WO2017193767A1 - 一种超支化聚醚酯的制备方法 - Google Patents

一种超支化聚醚酯的制备方法 Download PDF

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WO2017193767A1
WO2017193767A1 PCT/CN2017/080747 CN2017080747W WO2017193767A1 WO 2017193767 A1 WO2017193767 A1 WO 2017193767A1 CN 2017080747 W CN2017080747 W CN 2017080747W WO 2017193767 A1 WO2017193767 A1 WO 2017193767A1
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polyether ester
acid
hyperbranched polyether
nuclear
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李小杰
刘兴亮
罗静
刘晓亚
陈明清
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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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
    • C08G63/6822—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from hydroxy carboxylic acids
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/81—Preparation processes using solvents
    • 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
    • C08G83/008—Supramolecular polymers

Definitions

  • the invention relates to a preparation method of a hyperbranched polyether ester, belonging to the field of organic polymers.
  • the dendritic polymer has a highly ordered three-dimensional structure, which is very different in structure from the traditional linear polymer. It consists of a nucleus, an inner repeating unit and an outer end group, and has a high degree of geometric symmetry. , precise molecular structure, a large number of surface functional groups and internal cavities. However, it takes a lot of time to prepare a perfect dendrimer, which limits the application of dendrimers, and the price of dendrimers is generally higher due to difficulties in preparation. Compared with dendrimers, hyperbranched polymer molecules have an irregular three-dimensional quasi-spherical structure, and the molecules contain partially linear structural units. The functional groups are located on the surface of the molecule and partially in the interior of the molecule.
  • hyperbranched polymers The molecular weight distribution of hyperbranched polymers is higher. Wide, the degree of branching is between 0 and 1. Although the structure of hyperbranched polymers is not as perfect as dendrimers, its physicochemical properties are very similar to dendrimers, such as good solubility, small solution and melt viscosity, with a large number of terminal functional groups and intramolecular voids. Wait. In addition, hyperbranched polymers have their own advantages, such as a simple synthesis process, which can be synthesized by a one-step process. Hyperbranched polymers are entirely possible to replace dendrimers and are used in pharmaceutical carriers, polymer catalysts, curing agents, solventless coatings and polymer processing aids.
  • hyperbranched polymers there have been four main methods for preparing hyperbranched polymers, namely polycondensation, addition polymerization, self-condensation vinyl polymerization (SCVP) and ring-opening polymerization.
  • SCVP self-condensation vinyl polymerization
  • the most mature method is to prepare hyperbranched polymer by polycondensation reaction of AB 2 type monomer, which is universal and practical.
  • the AB 2 type monomer has not been commercialized in a large amount, and only a few kinds of AB 2 monomers on the market are insufficient to meet the demand, so the use of A 2 + B 3 type monomer polymerization to prepare a hyperbranched polymer has caused people to note. Since the A 2 and B 3 reactions are highly susceptible to gelation during the preparation process, we need to control the reaction by controlling the reaction time, the reaction ratio, and the reaction temperature.
  • the invention relates to a preparation method of a hyperbranched polyether ester, which can be applied in various aspects, for example, in the field of adhesives, toughening agents, polymer blending modification, epoxy resin curing agent and toughening agent, water Application research in the fields of gel preparation, preparation of porous membranes, photocurable coatings and functional coatings.
  • a hyperbranched polyether ester characterized in that the polymer end group contains a reactive group such as a phenolic hydroxyl group, a carboxyl group or a halogenated alkane, the number average molecular weight of the polymer is 5 to 20 KDa, and the polydispersity index of the polymer is 1.3 to 2,
  • the degree of branching of the polymer is from 0.5 to 0.8;
  • the structural formula of the hyperbranched polymer is as follows:
  • the preparation of hyperbranched polyether ester by a non-nuclear one-pot method is as follows: trifunctional hydroxy/carboxybenzene (1) Molar), difunctional haloalkane (0.75 to 3 moles), acid binding agent (1.5 to 7.2 moles), and solvent (0.1 to 1 g/mL) are added to the reactor at a time, and reacted at 20 to 100 ° C for 4 to 96 hours; After completion, the inorganic acid is acidified, and the precipitate is filtered off to obtain a filtrate; the filtrate is purified by precipitation in a precipitant and dried to give a colorless or pale yellow viscous solid.
