CN104892887A - 一种多臂丙烯酸酯嵌段共聚物的制备方法 - Google Patents

一种多臂丙烯酸酯嵌段共聚物的制备方法 Download PDF

Info

Publication number
CN104892887A
CN104892887A CN201510347178.8A CN201510347178A CN104892887A CN 104892887 A CN104892887 A CN 104892887A CN 201510347178 A CN201510347178 A CN 201510347178A CN 104892887 A CN104892887 A CN 104892887A
Authority
CN
China
Prior art keywords
block copolymer
preparation
arm
acrylate
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510347178.8A
Other languages
English (en)
Other versions
CN104892887B (zh
Inventor
李坚
刘新
孙仪琳
任强
汪称意
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changzhou University
Original Assignee
Changzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changzhou University filed Critical Changzhou University
Priority to CN201510347178.8A priority Critical patent/CN104892887B/zh
Publication of CN104892887A publication Critical patent/CN104892887A/zh
Application granted granted Critical
Publication of CN104892887B publication Critical patent/CN104892887B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/633—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polymers of compounds having carbon-to-carbon double bonds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/42—Nitriles
    • C08F120/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6245—Polymers having terminal groups containing active hydrogen
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/6262—Polymers of nitriles derived from alpha-beta ethylenically unsaturated 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/638—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers characterised by the use of compounds having carbon-to-carbon double bonds other than styrene and/or olefinic nitriles
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

本发明涉及一种多臂丙烯酸酯嵌段共聚物的制备方法，包括步骤：端羟基丙烯酸酯大分子引发剂的制备、端羟基丙烯酸酯嵌段共聚物的制备和多臂丙烯酸酯嵌段共聚物的制备。本发明的有益效果是：采用ARGET ATRP方法合成多臂丙烯酸酯嵌段共聚物，臂的组成和结构可以精确调控；通过ATRP控制聚合物的分散性，使嵌段共聚物规整度大幅提高，提高产物的性能；聚合反应可在相对开放的空间中进行，催化剂的量小于500ppm，产物不用除催化剂可直接使用，效率高，成本较传统方法低；利用羟基和异氰酸酯基的反应将臂键接到多异氰酸酯上，形成以多异氰酸酯为中心，丙烯酸酯嵌段共聚物为臂的多臂结构；利用先臂后核法，过程和实现难度简化。

