WO2018113495A1 - 一种含甲氧基二苯砜醚基的聚醚砜树脂及其合成方法和应用 - Google Patents

一种含甲氧基二苯砜醚基的聚醚砜树脂及其合成方法和应用 Download PDF

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WO2018113495A1
WO2018113495A1 PCT/CN2017/113749 CN2017113749W WO2018113495A1 WO 2018113495 A1 WO2018113495 A1 WO 2018113495A1 CN 2017113749 W CN2017113749 W CN 2017113749W WO 2018113495 A1 WO2018113495 A1 WO 2018113495A1
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sulfone
methoxydiphenyl
ether group
component
methoxy
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PCT/CN2017/113749
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English (en)
French (fr)
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代惊奇
高红军
陈锐斌
孙学科
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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Definitions

  • the invention belongs to the technical field of polymer materials, and particularly relates to a polyether sulfone resin containing methoxydiphenyl sulfone ether group, a synthesis method and application thereof.
  • the production monomer used in the commercially available polyethersulfone (PES) is bischlorodiphenyl sulfone, and for the thermal stability and molecular weight considerations, the terminal groups of the polymer chain contain a compound bond chlorine, and the general content is 3,000 ppm or more.
  • the level of halogen, especially chlorine, bound to the polymer is too high for many applications due to the potential for corrosion of the metal and generally does not meet the flame retardant requirements.
  • Applications in the electronics field such as switches, circuit breakers, fuses, IC holders, housings, foils, typically require very low chlorine content, such as less than 900 ppm.
  • known biphenyl polyether sulfone polymers also have a relatively high residual solvent content.
  • the preparation method of preparing low-chlorine content PPSU disclosed by the patent CN102365312B is to reduce the chlorine end group content to 800 ppm or less by adding monochlorodiphenyl sulfone, and at the same time, the elongation at break can be improved and the low shear can be improved. Fluidity, but studies have found that monochlorine and phenyl sulfone are less active, resulting in more residual unreacted monomer, which is not easily removed during post-treatment purification, resulting in heat resistance and color of the resin. Significant changes, and bubbles will be generated due to the gasification of small molecules, posing a hidden danger to normal use.
  • the method for preparing PPSU disclosed in the patent CN 102498158 A is to prepare a resin having a chlorine end group content of less than 400 ppm and a light color by adding a metal hydroxide aqueous solution in the late stage of polymerization, but the preparation process is difficult to stably control and exist.
  • Safety hazard because in the polymerization stage, the material system is at a high temperature higher than 190 ° C, if the addition of aqueous solution will produce a large amount of water vapor and high temperature material splashes or even spray out of the polymerization equipment.
  • the primary object of the present invention is to overcome the above-mentioned drawbacks of the prior art and to provide a methoxy sulfone sulfone ether-containing polyether sulfone resin which has a low chlorine content, a light color, a high transparency, and does not discolor at a long-term high temperature.
  • Another object of the present invention is to provide a method for synthesizing the above methoxy phenylsulfone ether group-containing polyether sulfone resin.
  • a polyethersulfone resin containing a methoxydiphenyl sulfone ether group which has the structural formula:
  • R 1 , R 2 and R 3 each independently represent H and —OCH 3 , and two of R 1 , R 2 and R 3 are simultaneously H and the other one is —OCH 3 ;
  • R 2 and R 3 are both H and R 1 is -OCH 3 .
  • a method for synthesizing a methoxy sulfone ether-containing polyether sulfone resin as described above which comprises component A: 4,4'-dihydroxydiphenyl sulfone, component B: 4, 4 ⁇ - Dichlorodiphenyl sulfone, component C: methoxydiphenyl sulfone metal phenate is a reactive monomer, sulfolane is used as a solvent, alkali metal carbonate is used as a salt forming agent, and polymerization is carried out by solution polymerization, including the following steps. : a.
  • the methoxydiphenyl sulfone metal phenate is sodium p-methoxydiphenyl sulfonate, potassium p-methoxydiphenyl sulfonate, sodium m-dihydroxy sulfonate, m-dimethoxy benzene sulfone phenol a mixture of one or more of potassium, sodium o-methoxydiphenylsulfonate or potassium o-methoxydiphenylsulfone, preferably sodium p-methoxydiphenylsulfonate or p-methoxydiphenylsulfone One or a mixture of two of phenol potassium.