  • the non-nuclear one-pot method for preparing a hyperbranched polyether ester characterized in that the trifunctional hydroxy/carboxybenzene is selected from the group consisting of 3,5-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 3, One of 4-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, and 5-hydroxyisophthalic acid.
  • the non-nuclear one-pot method for preparing a hyperbranched polyether ester characterized in that the difunctional haloalkane is selected from 1,10-dibromodecane, 1,2-dibromoethane, 1,6- Dibromohexane, 1,12-dibromododecane, 1,11-dibromoundecane, 1,9-dibromodecane, 1,7-dibromoheptane, 1,8-dibromooctyl Alkane, 1,5-dibromopentane, 1,4-dibromobutane, 1,3-dibromopropane, 1,10-dichlorodecane, 1,2-dichloroethane, 1,6- Dichlorohexane, 1,12-dichlorododecane, 1,11-dichloroundecane, 1,9-dichlorodecane, 1,7-dichloroheptane, 1,8
  • the non-nuclear one-pot method for preparing a hyperbranched polyether ester is characterized in that the acid binding agent is selected from the group consisting of potassium carbonate, sodium carbonate and sodium hydroxide.
  • the non-nuclear one-pot method for preparing a hyperbranched polyether ester characterized in that the organic solvent is selected from 1,4-dioxane, tetrahydrofuran, N,N'-dimethylformamide, N, N One of '-dimethylacetamide, N-methyl-pyrrolidone.
  • the non-nuclear one-pot method for preparing a hyperbranched polyether ester is characterized in that the inorganic acid is selected from one of hydrochloric acid, sulfuric acid and nitric acid.
  • the non-nuclear one-pot method for preparing a hyperbranched polyether ester is characterized in that the precipitating agent is selected from the group consisting of deionized water, anhydrous diethyl ether, petroleum ether, equal proportion of mixed ethanol and deionized water, and is mixed in equal proportion. Methanol and deionized water, mixed with diethyl ether and petroleum ether in equal proportions.
  • the nucleated one-pot method for preparing a hyperbranched polyether ester is as follows: trifunctional hydroxy/carboxybenzene (1 mol), difunctional haloalkane (0.75-3 mol), acid binding agent (1.5-7.2) Moore), central "nuclear molecule" (0.012 ⁇ 0.024 moles) and solvent (0.1 ⁇ 1g / mL) are added to the reactor at one time, reacted at 20 ⁇ 100 ° C for 4 ⁇ 96h; after the reaction is finished, acid acid is added, filtered off The precipitate obtained a filtrate; the filtrate was purified by precipitation in a precipitant and dried to give a colorless or pale yellow viscous solid.
  • nucleated one-pot process for preparing a hyperbranched polyether ester characterized in that the central "nuclear molecule" is selected from the group consisting of 1,3,5-benzenetricarboxylic acid, phloroglucinol, 1,3,5- One of benzenetrimethanol; the remaining ternary phenolic hydroxyl group and carboxyl compound, difunctional halogenated alkane, acid binding agent, solvent, inorganic acid, precipitant are selected in the same manner as the nucleated one-step hyperbranched polyether ester .
  • the present invention prepares a hyperbranched polyether ester having a regulatable active end group by a one-pot method, and the synthetic raw material is easily obtained, and the synthesis method is simple and the yield is high.
  • the hyperbranched polyether ester prepared by the invention has high selective activity, and obtains a polymer containing a large number of ether bonds and ester bonds, and the molecular weight and degree of branching of the product are high and controllable; In terms of traditional methods, it has unique advantages such as: it is not easy to gel, the operation is simple and easy, and the controllability is high.
  • Figure 1 is a 1 H nuclear magnetic resonance spectrum of a hyperbranched polyether ester
  • Figure 2 is a gel permeation chromatogram of a hyperbranched polyether ester with tetrahydrofuran as the mobile phase.
  • Cases 1-15 are examples of the preparation of polyetherester type hyperbranched polymers whose terminal groups are phenolic hydroxyl groups.