Description

一种多臂丙烯酸酯嵌段共聚物的制备方法
技术领域
本发明属于化工材料领域，涉及一种多臂丙烯酸酯嵌段共聚物的制备方法。
背景技术
嵌段共聚物是由化学结构不同的两种或两种以上的聚合物链段组成的，按照组成嵌段共聚物的单体种类的数量，可分为两嵌段、三嵌段、多嵌段等。它可以将多种聚合物的优良性质结合在一起，得到性能比较优越的功能聚合物材料。
嵌段共聚物的合成方法有多种，包括活性阴离子聚合，活性阳离子聚合，基团转移聚合，可控/活性自由基聚合等。嵌段共聚物作为一种特殊的线性共聚物，与共混物和接枝共聚物在结构和性质上是不同的。它的玻璃化温度由温度较低的聚合物决定的，而软化点却随该温度较高的聚合物而变化，因而处于高弹态的温度范围较宽。具有特定结构的嵌段聚合物会表现出与简单线形聚合物，以及许多无规共聚物甚至均聚物的混合物不同的性质，可用作热塑弹性体、共混相容剂、界面改性剂等。广泛地应用于生物医药、建筑、化工等各个领域，在理论研究和实际应用中都具有重要的意义。
多臂嵌段共聚物是指一种或多种嵌段共聚物链通过化学键连接到同一个中心核所形成的聚合物。由于每个臂的部分都可以设计其链段分子量及链段组成等，大大扩展了嵌段共聚物的种类和和性能的多样性，为嵌段共聚物的研究增添了新内容。它的一个重要特点是本体和液体粘度比相同分子量的线型聚合物要低的多，所以可以广泛用作涂料中流体调节剂、耐冲击修饰剂、压敏粘合剂和热塑性弹性体等。此外它还可用于共混增溶剂、耐冲击修饰剂、密封剂和模塑组份等。
近年来应用ATRP方法合成多臂/星型聚合物发展迅速，ATRP体系中星型聚合物的合成主要有三种方法：发散法、收敛法、微凝胶法。具有多于两个反应性的碳-卤键化合物可用作引发剂合成星型聚合物，臂数由引发中心的数目决定，臂长取决于初始单体/引发剂浓度比。
专利CN1486995公开了一种含多羟基官能团多臂星状超支化聚合物刷及其制备方法：先制备超支化大分子引发剂，然后在催化剂及配体存在下用原子转移自由基聚合反应(ATRP)引发含双键单体聚合，得到多臂星状超支化聚合物刷。专利CN101575402公开一种多臂星形聚合物及其制备方法：它先制备超支化聚苯乙烯大分子引发剂，然后引发单体的原子转移自由基聚合，得到多臂星形聚合物。
这些方法都可以用来合成多臂嵌段聚合物，而且都是制备结构复杂的大分子作为引发剂来合成多臂聚合物，属于先核后臂法，其超支化大分子引发剂的合成相对复杂实现难度相对较高。
本发明利用ARGET ATRP的可控优势，先合成具有预定结构带有端羟基的臂部分，臂的部分可以设计化学组成、分子量、嵌段比等。再利用羟基与异氰酸酯基反应，成功合成具有多臂结构的丙烯酸酯嵌段共聚物。这种方法和已经报道的方法相比，属先臂后核法，且不必合成结构复杂的超支化大分子引发剂，难度相对简化。
发明内容
本发明要解决的技术问题是：基于上述问题，本发明提供一种多臂丙烯酸酯嵌段共聚物的制备方法。
本发明解决其技术问题所采用的一个技术方案是：一种多臂丙烯酸酯嵌段共聚物的制备方法，其特征是：包括以下步骤：
(1)端羟基丙烯酸酯大分子引发剂的制备：将单体Ⅰ、引发剂、络合液、还原剂Ⅰ和溶剂Ⅰ加入到反应容器中，将反应体系抽真空充氮气重复操作数次，60～110℃反应0.5～10小时，制得端羟基丙烯酸酯大分子引发剂，分子量分布<2.0；
(2)端羟基丙烯酸酯嵌段共聚物的制备：步骤(1)制得的丙烯酸酯大分子引发剂中加入单体Ⅱ、还原剂Ⅱ和溶剂Ⅱ，将反应体系抽真空充氮气重复操作数次，60～110℃反应0.5～10小时，制得端羟基丙烯酸酯嵌段共聚物，分子量分布<2.0；
(3)多臂丙烯酸酯嵌段共聚物的制备：将步骤(2)制得的端羟基嵌段共聚物用溶剂Ⅲ溶解，加入催化剂和异氰酸酯，50～90℃反应1～9小时，制得多臂丙烯酸酯嵌段共聚物。
进一步地，步骤(1)中引发剂为一个端基为羟基的有机卤代化合物，引发剂具体为α-溴代异丁酸羟乙酯、α-氯代异丁酸羟乙酯、α-溴代异丁酸羟丁酯或α-氯代异丁酸羟丁酯中的一种。
进一步地，单体Ⅰ和单体Ⅱ均为丙烯酸酯类、甲基丙烯酸酯类、含氟丙烯酸酯类、含氟甲基丙烯酸酯类、苯乙烯或丙烯腈类中的一种，单体Ⅰ和单体Ⅱ具体为甲基丙烯酸丁酯、甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸异辛酯、丙烯酸甲酯、甲基丙烯酸二甲氨基乙酯、甲基丙烯酸三氟乙酯，甲基丙烯酸六氟丁酯、甲基丙烯酸十二氟庚酯、苯乙烯或丙烯腈中的一种；络合液为氧化态的过渡金属卤化物、配体和乙醇在常温下搅拌均匀而得，氧化态的过渡金属卤化物为CuCl2、CuBr2、FeCl3或FeBr3中的一种，配体为五甲基二乙烯基三胺三-(N，N-二甲氨基乙基)胺或1，1，4，7，10，10-六甲基三亚乙基四胺中的一种；还原剂Ⅰ和还原剂Ⅱ均为辛酸亚锡、抗坏血酸或葡萄糖中的一种。
