WO2020252967A1 - 制备超支化聚硫醚的方法 - Google Patents

制备超支化聚硫醚的方法 Download PDF

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WO2020252967A1
WO2020252967A1 PCT/CN2019/107484 CN2019107484W WO2020252967A1 WO 2020252967 A1 WO2020252967 A1 WO 2020252967A1 CN 2019107484 W CN2019107484 W CN 2019107484W WO 2020252967 A1 WO2020252967 A1 WO 2020252967A1
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hyperbranched
polysulfide
monomer
preparing
tris
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李小杰
魏玮
刘仁
刘晓亚
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Jiangnan University
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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
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules

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  • the invention relates to the field of organic polymers, in particular to a method for preparing hyperbranched polysulfide.
  • sulfur-containing hyperbranched polymers Due to the existence of sulfur atoms, sulfur-containing hyperbranched polymers have special functions that conventional hyperbranched polymers (HBP) do not possess, and have received more and more attention.
  • HBP hyperbranched polymers
  • the sulfhydryl click chemistry reaction has gradually become the main reaction for the preparation of sulfur-containing hyperbranched polymers due to its high reactivity, mild and efficient reaction, and wide monomer applicability.
  • the preparation methods of hyperbranched polymers mainly include two methods, AB 2 and A 2 +B 3 , and the synthesis of sulfur-containing hyperbranched polymers is mainly based on the AB 2 method.
  • Gao Chao of Zhejiang University Han J, Zhao B, Tang A, et al.
  • the present invention provides a method for preparing hyperbranched polysulfide:
  • the trifunctional trithiol monomers and difunctional glycidyl acrylate monomers are used as raw materials.
  • the trifunctional trithiol monomers and difunctional glycidyl acrylate monomers The volume molar ratio is 1:0.8 to 2.4, preferably 1:2.0 to 2.4.
  • the method is to mix a trifunctional trithiol monomer, a difunctional glycidyl acrylate monomer, a catalyst and a solvent, react for 2 to 48 hours and then purify to obtain a hyperbranched polysulfide.
  • the added amount of the catalyst is 0.5-5 mol% of the monomer amount; the purification includes rotary evaporation and concentration, dissolution-precipitation operation, and vacuum drying of the precipitate.
  • the concentration of the trifunctional trithiol monomer and the difunctional glycidyl acrylate monomer is in the range of 0.1-1.0 g mL -1 .
  • the solvent includes tetrahydrofuran, dioxane, dimethyl sulfoxide and N,N-dimethylformamide
  • the catalyst includes triethylamine, dimethylaminopyridine, 1,8-bis Azabicyclo[5,4,0]undec-7-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene; the temperature of the reaction is 20 ⁇ 100°C.
  • the trifunctional trithiol monomer includes trimethylolpropane-tris(3-mercaptopropionate), 1,3,5-benzenetrithiol, tris(2-hydroxyethyl) iso Cyanurate-tris(3-mercaptopropionate), diethanolamine-tris(3-mercaptopropionate); difunctional glycidyl acrylate monomers include glycidyl methacrylate.
  • Another object of the present invention is to provide a hyperbranched polysulfide prepared according to any of the above methods.
  • the hyperbranched polysulfide skeleton contains sulfide and hydroxyl, and the end groups can be effectively controlled to be mercapto groups or epoxy groups by the molar ratio of monomers, the number average molecular weight is 2.5-60 kDa, and the polydispersity index is 1.2-2.0.
  • the Mark-Houwink index ⁇ is 0.2 to 0.5.
  • hyperbranched polysulfide has the following structure:
  • hyperbranched polysulfide has the following structure:
  • the present invention uses difunctional glycidyl acrylate compound as AC monomer (A represents acrylate group, C represents epoxy group), trifunctional thiol is B 3 monomer, and one-pot synthesis of structural hyperbranched ⁇ polysulfide.
  • the reactivity of acrylate double bond and mercapto group in AC monomer is much higher than epoxy group.
