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CN117343345A - Hyperbranched polymer and synthesis method thereof - Google Patents

️Fri Jan 05 2024

CN117343345A - Hyperbranched polymer and synthesis method thereof - Google Patents

Hyperbranched polymer and synthesis method thereof Download PDF

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Publication number

CN117343345A

CN117343345A CN202311579863.4A CN202311579863A CN117343345A CN 117343345 A CN117343345 A CN 117343345A CN 202311579863 A CN202311579863 A CN 202311579863A CN 117343345 A CN117343345 A CN 117343345A Authority

China

Prior art keywords

chain

polystyrene

azide

alkynyl group

protected

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2023-11-23

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CN202311579863.4A

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郝乃蓉

刘鹏程

于艺

金鑫

刘俊鹏

于新民

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Aerospace Research Institute of Materials and Processing Technology

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Aerospace Research Institute of Materials and Processing Technology

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2023-11-23

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2023-11-23

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2024-01-05

2023-11-23 Application filed by Aerospace Research Institute of Materials and Processing Technology filed Critical Aerospace Research Institute of Materials and Processing Technology

2023-11-23 Priority to CN202311579863.4A priority Critical patent/CN117343345A/en

2024-01-05 Publication of CN117343345A publication Critical patent/CN117343345A/en

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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
- 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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Chemical & Material Sciences (AREA)
Health & Medical Sciences (AREA)
Chemical Kinetics & Catalysis (AREA)
Medicinal Chemistry (AREA)
Polymers & Plastics (AREA)
Organic Chemistry (AREA)
Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

本发明涉及一种超支化高分子及其合成方法。所述方法：将引发剂、苯乙烯单体、配体和溶剂混匀，然后在催化剂作用下反应，得到末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链；将末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与叠氮化钠反应，得到末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链；然后将其与四丁基氟化铵反应，得到末端带叠氮且链中间带有炔基的聚苯乙烯链；将两种聚苯乙烯链大单体和五甲基二乙烯三胺混匀，然后加入催化剂反应，得到超支化高分子。本发明方法可以合成分子量和分子量分布可控的长链超支化高分子。

The invention relates to a hyperbranched polymer and a synthesis method thereof. The method: mix the initiator, styrene monomer, ligand and solvent, and then react under the action of a catalyst to obtain polystyrene with bromine at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl. chain; react a polystyrene chain with bromine at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl with sodium azide to obtain an azide at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl Silicon-protected polystyrene chain; then react it with tetrabutylammonium fluoride to obtain a polystyrene chain with azide at the end and an alkynyl group in the middle of the chain; combine the two polystyrene chain macromonomers and Pentamethyldiethylenetriamine is mixed, and then a catalyst is added to react to obtain a hyperbranched polymer. The method of the invention can synthesize long-chain hyperbranched polymers with controllable molecular weight and molecular weight distribution.

Description

一种超支化高分子及其合成方法A kind of hyperbranched polymer and its synthesis method

技术领域Technical field

本发明属于高分子合成技术领域，尤其涉及一种超支化高分子及其合成方法。The invention belongs to the technical field of polymer synthesis, and in particular relates to a hyperbranched polymer and a synthesis method thereof.

背景技术Background technique

超支化高分子是一类重要的支化型拓扑高分子。根据支化点间线型子链的长度(或单体单元的数目)不同，可以将超支化高分子粗略分为短链型和长链型。对比而言，长链超支化高分子结合了传统线型和超支化高分子的优点，具有更为稀疏的支化结构及众多独特的性质，如更弱的空间位阻效应、更易端基功能化、更好的机械性能，以及独特的溶液和本体相行为。因此，长链超支化高分子在超分子化学、纳米科学技术、功能材料、生物医药和石油开采等领域具有巨大的应用潜力，在过去几年中受到了越来越多的关注。Hyperbranched polymers are an important type of branched topological polymers. According to the different lengths of linear sub-chains between branch points (or the number of monomer units), hyperbranched polymers can be roughly divided into short-chain and long-chain types. In contrast, long-chain hyperbranched polymers combine the advantages of traditional linear and hyperbranched polymers, and have a sparser branched structure and many unique properties, such as weaker steric hindrance effects and easier end-group functions. chemicalization, better mechanical properties, and unique solution and bulk phase behavior. Therefore, long-chain hyperbranched polymers have great application potential in the fields of supramolecular chemistry, nanoscience and technology, functional materials, biomedicine, and oil extraction, and have received increasing attention in the past few years.

根据聚合方式和反应机理，长链超支化高分子的合成方法可分为好几种，其中最常用的是AB₂大单体聚合等。AB₂大单体法是合成长链超支化高分子最有效且流行的策略。然而，传统的AB₂大单体法不能实现可控聚合，难以控制长链超支化高分子的分子量和分子量分布，从而限制了长链超支化高分子的溶液性质研究、性能开发以及应用等。According to the polymerization method and reaction mechanism, the synthesis methods of long-chain hyperbranched polymers can be divided into several types, the most commonly used of which is the polymerization of AB ₂ macromonomer. The AB ₂ macromonomer method is the most effective and popular strategy for the synthesis of long-chain hyperbranched polymers. However, the traditional AB ₂ macromonomer method cannot achieve controlled polymerization, and it is difficult to control the molecular weight and molecular weight distribution of long-chain hyperbranched polymers, thus limiting the research on solution properties, performance development and applications of long-chain hyperbranched polymers.

因此，如何利用AB₂大单体来可控地合成窄分布的长链超支化高分子，是亟待解决的问题。Therefore, how to use AB ₂ macromonomer to controllably synthesize narrow-distributed long-chain hyperbranched polymers is an urgent problem to be solved.

发明内容Contents of the invention

为了解决现有技术中存在的一个或者多个技术问题，本发明提供了一种超支化高分子及其合成方法。In order to solve one or more technical problems existing in the prior art, the present invention provides a hyperbranched polymer and a synthesis method thereof.

本发明在第一方面提供了一种超支化高分子的合成方法，所述方法包括如下步骤：In a first aspect, the present invention provides a method for synthesizing hyperbranched polymers, which method includes the following steps:

(1)将引发剂、苯乙烯单体、配体和溶剂混合均匀，然后在催化剂作用下进行反应，得到末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链，所述引发剂具有如下式I的结构：(1) Mix the initiator, styrene monomer, ligand and solvent evenly, and then react under the action of a catalyst to obtain polystyrene with bromine at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl. Chain, the initiator has the structure of the following formula I:

(2)将末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与叠氮化钠进行反应，得到末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链；(2) React a polystyrene chain with bromine at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl with sodium azide to obtain an azide at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl. Methylsilyl-protected polystyrene chains;

(3)将末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与四丁基氟化铵进行反应，得到末端带叠氮且链中间带有炔基的聚苯乙烯链；(3) React a polystyrene chain with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl with tetrabutylammonium fluoride to obtain an azide at the end and an alkynyl group in the middle of the chain. polystyrene chains;

(4)将末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链、末端带叠氮且链中间带有炔基的聚苯乙烯链和五甲基二乙烯三胺混合均匀，然后在催化剂作用下进行反应，得到超支化高分子。(4) Combine a polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl, a polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain, and pentamethylbis Ethylene triamine is mixed evenly, and then reacts under the action of a catalyst to obtain hyperbranched polymers.

优选地，在步骤(1)中：所述配体为三(2-二甲氨基乙基)胺、2,2’-联吡啶和五甲基二乙烯三胺中的一种或多种，优选的是，所述配体为三(2-二甲氨基乙基)胺，且在所述混合液中还添加有辛酸亚锡，更优选的是，三(2-二甲氨基乙基)胺与辛酸亚锡的摩尔比为1:1；所述溶剂为甲苯和/或苯甲醚；所述引发剂与所述苯乙烯单体的摩尔比为1：(100～1000)；所述引发剂与所述配体的摩尔比为1：(2～6)；所述催化剂为CuBr；所述配体与所述催化剂的摩尔比为(1～10)：1；和/或所述苯乙烯单体与所述溶剂的体积比为1：(0.5～2)。Preferably, in step (1): the ligand is one or more of tris(2-dimethylaminoethyl)amine, 2,2'-bipyridine and pentamethyldiethylenetriamine, Preferably, the ligand is tris(2-dimethylaminoethyl)amine, and stannous octoate is also added to the mixed solution. More preferably, tris(2-dimethylaminoethyl)amine is added. The molar ratio of amine to stannous octoate is 1:1; the solvent is toluene and/or anisole; the molar ratio of the initiator to the styrene monomer is 1: (100~1000); The molar ratio of the initiator to the ligand is 1: (2-6); the catalyst is CuBr; the molar ratio of the ligand to the catalyst is (1-10): 1; and/or the The volume ratio of styrene monomer to the solvent is 1: (0.5~2).

优选地，在步骤(1)中：所述反应的温度为80～110℃，所述反应的时间为1～48h，优选的是，所述反应的时间为3～6h。Preferably, in step (1): the temperature of the reaction is 80-110°C, and the reaction time is 1-48 hours. Preferably, the reaction time is 3-6 hours.

优选地，在步骤(2)中：末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与叠氮化钠的摩尔比为1：(2～10)；和/或所述反应为室温下反应48～60h。Preferably, in step (2): the molar ratio of the polystyrene chain with bromine at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl group to sodium azide is 1: (2-10); And/or the reaction is carried out at room temperature for 48 to 60 hours.

优选地，在步骤(3)为：将末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链溶于二氯甲烷中，得到聚苯乙烯链溶液，将聚苯乙烯链溶液通氮气除氧后加入四丁基氟化铵，在室温下搅拌反应6～24h，再经后处理，得到末端带叠氮且链中间带有炔基的聚苯乙烯链。Preferably, in step (3), the polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl is dissolved in methylene chloride to obtain a polystyrene chain solution, and The polystyrene chain solution is deoxygenated by nitrogen, then tetrabutylammonium fluoride is added, and the reaction is stirred at room temperature for 6 to 24 hours. After post-processing, a polystyrene chain with azide at the end and an alkynyl group in the middle of the chain is obtained.

优选地，所述聚苯乙烯链溶液中含有末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链的浓度为0.05～0.15g/mL；和/或所述四丁基氟化铵与所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链的摩尔比为(1～2)：(1～2)。Preferably, the polystyrene chain solution contains a polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and is protected by a trimethylsilyl group at a concentration of 0.05 to 0.15 g/mL; and/or the The molar ratio of the tetrabutylammonium fluoride to the polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and protected by a trimethylsilyl group is (1-2): (1-2).