进一步地，步骤(3)中催化剂为二月桂酸二丁基锡、三乙醇胺或辛酸亚锡中的一种，异氰酸酯为二异氰酸酯或多异氰酸酯以及异氰酸酯的加成物，异氰酸酯具体为二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、萘-1，5-二异氰酸酯、2，6-二异氰酸酯己酸甲酯、六甲基二异氰酸酯、六甲基二异氰酸酯三聚体、甲苯二异氰酸酯与三羟甲基丙烷加成物或异佛尔酮二异氰酸酯与季戊四醇加成物中的一种。
进一步地，步骤(1)、(2)和(3)中溶剂Ⅰ、溶剂Ⅱ和溶剂Ⅲ均为甲苯、苯甲醚、N，N-二甲基甲酰胺、四氢呋喃、乙酸乙酯或1-甲基-2-吡咯烷酮中的一种。
进一步地，单体Ⅰ：引发剂的摩尔比为20：1～500：1，单体Ⅱ：丙烯酸酯大分子引发剂的摩尔比为20：1～500：1，单体Ⅰ：氧化态的过渡金属卤化物的摩尔比为1：0.0005～1：0.00005氧化态的过渡金属卤化物：还原剂Ⅰ或还原剂Ⅱ的摩尔比为1：10～1：25，溶剂Ⅰ用量为单体Ⅰ质量的10～100％，溶剂Ⅱ用量为单体Ⅱ质量的10～100％。
进一步地，步骤(3)中的端羟基嵌段共聚物中羟基与异氰酸酯中异氰酸酯基的摩尔比为1：1.0～1：1.5。
进一步地，络合液中氧化态的过渡金属卤化物：配体的摩尔比为1：10～1：30。
本发明的有益效果是：1.本发明采用ARGET ATRP方法合成多臂丙烯酸酯嵌段共聚物，臂的组成和结构可以精确调控(分子量可控，分子量分布窄)；同时，也可以通过ATRP控制聚合物的分散性，使嵌段共聚物规整度大幅提高，从而提高产物的性能；聚合反应可在相对开放的空间中进行，所用催化剂的量小于500ppm，产物不用除催化剂可直接使用，效率高，成本较传统方法低；
2.本发明利用羟基和异氰酸酯基的反应将臂键接到多异氰酸酯上，形成以多异氰酸酯为中心，丙烯酸酯嵌段共聚物为臂的多臂结构；不同于报道中的先核后臂法，本发明利用先臂后核法，与已报道的超支化大分子引发剂的先核后臂方法相比，过程和实现难度简化。
具体实施方式
现在结合具体实施例对本发明作进一步说明，以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例1
(1)端羟基聚丙烯酸丁酯-b-聚甲基丙烯酸甲酯(HO-PBA-b-PMMA)的制备，分子量为40600，结构为：
其中，m＝200，n＝150。
在装有温度计、搅拌桨的500ml四口烧瓶中加入丙烯酸丁酯60.00g、α-溴代异丁酸羟丁酯0.5604g、CuBr20.04194g和五甲基二乙烯基三胺0.6490g、Sn(EH)21.517g以及溶剂甲苯30.00g，混合均匀后，通氮气鼓泡，在70℃油浴下反应210min，转化率达82.7％后，将称量好的甲基丙烯酸甲酯35.16g、甲苯18.00g和Sn(EH)21.138g用注射器加入反应瓶中，反应255min后停止，将产物过中性氧化铝层析柱，脱除聚合物中的催化剂，旋蒸后甲醇沉淀，然后置于50℃真空烘箱中干燥至恒重，得到产物79g，产率83％。
(2)多臂PBA-b-PMMA的制备
NCO/OH＝1.0：1
称取HO-PBA-PMMA 20.00g、多异氰酸酯(N3390，-NCO含量18％)0.1149g、二月桂酸二丁基锡1滴和甲苯40.00g加入装有搅拌桨、温度计的四口烧瓶中，升温至80℃，反应3小时后停止，甲醇沉淀出聚合物，50℃真空烘箱干燥至恒重，得到产物。
实施例2
(1)端羟基聚丙烯酸乙酯-b-聚甲基丙烯酸丁酯(HO-PEA-b-PBMA)的制备，分子量为32000，结构为：
其中，m＝200，n＝85。
在装有温度计、搅拌桨的500ml四口烧瓶中加入丙烯酸乙酯60.00g、α-溴代异丁酸羟丁酯0.7173g、CuBr20.05369g和五甲基二乙烯基三胺0.8308g、Sn(EH)21.942g以及溶剂甲苯30.00g，混合均匀后，通氮气鼓泡，在70℃油浴下反应210min，转化率达85％后，将称量好的甲基丙烯酸甲酯36.00g、甲苯18.00g和Sn(EH)20.8264g用注射器加入反应瓶中，反应260min后停止，将产物过中性氧化铝层析柱，脱除聚合物中的催化剂，旋蒸后甲醇沉淀，然后置于50℃真空烘箱中干燥至恒重，得到产物75g，产率78％。