  • the molar ratio of the 4,4'-dihydroxydiphenyl sulfone to 4,4'-dichlorodiphenyl sulfone is from 1:1.001 to 1:1.05.
  • the modified polyether sulfone resin composition of the present invention further comprises at least one of a reinforcing filler, another polymer resin, a pigment or a dye.
  • the modified polyethersulfone resin composition of the present invention can be blended and modified with the above-mentioned methoxy phenylsulfone ether-based polyethersulfone tree by a general method and technology, and the reinforcing filler comprises a fibrous reinforcing filler.
  • the fibrous reinforcing material has an average fiber length of 0.01 mm to 20 mm, preferably 0.1 mm to 6 mm, and an aspect ratio of 5:1 to 2000:1, preferably 30:1 to 600:1, based on the modified biphenyl.
  • the total weight of the polyether sulfone resin composition is from 10% by weight to 50% by weight, preferably from 10% by weight to 30% by weight, based on the glass fiber, the carbon fiber, the potassium titanate fiber, and the metal clad glass.
  • the filler has an average particle diameter of 0.001 ⁇ m-100 ⁇ m, preferably 0.01 ⁇ m-50 ⁇ m, and is selected from the group consisting of potassium titanate whiskers, zinc oxide whiskers, aluminum borate whiskers, wollastonite, zeolites, ruthenium Mica, kaolin, mica, talc, sticky , pyrophyllite, bentonite, montmorillonite, hectorite, synthetic mica, asbestos, aluminosilicate
  • the modified polyethersulfone resin composition of the present invention can be modified by resin blending with other polymer resins by using the above-mentioned methoxy phenylsulfone ether group-containing polyethersulfone tree by other methods and techniques, and other polymer resins.
  • polyamide resin PA
  • PC polycarbonate resin
  • PSU polysulfone resin
  • PES polyether sulfone resin
  • LCP liquid crystal polymer
  • PEEK polyetheretherketone resin
  • PEI polyether amide Imine resin
  • PI polyimide resin
  • the modified polyethersulfone resin composition of the present invention can be used to color the above methoxy phenylsulfone ether group-containing polyethersulfone tree by a general method and technique, including inorganic and organic pigments and dyes, which can be prepared in nature. Various colors.
  • the invention also provides the use of the above methoxy phenylsulfone ether-based polyether sulfone resin in electronic appliances, such as in switches, circuit breakers, fuses, IC holders, housings, foils.
  • the invention has the following beneficial effects:
  • the invention adopts a methoxy diphenyl sulfone metal phenate monomer as a blocking agent in a PES polymer, which not only can improve the reaction degree, reduce the content of chlorine element in the molecular chain, but also has a methoxy group due to the molecular chain end group.
  • Diphenyl sulfone ether end-group structure thus higher thermal stability, and no residue, even if there is a small amount of residual monomer in the polymerization stage, it can be dissolved in the post-treatment water washing and purification stage and is easily washed out to ensure the high temperature of the resin material.
  • the obtained methoxy sulfone sulfone ether group-containing polyether sulfone resin has a chlorine content of less than 900 ppm, a light transmittance of more than 83%, and a haze of less than 30%. 3%, yellowness index less than 15, with significantly improved transparency and color levels, while having long-term resistance to high temperatures and no discoloration.
  • filter The solution was slowly placed in non-ionized water to cool into a white strip of solid, which was then crushed into a powder by a pulverizer, boiled with ion-free water for 1 hour, and filtered to remove water, and this was repeated 10 times until the filtrate was checked for turbidity by using silver nitrate. It is indicated that the by-product salt in the powder is washed away.
  • the polymer is dried to a constant weight in a vacuum oven at 120 ° C to obtain a biphenyl polyethersulfone resin containing a methoxydiphenyl sulfone ether group; the performance index test results are shown in the table. 1 is shown.
  • the chlorine content was determined by means of ion chromatography. First, prepare the sample as follows:
  • the sample was decomposed using an oxygen decomposition apparatus from IKA, and 100 mg of a sample of a polyethersulfone resin containing methoxydiphenylsulfone ether group was weighed into an ignition line and connected to the two electrodes of the decomposition apparatus.
  • acetylbutyrate capsules As the absorbing solution, 10 ml of 30% hydrogen peroxide was used, ignition was carried out under 30 bar of oxygen, the decomposing solution was filtered, placed in a vial, and finally the chloride was analyzed by ion chromatography to obtain a chlorine content.