  • the invention has easy-to-obtain raw materials, simple steps, fast polymerization rate and good controllability.
  • the end groups of the hyperbranched polymer can be adjusted to be mercapto groups or epoxy groups, and both can be further functionally modified.
  • this method has the advantages of not easy to gel, simple and easy to operate, and high controllability.
  • Figure 1 is the infrared absorption spectrum of the mercapto-terminated hyperbranched polysulfide P3 and the monomer glycidyl methacrylate (GMA) prepared in Example 3.
  • Figure 2 is a hydrogen NMR spectrum of the mercapto-terminated hyperbranched polysulfide P3 and the monomer glycidyl methacrylate (GMA) prepared in Example 3.
  • Figure 3 is a GPC elution time curve of the mercapto-terminated hyperbranched polysulfide P3 prepared in Example 3.
  • Figure 5 is a hydrogen nuclear magnetic spectrum of epoxy-terminated hyperbranched polysulfide P7 prepared in Example 7.
  • Cases 1-10 are the preparation cases of hyperbranched polysulfide.
  • Figure 1 is the infrared absorption spectrum of the mercapto-terminated hyperbranched polysulfide P3 and the monomer glycidyl methacrylate (GMA) prepared in Example 3, where the stretching vibration absorption peak of OH at 3505cm -1 in the P3 spectrum characteristic peaks, 2570cm -1 is a characteristic absorption peak at a mercapto group, 910cm -1 at the disappearance of epoxy, P3 is a proof of mercapto-terminated;
  • Figure 2 is the hydrogen NMR spectrum of the sulfhydryl-terminated hyperbranched polysulfide P3 and the monomer glycidyl methacrylate (GMA) prepared in Example 3.
  • the proton signal peak of the double bond at 5.58-6.43 ppm disappears and at 1.65 ppm
  • the proton signal of the sulfhydryl group is weakened, the characteristic absorption peak of epoxy at 3.28ppm disappears, and the proton signal of the methylene adjacent to the S atom at 2.48-2.85ppm increases, which further proves that the end group of P3 is a sulfhydryl group;
  • Figure 3 is the GPC elution time curve of the sulfhydryl-terminated hyperbranched polysulfide P3 prepared in Example 3.
  • linear PS as a standard sample
  • PDI 1.57 .
  • the absolute molecular weight of P3 is 28.8kDa
  • Mark-Houwink index ⁇ is 0.342, which is within the range of 0.2-0.5 of hyperbranched polymer , Which proves that P3 has a highly branched structure.
  • FIG 4 is an end P7 epoxidized hyperbranched polythioethers infrared absorption spectrum of FIG. 7 embodiment Case prepared, wherein absorption peak at 3505cm -1 is the stretching vibration of OH, 910cm -1 is a characteristic peak at an epoxy, 2540cm -1 The characteristic absorption peak of the sulfhydryl group disappeared, proving that P7 is epoxy-terminated;
  • Figure 5 is the hydrogen NMR spectrum of the epoxy-terminated hyperbranched polysulfide P7 prepared in Example 7.
  • the proton signal peak of the double bond at 5.58-6.43 ppm disappears, the proton signal of the mercapto group at 1.65 ppm disappears, and the epoxy at 3.28 ppm
  • the characteristic absorption peak of P7 is weakened, and the methylene proton signal adjacent to the S atom at 2.48-2.85ppm is strengthened, which further proves that P7 is epoxy-terminated;
  • Figure 6 is the GPC elution time curve of epoxy-terminated hyperbranched polysulfide P7 prepared in Example 7.
  • the molar ratio is the molar ratio of the trifunctional trithiol monomer and the difunctional glycidyl acrylate monomer.
  • M w, GPC (kg/mol) and M w, GPC /M n, GPC were measured by gel permeation chromatography (Waters GPC 486), using linear polystyrene (PS) as the standard sample and tetrahydrofuran (THF) as Eluent.