(2)多臂PEA-b-PBMA的制备
NCO/OH＝1.1：1
称取HO-PEA-b-PBMA 20.00g、甲苯-2，4-二异氰酸酯(TDI)0.1197g、二月桂酸二丁基锡1滴和甲苯40.00g加入装有搅拌桨、温度计的四口烧瓶中，升温至70℃，反应3.5小时后停止，甲醇沉淀出聚合物，50℃真空烘箱干燥至恒重，得到产物。
实施例3
(1)端羟基聚丙烯酸甲酯-b-聚丙烯酸异辛酯(HO-PMA-b-PEHA)的制备，分子量为21000，结构为：
其中，m＝100，n＝68。
在装有温度计、搅拌桨的500ml四口烧瓶中加入丙烯酸甲酯60.00g、α-溴代异丁酸羟丁酯1.668g、CuBr20.06251g和五甲基二乙烯基三胺0.967g、Sn(EH)22.261g以及溶剂甲苯30.00g，混合均匀后，通氮气鼓泡，在70℃油浴下反应250min，转化率达81％后，将称量好的丙烯酸异辛酯86.57g、甲苯43.00g和Sn(EH)21.525g用注射器加入反应瓶中，70℃下反应300min后停止，将产物过中性氧化铝层析柱，脱除聚合物中的催化剂，旋蒸后甲醇沉淀，然后置于50℃真空烘箱中干燥至恒重，得到产物103g，产率70.2％。
(2)多臂PMA-b-PEHA的制备
NCO/OH＝1.2：1
称取HO-PMA-b-PEHA 20.00g、甲苯-2，4-二异氰酸酯-三羟甲基丙烷加成物(TDI-TMP加合物，-NCO含量13％)0.3692g、二月桂酸二丁基锡1滴和甲苯40.00g加入装有搅拌桨、温度计的四口烧瓶中，升温至80℃，反应4.5小时后停止，甲醇沉淀出聚合物，50℃真空烘箱干燥至恒重，得到产物。
实施例4
(1)端羟基聚丙烯酸丁酯-b-聚丙烯腈(HO-PBA-b-PAN)的制备，分子量为10100，结构为：
其中，m＝50，n＝70。
在装有温度计、搅拌桨的500ml四口烧瓶中加入丙烯酸丁酯60.00g、α-溴代异丁酸羟丁酯2.242g、CuBr20.04200g和五甲基二乙烯基三胺0.6499g、Sn(EH)21.519g以及溶剂甲苯30.00g，混合均匀后，通氮气鼓泡，在70℃油浴下反应200min，转化率达86％后，将称量好的丙烯腈34.69g、甲苯17.00g和Sn(EH)22.121g用注射器加入反应瓶中，90℃下反应280min后停止，将产物过中性氧化铝层析柱，脱除聚合物中的催化剂，旋蒸后甲醇沉淀，然后置于50℃真空烘箱中干燥至恒重，得到产物64g，产率67.6％。
(2)多臂PBA-b-PAN的制备
NCO/OH＝1.3：1
称取HO-PBA-b-PAN 20.00g、异佛尔酮二异氰酸酯-季戊四醇加成物(-NCO含量15％)0.7207g、二月桂酸二丁基锡1滴和甲苯40.00g加入装有搅拌桨、温度计的四口烧瓶中，升温至80℃，反应5.5小时后停止，甲醇沉淀出聚合物，50℃真空烘箱干燥至恒重，得到产物。
实施例5
(1)端羟基聚苯乙烯-b-聚甲基丙烯酸三氟乙酯(HO-PS-b-PTFEMA)的制备，分子量为5100，结构为：
其中，m＝20，n＝18。
在装有温度计、搅拌桨的500ml四口烧瓶中加入苯乙烯60.00g、α-溴代异丁酸羟丁酯6.897g、CuBr20.05169g和五甲基二乙烯基三胺0.7998g、Sn(EH)21.870g以及溶剂甲苯30.00g，混合均匀后，通氮气鼓泡，在110℃油浴下反应360min，转化率达80％后，调节温度至75℃，将称量好的甲基丙烯酸三氟乙酯87.12g、甲苯44.00g和Sn(EH)21.680g用注射器加入反应瓶中，反应180min后停止，将产物过中性氧化铝层析柱，脱除聚合物中的催化剂，旋蒸后甲醇沉淀，然后置于50℃真空烘箱中干燥至恒重，得到产物102g，产率69.3％。
(2)多臂PS-b-PTFEMA的制备
NCO/OH＝1.5：1
称取HO-PS-b-PTFEMA 20.00g、异佛尔酮二异氰酸酯(IPDI)1.308g、二月桂酸二丁基锡1滴和甲苯40.00g加入装有搅拌桨、温度计的四口烧瓶中，升温至80℃，反应3.5小时后停止，甲醇沉淀出聚合物，50℃真空烘箱干燥至恒重，得到产物。
以上述依据本发明的理想实施例为启示，通过上述的说明内容，相关工作人员完全可以在不偏离本项发明技术思想的范围内，进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容，必须要根据权利要求范围来确定其技术性范围。