  • Light transmittance measured with ASTM D-1003 in 2 mm thick samples
  • Yellowness index A 2 mm thick sample was measured using ASTM D-1925.
  • the present invention reduces the chlorine content by introducing a methoxydiphenyl sulfone metal phenate monomer as a blocking agent in the PES polymer, and meets the low halogen requirement of the electronic appliance.
  • the color is light, the transparency is high, and it does not change color under long-term high temperature.

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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)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明公开了一种含甲氧基二苯砜醚基的聚醚砜树脂及其合成方法和应用，其结构式为：其中，R1，R2，R3分别独立的代表H和-OCH3，且R1，R2，R3中两个同时为H，其余一个为-OCH3；； n＝2-2000。其合成方法以组分A：4,4'-二羟基二苯砜，组分B：4,4-二氯二苯砜，组分C：甲氧基二苯砜金属酚盐为反应单体，以环丁砜为溶剂，以碱金属碳酸盐为成盐剂，采用溶液聚合技术进行聚合。本发明通过在PES聚合物中引入甲氧基二苯砜金属酚盐单体作为封端剂，制备得到的该含甲氧基二苯砜醚基的聚醚砜树脂的氯含量小于900ppm，且透光率大于83％，雾度小于3％，黄度指数小于15，具有显著改善的透明度和颜色水平，同时具有长期耐高温不变色的特性。

Description

一种含甲氧基二苯砜醚基的聚醚砜树脂及其合成方法和应用 技术领域
本发明属于高分子材料技术领域，具体涉及一种含甲氧基二苯砜醚基的聚醚砜树脂及其合成方法和应用。
背景技术
市售的聚醚砜(PES)所用的生产单体为双氯二苯砜，而且为了热稳定性和分子量的考量，高分子链的端基均含化合键氯，一般含量在3000ppm以上。与聚合物键接的卤素、尤其氯的含量对于许多应用而言过高，因其存在腐蚀金属的隐患，并且通常不能符合阻燃需要。在电子领域中的应用，例如开关、断路器、熔断器、IC支架、外壳、箔，通常需要非常低的氯含量，例如小于900ppm。此外，已知的联苯聚醚砜聚合物还具有较高残留的溶剂含量。
专利CN102365312B公布的制备低氯含量的PPSU的制备方法，是通过添加单氯二苯基砜，达到降低氯端基含量至800ppm以下的效果，同时可以提高断裂伸长率和提高低剪切下的流动性，但是研究发现，单氯而苯基砜的活性较低，会产生较多未反应单体的残留，在后处理纯化过程中也不容易被除去，导致树脂的耐热性和颜色的明显变化，同时会因为小分子气化而产生气泡，给正常使用带来隐患。专利CN 102498158 A公布的制备PPSU的方法是在聚合后期通过添加金属氢氧化物水溶液的方法制备出氯端基含量低于400ppm及颜色较浅的树脂，但是这种制备工艺较难以稳定控制及存在安全隐患，因为在聚合阶段，物料体系处于高于190℃的高温，如果加入水溶液会产生大量水蒸气和高温物料飞溅甚至喷射出聚合设备。
发明内容
本发明的首要目的在于克服上述现有技术缺陷，提供一种低氯含量、颜色浅、透明度高、长期高温下不变色的含甲氧基二苯砜醚基的聚醚砜树脂。
本发明的另一目的在于提供上述含甲氧基二苯砜醚基的聚醚砜树脂的合成方法。
本发明通过如下技术方案实现：
一种含甲氧基二苯砜醚基的聚醚砜树脂，其结构式为：
Figure PCTCN2017113749-appb-000001