优选地，在步骤(4)中：所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链的摩尔比为1：(10～160)；所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链用量之和与所述五甲基二乙烯三胺的用量的摩尔比为1：(2～4)；所述催化剂为CuBr；所述五甲基二乙烯三胺与所述催化剂的摩尔比为1:1；和/或在进行反应时，以N,N’-二甲基甲酰胺作为溶剂，所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链在N,N’-二甲基甲酰胺中的浓度之和为0.05～0.15g/mL。Preferably, in step (4): the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl and the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain The molar ratio of the polystyrene chain is 1: (10~160); the polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and protected by a trimethylsilyl group and the azide at the end And the molar ratio of the sum of the amount of polystyrene chains with an alkynyl group in the middle of the chain to the amount of pentamethyldiethylenetriamine is 1: (2-4); the catalyst is CuBr; the pentamethyl The molar ratio of diethylenetriamine to the catalyst is 1:1; and/or when performing the reaction, N,N'-dimethylformamide is used as the solvent, the terminal has an azide and the chain has an alkyne in the middle The sum of the concentrations of the polystyrene chain protected by trimethylsilyl and the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain in N,N'-dimethylformamide is 0.05～0.15g/mL.

优选地，在步骤(4)中：所述反应为室温下反应36～48h。Preferably, in step (4): the reaction is carried out at room temperature for 36 to 48 hours.

优选地，所述超支化高分子的重均分子量为1×10⁴～2×10⁶g/mol；所述分子量分布为1.25～1.65。Preferably, the weight average molecular weight of the hyperbranched polymer is 1×10 ⁴ to 2×10 ⁶ g/mol; the molecular weight distribution is 1.25 to 1.65.

本发明在第二方面提供了本发明在第一方面所述的合成方法合成的超支化高分子。In a second aspect, the present invention provides a hyperbranched polymer synthesized by the synthesis method described in the first aspect of the present invention.

本发明与现有技术相比至少具有如下有益效果：Compared with the prior art, the present invention at least has the following beneficial effects:

本发明中超支化高分子(长链超支化高分子)是由末端带叠氮且链中间带有炔基并被TMS基团(三甲基硅基)保护的聚苯乙烯链和末端带叠氮且链中间带有炔基的聚苯乙烯链通过Click反应得到的。本发明创造性地通过在AB₂型聚苯乙烯链中引入末端带叠氮且链中间带有炔基且并被TMS基团(三甲基硅基)保护的聚苯乙烯链的合成方式，得到了一种分子量参数可控，具有窄的分子量分布的长链超支化高分子；相比于AB₂大单体法，本发明所述的合成方法可通过调节B₂型大单体与AB₂型大单体的比例，来控制长链超支化高分子的分子量，AB₂型大单体/B₂型大单体的摩尔比越大，长链超支化高分子的分子量越大，此外，本发明中的合成方法制备的长链超支化高分子具有窄的分子量分布，且其支化链长是相同的，这意味着可以实现长链超支化聚苯乙烯材料的定制化，拓展其应用领域。The hyperbranched polymer (long-chain hyperbranched polymer) in the present invention is composed of a polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and protected by a TMS group (trimethylsilyl) and an azide at the end. Polystyrene chains containing nitrogen and an alkynyl group in the middle are obtained through the Click reaction. The present invention creatively introduces the synthesis method of a polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and protected by a TMS group (trimethylsilyl) into the AB _2- type polystyrene chain to obtain A kind of long-chain hyperbranched polymer with controllable molecular weight parameters and narrow molecular weight distribution; compared with the AB ₂ macromonomer method, the synthesis method of the present invention can adjust the B ₂ type macromonomer and AB ₂ The proportion of type 2 macromonomers is used to control the molecular weight of long-chain hyperbranched polymers. The greater the molar ratio of AB _2- type macromonomer/B ₂ -type macromonomer, the greater the molecular weight of long-chain hyperbranched polymers. In addition, The long-chain hyperbranched polymers prepared by the synthesis method in the present invention have a narrow molecular weight distribution, and their branch chain lengths are the same, which means that the long-chain hyperbranched polystyrene materials can be customized and their applications can be expanded. field.

附图说明Description of drawings

图1是本发明一些具体实施方式中的超支化高分子的合成过程示意图；图中，St为苯乙烯单体，anisole为苯甲醚；Figure 1 is a schematic diagram of the synthesis process of hyperbranched polymers in some specific embodiments of the present invention; in the figure, St is styrene monomer and anisole is anisole;

图2是本发明实施例1中合成的超支化高分子的GPC(凝胶渗透色谱)图；Figure 2 is a GPC (gel permeation chromatography) diagram of the hyperbranched polymer synthesized in Example 1 of the present invention;

图3是本发明实施例2中合成的超支化高分子的GPC(凝胶渗透色谱)图。Figure 3 is a GPC (gel permeation chromatography) chart of the hyperbranched polymer synthesized in Example 2 of the present invention.

具体实施方式Detailed ways

为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明的技术方案进行清楚、完整地描述。显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purpose, technical solutions and advantages of the present invention more clear, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without any creative work fall within the scope of protection of the present invention.

(1)将引发剂、苯乙烯单体、配体和溶剂混合均匀，然后在催化剂作用下进行反应，得到末端带溴且链中间带有炔基并被三甲基硅基(TMS基团)保护的聚苯乙烯链，所述引发剂具有如下式I的结构：(1) Mix the initiator, styrene monomer, ligand and solvent evenly, and then react under the action of a catalyst to obtain a product with bromine at the end and an alkynyl group in the middle of the chain and trimethylsilyl (TMS group) Protected polystyrene chain, the initiator has the structure of the following formula I:

本发明步骤(1)通过原子转移自由基聚合(ATRP)法，采用苯乙烯作为单体，采用如式I所示结构的引发剂合成了末端带溴且链中间带有炔基并被三甲基硅基(TMS基团)保护的聚苯乙烯链，在本发明中，“链中间带有炔基并被三甲基硅基保护”指的是链中间带有炔基且链中间的炔基被三甲基硅基保护；在本发明中，如式I所示的引发剂可以通过现有已知的方法合成而成，例如可以参考现有技术博士论文《超支化高分子在稀溶液中的链构象研究》中的化合物IV的合成方式，只是在合成过程中采用三甲硅基丙炔醇(别名：三甲基硅基丙炔醇)替换丙炔醇进行实验，即可得到如式I所示的引发剂；所述化合物IV具有如式II所示的结构：Step (1) of the present invention adopts the atom transfer radical polymerization (ATRP) method, using styrene as a monomer, and using an initiator with a structure as shown in formula I to synthesize a bromine-bearing terminal and an alkynyl group in the middle of the chain and trimethyl A polystyrene chain protected by a silyl group (TMS group). In the present invention, "having an alkynyl group in the middle of the chain and protected by a trimethylsilyl group" refers to an alkynyl group in the middle of the chain and an alkyne in the middle of the chain. The group is protected by a trimethylsilyl group; in the present invention, the initiator shown in Formula I can be synthesized by existing known methods. For example, please refer to the prior art doctoral thesis "Hyperbranched Polymers in Dilute Solutions" The synthesis method of compound IV in "Chain Conformation Research" is just to use trimethylsilyl propargyl alcohol (alias: trimethylsilyl propargyl alcohol) to replace propargyl alcohol in the synthesis process, and you can get the formula: The initiator shown in I; the compound IV has a structure shown in formula II:

(2)将末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与叠氮化钠(NaN₃)进行反应，得到末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链；在本发明中，通过叠氮化反应实现聚苯乙烯链末端从溴基团到叠氮基团的转化，得到了末端带叠氮且链中间带有炔基并被三甲基硅基(TMS基团)保护的聚苯乙烯链，记为B₂型大单体；(2) React a polystyrene chain with bromine at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl with sodium azide (NaN ₃ ) to obtain an azide at the end and an alkyne in the middle of the chain. A polystyrene chain whose base is protected by a trimethylsilyl group; in the present invention, the end of the polystyrene chain is converted from a bromine group to an azide group through an azidation reaction, thereby obtaining a terminal with an azide and The polystyrene chain with an alkynyl group in the middle and protected by a trimethylsilyl group (TMS group) is recorded as B ₂ type macromonomer;

(3)将末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与四丁基氟化铵(TBAF)进行反应，得到末端带叠氮且链中间带有炔基的聚苯乙烯链；在本发明中，使用四丁基氟化铵(TBAF)脱除三甲基硅基(TMS基团)，得到末端带叠氮且链中间带有炔基的聚苯乙烯链，记为AB₂型大单体；(3) React a polystyrene chain with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl with tetrabutylammonium fluoride (TBAF) to obtain an azide at the end and an alkynyl group in the middle of the chain. A polystyrene chain with an alkynyl group; in the present invention, tetrabutylammonium fluoride (TBAF) is used to remove the trimethylsilyl group (TMS group) to obtain a polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain. Polystyrene chain, recorded as AB type ₂ macromonomer;

(4)将末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链、末端带叠氮且链中间带有炔基的聚苯乙烯链和五甲基二乙烯三胺混合均匀，然后在催化剂作用下进行反应，得到超支化高分子；本发明发现，通过调节B₂型大单体/AB₂型大单体的投入比例，通过叠氮和炔基发生点击(Click)反应，可以合成不同分子量的窄分布长链超支化聚苯乙烯；本发明方法可以合成分子量和分子量分布可控的长链超支化高分子。(4) Combine a polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl, a polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain, and pentamethylbis Ethylene triamine is mixed evenly, and then reacts under the action of a catalyst to obtain a hyperbranched polymer; the present invention finds that by adjusting the input ratio of B ₂ type macromonomer/AB ₂ type macromonomer, the reaction occurs through azide and alkynyl groups. Click reaction can synthesize narrow-distribution long-chain hyperbranched polystyrenes with different molecular weights; the method of the invention can synthesize long-chain hyperbranched polymers with controllable molecular weight and molecular weight distribution.