Claims (8)

1.一种多臂丙烯酸酯嵌段共聚物的制备方法，其特征是：包括以下步骤：
(1)端羟基丙烯酸酯大分子引发剂的制备：将单体Ⅰ、引发剂、络合液、还原剂Ⅰ和溶剂Ⅰ加入到反应容器中，将反应体系抽真空充氮气重复操作数次，60～110℃反应0.5～10小时，制得端羟基丙烯酸酯大分子引发剂，分子量分布<2.0；
(2)端羟基丙烯酸酯嵌段共聚物的制备：步骤(1)制得的丙烯酸酯大分子引发剂中加入单体Ⅱ、还原剂Ⅱ和溶剂Ⅱ，将反应体系抽真空充氮气重复操作数次，60～110℃反应0.5～10小时，制得端羟基丙烯酸酯嵌段共聚物，分子量分布<2.0；
(3)多臂丙烯酸酯嵌段共聚物的制备：将步骤(2)制得的端羟基嵌段共聚物用溶剂Ⅲ溶解，加入催化剂和异氰酸酯，50～90℃反应1～9小时，制得多臂丙烯酸酯嵌段共聚物。
2.根据权利要求1所述的一种多臂丙烯酸酯嵌段共聚物的制备方法，其特征是：所述的步骤(1)中引发剂为一个端基为羟基的有机卤代化合物，引发剂具体为α-溴代异丁酸羟乙酯、α-氯代异丁酸羟乙酯、α-溴代异丁酸羟丁酯或α-氯代异丁酸羟丁酯中的一种。
3.根据权利要求1所述的一种多臂丙烯酸酯嵌段共聚物的制备方法，其特征是：所述的单体Ⅰ和单体Ⅱ均为丙烯酸酯类、甲基丙烯酸酯类、含氟丙烯酸酯类、含氟甲基丙烯酸酯类、苯乙烯或丙烯腈类中的一种，单体Ⅰ和单体Ⅱ具体为甲基丙烯酸丁酯、甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸异辛酯、丙烯酸甲酯、甲基丙烯酸二甲氨基乙酯、甲基丙烯酸三氟乙酯，甲基丙烯酸六氟丁酯、甲基丙烯酸十二氟庚酯、苯乙烯或丙烯腈中的一种；络合液为氧化态的过渡金属卤化物、配体和乙醇在常温下搅拌均匀而得，氧化态的过渡金属卤化物为CuCl2、CuBr2、FeCl3或FeBr3中的一种，配体为五甲基二乙烯基三胺，三-(N，N-二甲氨基乙基)胺或1，1，4，7，10，10-六甲基三亚乙基四胺中的一种；还原剂Ⅰ和还原剂Ⅱ均为辛酸亚锡、抗坏血酸或葡萄糖中的一种。
4.根据权利要求1所述的一种多臂丙烯酸酯嵌段共聚物的制备方法，其特征是：所述的步骤(3)中催化剂为二月桂酸二丁基锡、三乙醇胺或辛酸亚锡中的一种，异氰酸酯为二异氰酸酯或多异氰酸酯以及异氰酸酯的加成物，异氰酸酯具体为二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、萘-1，5-二异氰酸酯、2，6-二异氰酸酯己酸甲酯、六甲基二异氰酸酯、六甲基二异氰酸酯三聚体、甲苯二异氰酸酯与三羟甲基丙烷加成物或异佛尔酮二异氰酸酯与季戊四醇加成物中的一种。
5.根据权利要求1所述的一种多臂丙烯酸酯嵌段共聚物的制备方法，其特征是：所述的步骤(1)、(2)和(3)中溶剂Ⅰ、溶剂Ⅱ和溶剂Ⅲ均为甲苯、苯甲醚、N，N-二甲基甲酰胺、四氢呋喃、乙酸乙酯或1-甲基-2-吡咯烷酮中的一种。
6.根据权利要求1或3所述的一种多臂丙烯酸酯嵌段共聚物的制备方法，其特征是：所述的单体Ⅰ：引发剂的摩尔比为20：1～500：1，单体Ⅱ：丙烯酸酯大分子引发剂的摩尔比为20：1～500：1，单体Ⅰ：氧化态的过渡金属卤化物的摩尔比为1：0.0005～1：0.00005，氧化态的过渡金属卤化物：还原剂Ⅰ或还原剂Ⅱ的摩尔比为1：10～1：25，溶剂Ⅰ用量为单体Ⅰ质量的10～100％，溶剂Ⅱ用量为单体Ⅱ质量的10～100％。
7.根据权利要求1所述的一种多臂丙烯酸酯嵌段共聚物的制备方法，其特征是：所述的步骤(3)中的端羟基嵌段共聚物中羟基与异氰酸酯中异氰酸酯基的摩尔比为1：1.0～1：1.5。
8.根据权利要求3所述的一种多臂丙烯酸酯嵌段共聚物的制备方法，其特征是：所述的络合液中氧化态的过渡金属卤化物：配体的摩尔比为1：10～1：30。
CN201510347178.8A 2015-02-04 2015-06-19 一种多臂丙烯酸酯嵌段共聚物的制备方法 Expired - Fee Related CN104892887B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510347178.8A CN104892887B (zh) 2015-02-04 2015-06-19 一种多臂丙烯酸酯嵌段共聚物的制备方法