  • the reaction time is changed from 96h to 48h, and the others are the same as the first embodiment.

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  • Health & Medical Sciences (AREA)
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Abstract

本发明涉及了一种超支化聚醚酯的制备方法。本发明利用商品化的二官能度卤代烷及三官能度羟/羧基苯为原料，通过A2+B3聚合方法，一锅法合成超支化聚醚酯。本发明原料易得、步骤简单，制备的超支化聚醚酯含有高反应活性的端基，可以进一步通过缩合反应、开环反应将各种功能基团或聚合物链引入超支化聚醚酯中，从而制备性能多样、功能独特的超支化聚合物。

Description

一种超支化聚醚酯的制备方法 技术领域
本发明涉及了一种超支化聚醚酯的制备方法，属于有机高分子领域。
背景技术
树枝状聚合物具有高度有序的三维立体结构，与传统的线性聚合物在结构上有着很大的区别，它由引发核、内层重复单元和外层端基组成，具有高度的几何对称性、精确的分子结构、大量的表面官能团和内部空腔。但是要制备一个完美的树枝状聚合物往往需要大量时间，这就限制了树枝状聚合物的应用，并且由于制备困难使得树枝状聚合物的价格一般都比较高。与树枝状聚合物相比，超支化聚合物分子呈不规则的三维准球形结构，分子中包含部分线性结构单元，官能团部分位于分子表面，部分存在于分子内部；超支化聚合物的分子量分布较宽，支化度在0到1之间。虽然超支化聚合物的结构不如树枝状聚合物完美，但它的物理化学性质与树枝状聚合物极为相似，如良好的溶解性，较小的溶液和熔融粘度，具有大量末端官能团和分子内空隙等。另外，超支化聚合物还有其自身的优点，如合成过程简单，可以通过一步法合成等。超支化聚合物完全有可能取代树枝状聚合物，在药物载体、高分子催化剂、固化剂、无溶剂涂料和聚合物加工助剂等方面开发应用。
到目前为止，超支化聚合物的制备方法主要有四种，分别是缩聚反应、加成聚合反应、自缩合乙烯基聚合(SCVP)和开环聚合。其中，最为成熟的方法就是通过AB2型单体的缩聚反应来制备超支化聚合物，这种方法具有普遍性和实用性。但是目前AB2型单体还没有大量商业化，市面上仅有的几种AB2单体不足以满足需求，因此利用A2+B3型单体聚合反应制备超支化聚合物引起了人们的注意。由于A2和B3反应在制备过程中极易发生凝胶化反应，因此我们就需要通过控制反应时间、反应比例、反应温度来控制反应进行。
目前聚醚酯类超支化聚合物中很少有主链同时含有刚性的芳香基团和柔韧性的脂肪族烷基链的。但是，这种独特的组合往往会给聚合物带来许多与众不同的 性质。含有大量芳香基团的超支化聚合物，过强的刚性会造成较大的空间位阻效应，从而大大降低了其使用性能。而将芳香基团和脂肪链同时引入到超支化聚合物中就可以很好的调控超支化聚合物的刚性和柔顺性。柔性链段的存在可以有效降低空间位阻作用，使得作用更为充分；而骨架中刚性基团可以大大提升玻璃化温度(Tg)，提供优异的加工性能和力学性能。
技术问题
本发明涉及了一种超支化聚醚酯的制备方法，可以应用在诸多方面，例如在胶黏剂、增韧剂、聚合物共混改性、环氧树脂固化剂及增韧剂领域、水凝胶的制备、多孔膜的制备、光固化涂料及功能涂层等领域的应用研究。
问题的解决方案
技术解决方案