本发明首次采用如式I所示的引发剂通过原子转移自由基聚合(ATRP)法，采用苯乙烯作为单体，合成了末端带溴且链中间带有炔基并被三甲基硅基(TMS基团)保护的聚苯乙烯链，进而通过叠氮化反应得到了末端带叠氮且链中间带有炔基并被三甲基硅基(TMS基团)保护的聚苯乙烯链作为B₂型大单体，进而创造性地通过在AB₂型聚苯乙烯链中引入末端带叠氮、链中间带有炔基且被TMS基团(三甲基硅基)保护的聚苯乙烯链(B₂型大单体)的合成方式，得到了一种分子量参数可控，具有窄的分子量分布的长链超支化高分子，本发明中的B₂型大单体采用三甲基硅基对炔基进行保护，有效地提高了合成的可选择性和控制性，有助于实现超支化高分子的有序构建；相比于AB₂大单体法，本发明所述的合成方法在其它合成条件相同的条件下，可通过调节B₂型大单体与AB₂型大单体的比例，来控制长链超支化高分子的分子量，AB₂型大单体/B₂型大单体的摩尔比越大，长链超支化高分子的分子量越大，此外，本发明中的合成方法制备的长链超支化高分子具有窄的分子量分布，且其支化链长是相同的，这意味着可以实现长链超支化聚苯乙烯材料的定制化，拓展其应用领域。For the first time, the present invention adopts the initiator shown in formula I through the atom transfer radical polymerization (ATRP) method, and uses styrene as the monomer to synthesize a bromine-containing terminal and an alkynyl group in the middle of the chain and a trimethylsilyl ( TMS group) protected polystyrene chain, and then through the azidation reaction, a polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain protected by a trimethylsilyl group (TMS group) was obtained as B Type ₂ macromonomer, and then creatively introduced into the AB type ₂ polystyrene chain a polystyrene chain with an azide at the end, an alkynyl group in the middle of the chain, and protection by a TMS group (trimethylsilyl) ( B ₂ type macromonomer), a long-chain hyperbranched polymer with controllable molecular weight parameters and a narrow molecular weight distribution is obtained. The B ₂ type macromonomer in the present invention adopts trimethylsilyl pair The alkynyl group is protected, which effectively improves the selectivity and controllability of synthesis, and helps to achieve the orderly construction of hyperbranched polymers; compared with the AB ₂ macromonomer method, the synthesis method of the present invention has other advantages. Under the same synthesis conditions, the molecular weight of long-chain hyperbranched polymers can be controlled by adjusting the ratio of B type ₂ macromonomer to AB type ₂ macromonomer, AB type ₂ macromonomer/B type ₂ macromonomer The greater the molar ratio, the greater the molecular weight of the long-chain hyperbranched polymer. In addition, the long-chain hyperbranched polymer prepared by the synthesis method of the present invention has a narrow molecular weight distribution, and the branch chain lengths are the same. This is This means that long-chain hyperbranched polystyrene materials can be customized and their application areas expanded.

根据一些优选的实施方式，在步骤(1)中：所述配体为三(2-二甲氨基乙基)胺(Me₆TREN)、2,2’-联吡啶(bpy)和五甲基二乙烯三胺(PMDETA)中的一种或多种，优选的是，所述配体为三(2-二甲氨基乙基)胺(Me₆TREN)，且在所述混合液中还添加有辛酸亚锡(Sn(EH)₂)，更优选的是，三(2-二甲氨基乙基)胺与辛酸亚锡的摩尔比为1:1；所述溶剂为甲苯和/或苯甲醚；所述引发剂与所述苯乙烯单体的摩尔比为1：(100～1000)(例如为1:100、1:200、1:300、1:400、1:500、1:600、1:700、1:800、1:900或1:1000)；所述引发剂与所述配体的摩尔比为1：(2～6)(例如为1:2、1:3、1:4、1:5或1:6)；所述催化剂为CuBr；所述配体与所述催化剂的摩尔比为(1～10)：1(例如为10:1、3:1或1:1)；和/或所述苯乙烯单体与所述溶剂的体积比为1：(0.5～2)(例如为1:0.5、1:1、1:1.5或1:2)。According to some preferred embodiments, in step (1): the ligand is tris(2-dimethylaminoethyl)amine (Me ₆ TREN), 2,2'-bipyridyl (bpy) and pentamethyl One or more diethylenetriamines (PMDETA), preferably, the ligand is tris(2-dimethylaminoethyl)amine (Me ₆ TREN), and is also added to the mixed solution There is stannous octoate (Sn(EH) ₂ ), and more preferably, the molar ratio of tris(2-dimethylaminoethyl)amine to stannous octoate is 1:1; the solvent is toluene and/or benzene Ether; the molar ratio of the initiator to the styrene monomer is 1: (100~1000) (for example, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600 , 1:700, 1:800, 1:900 or 1:1000); the molar ratio of the initiator to the ligand is 1: (2~6) (for example, 1:2, 1:3, 1 :4, 1:5 or 1:6); the catalyst is CuBr; the molar ratio of the ligand to the catalyst is (1 to 10): 1 (for example, 10:1, 3:1 or 1: 1); and/or the volume ratio of the styrene monomer to the solvent is 1: (0.5-2) (for example, 1:0.5, 1:1, 1:1.5 or 1:2).

根据一些优选的实施方式，在步骤(1)中：所述反应的温度为80～110℃(例如为80℃、90℃、100℃或110℃)，所述反应的时间为1～48h(例如为1、3、6、12、24或48h)，优选的是，所述反应的时间为3～6h(例如为3、4、5或6h)。According to some preferred embodiments, in step (1): the reaction temperature is 80-110°C (for example, 80°C, 90°C, 100°C or 110°C), and the reaction time is 1-48h ( For example, 1, 3, 6, 12, 24 or 48 hours), preferably, the reaction time is 3 to 6 hours (for example, 3, 4, 5 or 6 hours).

根据一些具体的实施方式，步骤(1)为：将如式I所示的引发剂、苯乙烯单体、配体和溶剂混合均匀，随后通过三次冷冻-泵抽-解冻循环操作除氧，之后加入催化剂CuBr引发聚合反应，聚合反应一定时间后，用四氢呋喃(THF)稀释反应混合物快速通过中性氧化铝柱除去铜盐，催灭反应，再通过旋转蒸发除去溶剂和未反应的单体，得到聚合物溶液，并将聚合物溶液在甲醇或者甲醇和水的混合物中沉淀两次，最后真空干燥过夜即可得到末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链；在本发明中，甲醇和水的混合物中甲醇和水的体积比为1：(0.1～0.3)(例如为1:0.1、1:0.2或1:0.3)；在本发明中，涉及到的真空干燥例如可以为40～80℃真空干燥8～48h。According to some specific embodiments, step (1) is: mix the initiator, styrene monomer, ligand and solvent as shown in Formula I evenly, and then remove oxygen through three freezing-pumping-thawing cycles, and then The catalyst CuBr is added to initiate the polymerization reaction. After the polymerization reaction for a certain period of time, the reaction mixture is diluted with tetrahydrofuran (THF) and quickly passed through a neutral alumina column to remove the copper salt to extinguish the reaction. The solvent and unreacted monomers are then removed by rotary evaporation to obtain The polymer solution is precipitated twice in methanol or a mixture of methanol and water, and finally vacuum dried overnight to obtain a polyphenylene with bromine at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl. Ethylene chain; in the present invention, the volume ratio of methanol and water in the mixture of methanol and water is 1: (0.1~0.3) (for example, 1:0.1, 1:0.2 or 1:0.3); in the present invention, it relates to The obtained vacuum drying can be, for example, vacuum drying at 40 to 80° C. for 8 to 48 hours.

根据一些优选的实施方式，在步骤(2)中：末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与叠氮化钠的摩尔比为1：(2～10)(例如为1:2、1:3、1:4、1:5、1:6、1:7、1:8、1:9或1:10)；在本发明中，室温指的是室温15～35℃；和/或所述反应为室温下反应48～60h(例如为48、50、52、54、56、58或60h)。According to some preferred embodiments, in step (2): the molar ratio of the polystyrene chain with bromine at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl to sodium azide is 1: (2 ~10) (for example, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10); in the present invention, room temperature refers to The temperature is 15-35°C at room temperature; and/or the reaction is at room temperature for 48-60 hours (for example, 48, 50, 52, 54, 56, 58 or 60 hours).

根据一些具体的实施方式，步骤(2)为：将末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链、NaN₃和N,N’-二甲基甲酰胺(DMF)在室温下搅拌反应一定时间，再加入二氯甲烷混合均匀，之后在甲醇或者甲醇和水的混合物中沉淀，用适量THF将沉淀物溶解，并再次进行沉淀提纯，之后置于真空烘箱中真空干燥过夜得到末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链(B₂型大单体)；在步骤(2)中进行所述反应时，以N,N’-二甲基甲酰胺(DMF)为溶剂，所述末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与N,N’-二甲基甲酰胺的质量比为1：(4～6)(例如为1:4、1:5或1:6)，且在该步骤(2)中，N,N’-二甲基甲酰胺与二氯甲烷的体积比为1：(0.1～0.3)(例如为1:0.1、1:0.2或1:0.3)，所述甲醇和水的混合物中甲醇和水的体积比为1：(0.1～0.3)(例如为1:0.1、1:0.2或1:0.3)。According to some specific embodiments, step (2) is: combining a polystyrene chain with bromine at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl, NaN ₃ and N,N'-dimethylmethyl Stir the amide (DMF) at room temperature for a certain period of time, then add dichloromethane and mix evenly, then precipitate in methanol or a mixture of methanol and water, dissolve the precipitate with an appropriate amount of THF, and perform precipitation and purification again, and then place it in a vacuum Dry under vacuum in an oven overnight to obtain a polystyrene chain (B ₂ type macromonomer) with an azide at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl; when performing the reaction in step (2) , using N,N'-dimethylformamide (DMF) as the solvent, the polystyrene chain with bromine at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl is mixed with N,N'-dimethylformamide. The mass ratio of methylformamide is 1: (4～6) (for example, 1:4, 1:5 or 1:6), and in this step (2), N,N'-dimethylformamide The volume ratio to dichloromethane is 1: (0.1-0.3) (for example, 1:0.1, 1:0.2 or 1:0.3), and the volume ratio of methanol and water in the mixture of methanol and water is 1: (0.1 ~0.3) (for example, 1:0.1, 1:0.2 or 1:0.3).