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN2015100589735 2015-02-04
CN201510058973.5A CN104558495A (zh) 2015-02-04 2015-02-04 一种聚氨酯接枝聚丙烯酸酯水分散体的制备方法
CN201510347178.8A CN104892887B (zh) 2015-02-04 2015-06-19 一种多臂丙烯酸酯嵌段共聚物的制备方法

Publications (2)

Publication Number Publication Date
CN104892887A true CN104892887A (zh) 2015-09-09
CN104892887B CN104892887B (zh) 2018-07-17

Family

ID=53075634

Family Applications (5)

Application Number Title Priority Date Filing Date
CN201510058973.5A Withdrawn CN104558495A (zh) 2015-02-04 2015-02-04 一种聚氨酯接枝聚丙烯酸酯水分散体的制备方法
CN201510306786.4A Pending CN104892805A (zh) 2015-02-04 2015-06-06 一种聚氨酯接枝聚苯乙烯水分散体的制备方法
CN201510306669.8A Expired - Fee Related CN104861147B (zh) 2015-02-04 2015-06-06 一种聚氨酯接枝聚丙烯酸酯水分散体的制备方法
CN201510306733.2A Expired - Fee Related CN104861151B (zh) 2015-02-04 2015-06-06 一种聚氨酯‑聚甲基丙烯酸甲酯嵌段共聚物的制备方法
CN201510347178.8A Expired - Fee Related CN104892887B (zh) 2015-02-04 2015-06-19 一种多臂丙烯酸酯嵌段共聚物的制备方法

Family Applications Before (4)

Application Number Title Priority Date Filing Date
CN201510058973.5A Withdrawn CN104558495A (zh) 2015-02-04 2015-02-04 一种聚氨酯接枝聚丙烯酸酯水分散体的制备方法
CN201510306786.4A Pending CN104892805A (zh) 2015-02-04 2015-06-06 一种聚氨酯接枝聚苯乙烯水分散体的制备方法
CN201510306669.8A Expired - Fee Related CN104861147B (zh) 2015-02-04 2015-06-06 一种聚氨酯接枝聚丙烯酸酯水分散体的制备方法
CN201510306733.2A Expired - Fee Related CN104861151B (zh) 2015-02-04 2015-06-06 一种聚氨酯‑聚甲基丙烯酸甲酯嵌段共聚物的制备方法