一种超支化聚醚酯，其特征在于，聚合物端基含有酚羟基、羧基或卤代烷等反应性基团，聚合物数均分子量为5～20KDa，聚合物多分散性指数为1.3～2，聚合物支化度为0.5～0.8；所述超支化聚合物的结构式如下：
Figure PCTCN2017080747-appb-000001
采用无核一锅法制备超支化聚醚酯，具体步骤如下：将三官能度羟/羧基苯(1 摩尔)、二官能度卤代烷(0.75～3摩尔)、缚酸剂(1.5～7.2摩尔)和溶剂(0.1～1g/mL)一次性加入反应器，在20～100℃下反应4～96h；反应结束后加无机酸酸化，滤掉沉淀物得到滤液；将滤液在沉淀剂中沉淀纯化并干燥后得到无色或淡黄色黏性固体。
所述的无核一锅法制备超支化聚醚酯，其特征在于所述的三官能度羟/羧基苯选自3，5-二羟基苯甲酸，2，4-二羟基苯甲酸，3，4-二羟基苯甲酸，2，6-二羟基苯甲酸，2，3-二羟基苯甲酸，5-羟基间苯二甲酸中的一种。
所述的无核一锅法制备超支化聚醚酯，其特征在于：所述的二官能度卤代烷选自1，10-二溴癸烷，1，2-二溴乙烷，1，6-二溴己烷，1，12-二溴十二烷，1，11-二溴十一烷，1，9-二溴壬烷，1，7-二溴庚烷，1，8-二溴辛烷，1，5-二溴戊烷，1，4-二溴丁烷，1，3-二溴丙烷，1，10-二氯癸烷，1，2-二氯乙烷，1，6-二氯己烷，1，12-二氯十二烷，1，11-二氯十一烷，1，9-二氯壬烷，1，7-二氯庚烷，1，8-二氯辛烷，1，5-二氯戊烷，1，4-二氯丁烷，1，3-二氯丙烷中的一种。
所述的无核一锅法制备超支化聚醚酯，其特征在于：所述的缚酸剂选自碳酸钾，碳酸钠，氢氧化钠中的一种。
所述的无核一锅法制备超支化聚醚酯，其特征在于：所述的有机溶剂选1，4-二氧六环，四氢呋喃，N，N′-二甲基甲酰胺，N，N′-二甲基乙酰胺，N-甲基-吡咯烷酮中的一种。
所述的无核一锅法制备超支化聚醚酯，其特征在于：所述的无机酸选自盐酸，硫酸，硝酸中的一种。
所述的无核一锅法制备超支化聚醚酯，其特征在于：所述的沉淀剂选自去离子水，无水乙醚，石油醚，等比例混合的乙醇与去离子水，等比例混合的甲醇与去离子水，等比例混合的乙醚与石油醚。
所述的有核一锅法制备超支化聚醚酯，具体步骤如下：将三官能度羟/羧基苯(1摩尔)、二官能度卤代烷(0.75～3摩尔)、缚酸剂(1.5～7.2摩尔)、中心“核分子”(0.012～0.024摩尔)和溶剂(0.1～1g/mL)一次性加入反应器，在20～100℃下反应4～96h；反应结束后加无机酸酸化，滤掉沉淀物得到滤液；将滤液在沉淀剂中沉淀纯化并干燥后得到无色或淡黄色黏性固体。
所述的有核一锅法制备超支化聚醚酯，其特征在于：所述的中心“核分子”选自1，3，5-苯三甲酸，间苯三酚，1，3，5-苯三甲醇中的一种；其余三元含酚羟基及羧基化合物、二官能度卤代烷、缚酸剂、溶剂、无机酸、沉淀剂的选择与有核一步法超支化聚醚酯的制备方法相同。
发明的有益效果
有益效果
本发明的优点：
1.本发明通过一锅法制备具有可调控活性端基的超支化聚醚酯，合成原料易得，合成方法简单且产率高。
2.本发明所制备的超支化聚醚酯具有很高的选择活性，获得含有大量醚键和酯键的聚合物，产物的分子量和支化度较高且可调控；这种方法相比于传统方法而言，具有独特的优点，如：不易于凝胶，操作简单易行，可控性高等。
对附图的简要说明
附图说明
图1是超支化聚醚酯的1H核磁共振谱图；
图2是超支化聚醚酯以四氢呋喃为流动相的凝胶渗透色谱图。
发明实施例
本发明的实施方式
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1-15为端基为酚羟基的聚醚酯型超支化聚合物的制备案例。