根据一些优选的实施方式，在步骤(3)为：将末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链溶于二氯甲烷中，得到聚苯乙烯链溶液，将聚苯乙烯链溶液通氮气除氧后加入四丁基氟化铵，在室温下搅拌反应6～24h(例如6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23或24h)，再经后处理，得到末端带叠氮且链中间带有炔基的聚苯乙烯链。According to some preferred embodiments, step (3) is: dissolving the polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl in methylene chloride to obtain polystyrene. For chain solution, pass nitrogen gas to remove oxygen from the polystyrene chain solution, add tetrabutylammonium fluoride, stir and react at room temperature for 6 to 24 hours (for example, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24h), and then post-processed to obtain a polystyrene chain with azide at the end and an alkynyl group in the middle of the chain.

根据一些优选的实施方式，所述聚苯乙烯链溶液中含有末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链的浓度为0.05～0.15g/mL(例如为0.05、0.06、0.07、0.08、0.09、0.10、0.11、0.12、0.13、0.14或0.15g/mL)；在本发明中，优选的是，所述四丁基氟化铵与所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链的摩尔比为(1～2)：(1～2)，如此可以使得四丁基氟化铵能够高效地脱除TMS基团，得到纯度高的目标物末端带叠氮且链中间带有炔基的聚苯乙烯链。According to some preferred embodiments, the polystyrene chain solution contains a polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and is protected by a trimethylsilyl group at a concentration of 0.05 to 0.15 g/mL ( For example, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14 or 0.15g/mL); in the present invention, it is preferred that the tetrabutylammonium fluoride and the terminal band The molar ratio of polystyrene chains that are azide and have an alkynyl group in the middle of the chain and are protected by trimethylsilyl groups is (1~2): (1~2), which allows tetrabutylammonium fluoride to be efficiently The TMS group is removed to obtain the highly pure target polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain.

根据一些具体的实施方式，步骤(3)为：将末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链溶于二氯甲烷中，通氮气除氧后加入四丁基氟化铵(TBAF)，在室温下搅拌反应一定时间，在甲醇或者甲醇和水的混合物中沉淀，用适量THF将沉淀物溶解，并再次进行沉淀提纯，之后置于真空烘箱中真空干燥过夜得到末端带叠氮且链中间带有炔基的聚苯乙烯链(AB₂型大单体)；在该步骤(3)中，所述甲醇和水的混合物中甲醇和水的体积比为1：(0.1～0.3)(例如为1:0.1、1:0.2或1:0.3)。According to some specific embodiments, step (3) is: dissolving the polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl in methylene chloride, and then deoxygenating it by flowing nitrogen Add tetrabutylammonium fluoride (TBAF), stir and react at room temperature for a certain period of time, precipitate in methanol or a mixture of methanol and water, dissolve the precipitate with an appropriate amount of THF, and perform precipitation and purification again, and then place it in a vacuum oven Vacuum dry overnight to obtain a polystyrene chain with azide at the end and an alkynyl group in the middle (AB ₂ type macromonomer); in this step (3), the volume of methanol and water in the mixture of methanol and water The ratio is 1: (0.1～0.3) (for example, 1:0.1, 1:0.2 or 1:0.3).

根据一些优选的实施方式，在步骤(4)中：所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链的摩尔比为1：(10～160)(例如为1:10、1:20、1:30、1:40、1:50、1:60、1:70、1:80、1:90、1:100、1:110、1:120、1:130、1:140、1:150或1:160)；在本发明中，优选的是，通过所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链的摩尔比为1：(10～160)，可以有效地调整每次点击反应中的功能团配对，从而控制产物达到所需的分子量，并且可以有助于产生分子量分布窄的超支化高分子；本发明发现，若两者的摩尔比大于1:10，会导致出现较低分子量的聚合物且出现一些分支较少的聚合物，导致形成不均匀的分子链结构，这不仅仅使得超支化高分子的分子量较低，无法满足特定应用的需求，且由于聚合物的分子链结构的不均匀性也会导致分子量分布会较宽，同样限制其应用；而若两者的摩尔比小于1:160，虽然可以增加产物的分子量，但会导致反应变得不可控，同样会导致形成不均匀的分子链结构，而不是具有高度可预测和可控的超支化结构，这种不规则性会影响超支化高分子的性质和应用。According to some preferred embodiments, in step (4): the polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and protected by a trimethylsilyl group and the azide at the end with an alkynyl group in the middle of the chain The molar ratio of polystyrene chains with alkynyl groups is 1: (10~160) (for example, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70 , 1:80, 1:90, 1:100, 1:110, 1:120, 1:130, 1:140, 1:150 or 1:160); in the present invention, it is preferred that by The molar ratio of the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl to the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain is 1: ( 10-160), can effectively adjust the functional group pairing in each click reaction, thereby controlling the product to reach the required molecular weight, and can help produce hyperbranched polymers with narrow molecular weight distribution; the present invention found that if both The molar ratio is greater than 1:10, which will lead to the emergence of lower molecular weight polymers and the emergence of some polymers with fewer branches, resulting in the formation of uneven molecular chain structures. This not only makes the molecular weight of hyperbranched polymers lower and cannot To meet the needs of specific applications, and due to the inhomogeneity of the molecular chain structure of the polymer, the molecular weight distribution will also be wider, which also limits its application; and if the molar ratio of the two is less than 1:160, although the molecular weight of the product can be increased , but it will cause the reaction to become uncontrollable, and it will also lead to the formation of a non-uniform molecular chain structure instead of a highly predictable and controllable hyperbranched structure. This irregularity will affect the properties and applications of hyperbranched polymers. .

根据一些优选的实施方式，在步骤(4)中，所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链用量之和与所述五甲基二乙烯三胺的用量的摩尔比为1：(2～4)(例如为1:2、1:3或1:4)；在本发明中，优选的是，所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链用量之和与所述五甲基二乙烯三胺的用量的摩尔比为1：(2～4)，本发明发现，合适的大单体与配体的摩尔比对于获得分子量可控、分子量分布窄的超支化高分子能起到重要作用，可以避免副反应或者杂质的生成，有助于提高合成的选择性和聚合物的纯度。According to some preferred embodiments, in step (4), the polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl is the same as the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain. The molar ratio of the sum of the amounts of polystyrene chains with alkynyl groups to the amount of pentamethyldiethylenetriamine is 1: (2-4) (for example, 1:2, 1:3 or 1:4) ; In the present invention, it is preferred that the polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl is the same as the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain. The molar ratio of the sum of the polystyrene chain amounts and the amount of pentamethyldiethylenetriamine is 1: (2-4). The present invention found that the appropriate molar ratio of macromonomers and ligands is essential for obtaining the molecular weight. Hyperbranched polymers with controllable and narrow molecular weight distribution can play an important role in avoiding side reactions or the generation of impurities, helping to improve the selectivity of synthesis and the purity of polymers.

根据一些优选的实施方式，在步骤(4)中，所述催化剂为CuBr；所述五甲基二乙烯三胺与所述催化剂的摩尔比为1:1；和/或在进行反应时，以N,N’-二甲基甲酰胺作为溶剂，所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链在N,N’-二甲基甲酰胺中的浓度之和为0.05～0.15g/mL(例如为0.05、0.06、0.07、0.08、0.09、0.10、0.11、0.12、0.13、0.14或0.15g/mL)。According to some preferred embodiments, in step (4), the catalyst is CuBr; the molar ratio of the pentamethyldiethylenetriamine to the catalyst is 1:1; and/or when performing the reaction, N,N'-dimethylformamide is used as a solvent. The polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and protected by a trimethylsilyl group is the same as the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain. The sum of the concentrations of polystyrene chains with alkynyl groups in N,N'-dimethylformamide is 0.05 to 0.15g/mL (for example, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14 or 0.15g/mL).

根据一些优选的实施方式，在步骤(4)中：所述反应为室温下反应36～48h(例如为36、38、40、42、44、46或48h)。According to some preferred embodiments, in step (4): the reaction is carried out at room temperature for 36 to 48 hours (for example, 36, 38, 40, 42, 44, 46 or 48 hours).

根据一些具体的实施方式，步骤(4)为：将所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链、所述末端带叠氮且链中间带有炔基的聚苯乙烯链、配体五甲基二乙烯三胺(PMDETA)和DMF加入反应瓶内，通过四次冷冻-泵抽真空-解冻循环操作除氧后，在冷却状态下，向烧瓶中加入CuBr并除氧。在室温下反应数小时后，反应混合物用THF稀释，通过中性氧化铝柱子除去铜盐，经浓缩后在甲醇中沉淀，真空干燥后得到产物，即为超支化高分子，在本发明中，也将超支化高分子记作长链超支化高分子。According to some specific embodiments, step (4) is: combining the polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl; The polystyrene chain with an alkynyl group, the ligand pentamethyldiethylenetriamine (PMDETA) and DMF are added into the reaction bottle, and after four freeze-pump vacuum-thawing cycles to remove oxygen, in the cooling state, Add CuBr to the flask and remove oxygen. After reacting at room temperature for several hours, the reaction mixture is diluted with THF, and the copper salt is removed through a neutral alumina column. After concentration, it is precipitated in methanol. After vacuum drying, the product is obtained, which is a hyperbranched polymer. In the present invention, Hyperbranched polymers are also referred to as long-chain hyperbranched polymers.

根据一些优选的实施方式，所述超支化高分子的重均分子量为1×10⁴～2×10⁶g/mol，优选为1.8×10⁵～2×10⁶g/mol；所述分子量分布为1.25～1.65，优选为1.3～1.46。According to some preferred embodiments, the weight average molecular weight of the hyperbranched polymer is 1×10 ⁴ to 2×10 ⁶ g/mol, preferably 1.8×10 ⁵ to 2×10 ⁶ g/mol; the molecular weight distribution It is 1.25-1.65, Preferably it is 1.3-1.46.

本发明在第二方面提供了由本发明在第一方面所述的合成方法合成的超支化高分子。In a second aspect, the present invention provides a hyperbranched polymer synthesized by the synthesis method described in the first aspect of the present invention.

下文将通过举例的方式对本发明进行进一步的说明，但是本发明的保护范围不限于这些实施例。The present invention will be further described below by way of examples, but the protection scope of the present invention is not limited to these examples.