Country Status (1)

Country Link
CN (5) CN104558495A (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106467591A (zh) * 2016-09-06 2017-03-01 常州大学 一种含多环及线性链段的环状聚合物的合成方法
CN106750057A (zh) * 2017-01-10 2017-05-31 上海鲁聚聚合物技术有限公司 一种苯乙烯‑含氟丙烯酸酯嵌段共聚物及其制备方法
CN107880229A (zh) * 2017-12-08 2018-04-06 万华化学集团股份有限公司 一种端基改性的聚丙烯酸酯嵌段共聚物的制备方法及其制得的聚丙烯酸酯嵌段共聚物

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104558495A (zh) * 2015-02-04 2015-04-29 常州大学 一种聚氨酯接枝聚丙烯酸酯水分散体的制备方法
CN105199050B (zh) * 2015-09-11 2018-06-08 湘潭大学 一种聚氨酯接枝共聚物及其制备方法
CN105601828A (zh) * 2015-12-19 2016-05-25 高明志 蓖麻油基聚氨酯-丙烯酸酯乳液的制备方法
CN106751070A (zh) * 2016-12-16 2017-05-31 安徽亚兰密封件有限公司 一种高韧性耐低温改性橡胶密封件及其制备方法
CN109206570B (zh) * 2017-06-30 2023-04-25 厦门天策材料科技有限公司 一种柔性物理分相超分子动态聚合物及其应用
CN107629673B (zh) * 2017-09-28 2021-01-08 宁波帅特龙集团有限公司 一种高强度的涂层材料及其涂装工艺
CN107694868B (zh) * 2017-09-28 2021-01-19 宁波帅特龙集团有限公司 一种汽车内饰件的涂装工艺
CN108047367B (zh) * 2017-11-13 2020-09-11 四川大学 含氟聚丙烯酸酯二元醇及其制备方法
CN107903348B (zh) * 2017-11-28 2020-06-26 常州大学 一种聚乙二醇接枝聚甲基丙烯酸甲酯两亲性接枝共聚物的制备方法
CN108467471B (zh) * 2018-04-04 2020-10-30 优美特（北京）环境材料科技股份公司 一种梳状多支化水性聚氨酯分散体及其制备与应用
CN108409993B (zh) * 2018-04-19 2020-02-21 南通纺织丝绸产业技术研究院 一种含氟聚己内酯膜及其制备方法
CN110577648B (zh) * 2018-04-19 2021-09-28 苏州大学 一种疏水型聚己内酯的制备方法
CN108676141A (zh) * 2018-05-25 2018-10-19 北京化工大学 以聚苯乙烯为硬段的嵌段聚氨酯制备方法
CN109134745B (zh) * 2018-08-21 2021-06-01 深圳市广业电子科技有限公司 一种制备（甲基）丙烯酸-聚酯嵌段共聚物的无溶剂聚合产生技术
CN109810224B (zh) * 2019-01-24 2020-06-09 中国石油大学(北京) 电子转移活化再生催化剂引发体系及成胶时间控制方法
CN110407994A (zh) * 2019-06-20 2019-11-05 宜兴鸿兴瑞奇新材料科技有限公司 一种环保型水性聚氨酯室内装饰用合成皮革的制备方法及其专用树脂
CN110845738A (zh) * 2019-11-28 2020-02-28 科迈特新材料有限公司 一种用于高分子合成材料加工的配比工艺
CN110982035A (zh) * 2019-12-11 2020-04-10 上海三恩化工有限公司 一种植绒胶用水性聚氨酯及其制备方法
CN111423558A (zh) * 2020-05-26 2020-07-17 福建华夏蓝新材料科技有限公司 一种自消光水性聚氨酯分散体的制备方法
CN112375174A (zh) * 2020-09-22 2021-02-19 苏州双象光学材料有限公司 一种用于注塑导光板的pmma材料粒子制备方法
CN113292684B (zh) * 2021-05-28 2022-08-05 万华化学集团股份有限公司 一种改性聚甲基丙烯酸甲酯及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1486995A (zh) * 2003-07-31 2004-04-07 上海交通大学 含多羟基官能团多臂星状超支化聚合物刷及其制备方法
CN101575402A (zh) * 2009-05-31 2009-11-11 中国科学院化学研究所 一种多臂星型聚合物及其制备方法
CN101921380A (zh) * 2010-02-05 2010-12-22 江苏工业学院 一种聚丙烯酸酯-氨酯共聚物及其制备方法
CN104031224A (zh) * 2014-06-16 2014-09-10 常州大学 一种聚丙烯酸酯-聚氨酯热塑性弹性体的制备方法
CN104231898A (zh) * 2014-09-11 2014-12-24 常州大学 一种星形丙烯酸酯树脂高固体分涂料及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5911894B2 (ja) * 1976-11-16 1984-03-19 王子製紙株式会社 感光性組成物
US4264755A (en) * 1976-11-19 1981-04-28 Mobay Chemical Corporation Hydroxy-functional vinyl copolymers
CN101445579A (zh) * 2008-12-11 2009-06-03 东华大学 聚氨酯大单体HPU/苯乙烯St互穿网络复合材料的制备方法
CN102604029B (zh) * 2012-02-22 2014-05-28 常州大学 一种含氟水性聚氨酯及其制备方法
CN104558495A (zh) * 2015-02-04 2015-04-29 常州大学 一种聚氨酯接枝聚丙烯酸酯水分散体的制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1486995A (zh) * 2003-07-31 2004-04-07 上海交通大学 含多羟基官能团多臂星状超支化聚合物刷及其制备方法
CN101575402A (zh) * 2009-05-31 2009-11-11 中国科学院化学研究所 一种多臂星型聚合物及其制备方法
CN101921380A (zh) * 2010-02-05 2010-12-22 江苏工业学院 一种聚丙烯酸酯-氨酯共聚物及其制备方法
CN104031224A (zh) * 2014-06-16 2014-09-10 常州大学 一种聚丙烯酸酯-聚氨酯热塑性弹性体的制备方法
CN104231898A (zh) * 2014-09-11 2014-12-24 常州大学 一种星形丙烯酸酯树脂高固体分涂料及其制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106467591A (zh) * 2016-09-06 2017-03-01 常州大学 一种含多环及线性链段的环状聚合物的合成方法
CN106467591B (zh) * 2016-09-06 2019-02-12 常州大学 一种含多环及线性链段的环状聚合物的合成方法
CN106750057A (zh) * 2017-01-10 2017-05-31 上海鲁聚聚合物技术有限公司 一种苯乙烯‑含氟丙烯酸酯嵌段共聚物及其制备方法
CN107880229A (zh) * 2017-12-08 2018-04-06 万华化学集团股份有限公司 一种端基改性的聚丙烯酸酯嵌段共聚物的制备方法及其制得的聚丙烯酸酯嵌段共聚物