  • PS linear polystyrene
  • THF tetrahydrofuran
  • M w, MALLS (kg/mol) and ⁇ are measured by the gel permeation chromatography-multi-angle laser light scattering-viscosity triple system (GPC-MALLS, DAWN HELEOS II System).
  • the original data is processed with Astra VI software, the absolute weight average molecular weight M w,MALLS (kg/mol) of the sample is fitted by dn/dc, and the mark is fitted by the intrinsic viscosity and absolute weight average molecular weight. Howenk Index ⁇ .
  • the hyperbranched polysulfide prepared by the method of the present invention has a highly branched structure, and according to the method of the present invention, the end group of the hyperbranched polymer can be adjusted to be a mercapto group by changing the molar ratio of monomers. Or epoxy groups.

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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)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

一种基于选择性巯基-烯和巯基-环氧点击化学制备超支化聚硫醚的方法。以二官能度丙烯酸缩水甘油酯类单体和三官能度硫醇为原料，一锅法合成骨架和端基均可调控的超支化聚硫醚。原料易得、步骤简单、聚合速率快且可控性好，制备的超支化聚硫醚的骨架可调控，端基可以利用单体摩尔比有效控制为巯基或环氧，均可以进一步进行功能化改性，从而制备具有特定性能的超支化聚硫醚。

Description

一种制备超支化聚硫醚的方法 技术领域
本发明涉及有机高分子领域，具体地涉及一种制备超支化聚硫醚的方法。
背景技术
含硫超支化聚合物由于硫原子的存在，具备常规超支化聚合物(HBP)不具备的特殊功能性，受到了越来越多的重视。巯基点击化学反应由于其较高的反应活性、反应温和高效、单体适用性广，逐渐成为制备含硫超支化聚合物的主要反应。目前超支化聚合物的制备方法主要有AB 2和A 2+B 3两种方法，而含硫超支化聚合物的合成以AB 2法为主。其中，浙江大学的高超等(Han J,Zhao B,Tang A,et al.Polymer Chemistry,2012,3(7):1918-1925.)以3,6-二氧杂辛烷-1,8-二巯基和炔丙基溴为原料制备了一端为巯基，一端为炔烃的AB 2单体，然后利用巯基-炔点击化学反应将AB 2单体聚合制备得到端基为炔的超支化聚硫醚，可以应用在金属离子吸附、耐油性、抗氧化性树脂等领域；Gadwal等(Gadwal I,Binder S,Stuparu M C,et al.Macromolecules,2014,47(15):5070-5080.)