其中，R1，R2，R3分别独立的代表H和-OCH3，且R1，R2，R3中两个同时为H，其余一个为-OCH3；
n＝2-2000。
优选的，R2，R3同时为H，R1为-OCH3。
一种如上述的含甲氧基二苯砜醚基的聚醚砜树脂的合成方法，该方法以组分A：4,4’-二羟基二苯砜，组分B：4,4￠-二氯二苯砜，组分C：甲氧基二苯砜金属酚盐为反应单体，以环丁砜为溶剂，以碱金属碳酸盐为成盐剂，采用溶液聚合技术进行聚合，包括以下步骤：a、在装有温度计、通氮气管、冷凝分水器、搅拌器的聚合釜中依次加入4,4’-二羟基二苯砜，4,4’-二氯二苯砜，再加入环丁砜，搅拌并升温至100℃溶解单体至溶液透明，加入成 盐剂，随后加入二甲苯，继续搅拌下升温至成盐反应开始，体系中生成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；
b、维持温度在200℃-210℃的范围，当收集水量达到理论值时，再继续回流20-30min，观察不到有水珠落下，证明成盐完全，蒸馏并放出二甲苯，逐渐升温至220-240℃开始聚合反应，恒温1-3小时后，聚合反应基本完成；
c、加入甲氧基二苯砜金属酚盐继续反应20-30min，结束反应，停止搅拌和加热，加入环丁砜进行稀释后再放入过滤器中滤去固体成分，把滤液缓慢放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1-2小时，过滤去水分，如此重复，直至滤液用硝酸银检测不变浑浊，过滤后把聚合物用真空烘箱干燥至恒重，即得产品。
所述甲氧基二苯砜金属酚盐为对甲氧基二苯砜酚钠、对甲氧基二苯砜酚钾、间甲氧基二苯砜酚钠、间甲氧基二苯砜酚钾、邻甲氧基二苯砜酚钠或邻甲氧基二苯砜酚钾中的一种或几种的混合，优选为对甲氧基二苯砜酚钠或对甲氧基二苯砜酚钾中的一种或两种的混合。
所述4,4’-二羟基二苯砜与4,4’-二氯二苯砜的摩尔比为1：1.001～1：1.05。
所述组分C与组分A和组分B的摩尔数满足关系式：C＝2*(B-A)。
所述碱金属碳酸盐为Na2CO3、K2CO3或者其不同比例的混合物。
本发明还提供了一种改性聚醚砜树脂组合物，包含上述含甲氧基二苯砜醚基的聚醚砜树脂。
本发明所述的改性聚醚砜树脂组合物，还包括增强填料、其他聚合物树脂、颜料或染料中的至少一种。
本发明的改性聚醚砜树脂组合物可以将上述含甲氧基二苯砜醚基的聚醚砜树采用通用的方法和技术与增强填料进行共混改性，增强填料包括纤维状增强填料，纤维状增强材料的纤维平均长度为0.01mm-20mm，优选为0.1mm-6mm，其长径比为5:1-2000:1，优选为30:1-600:1，基于改性联苯聚醚砜树脂组合物的总重量，所述纤维状增强填料的含量为10wt％-50wt％，优选为10wt％-30wt％；选自玻璃纤维、碳纤维、钛酸钾纤维、金属包层的玻璃纤维、陶瓷纤维、硅灰石纤维、金属碳化物纤维、金属固化纤维、石棉纤维、氧化铝纤维、碳化硅纤维、石膏纤维或硼纤维的一种或几种，优选为玻璃纤维和碳纤维；也包括非纤维状填料增强，其填料平均粒径为0.001μm-100μm，优选为0.01μm-50μm，选自钛酸钾晶须、氧化锌晶须、硼酸铝晶须、硅灰石、沸石、绢云母、高岭土、云母、滑石、粘土、叶腊石、膨润土、蒙脱土、锂蒙脱土、合成云母、石棉、硅铝酸盐、氧化铝、氧化硅、氧化镁、氧化锆、氧化钛、氧化铁、碳酸钙、碳酸镁、白云石、硫酸钙、硫酸钡、氢氧化镁、氢氧化钙、氢氧化铝、玻璃珠、陶瓷珠、氮化硼、碳化硅或二氧化硅的一种或几种。
本发明的改性聚醚砜树脂组合物可以将上述含甲氧基二苯砜醚基的聚醚砜树采用通用的方法和技术与其他聚合物树脂进行树脂共混改性，其他聚合物树脂包括聚酰胺树脂(PA)，聚碳酸酯树脂(PC)，聚砜树脂(PSU)，聚醚砜树脂(PES)，液晶聚合物(LCP)，聚醚醚酮树脂(PEEK)，聚醚酰亚胺树脂(PEI)，聚酰亚胺树脂(PI)等。
本发明的改性聚醚砜树脂组合物可以将上述含甲氧基二苯砜醚基的聚醚砜树采用通用的方法和技术进行着色，包括无机和有机的颜料和染料，可以制备自然界中的各种颜色。
本发明还提供了上述含甲氧基二苯砜醚基的聚醚砜树脂在电子电器中的应用，例如在开关、断路器、熔断器、IC支架、外壳、箔中的应用。