实施例1Example 1

①向一个配备搅拌磁子的三口瓶中加入如式I所示的引发剂(0.173mmol)、苯乙烯(173mmol)、三(2-二甲氨基乙基)胺(配体)(0.346mmol)、辛酸亚锡(0.346mmol)和苯甲醚(溶剂)，苯乙烯与苯甲醚的体积比为1:2，随后通过三次冷冻-泵抽-解冻循环操作除氧，之后加入催化剂CuBr(0.0346mmol)，再放入90℃油浴锅中，反应4h后，用200mL THF稀释反应混合物快速通过中性氧化铝柱除去铜盐，催灭反应，再通过旋转蒸发除去溶剂和单体，得到聚合物溶液，并将聚合物溶液在500mL甲醇中沉淀两次，最后真空干燥10h，即得到末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链(重均分子量M_W＝21000g/mol)。① Add the initiator shown in formula I (0.173mmol), styrene (173mmol), and tris(2-dimethylaminoethyl)amine (ligand) (0.346mmol) to a three-necked flask equipped with a stirring magnet. , stannous octoate (0.346mmol) and anisole (solvent), the volume ratio of styrene to anisole is 1:2, followed by three freezing-pumping-thawing cycles to remove oxygen, and then add the catalyst CuBr (0.0346 mmol), and then put it into a 90°C oil bath. After 4 hours of reaction, dilute the reaction mixture with 200 mL THF and quickly pass it through a neutral alumina column to remove the copper salt to quench the reaction. Then remove the solvent and monomer by rotary evaporation to obtain polymerization. The polymer solution was precipitated twice in 500 mL methanol, and finally vacuum dried for 10 h to obtain a polystyrene chain with bromine at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl (weight average molecular weight M _W =21000g/mol).

②在圆底烧瓶中装入末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链(0.19mmol)、NaN₃(1.9mmol)和DMF在室温25℃下搅拌48h，再加入二氯甲烷，之后在264mL甲醇中沉淀，用适量THF将沉淀物溶解，并再次进行沉淀提纯，之后置于真空烘箱中真空干燥10h，得到末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链；其中，末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与DMF的质量比为1:5.7，DMF与二氯甲烷的体积比为1:0.1。②Put a polystyrene chain (0.19mmol) with bromine at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl, NaN ₃ (1.9mmol) and DMF into a round-bottomed flask and stir at room temperature 25°C. 48h, then add methylene chloride, then precipitate in 264mL methanol, dissolve the precipitate with an appropriate amount of THF, and perform precipitation purification again, and then place it in a vacuum oven to vacuum dry for 10h to obtain an azide at the end and an alkyne in the middle of the chain. A polystyrene chain with a bromine group at the end and an alkynyl group in the middle of the chain, protected by a trimethylsilyl group, and the mass ratio of DMF to DMF is 1:5.7. The volume ratio of DMF to methylene chloride is 1:0.1.

③将末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链(0.095mmol)溶于二氯甲烷中，得到聚苯乙烯链溶液，将聚苯乙烯链溶液通氮气除氧后加入四丁基氟化铵(0.095mmol)，在室温25℃下搅拌24h，之后在154mL甲醇中沉淀，用适量THF将沉淀物溶解，并再次进行沉淀提纯，之后置于真空烘箱中真空干燥10h，得到末端带叠氮且链中间带有炔基的聚苯乙烯链；其中，聚苯乙烯链溶液中含有末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链的浓度为0.13g/mL。③ Dissolve the polystyrene chain (0.095mmol) with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl in methylene chloride to obtain a polystyrene chain solution. After deoxygenating with nitrogen, add tetrabutylammonium fluoride (0.095mmol), stir at room temperature 25°C for 24 hours, and then precipitate in 154 mL methanol. Dissolve the precipitate with an appropriate amount of THF, and perform precipitation and purification again, and then place it in a vacuum. Dry in an oven under vacuum for 10 hours to obtain a polystyrene chain with azide at the end and an alkynyl group in the middle of the chain; the polystyrene chain solution contains an azide at the end and an alkynyl group in the middle of the chain and is covered with trimethylsilane. The concentration of group-protected polystyrene chains was 0.13 g/mL.

④在一个配备有搅拌磁子和三个橡胶塞的三口瓶中加入末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链(0.0047mmol)、末端带叠氮且链中间带有炔基的聚苯乙烯链(0.047mmol)、PMDETA(0.104mmol)和DMF，通过四次冷冻-泵抽真空-解冻循环操作除氧后，在冷却状态下，向烧瓶中加入CuBr(0.104mmol)并除氧，在室温25℃下反应36h后，反应混合物用THF稀释，通过中性氧化铝柱子除去铜盐，经浓缩后在甲醇中沉淀，真空干燥后得到产物，即为长链超支化高分子；其中，所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链在DMF中的浓度之和为0.08g/mL。④Into a three-necked flask equipped with a stirring magnet and three rubber stoppers, add a polystyrene chain (0.0047mmol) with azide at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl, and azide at the end. Nitrogen and polystyrene chains with alkynyl groups in the middle (0.047mmol), PMDETA (0.104mmol) and DMF were deoxygenated through four freezing-pumping-thawing cycles, and then were added to the flask in a cooling state. Add CuBr (0.104mmol) and remove oxygen. After reacting for 36 hours at room temperature 25°C, the reaction mixture is diluted with THF. The copper salt is removed through a neutral alumina column. After concentration, it is precipitated in methanol. After drying under vacuum, the product is obtained, namely It is a long-chain hyperbranched polymer; wherein, the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl group is the same as the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain. The sum of the concentrations of polystyrene chains in DMF is 0.08g/mL.

本实施例合成的长链超支化高分子的重均分子量为2.54×10⁵g/mol，分子量分布在1.35，本实施例合成的长链超支化高分子的GPC图如图2所示。The weight average molecular weight of the long-chain hyperbranched polymer synthesized in this example is 2.54×10 ⁵ g/mol, and the molecular weight distribution is 1.35. The GPC chart of the long-chain hyperbranched polymer synthesized in this example is shown in Figure 2.

实施例2Example 2

①向一个配备搅拌磁子的三口瓶中加入如式I所示的引发剂(0.25mmol)、苯乙烯(100mmol)、2,2’-联吡啶(1.5mmol)和苯甲醚(溶剂)，苯乙烯与苯甲醚的体积比为1:1.04，随后通过三次冷冻-泵抽-解冻循环操作除氧，之后加入催化剂CuBr(0.5mmol)，再放入105℃油浴锅中，反应21h后，用200mLTHF稀释反应混合物快速通过中性氧化铝柱除去铜盐，催灭反应，再通过旋转蒸发除去溶剂和单体，得到聚合物溶液，并将聚合物溶液在500mL甲醇中沉淀两次，最后真空干燥10h，即末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链(M_W＝8200g/mol)。① Add the initiator shown in formula I (0.25mmol), styrene (100mmol), 2,2'-bipyridine (1.5mmol) and anisole (solvent) to a three-necked flask equipped with a stirring magnet. The volume ratio of styrene to anisole is 1:1.04, and then the oxygen is removed through three freezing-pumping-thawing cycles. Then the catalyst CuBr (0.5mmol) is added, and then placed in a 105°C oil bath. After 21 hours of reaction , dilute the reaction mixture with 200mL THF and quickly pass it through a neutral alumina column to remove the copper salt to quench the reaction. Then remove the solvent and monomer by rotary evaporation to obtain a polymer solution, and precipitate the polymer solution twice in 500mL methanol. Finally, Dry in vacuum for 10 hours, that is, a polystyrene chain with bromine at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl (M _W = 8200 g/mol).

②在圆底烧瓶中装入末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链(0.244mmol)、NaN₃(0.95mol)和DMF在室温25℃下搅拌24h，再加入二氯甲烷，之后在132mL甲醇中沉淀，用适量THF将沉淀物溶解，并再次进行沉淀提纯，之后置于真空烘箱中真空干燥10h，得到末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链；其中，末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与DMF的质量比为1:5.69，DMF与二氯甲烷的体积比为1:0.1。②Put a polystyrene chain (0.244mmol), NaN ₃ (0.95mol), and DMF with bromine at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl into a round-bottomed flask and stir at room temperature 25°C. 24h, then add methylene chloride, and then precipitate in 132mL methanol, dissolve the precipitate with an appropriate amount of THF, and perform precipitation purification again, and then place it in a vacuum oven for vacuum drying for 10h to obtain an azide at the end and an alkyne in the middle of the chain. Polystyrene chain with trimethylsilyl group protection; wherein, the mass ratio of polystyrene chain with bromine at the end and alkynyl group in the middle of the chain with trimethylsilyl protection and DMF is 1:5.69, The volume ratio of DMF to methylene chloride is 1:0.1.

③将末端带叠氮且链中间带有炔基并被三甲基硅基团保护的聚苯乙烯链(0.183mmol)溶于二氯甲烷中，得到聚苯乙烯链溶液，将聚苯乙烯链溶液通氮气除氧后加入四丁基氟化铵(0.183mmol)，在室温25℃下搅拌24h，之后在115mL甲醇中沉淀，用适量THF将沉淀物溶解，并再次进行沉淀提纯，之后置于真空烘箱中真空干燥10h，得到末端带叠氮且链中间带有炔基的聚苯乙烯链；其中，聚苯乙烯链溶液中含有末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链的浓度为0.13g/mL。③ Dissolve the polystyrene chain (0.183mmol) with azide at the end and an alkynyl group in the middle of the chain and protected by a trimethylsilyl group in methylene chloride to obtain a polystyrene chain solution. After the solution was deoxygenated by nitrogen, tetrabutylammonium fluoride (0.183 mmol) was added, stirred at room temperature 25°C for 24 hours, and then precipitated in 115 mL methanol. The precipitate was dissolved with an appropriate amount of THF, and precipitated and purified again, and then placed in Vacuum dry in a vacuum oven for 10 hours to obtain a polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain; the polystyrene chain solution contains an azide at the end and an alkynyl group in the middle of the chain and is trimethylated. The concentration of silicon-protected polystyrene chains was 0.13 g/mL.