通过系列有机合成制备了含有两个环氧基团和一个巯基的AB 2单体，进而利用巯基-环氧点击化学反应制备了端基为环氧的超支化聚硫醚；但由于AB 2型单体种类极少、单体制备过程繁琐，而A 2+B 3聚合体系缺乏选择性，在聚合过程中具有凝胶化风险，严重限制了超支化聚硫醚的制备及应用。此外，受限于单体结构及聚合体系，目前报道的AB 2和A 2+B 3体系大多只能制备特定骨架及端基的超支化聚硫醚，较难同时调控超支化聚硫醚的骨架及端基基团，从而限制了超支化聚硫醚的功能及应用领域。
发明内容
本发明为了解决上述问题，提供了一种制备超支化聚硫醚的方法：
以二官能度丙烯酸缩水甘油酯类单体和三官能度硫醇为原料，一锅法制备超支化聚硫醚，所述三官能度三硫醇单体和二官能度丙烯酸缩水甘油酯类单体摩尔比为1:0.8～2.4，优选为1:2.0～2.4。
进一步地，所述方法为将三官能度三硫醇单体、二官能度丙烯酸缩水甘油酯类单体、催化剂和溶剂混合，反应2～48h后纯化得到超支化聚硫醚。
进一步地，所述催化剂的添加量为单体量的0.5～5mol％；所述纯化包括旋蒸浓缩，进行溶解-沉淀操作，沉淀物真空干燥。
进一步地，所述三官能度三硫醇单体、二官能度丙烯酸缩水甘油酯类单体的浓度为 0.1～1.0g mL -1范围内。
进一步地，所述的溶剂包括四氢呋喃、二氧六环、二甲基亚砜和N,N-二甲基甲酰胺；所述的催化剂包括三乙胺、二甲氨基吡啶、1,8-双氮杂二环[5,4,0]十一碳-7-烯、1,5,7-三氮杂二环[4.4.0]癸-5-烯；所述的反应的温度为20～100℃。
进一步地，所述三官能度三硫醇单体包括三羟甲基丙烷-三(3-巯基丙酸酯)、1,3,5-苯三硫酚、三(2-羟乙基)异氰尿酸酯-三(3-巯基丙酸酯)、二乙醇胺-三(3-巯基丙酸酯)；二官能度丙烯酸缩水甘油酯类单体包括甲基丙烯酸缩水甘油酯。
本发明的另一个目的在于提供一种超支聚硫醚，按照上述任一方法制备得来。
进一步地，所述超支聚硫醚骨架含有硫醚和羟基，端基可以通过单体摩尔比有效控制为巯基或环氧基，数均分子量为2.5～60kDa，多分散性指数为1.2～2.0，马克-霍温克指数α为0.2～0.5。
进一步地，所述超支聚硫醚具有以下结构：
Figure PCTCN2019107484-appb-000001
进一步地，所述超支聚硫醚具有以下结构：
Figure PCTCN2019107484-appb-000002
本发明的优点：
本发明以二官能度丙烯酸缩水甘油酯类化合物为AC单体(A代表丙烯酸酯类基团、C代表环氧基团)，三官能度硫醇为B 3单体，一锅法合成结构超支化聚硫醚。AC单体中丙烯酸酯类双键与巯基的反应活性远高于环氧基团，通过控制反应条件，在聚合反应初期，AC单体和B 3单体反应生成CB 2或BC 2型中间体，随后进一步聚合得到骨架和端基均可调控的超支化聚硫醚，聚合体系可控且有效避免凝胶。本发明原料易得、步骤简单、聚合速率快且可控性好，通过控制单体摩尔比可以调控超支化聚合物的端基为巯基或环氧基团，均可以进一步进行功能化改性。这种方法相比于传统方法而言，具有不易于凝胶，操作简单易行，可控性高等的优点。
附图说明
图1是实施案例3制备的端巯基超支化聚硫醚P3和单体甲基丙烯酸缩水甘油酯(GMA)的红外吸收光谱图。
图2是实施案例3制备的端巯基超支化聚硫醚P3和单体甲基丙烯酸缩水甘油酯(GMA)的核磁氢谱图。
图3是实施案例3制备的端巯基超支化聚硫醚P3的GPC流出时间曲线。
图4是实施案例7制备的端环氧超支化聚硫醚P7的红外吸收光谱图。
