐热性能有明显提高。从图2的热稳定性变化趋势可以看出，用毛细管流变仪检测物料经过长时间受热后的粘度变化率表征物料热稳定性，条件是360℃，恒定剪切速率1000-1，时间2小时，可以看出实施例1、5、8比对比例1 经过2h后的粘度变化率小，说明热稳定性提高。同时，将该砜聚合物的组合物应用到高温聚合物中，同样能够明显改善最终制品的加工流动性、透明度、耐热性和颜色；当砜聚合物的组合物的苯环结构上存在的邻位醚氧基取代基异构体含量小于1:100000，如对比例1和2所示，该砜聚合物的组合物的加工流动性、透明度和耐热性能较差。

Claims (8)

  1. 一种砜聚合物的组合物，其中分子链结构以苯环为骨架，在苯环的对位以砜基和醚氧键相连，同时苯环上存在邻位的醚氧基取代基异构体，具有包括式I和式II的结构通式：
    Figure PCTCN2016109986-appb-100001
    其中，式I中的m为大于0的正整数，n为大于0的正整数；式II中的x为大于0的正整数。
  2. 一种如权利要求1所述的砜聚合物的组合物，其特征在于，所述砜聚合物的组合物式I的结构通式中m：n的比例为1：100000-5：100，优选为1：2000-3：100。
  3. 一种如权利要求1或2所述的砜聚合物的组合物的制备方法，其特征在于，所述砜聚合物的组合物通过溶液法缩聚制备得到，采用的合成单体包括二卤基砜化合物和二羟基砜化合物；其中，所述二羟基砜化合物选自结构通式为II的4,4’-二羟基二苯砜和/或结构通式为III的2,4-二羟基二苯砜，所述二卤基砜化合物选自结构通式为VI的4,4’-二卤基二苯砜和/或结构通式为V的2,4-二卤基二苯砜；
    Figure PCTCN2016109986-appb-100002
    Figure PCTCN2016109986-appb-100003
    其中，X，X'为相同或不同的卤素，优选Cl和/或F；合成单体III和/或V与合成单体II和/或VI的摩尔比例为1：100000-5：100，优选为1：2000-3：100。
  4. 根据权利要求3所述的砜聚合物的组合物的制备方法，其特征在于，所述溶剂选自二苯砜、环丁砜、二甲基砜、N-甲基吡咯烷酮、二甲基亚砜、N-甲基甲酰胺、N-甲基乙酰胺、联苯基苯亚磺酰中的一种或多种；优选为环丁砜、N-甲基吡咯烷酮、二甲基亚砜中的一种或多种。
  5. 根据权利要求3所述的砜聚合物的组合物的制备方法，其特征在于，所述成盐剂选自碱、碱金属碳酸盐、碱金属碳酸氢盐中的一种或多种；优选为KOH、NaOH、K2CO3、Na2CO3、KHCO3、NaHCO3中的一种或多种。
  6. 如权利要求3-5任一项所述的砜聚合物的组合物的制备方法得到的砜聚合物的组合物应用于包括航空航天、医疗卫生，食品安全，家用电器，电子电器，能源化工应用领域的耐高温，耐溶剂和透明条件。
  7. 如权利要求3-5任一项所述的砜聚合物的组合物的制备方法得到的砜聚合物的组合物应用于与其它高分子聚合物任意比例共混的应用；所述其它高分子聚合物选自高温工程塑料和/或通用工程塑料；所述高温工程塑料选自PI、PAI、PEI、LCP、PEEK、PPS中的一种或几种；所述通用工程塑料选自PA、PS、PC中的一种或几种。
  8. 如权利要求3-5任一项所述的砜聚合物的组合物的制备方法得到的砜聚合物的组合物应用于其它共混改性中的应用；所述其它共混改性选自染色、填充、纤维增强中的一种或几种；所述染色为采用有机和/或无机色粉进行染色；所述填充选自无机物进行填充；所述纤维增强选自玻璃纤维和/或碳纤维进行纤维增强。
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