本发明与现有技术相比，具有如下有益效果：
本发明通过在PES聚合物中引入甲氧基二苯砜金属酚盐单体作为封端剂，不但能提高反应程度，降低分子链中氯元素的含量，而且由于分子链端基含有甲氧基二苯砜醚端基结构，从而热稳定性更高，而且无残留，即使在聚合阶段有少量剩余残留单体，在后处理水洗纯化阶段也可溶解而被容易洗除，保证树脂材料的高温条件下不会因小分子残留而影响变色或产生气泡，制备得到的该含甲氧基二苯砜醚基的聚醚砜树脂的氯含量小于900ppm，且透光率大于83％，雾度小于3％，黄度指数小于15，具有显著改善的透明度和颜色水平，同时具有长期耐高温不变色的特性。
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具体的实施方式，但本发明的实施方式并不受下述实施例的限制。
本发明实施例和对比例所采用的原料均来源于市购。
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，3.505kg(33mol)成盐剂Na2CO3，随后加入2L二甲苯，继续搅拌下升温至成盐反应开始，体系中生成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，恒温2.5小时后，聚合反应基本完成；加入0.344kg(1.2mol)对甲氧基二苯砜酚钠继续反应30min，结束反应；停止搅拌和加热，加入环丁砜7kg进行稀释后再放入过滤器中滤去固体 成分，把滤液缓慢放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，即得含甲氧基二苯砜醚基的联苯聚醚砜树脂；性能指标测试结果如表1所示。
实施例2：
在聚合后期添加的0.344kg(1.2mol)对甲氧基二苯砜酚钠更换为0.344kg(1.2mol)间甲氧基二苯砜酚钠，其余制备工艺条件同实施例1。
实施例3：
在聚合后期添加的0.344kg(1.2mol)对甲氧基二苯砜酚钠更换为0.344kg(1.2mol)邻甲氧基二苯砜酚钠，其余制备工艺条件同实施例1。
实施例4：
在聚合后期添加的0.344kg(1.2mol)对甲氧基二苯砜酚钠更换为0.363kg(1.2mol)对甲氧基二苯砜酚钾，其余制备工艺条件同实施例1。
实施例5：
将原料单体4,4’-二氯二苯砜的添加量更换为8.623kg(30.03mol)，在聚合后期添加的对甲氧基二苯砜酚钠更换为17.2g(0.06mol)，其余同实施例1。
实施例6：
将原料单体4,4’-二氯二苯砜的添加量更换为8.701kg(30.3mol)，在聚合后期添加的对甲氧基二苯砜酚钠更换为0.172kg(0.6mol)，其余同实施例1。
实施例7：
将原料单体4,4’-二氯二苯砜的添加量更换为9.045kg(30.9mol)，在聚合后期添加的对甲氧基二苯砜酚钠更换为0.516kg(1.8mol)，其余同实施例1。
实施例8：
将原料单体4,4’-二氯二苯砜的添加量更换为9.045kg(31.5mol)，在聚合后期添加的对甲氧基二苯砜酚钠更换为0.86kg(3mol)，其余同实施例1。
对比例1：
在聚合后期不添加对甲氧基二苯砜酚钠，其余制备工艺条件同实施例1。
对比例2：
在聚合后期不添加对甲氧基二苯砜酚钠，其余制备工艺条件同实施例5。
对比例3：
在聚合后期不添加对甲氧基二苯砜酚钠，其余制备工艺条件同实施例8。
性能测试方法：
氯含量的测定方法：
借助离子色谱法测定氯含量。首先，如下准备样品：
为了测定氯含量，用IKA公司的氧分解装置实施样品的分解，将100毫克含甲氧基二苯砜醚基的聚醚砜树脂样品称入配有点火线并与分解装置的两个电极相连的乙酰丁酸酯胶囊中， 作为吸收溶液，使用10毫升30％的过氧化氢，在30巴氧气下实施点火，将分解溶液过滤，装入管瓶中，最后通过离子色谱法分析氯化物，通过计算得到氯含量。
用下列参数实施离子色谱法：
装置:ICS-90(公司Dionex)
柱:IonPac AS12A Analytical Column(4×200mm)
洗脱剂:2.7mM碳酸钠
0.3mM碳酸氢钠
检测:电导率检测器