图5是实施案例7制备的端环氧超支化聚硫醚P7的核磁氢谱图。
图6是实施案例7制备的端环氧超支化聚硫醚P7的GPC流出时间曲线。
具体实施方式
以下结合具体实施案例对本发明作进一步的阐述。应理解，本发明不限于以下实施案例，所述方法如无特别说明均视为常规方法。所述材料如无特别说明均能从公开商业途径获得。
案例1～10为超支化聚硫醚的制备案例。
实施案例1：
将9.965g(25mmol)三羟甲基丙烷-三(3-巯基丙酸酯)，75mL四氢呋喃(THF)和3.56g(25mmol)甲基丙烯酸缩水甘油酯和0.1012g(1.0mmol)三乙胺一次性加入反应器中，室温下N 2保护反应24h；反应结束后将反应液旋蒸浓缩，用氯仿重新溶解后 在无水乙醚中沉淀，重复溶解-沉淀操作3次，沉淀物真空干燥后得到无色粘性端巯基超支化聚硫醚P1(9.50g，产率为70.4％)。
实施案例2：
将9.965g(25mmol)三羟甲基丙烷-三(3-巯基丙酸酯)、75mL N,N-二甲基甲酰胺(DMF)、3.56g(25mmol)甲基丙烯酸缩水甘油酯和0.1222g(1.0mmol)N,N-二甲基吡啶一次性加入反应器中，室温下N 2保护反应24h；反应结束后将反应液旋蒸浓缩，用氯仿重新溶解后在无水乙醚中沉淀，重复溶解-沉淀操作3次，沉淀物真空干燥后得到无色粘性端巯基超支化聚硫醚P2(9.26g，产率为68.5％)。
实施案例3：
将9.965g(25mmol)三羟甲基丙烷-三(3-巯基丙酸酯)，75mL DMF和3.56g(25mmol)甲基丙烯酸缩水甘油酯和0.1522g(1.0mmol)1,8-双氮杂二环[5,4,0]十一碳-7-烯(DBU)一次性加入反应器中，室温下N 2保护反应24h；反应结束后将反应液旋蒸浓缩，用氯仿重新溶解后在无水乙醚中沉淀，重复溶解-沉淀操作3次，沉淀物真空干燥后得到无色粘性端巯基超支化聚硫醚P3(8.57g，产率为63.4％)。
图1是实施案例3制备的端巯基超支化聚硫醚P3和单体甲基丙烯酸缩水甘油酯(GMA)的红外吸收光谱图，其中P3谱图中3505cm -1处为OH的伸缩振动吸收峰，2570cm -1处为巯基的特征吸收峰，910cm -1处环氧的特征峰消失，证明P3为巯基封端；
图2是实施案例3制备的端巯基超支化聚硫醚P3和单体甲基丙烯酸缩水甘油酯(GMA)的核磁氢谱图,5.58-6.43ppm处双键的质子信号峰消失，1.65ppm处巯基的质子信号减弱，3.28ppm处环氧的特征吸收峰消失，2.48-2.85ppm处与S原子相邻的亚甲基质子信号增强，进一步证明P3的端基为巯基；
图3是实施案例3制备的端巯基超支化聚硫醚P3的GPC流出时间曲线，以线性PS作为标准样，从GPC流出时间曲线拟合出P3的相对分子量M w＝7.6kDa，PDI＝1.57。利用光散射-粘度-GPC三联用，结合dn/dc值0.0580拟合出P3的绝对分子量分别是28.8kDa，马克-霍温克指数α为0.342，在超支化聚合物的0.2-0.5范围之内，证明P3具有高度支化结构。
实施案例4：
将4.357g(25mmol)1,3,5-苯三硫酚、40mL DMF、3.56g(25mmol)甲基丙烯酸缩水甘油酯和0.1522g(1.0mmol)1,8-双氮杂二环[5,4,0]十一碳-7-烯(DBU)一次性加入反应器中一次性加入反应器中，室温下N 2保护反应24h；反应结束后将反应液旋蒸浓 缩，用氯仿重新溶解后在无水乙醚中沉淀，重复溶解-沉淀操作3次，沉淀物真空干燥后得到无色粘性端巯基超支化聚硫醚P4(8.57g，产率为63.4％)。
实施案例5：