实施案例1
将10.0g(0.065mol)的2，3-二羟基苯甲酸，53.9g(0.39mol)的缚酸剂碳酸钾，31.6g(0.13mol)的1，6-二溴己烷，同时加入反应器中并用83.2mL的N，N′-二甲基甲酰胺溶解；升温20℃反应96h；反应结束后加无机酸酸化，过滤沉淀物得到滤液；将滤液在 等体积混合的乙醇和去离子水混溶的沉淀剂中沉淀，干燥24h，得到8.6g的淡黄色固体，产率为86％。
实施案例2
本实施方式在无核一锅法制备超支化聚醚酯的制备过程中，原料10.0g(0.065mol)3，5-二羟基苯甲酸换成10.0g(0.065mol)3，4-二羟基苯甲酸，其他与实施案例1相同。
实施案例3
本实施方式在无核一锅法制备超支化聚醚酯的制备过程中，原料10.0g(0.065mol)3，5-二羟基苯甲酸换成10.0g(0.065mol)2，6-二羟基苯甲酸，其他与实施案例1相同。
实施案例4
本实施方式在无核一锅法制备超支化聚醚酯的制备过程中，原料10.0g(0.065mol)3，5-二羟基苯甲酸换成10.0g(0.065mol)2，3-二羟基苯甲酸，其他与实施案例1相同。
实施案例5
本实施方式在无核一锅法制备超支化聚醚酯的制备过程中，原料10.0g(0.065mol)3，5-二羟基苯甲酸换成10.0g(0.065mol)3，4-二羟基苯甲酸，其他与实施案例1相同。
实施案例6
本实施方式在无核一锅法制备超支化聚醚酯的制备过程中，原料10.0g(0.065mol)3，5-二羟基苯甲酸换成10.0g(0.065mol)2，4-二羟基苯甲酸，其他与实施案例1相同。
实施案例7
本实施方式在无核一锅法制备超支化聚醚酯的制备过程中，原料31.6g(0.13mol)1，6-二溴己烷换成28.1g(0.13mol)1，4-二溴丁烷，其他与实施案例1相同。
实施例8
本实施方式在无核一锅法制备超支化聚醚酯的制备过程中，原料31.6g(0.13mol)1，6-二溴己烷换成29.9g(0.13mol)1，5-二溴戊烷，其他与实施案例1相同。
实施例9
本实施方式在无核一锅法制备超支化聚醚酯的制备过程中，原料31.6g(0.13mol)1，6-二溴己烷换成37.2g(0.13mol)1，9-二溴壬烷，其他与实施案例1相同。
实施案例10
本实施方式在无核一锅法制备超支化聚醚酯的制备过程中，原料31.6g(0.13mol)1，6-二溴己烷换成37.2g(0.13mol)1，9-二氯壬烷，其他与实施案例1相同。
实施例11
本实施方式在超支化聚醚酯的制备过程中，原料83.2mL N，N′-二甲基甲酰胺换成83.2mL N，N′-二甲基乙酰胺，其他与实施案例1相同。
实施例12
本实施方式在无核一锅法制备超支化聚醚酯的制备过程中，反应时间从96h换成48h，其他与实施案例1相同。
实施例13
本实施方式在无核一锅法制备超支化聚醚酯的制备过程中，所用53.9g(0.39mol)缚酸剂碳酸钾换成15.6g(0.39mol)缚酸剂氢氧化钠，其他与实施案例1相同。
实施例14
将10.0g(0.065mol)的2，4-二羟基苯甲酸，53.9g(0.39mol)的缚酸剂碳酸钾，31.6g(0.13mol)1，6-二溴己烷，0.33g(0.002mol)中心“核分子”均苯三甲酸，同时加入反应器中并用83.2mL的N，N′-二甲基甲酰胺溶解；升温100℃反应96h；反应结束后加无机酸酸化，过滤沉淀物得到滤液；将滤液在等体积混合的乙醇和去离子水混溶的沉淀剂中沉淀，干燥24h，得到8.3g的淡黄色固体，产率为83％。
实施案例15