流速:1ml/min。
用外标法进行评估。为此，由3种已知浓度的不同氯化物溶液测定校准曲线。
透光率：以2mm厚样品采用ASTM D-1003进行测定；
雾度：以2mm厚样品采用ASTM D-1003进行测定；
黄度指数：以2mm厚样品采用ASTM D-1925进行测定。
表1性能测试结果
Figure PCTCN2017113749-appb-000002
Figure PCTCN2017113749-appb-000003
由表1实施例和对比例的结果可以看出，本发明通过在PES聚合物中引入甲氧基二苯砜金属酚盐单体作为封端剂，降低了氯含量，满足电子电器低卤素要求，同时颜色浅、透明度高，且长期高温下不变色。

Claims (10)

  1. 一种含甲氧基二苯砜醚基的聚醚砜树脂，其结构式为：
    Figure PCTCN2017113749-appb-100001
    其中，R1，R2，R3分别独立的代表H和-OCH3，且R1，R2，R3中两个同时为H，其余一个为-OCH3；
    n＝2-2000。
  2. 根据权利要求1所述的一种含甲氧基二苯砜醚基的聚醚砜树脂，其特征在于，R2，R3同时为H，R1为-OCH3。
  3. 一种如权利要求1所述的含甲氧基二苯砜醚基的聚醚砜树脂的合成方法，其特征在于，该方法以组分A：4,4’-二羟基二苯砜，组分B：4,4
    Figure PCTCN2017113749-appb-100002
    -二氯二苯砜，组分C：甲氧基二苯砜金属酚盐为反应单体，以环丁砜为溶剂，以碱金属碳酸盐为成盐剂，采用溶液聚合技术进行聚合，包括以下步骤：
    a、在装有温度计、通氮气管、冷凝分水器、搅拌器的聚合釜中依次加入4,4’-二羟基二苯砜，4,4’-二氯二苯砜，再加入环丁砜，搅拌并升温至100℃溶解单体至溶液透明，加入成盐剂，随后加入二甲苯，继续搅拌下升温至成盐反应开始，体系中生成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；
    b、维持温度在200℃-210℃的范围，当收集水量达到达到理论值时，再继续回流20-30min，观察不到有水珠落下时，证明成盐完全，蒸馏并放出二甲苯，逐渐升温至220-240℃开始聚合反应，恒温1-3小时后，聚合反应基本完成；
    c、加入甲氧基二苯砜金属酚盐继续反应20-30min，结束反应，停止搅拌和加热，加入环丁砜进行稀释后再放入过滤器中滤去固体成分，把滤液缓慢放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1-2小时，过滤去水分，如此重复，直至滤液用硝酸银检测不变浑浊，过滤后把聚合物用真空烘箱干燥至恒重，即得产品。
  4. 根据权利要求3所述的含甲氧基二苯砜醚基的聚醚砜树脂的合成方法，其特征在于，所述甲氧基二苯砜金属酚盐为对甲氧基二苯砜酚钠、对甲氧基二苯砜酚钾、间甲氧基二苯砜酚钠、间甲氧基二苯砜酚钾、邻甲氧基二苯砜酚钠或邻甲氧基二苯砜酚钾中的一种或几种的混合，优选为对甲氧基二苯砜酚钠或对甲氧基二苯砜酚钾中的一种或两种的混合。
  5. 根据权利要求3所述的含甲氧基二苯砜醚基的聚醚砜树脂的合成方法，其特征在于，所述4,4’-二羟基二苯砜与4,4’-二氯二苯砜的摩尔比为1：1.001～1：1.05。
  6. 根据权利要求3所述的含甲氧基二苯砜醚基的聚醚砜树脂的合成方法，其特征在于，所述组分C与组分A和组分B的摩尔数满足关系式：C＝2*(B-A)。
  7. 根据权利要求3所述的含甲氧基二苯砜醚基的聚醚砜树脂的合成方法，其特征在于，所述碱金属碳酸盐为Na2CO3、K2CO3或者其不同比例的混合物。
  8. 一种改性聚醚砜树脂组合物，包含权利要求1所述的含甲氧基二苯砜醚基的聚醚砜树脂。
  9. 根据权利要求8所述的改性聚醚砜树脂组合物，其特征在于，还包括增强填料、其他聚合物树脂、颜料或染料中的至少一种。
  10. 如权利要求1所述的含甲氧基二苯砜醚基的聚醚砜树脂在电子电器中的应用。
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