将13.14g(25mmol)三(2-羟乙基)异氰尿酸酯-三(3-巯基丙酸酯)(THMP)、83mL DMF、3.56g(25mmol)甲基丙烯酸缩水甘油酯和0.1522g(1.0mmol)1,8-双氮杂二环[5,4,0]十一碳-7-烯(DBU)一次性加入反应器中，室温下N 2保护反应24h；反应结束后将反应液旋蒸浓缩，用氯仿重新溶解后在无水乙醚中沉淀，重复溶解-沉淀操作3次，沉淀物真空干燥后得到无色粘性端巯基超支化聚硫醚P6(10.80g，产率为64.7％)。
实施案例6：
将9.965g(25mmol)三羟甲基丙烷-三(3-巯基丙酸酯)、75mL四氢呋喃、7.11g(50mmol)甲基丙烯酸缩水甘油酯和0.1012g(1.0mmol)三乙胺一次性加入反应器中，室温下N 2保护反应24h；反应结束后将反应液旋蒸浓缩，用氯仿重新溶解后在无水乙醚中沉淀，重复溶解-沉淀操作3次，沉淀物真空干燥后得到无色粘性端环氧超支化聚硫醚P5(9.92g，产率为58.3％)。
实施案例7：
将9.965g(25mmol)三羟甲基丙烷-三(3-巯基丙酸酯)、75mL DMF、7.11g(50mmol)甲基丙烯酸缩水甘油酯和0.1522g(1.0mmol)1,8-双氮杂二环[5,4,0]十一碳-7-烯一次性加入反应器中，室温下N 2保护反应24h；反应结束后将反应液旋蒸浓缩，用氯仿重新溶解后在无水乙醚中沉淀，重复溶解-沉淀操作3次，沉淀物真空干燥后得到无色粘性端环氧超支化聚硫醚P7(10.14g，产率为59.4％)。
图4是实施案例7制备的端环氧超支化聚硫醚P7的红外吸收光谱图，其中3505cm -1处为OH的伸缩振动吸收峰，910cm -1处为环氧的特征峰，2540cm -1处巯基的特征吸收峰消失，证明P7为环氧封端；
图5是实施案例7制备的端环氧超支化聚硫醚P7的核磁氢谱图,5.58-6.43ppm处双键的质子信号峰消失，1.65ppm处巯基的质子信号消失，3.28ppm处环氧的特征吸收峰减弱，2.48-2.85ppm处与S原子相邻的亚甲基质子信号增强，进一步证明P7为环氧封端；
图6是实施案例7制备的端环氧超支化聚硫醚P7的GPC流出时间曲线，以线性PS作为标准样，从GPC流出时间曲线拟合出P7的相对分子量为M w＝6.0kDa，PDI＝ 1.50；利用光散射-粘度-GPC三联用，结合dn/dc值0.0580拟合出P7的绝对分子量分别是25.3kDa；马克-霍温克指数α为0.394，在超支化聚合物的0.2-0.5范围之内，证明了P7具有预期的高度支化结构。
实施案例8：
将4.357g(25mmol)1,3,5-苯三硫酚、57mL四氢呋喃、7.11g(50mmol)甲基丙烯酸缩水甘油酯和0.1522g(1.0mmol)1,8-双氮杂二环[5,4,0]十一碳-7-烯(DBU)一次性加入反应器中，室温下N 2保护反应24h；反应结束后将反应液旋蒸浓缩，用氯仿重新溶解后在无水乙醚中沉淀，重复溶解-沉淀操作3次，沉淀物真空干燥后得到无色粘性端环氧的超支化聚硫醚P8(8.52g，产率为74.3％)。
实施案例9：
将13.14g(25mmol)三(2-羟乙基)异氰尿酸酯-三(3-巯基丙酸酯)(THMP)、100mL四氢呋喃、7.11g(50mmol)甲基丙烯酸缩水甘油酯和0.1522g(1.0mmol)1,8-双氮杂二环[5,4,0]十一碳-7-烯一次性加入反应器中，室温下N 2保护反应24h；反应结束后将反应液旋蒸浓缩，用氯仿重新溶解后在无水乙醚中沉淀，重复溶解-沉淀操作3次，沉淀物真空干燥后得到无色粘性端环氧的超支化聚硫醚P9(12.41g，产率为61.3％)。
实施案例1-9制备的超支化聚硫醚P1-P9的各项结构参数如下表所示。
表1