④在一个配备有搅拌磁子和三个橡胶塞的三口瓶中加入末端带叠氮且链中间带有炔基并被TMS基团保护的聚苯乙烯链(0.006mmol)、末端带叠氮且链中间带有炔基的聚苯乙烯链(0.12mmol)、PMDETA(0.252mmol)和DMF，通过四次冷冻-泵抽真空-解冻循环操作除氧后，在冷却状态下，向烧瓶中加入CuBr(0.252mmol)并除氧。在室温25℃下反应36h后，反应混合物用THF稀释，通过中性氧化铝柱子除去铜盐，经浓缩后在甲醇中沉淀，真空干燥后得到产物，即得到长链超支化高分子；其中，所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链在DMF中的浓度之和为0.1g/mL。④Into a three-necked flask equipped with a stirring magnet and three rubber stoppers, add a polystyrene chain (0.006 mmol) with an azide at the end and an alkynyl group in the middle of the chain and protected by a TMS group. The polystyrene chain with an alkynyl group in the middle (0.12mmol), PMDETA (0.252mmol) and DMF were deoxygenated through four freezing-pumping-thawing cycles, and then CuBr was added to the flask in a cooling state. (0.252mmol) and remove oxygen. After reacting for 36 hours at room temperature of 25°C, the reaction mixture was diluted with THF, passed through a neutral alumina column to remove the copper salt, concentrated and precipitated in methanol, and the product was obtained after vacuum drying, that is, a long-chain hyperbranched polymer was obtained; wherein, The concentration of the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl and the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain in DMF The sum is 0.1g/mL.

本实施例合成的长链超支化高分子的重均分子量为1.86×10⁵g/mol，分子量分布在1.42，本实施例合成的长链超支化高分子的GPC图如图3所示。The weight average molecular weight of the long-chain hyperbranched polymer synthesized in this example is 1.86×10 ⁵ g/mol, and the molecular weight distribution is 1.42. The GPC chart of the long-chain hyperbranched polymer synthesized in this example is shown in Figure 3 .

实施例3Example 3

实施例3与实施例1基本相同，不同之处在于：Embodiment 3 is basically the same as Embodiment 1, except that:

④在一个配备有搅拌磁子和三个橡胶塞的三口瓶中加入末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链(0.0047mmol)、末端带叠氮且链中间带有炔基的聚苯乙烯链(0.235mmol)、PMDETA(0.4794mmol)和DMF，通过四次冷冻-泵抽真空-解冻循环操作除氧后，在冷却状态下，向烧瓶中加入CuBr(0.4794mmol)并除氧，在室温25℃下反应36h后，反应混合物用THF稀释，通过中性氧化铝柱子除去铜盐，经浓缩后在甲醇中沉淀，真空干燥后得到产物，即为长链超支化高分子；其中，所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链在DMF中的浓度之和为0.08g/mL。④Into a three-necked flask equipped with a stirring magnet and three rubber stoppers, add a polystyrene chain (0.0047mmol) with azide at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl, and azide at the end. Nitrogen and a polystyrene chain with an alkynyl group in the middle (0.235mmol), PMDETA (0.4794mmol) and DMF were deoxygenated through four freeze-pump vacuum-thaw cycles, and then were added to the flask in a cooling state. CuBr (0.4794mmol) was added and oxygen was removed. After reacting for 36 hours at room temperature 25°C, the reaction mixture was diluted with THF, passed through a neutral alumina column to remove copper salts, concentrated and precipitated in methanol, and the product was obtained after vacuum drying, namely It is a long-chain hyperbranched polymer; wherein, the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl group is the same as the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain. The sum of the concentrations of polystyrene chains in DMF is 0.08g/mL.

本实施例合成的长链超支化高分子的重均分子量为1.15×10⁶g/mol，分子量分布在1.38。The weight average molecular weight of the long-chain hyperbranched polymer synthesized in this example is 1.15×10 ⁶ g/mol, and the molecular weight distribution is 1.38.

实施例4Example 4

实施例4与实施例1基本相同，不同之处在于：Embodiment 4 is basically the same as Embodiment 1, except that:

④在一个配备有搅拌磁子和三个橡胶塞的三口瓶中加入末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链(0.0047mmol)、末端带叠氮且链中间带有炔基的聚苯乙烯链(0.47mmol)、PMDETA(0.9494mmol)和DMF，通过四次冷冻-泵抽真空-解冻循环操作除氧后，在冷却状态下，向烧瓶中加入CuBr(0.9494mmol)并除氧，在室温25℃下反应36h后，反应混合物用THF稀释，通过中性氧化铝柱子除去铜盐，经浓缩后在甲醇中沉淀，真空干燥后得到产物，即为长链超支化高分子；其中，所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链在DMF中的浓度之和为0.08g/mL。④Into a three-necked flask equipped with a stirring magnet and three rubber stoppers, add a polystyrene chain (0.0047mmol) with azide at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl, and azide at the end. Nitrogen and a polystyrene chain with an alkynyl group in the middle (0.47mmol), PMDETA (0.9494mmol) and DMF were deoxygenated through four freeze-pump vacuum-thawing cycles, and then were added to the flask in a cooling state. CuBr (0.9494mmol) was added and oxygen was removed. After reacting for 36 hours at room temperature 25°C, the reaction mixture was diluted with THF, passed through a neutral alumina column to remove copper salts, concentrated and precipitated in methanol, and the product was obtained after vacuum drying, namely It is a long-chain hyperbranched polymer; wherein, the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl group is the same as the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain. The sum of the concentrations of polystyrene chains in DMF is 0.08g/mL.

本实施例合成的长链超支化高分子的重均分子量为2.20×10⁶g/mol，分子量分布在1.40。The weight average molecular weight of the long-chain hyperbranched polymer synthesized in this example is 2.20×10 ⁶ g/mol, and the molecular weight distribution is 1.40.

实施例5Example 5

实施例5与实施例1基本相同，不同之处在于：Embodiment 5 is basically the same as Embodiment 1, except that:

④在一个配备有搅拌磁子和三个橡胶塞的三口瓶中加入末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链(0.0047mmol)、末端带叠氮且链中间带有炔基的聚苯乙烯链(0.752mmol)、PMDETA(1.5134mmol)和DMF，通过四次冷冻-泵抽真空-解冻循环操作除氧后，在冷却状态下，向烧瓶中加入CuBr(1.5134mmol)并除氧，在室温25℃下反应36h后，反应混合物用THF稀释，通过中性氧化铝柱子除去铜盐，经浓缩后在甲醇中沉淀，真空干燥后得到产物，即为长链超支化高分子；其中，所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链在DMF中的浓度之和为0.08g/mL。④Into a three-necked flask equipped with a stirring magnet and three rubber stoppers, add a polystyrene chain (0.0047mmol) with azide at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl, and azide at the end. Nitrogen and a polystyrene chain with an alkynyl group in the middle (0.752mmol), PMDETA (1.5134mmol) and DMF were deoxygenated through four freeze-pump vacuum-thawing cycles, and then were added to the flask in a cooling state. Add CuBr (1.5134mmol) and remove oxygen. After reacting at room temperature 25°C for 36 hours, the reaction mixture was diluted with THF. The copper salt was removed through a neutral alumina column. After concentration, it was precipitated in methanol. After drying under vacuum, the product was obtained, namely It is a long-chain hyperbranched polymer; wherein, the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl group is the same as the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain. The sum of the concentrations of polystyrene chains in DMF is 0.08g/mL.

本实施例合成的长链超支化高分子的重均分子量为1.98×10⁶g/mol，分子量分布在1.46。The weight average molecular weight of the long-chain hyperbranched polymer synthesized in this example is 1.98×10 ⁶ g/mol, and the molecular weight distribution is 1.46.

实施例6Example 6

实施例6与实施例1基本相同，不同之处在于：Embodiment 6 is basically the same as Embodiment 1, except that:

④在一个配备有搅拌磁子和三个橡胶塞的三口瓶中加入末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链(0.0047mmol)、末端带叠氮且链中间带有炔基的聚苯乙烯链(0.0235mmol)、PMDETA(0.0564mmol)和DMF，通过四次冷冻-泵抽真空-解冻循环操作除氧后，在冷却状态下，向烧瓶中加入CuBr(0.0564mmol)并除氧，在室温25℃下反应36h后，反应混合物用THF稀释，通过中性氧化铝柱子除去铜盐，经浓缩后在甲醇中沉淀，真空干燥后得到产物，即为长链超支化高分子；其中，所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链在DMF中的浓度之和为0.08g/mL。④Into a three-necked flask equipped with a stirring magnet and three rubber stoppers, add a polystyrene chain (0.0047mmol) with azide at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl, and azide at the end. Nitrogen and a polystyrene chain with an alkynyl group in the middle (0.0235mmol), PMDETA (0.0564mmol) and DMF were deoxygenated through four freeze-pump vacuum-thawing cycles, and then were added to the flask in a cooling state. Add CuBr (0.0564mmol) and remove oxygen. After reacting for 36 hours at room temperature 25°C, the reaction mixture is diluted with THF. The copper salt is removed through a neutral alumina column. After concentration, it is precipitated in methanol. After drying under vacuum, the product is obtained, namely It is a long-chain hyperbranched polymer; wherein, the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl group is the same as the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain. The sum of the concentrations of polystyrene chains in DMF is 0.08g/mL.

本实施例合成的长链超支化高分子的重均分子量为1.6×10⁵g/mol，分子量分布在1.56。The weight average molecular weight of the long-chain hyperbranched polymer synthesized in this example is 1.6×10 ⁵ g/mol, and the molecular weight distribution is 1.56.

实施例7Example 7

实施例7与实施例1基本相同，不同之处在于：Embodiment 7 is basically the same as Embodiment 1, except that:

④在一个配备有搅拌磁子和三个橡胶塞的三口瓶中加入末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链(0.0047mmol)、末端带叠氮且链中间带有炔基的聚苯乙烯链(0.94mmol)、PMDETA(1.8894mmol)和DMF，通过四次冷冻-泵抽真空-解冻循环操作除氧后，在冷却状态下，向烧瓶中加入CuBr(1.8894mmol)并除氧，在室温25℃下反应36h后，反应混合物用THF稀释，通过中性氧化铝柱子除去铜盐，经浓缩后在甲醇中沉淀，真空干燥后得到产物，即为长链超支化高分子；其中，所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链在DMF中的浓度之和为0.08g/mL。④Into a three-necked flask equipped with a stirring magnet and three rubber stoppers, add a polystyrene chain (0.0047mmol) with azide at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl, and azide at the end. Nitrogen and a polystyrene chain with an alkynyl group in the middle (0.94mmol), PMDETA (1.8894mmol) and DMF were deoxygenated through four freeze-pump vacuum-thaw cycles, and then added to the flask in a cooling state. Add CuBr (1.8894mmol) and remove oxygen. After reacting for 36 hours at room temperature 25°C, the reaction mixture is diluted with THF. The copper salt is removed through a neutral alumina column. After concentration, it is precipitated in methanol. After vacuum drying, the product is obtained, namely It is a long-chain hyperbranched polymer; wherein, the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl group is the same as the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain. The sum of the concentrations of polystyrene chains in DMF is 0.08g/mL.