本实施方式在有核一锅法制备超支化聚醚酯的制备过程中，所用0.33g(0.002mol)中心“核分子”均苯三甲酸换成0.33g(0.002mol)中心“核分子”1，3，5-苯三甲醇，其他与实施案例14相同。

Claims (1)

  1. 一种超支化聚醚酯的制备方法，利用商品化的二官能度卤代烷及三官能度羟/羧基苯为原料，通过A2+B3聚合方法，有核/无核一锅法合成超支化聚醚酯；该超支化聚醚酯的特征在于，聚合物端基含有酚羟基、羧基或卤代烷等反应性基团，聚合物数均分子量为5～20KDa，聚合物多分散性指数为1.3～2，聚合物支化度为0.5～0.8；所述超支化聚醚酯的结构如下：
    Figure PCTCN2017080747-appb-100001
    根据权利要求1所述无核一锅法制备超支化聚醚酯，具体步骤如下：将三官能度羟/羧基苯(1摩尔)、二官能度卤代烷(0.75～3摩尔)、缚酸剂(1.5～7.2摩尔)和溶剂(0.1～1g/mL)一次性加入反应器，在20～100℃下反应4～96h；反应结束后加无机酸酸化，滤掉沉淀物得到滤液；将滤液在沉淀剂中沉淀纯化并干燥后得到无色或淡黄色黏性固体。
    根据权利要求2所述无核一锅法制备超支化聚醚酯，其特征在于所述的三官能度羟/羧基苯选自3，5-二羟基苯甲酸，2，4-二羟基苯甲酸，3，4-二羟基苯甲酸，2，6-二羟基苯甲酸，2，3-二羟基苯甲酸，5-羟基间苯二甲酸中的一种。
    根据权利要求2所述无核一锅法制备超支化聚醚酯，其特征在于所 述的二官能度卤代烷选自1，10-二溴癸烷，1，2-二溴乙烷，1，6-二溴己烷，1，12-二溴十二烷，1，11-二溴十一烷，1，9-二溴壬烷，1，7-二溴庚烷，1，8-二溴辛烷，1，5-二溴戊烷，1，4-二溴丁烷，1，3-二溴丙烷，1，10-二氯癸烷，1，2-二氯乙烷，1，6-二氯己烷，1，12-二氯十二烷，1，11-二氯十一烷，1，9-二氯壬烷，1，7-二氯庚烷，1，8-二氯辛烷，1，5-二氯戊烷，1，4-二氯丁烷，1，3-二氯丙烷中的一种。
    根据权利要求2所述无核一锅法制备超支化聚醚酯，其特征在于所述的缚酸剂选自碳酸钾，碳酸钠，氢氧化钠中的一种。
    根据权利要求2所述无核一锅法制备超支化聚醚酯，其特征在于所述的溶剂选自1，4-二氧六环，四氢呋喃，N，N′-二甲基甲酰胺，N，N′-二甲基乙酰胺，N-甲基-吡咯烷酮中的一种。
    根据权利要求2所述无核一锅法制备超支化聚醚酯，其特征在于所述的无机酸选自盐酸，硫酸，硝酸中的一种。
    根据权利要求2所述无核一锅法制备超支化聚醚酯，其特征在于所述的沉淀剂选自去离子水，无水乙醚，石油醚，等比例混合的乙醇与去离子水，等比例混合的甲醇与去离子水，等比例混合的乙醚与石油醚。
    根据权利要求1所述有核一锅法制备超支化聚醚酯，具体步骤如下：将三官能度羟/羧基苯(1摩尔)、二官能度卤代烷(0.75～3摩尔)、缚酸剂(1.5～7.2摩尔)、中心“核分子”(0.012～0.024摩尔)和溶剂(0.1～1g/mL)一次性加入反应器，在20～100℃下反应4～96h；反应结束后加无机酸酸化，滤掉沉淀物得到滤液；将滤液在沉淀剂中沉淀纯化并干燥后得到无色或淡黄色黏性固体。
    根据权利要求3所述有核一锅法制备超支化聚醚酯，其特征在于所述的中心“核分子”选自1，3，5-苯三甲酸，间苯三酚，1，3，5-苯三甲醇中的一种；其余三官能度羟/羧基苯、二官能度卤代烷、缚酸剂、溶剂、无机酸、沉淀剂的选择与权利要求2中相同。
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