Figure PCTCN2019107484-appb-000003
注：
摩尔比为三官能度三硫醇单体和二官能度丙烯酸缩水甘油酯类单体摩尔比。
M w,GPC(kg/mol)和M w,GPC/M n,GPC由凝胶渗透色谱(Waters GPC 486)测得，以线性聚苯乙烯(PS)作为标样，以四氢呋喃(THF)为洗脱剂。
M w,MALLS(kg/mol)和α(马克-霍温克指数)由凝胶渗透色谱-多角度激光光散射-黏 度仪三联用系统(GPC-MALLS,DAWN HELEOS II System)测得，以N,N-二甲基甲酰胺(DMF)为洗脱剂，通过使用Wyatt Optilab折射率检测器(λ＝658nm)测量样品的比折射率增量(dn/dc)；利用粘度检测器表征聚合物的特性粘度；原始数据用Astra VI软件进行处理，通过dn/dc拟合出样品的绝对重均分子量M w,MALLS(kg/mol)，利用特性粘度和绝对重均分子量拟合出马克-霍温克指数α。
由上述表格可以看到应用本发明的方法所制备的超支化聚硫醚均具有高度支化结构，并且按照发明的方法可以通过单体的摩尔比的变化调控超支化聚合物的端基为巯基或环氧基团。

Claims (10)

  1. 一种制备超支化聚硫醚的方法，其特征在于，以二官能度丙烯酸缩水甘油酯类单体和三官能度硫醇为原料，一锅法制备超支化聚硫醚，所述三官能度三硫醇单体和二官能度丙烯酸缩水甘油酯类单体摩尔比为1:0.8～2.4，优选为1:2.0～2.4。
  2. 根据权利要求1所述一种制备超支化聚硫醚的方法，其特征在于，所述方法为将三官能度三硫醇单体、二官能度丙烯酸缩水甘油酯类单体、催化剂和溶剂混合，反应2～48h后纯化得到超支化聚硫醚。
  3. 根据权利要求2所述的一种制备超支化聚硫醚的方法，其特征在于，所述催化剂的添加量为单体量的0.5～5mol％；所述纯化为旋蒸浓缩后，进行溶解-沉淀操作，沉淀物真空干燥。
  4. 根据权利要求1所述一种制备超支化聚硫醚的方法，其特征在于，所述三官能度三硫醇单体、二官能度丙烯酸缩水甘油酯类单体的浓度为0.1～1.0g mL -1范围内。
  5. 根据权利要求2所述一种制备超支化聚硫醚的方法，其特征在于，所述的溶剂包括四氢呋喃、二氧六环、二甲基亚砜和N,N-二甲基甲酰胺；所述的催化剂包括三乙胺、二甲氨基吡啶、1,8-双氮杂二环[5,4,0]十一碳-7-烯、1,5,7-三氮杂二环[4.4.0]癸-5-烯；所述的反应的温度为20～100℃。
  6. 根据权利要求1所述的一种制备超支化聚硫醚的方法，其特征在于，所述三官能度三硫醇单体包括三羟甲基丙烷-三(3-巯基丙酸酯)、1,3,5-苯三硫酚、三(2-羟乙基)异氰尿酸酯-三(3-巯基丙酸酯)、二乙醇胺-三(3-巯基丙酸酯)；二官能度丙烯酸缩水甘油酯类单体包括甲基丙烯酸缩水甘油酯。
  7. 一种超支聚硫醚，其特征在于，按照权利要求1～6任一方法制备得来。
  8. 一种超支聚硫醚，其特征在于，所述超支聚硫醚骨架含有硫醚和羟基，端基可以通过单体摩尔比有效控制为巯基或环氧，数均分子量为2.5～60kDa，多分散性指数为1.2～2.0，马克-霍温克指数α为0.2～0.5。
  9. 根据权利要求7所述的一种超支聚硫醚，其特征在于，所述超支聚硫醚具有以下结构：
    Figure PCTCN2019107484-appb-100001
  10. 根据权利要求7所述的一种超支聚硫醚，其特征在于，所述超支聚硫醚具有以下结构：
    Figure PCTCN2019107484-appb-100002
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