本实施例合成的长链超支化高分子的重均分子量为7.2×10⁶g/mol，分子量分布在1.95。The weight average molecular weight of the long-chain hyperbranched polymer synthesized in this example is 7.2×10 ⁶ g/mol, and the molecular weight distribution is 1.95.

实施例8Example 8

实施例8与实施例1基本相同，不同之处在于：Embodiment 8 is basically the same as Embodiment 1, except that:

④在一个配备有搅拌磁子和三个橡胶塞的三口瓶中加入末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链(0.0047mmol)、末端带叠氮且链中间带有炔基的聚苯乙烯链(0.047mmol)、PMDETA(0.0517mmol)和DMF，通过四次冷冻-泵抽真空-解冻循环操作除氧后，在冷却状态下，向烧瓶中加入CuBr(0.0517mmol)并除氧，在室温25℃下反应36h后，反应混合物用THF稀释，通过中性氧化铝柱子除去铜盐，经浓缩后在甲醇中沉淀，真空干燥后得到产物，即为长链超支化高分子；其中，所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链在DMF中的浓度之和为0.08g/mL。④Into a three-necked flask equipped with a stirring magnet and three rubber stoppers, add a polystyrene chain (0.0047mmol) with azide at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl, and azide at the end. Nitrogen and a polystyrene chain with an alkynyl group in the middle (0.047mmol), PMDETA (0.0517mmol) and DMF were deoxygenated through four freeze-pump vacuum-thaw cycles, and then were added to the flask in a cooling state. Add CuBr (0.0517mmol) and remove oxygen. After reacting for 36 hours at room temperature 25°C, the reaction mixture is diluted with THF. The copper salt is removed through a neutral alumina column. After concentration, it is precipitated in methanol. After vacuum drying, the product is obtained, namely It is a long-chain hyperbranched polymer; wherein, the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl group is the same as the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain. The sum of the concentrations of polystyrene chains in DMF is 0.08g/mL.

本实施例合成的长链超支化高分子的重均分子量为4.0×10⁵g/mol，分子量分布在1.49。The weight average molecular weight of the long-chain hyperbranched polymer synthesized in this example is 4.0×10 ⁵ g/mol, and the molecular weight distribution is 1.49.

实施例9Example 9

④在一个配备有搅拌磁子和三个橡胶塞的三口瓶中加入末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链(0.0047mmol)、末端带叠氮且链中间带有炔基的聚苯乙烯链(0.047mmol)、PMDETA(0.3102mmol)和DMF，通过四次冷冻-泵抽真空-解冻循环操作除氧后，在冷却状态下，向烧瓶中加入CuBr(0.3102mmol)并除氧，在室温25℃下反应36h后，反应混合物用THF稀释，通过中性氧化铝柱子除去铜盐，经浓缩后在甲醇中沉淀，真空干燥后得到产物，即为长链超支化高分子；其中，所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链在DMF中的浓度之和为0.08g/mL。④Into a three-necked flask equipped with a stirring magnet and three rubber stoppers, add a polystyrene chain (0.0047mmol) with azide at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl, and azide at the end. Nitrogen and a polystyrene chain with an alkynyl group in the middle (0.047mmol), PMDETA (0.3102mmol) and DMF were deoxygenated through four freeze-pump vacuum-thawing cycles, and then were added to the flask in a cooling state. Add CuBr (0.3102mmol) and remove oxygen. After reacting for 36 hours at room temperature 25°C, the reaction mixture is diluted with THF. The copper salt is removed through a neutral alumina column. After concentration, it is precipitated in methanol. After vacuum drying, the product is obtained, namely It is a long-chain hyperbranched polymer; wherein, the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl group is the same as the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain. The sum of the concentrations of polystyrene chains in DMF is 0.08g/mL.

本实施例合成的长链超支化高分子的重均分子量为7.26×10⁵g/mol，分子量分布在1.53。The weight average molecular weight of the long-chain hyperbranched polymer synthesized in this example is 7.26×10 ⁵ g/mol, and the molecular weight distribution is 1.53.

对比例1Comparative example 1

①与实施例1的步骤①相同。①Same as step ① in Example 1.

②与实施例1的步骤②相同。②Same as step ② in Example 1.

③在一个配备有搅拌磁子和三个橡胶塞的三口瓶中加入末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链(B₂型大单体)(0.00517mmol)、PMDETA(0.104mmol)和DMF，通过四次冷冻-泵抽真空-解冻循环操作除氧后，在冷却状态下，向烧瓶中加入CuBr(0.104mmol)并除氧，在室温25℃下反应36h后，反应混合物用THF稀释，通过中性氧化铝柱子除去铜盐，经浓缩后在甲醇中沉淀，真空干燥后得到产物；其中，所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链在DMF中的浓度为0.08g/mL。③Into a three-necked flask equipped with a stirring magnet and three rubber stoppers, add a polystyrene chain (B ₂ type macromonomer) with an azide at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl. (0.00517mmol), PMDETA (0.104mmol) and DMF, after deoxygenation through four freezing-pumping-thawing cycle operations, in the cooling state, add CuBr (0.104mmol) to the flask and deoxygenate, at room temperature 25 After reacting for 36 hours at ℃, the reaction mixture was diluted with THF, the copper salt was removed through a neutral alumina column, concentrated and precipitated in methanol, and the product was obtained after vacuum drying; wherein, the end has an azide and an alkyne in the middle of the chain The concentration of polystyrene chains protected by trimethylsilyl groups in DMF was 0.08 g/mL.

本对比例的产物依然是B₂大单体，重均分子量为21000g/mol。The product of this comparative example is still _B2 macromonomer, with a weight average molecular weight of 21000g/mol.

对比例2Comparative example 2

①与实施例1的步骤①相同。①Same as step ① in Example 1.

②与实施例1的步骤②相同。②Same as step ② in Example 1.

③与实施例1的步骤③相同。③Same as step ③ in Example 1.

④在一个配备有搅拌磁子和三个橡胶塞的三口瓶中加入末端带叠氮且链中间带有炔基的聚苯乙烯链(0.0517mmol)、PMDETA(0.104mmol)和DMF，通过四次冷冻-泵抽真空-解冻循环操作除氧后，在冷却状态下，向烧瓶中加入CuBr(0.104mmol)并除氧，在室温25℃下反应36h后，反应混合物用THF稀释，通过中性氧化铝柱子除去铜盐，经浓缩后在甲醇中沉淀，真空干燥后得到产物；其中，所述末端带叠氮且链中间带有炔基的聚苯乙烯链在DMF中的浓度为0.08g/mL。④ In a three-necked flask equipped with a stirring magnet and three rubber stoppers, add a polystyrene chain with azide at the end and an alkynyl group in the middle (0.0517mmol), PMDETA (0.104mmol) and DMF, and pass it through four times After deoxygenation by freezing-pumping-thawing cycle operation, CuBr (0.104mmol) was added to the flask in a cooling state and deoxygenated. After reacting for 36 hours at room temperature 25°C, the reaction mixture was diluted with THF and neutralized through neutral oxidation. An aluminum column was used to remove the copper salt, and after concentration, it was precipitated in methanol, and the product was obtained after vacuum drying; wherein, the concentration of the polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain in DMF was 0.08g/mL. .

本对比例合成的产物的重均分子量为8.79×10⁶g/mol分子量分布在2.89。The weight average molecular weight of the product synthesized in this comparative example is 8.79×10 ⁶ g/mol, and the molecular weight distribution is 2.89.

对比例3Comparative example 3

①向一个配备搅拌磁子的三口瓶中加入如式II所示的引发剂(化合物IV)(0.173mmol)、苯乙烯(173mmol)、三(2-二甲氨基乙基)胺(配体)(0.346mmol)、辛酸亚锡(0.346mmol)和苯甲醚(溶剂)，苯乙烯与苯甲醚的体积比为1:2，随后通过三次冷冻-泵抽-解冻循环操作除氧，之后加入催化剂CuBr(0.0346mmol)，再放入90℃油浴锅中，反应4h后，用200mL THF稀释反应混合物快速通过中性氧化铝柱除去铜盐，催灭反应，再通过旋转蒸发除去溶剂和单体，得到聚合物溶液，并将聚合物溶液在500mL甲醇中沉淀两次，最后真空干燥10h，即得到末端带溴且链中间带有炔基的聚苯乙烯链；其中，式II的结构为：①Add the initiator (compound IV) (0.173mmol), styrene (173mmol), and tris(2-dimethylaminoethyl)amine (ligand) as shown in Formula II to a three-necked flask equipped with a stirring magnet. (0.346mmol), stannous octoate (0.346mmol) and anisole (solvent), the volume ratio of styrene to anisole is 1:2, and then the oxygen is removed through three freezing-pumping-thawing cycles, and then added Catalyst CuBr (0.0346mmol) was put into a 90°C oil bath. After 4 hours of reaction, the reaction mixture was diluted with 200mL THF and quickly passed through a neutral alumina column to remove the copper salt to quench the reaction. The solvent and monomer were then removed by rotary evaporation. The polymer solution was obtained, and the polymer solution was precipitated twice in 500 mL methanol, and finally vacuum dried for 10 h to obtain a polystyrene chain with bromine at the end and an alkynyl group in the middle of the chain; wherein, the structure of Formula II is :

②在圆底烧瓶中装入末端带溴且链中间带有炔基的聚苯乙烯链(0.19mmol)、NaN₃(1.9mmol)和DMF在室温25℃下搅拌48h，再加入二氯甲烷，之后在264mL甲醇中沉淀，用适量THF将沉淀物溶解，并再次进行沉淀提纯，之后置于真空烘箱中真空干燥10h，得到末端带叠氮且链中间带有炔基的聚苯乙烯链；其中，末端带溴且链中间带有炔基的聚苯乙烯链与DMF的质量比为1:5.7，DMF与二氯甲烷的体积比为1:0.1。②Put a polystyrene chain with bromine at the end and an alkynyl group in the middle (0.19mmol), NaN ₃ (1.9mmol) and DMF into a round-bottomed flask. Stir at room temperature 25°C for 48h, then add dichloromethane. Then precipitate in 264 mL methanol, dissolve the precipitate with an appropriate amount of THF, and precipitate and purify again, and then place it in a vacuum oven for vacuum drying for 10 hours to obtain a polystyrene chain with azide at the end and an alkynyl group in the middle of the chain; where , the mass ratio of the polystyrene chain with bromine at the end and an alkynyl group in the middle of the chain to DMF is 1:5.7, and the volume ratio of DMF to dichloromethane is 1:0.1.

③在一个配备有搅拌磁子和三个橡胶塞的三口瓶中加入末端带叠氮且链中间带有炔基的聚苯乙烯链(0.0517mmol)、PMDETA(0.104mmol)和DMF，通过四次冷冻-泵抽真空-解冻循环操作除氧后，在冷却状态下，向烧瓶中加入CuBr(0.104mmol)并除氧，在室温25℃下反应36h后，反应混合物用THF稀释，通过中性氧化铝柱子除去铜盐，经浓缩后在甲醇中沉淀，真空干燥后得到产物；其中，所述末端带叠氮且链中间带有炔基的聚苯乙烯链在DMF中的浓度为0.08g/mL。③Into a three-necked flask equipped with a stirring magnet and three rubber stoppers, add a polystyrene chain with azide at the end and an alkynyl group in the middle (0.0517mmol), PMDETA (0.104mmol) and DMF, and pass it through four times After deoxygenation by freezing-pumping-thawing cycle operation, CuBr (0.104mmol) was added to the flask in a cooling state and deoxygenated. After reacting for 36 hours at room temperature 25°C, the reaction mixture was diluted with THF and neutralized through neutral oxidation. An aluminum column was used to remove the copper salt, and after concentration, it was precipitated in methanol, and the product was obtained after vacuum drying; wherein, the concentration of the polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain in DMF was 0.08g/mL. .

本对比例合成的产物的重均分子量为9.13×10⁶g/mol，分子量分布在2.91。The weight average molecular weight of the product synthesized in this comparative example is 9.13×10 ⁶ g/mol, and the molecular weight distribution is 2.91.

本发明未详细说明部分为本领域技术人员公知技术。The parts of the present invention that are not described in detail are well known to those skilled in the art.

最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that it can still be used Modifications are made to the technical solutions described in the foregoing embodiments, or equivalent substitutions are made to some of the technical features; however, these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1.一种超支化高分子的合成方法，其特征在于，所述方法包括如下步骤：1. A method for synthesizing hyperbranched polymers, characterized in that the method includes the following steps: (1)将引发剂、苯乙烯单体、配体和溶剂混合均匀，然后在催化剂作用下进行反应，得到末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链，所述引发剂具有如下式I的结构：(1) Mix the initiator, styrene monomer, ligand and solvent evenly, and then react under the action of a catalyst to obtain polystyrene with bromine at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl. Chain, the initiator has the structure of the following formula I: (2)将末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与叠氮化钠进行反应，得到末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链；(2) React a polystyrene chain with bromine at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl with sodium azide to obtain an azide at the end and an alkynyl group in the middle of the chain protected by trimethylsilyl. Methylsilyl-protected polystyrene chains; (3)将末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与四丁基氟化铵进行反应，得到末端带叠氮且链中间带有炔基的聚苯乙烯链；(3) React a polystyrene chain with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl with tetrabutylammonium fluoride to obtain an azide at the end and an alkynyl group in the middle of the chain. polystyrene chains; (4)将末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链、末端带叠氮且链中间带有炔基的聚苯乙烯链和五甲基二乙烯三胺混合均匀，然后在催化剂作用下进行反应，得到超支化高分子。(4) Combine a polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl, a polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain, and pentamethylbis Ethylene triamine is mixed evenly, and then reacts under the action of a catalyst to obtain hyperbranched polymers. 2.根据权利要求1所述的合成方法，其特征在于，在步骤(1)中：2. The synthesis method according to claim 1, characterized in that, in step (1): 所述配体为三(2-二甲氨基乙基)胺、2,2’-联吡啶和五甲基二乙烯三胺中的一种或多种，优选的是，所述配体为三(2-二甲氨基乙基)胺，且在所述混合液中还添加有辛酸亚锡，更优选的是，三(2-二甲氨基乙基)胺与辛酸亚锡的摩尔比为1:1；The ligand is one or more of tris(2-dimethylaminoethyl)amine, 2,2'-bipyridine and pentamethyldiethylenetriamine. Preferably, the ligand is tris(2-dimethylaminoethyl)amine. (2-dimethylaminoethyl)amine, and stannous octoate is also added to the mixed solution. More preferably, the molar ratio of tris(2-dimethylaminoethyl)amine to stannous octoate is 1 :1; 所述溶剂为甲苯和/或苯甲醚；The solvent is toluene and/or anisole; 所述引发剂与所述苯乙烯单体的摩尔比为1：(100～1000)；The molar ratio of the initiator to the styrene monomer is 1: (100~1000); 所述引发剂与所述配体的摩尔比为1：(2～6)；The molar ratio of the initiator to the ligand is 1: (2-6); 所述催化剂为CuBr；The catalyst is CuBr; 所述配体与所述催化剂的摩尔比为(1～10)：1；和/或The molar ratio of the ligand to the catalyst is (1-10):1; and/or 所述苯乙烯单体与所述溶剂的体积比为1：(0.5～2)。The volume ratio of the styrene monomer to the solvent is 1: (0.5-2). 3.根据权利要求1所述的合成方法，其特征在于，在步骤(1)中：3. The synthesis method according to claim 1, characterized in that, in step (1): 所述反应的温度为80～110℃，所述反应的时间为1～48h，优选的是，所述反应的时间为3～6h。The temperature of the reaction is 80-110°C, and the reaction time is 1-48 hours. Preferably, the reaction time is 3-6 hours. 4.根据权利要求1所述的合成方法，其特征在于，在步骤(2)中：4. The synthesis method according to claim 1, characterized in that, in step (2): 末端带溴且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与叠氮化钠的摩尔比为1：(2～10)；和/或The molar ratio of the polystyrene chain with bromine at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl group to sodium azide is 1: (2～10); and/or 所述反应为室温下反应48～60h。The reaction takes place at room temperature for 48 to 60 hours. 5.根据权利要求1所述的合成方法，其特征在于：5. The synthesis method according to claim 1, characterized in that: 在步骤(3)为：将末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链溶于二氯甲烷中，得到聚苯乙烯链溶液，将聚苯乙烯链溶液通氮气除氧后加入四丁基氟化铵，在室温下搅拌反应6～24h，再经后处理，得到末端带叠氮且链中间带有炔基的聚苯乙烯链。In step (3), a polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain protected by a trimethylsilyl group is dissolved in methylene chloride to obtain a polystyrene chain solution, and the polystyrene chain is After deoxygenating the chain solution with nitrogen, add tetrabutylammonium fluoride, stir and react at room temperature for 6 to 24 hours, and then undergo post-processing to obtain a polystyrene chain with azide at the end and an alkynyl group in the middle of the chain. 6.根据权利要求5所述的合成方法，其特征在于：6. The synthesis method according to claim 5, characterized in that: 所述聚苯乙烯链溶液中含有末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链的浓度为0.05～0.15g/mL；和/或The polystyrene chain solution contains a polystyrene chain with an azide terminal and an alkynyl group in the middle of the chain and is protected by a trimethylsilyl group at a concentration of 0.05 to 0.15 g/mL; and/or 所述四丁基氟化铵与所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链的摩尔比为(1～2)：(1～2)。The molar ratio of the tetrabutylammonium fluoride to the polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and protected by a trimethylsilyl group is (1~2): (1~2) . 7.根据权利要求1所述的合成方法，其特征在于，在步骤(4)中：7. The synthesis method according to claim 1, characterized in that, in step (4): 所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链的摩尔比为1：(10～160)；The molar ratio of the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl to the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain is 1 :(10~160); 所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链用量之和与所述五甲基二乙烯三胺的用量的摩尔比为1：(2～4)；The sum of the amounts of the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain and protected by trimethylsilyl and the polystyrene chain with azide at the end and an alkynyl group in the middle of the chain is The molar ratio of the amount of pentamethyldiethylenetriamine is 1: (2～4); 所述催化剂为CuBr；The catalyst is CuBr; 所述五甲基二乙烯三胺与所述催化剂的摩尔比为1:1；和/或The molar ratio of the pentamethyldiethylenetriamine to the catalyst is 1:1; and/or 在进行反应时，以N,N’-二甲基甲酰胺作为溶剂，所述末端带叠氮且链中间带有炔基并被三甲基硅基保护的聚苯乙烯链与所述末端带叠氮且链中间带有炔基的聚苯乙烯链在N,N’-二甲基甲酰胺中的浓度之和为0.05～0.15g/mL。During the reaction, N,N'-dimethylformamide is used as the solvent, and the polystyrene chain with an azide at the end and an alkynyl group in the middle of the chain and protected by a trimethylsilyl group and the polystyrene chain with an azide at the end are The sum of the concentrations of polystyrene chains that are azide and have an alkynyl group in the middle of the chain in N,N'-dimethylformamide is 0.05 to 0.15g/mL. 8.根据权利要求1所述的合成方法，其特征在于，在步骤(4)中：8. The synthesis method according to claim 1, characterized in that, in step (4): 所述反应为室温下反应36～48h。The reaction takes place at room temperature for 36 to 48 hours. 9.根据权利要求1所述的合成方法，其特征在于：9. The synthesis method according to claim 1, characterized in that: 所述超支化高分子的重均分子量为1×10⁴～2×10⁶g/mol；The weight average molecular weight of the hyperbranched polymer is 1×10 ⁴ to 2×10 ⁶ g/mol; 所述分子量分布为1.25～1.65。The molecular weight distribution is 1.25 to 1.65. 10.由权利要求1至9中任一项所述的合成方法合成的超支化高分子。10. A hyperbranched polymer synthesized by the synthesis method according to any one of claims 1 to 9.

CN202311579863.4A 2023-11-23 2023-11-23 Hyperbranched polymer and synthesis method thereof Pending CN117343345A (en)

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CN118420923A (en) *	2024-07-02	2024-08-02	榆林学院	Preparation method of hyperbranched polymer for wastewater treatment

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Publication number	Priority date	Publication date	Assignee	Title
CN118420923A (en) *	2024-07-02	2024-08-02	榆林学院	Preparation method of hyperbranched polymer for wastewater treatment

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CN117343345A - Hyperbranched polymer and synthesis method thereof - Google Patents