Also Published As

Publication number Publication date
CN104861151A (zh) 2015-08-26
CN104861147B (zh) 2017-08-01
CN104861151B (zh) 2017-09-08
CN104892887B (zh) 2018-07-17
CN104861147A (zh) 2015-08-26
CN104892805A (zh) 2015-09-09
CN104558495A (zh) 2015-04-29

Similar Documents

Publication Publication Date Title
CN104892887A (zh) 一种多臂丙烯酸酯嵌段共聚物的制备方法
CN102702536B (zh) 一种三嵌段聚合物的合成方法
Xu et al. pH-and temperature-responsive hydrogels from crosslinked triblock copolymers prepared via consecutive atom transfer radical polymerizations
JP4856547B2 (ja) 反応性ホットメルト接着剤を製造するための混合物およびこれから得られる反応性ホットメルト接着剤
CN1961014B (zh) 催化组合物
CN110003481B (zh) 一种八臂杂臂星形聚合物的制备方法
CN103261236B (zh) 在链末端附近具有湿气可固化官能团簇的可固化组合物
CN103224627A (zh) 聚乳酸乙醇酸-聚肽-聚乙二醇二嵌段-接枝共聚物的制备方法
Wever et al. Comb-like thermoresponsive polymeric materials: Synthesis and effect of macromolecular structure on solution properties
US6121380A (en) Preparation of adhesive (CO) polymers from isocyanate chain extended narrow molecular weight distribution telechelic (CO) polymers made by pseudo living polymerization
CN104755506A (zh) (甲基)丙烯酸单体的受控自由基聚合
EP2303940A1 (de) Blockcopolymere auf (meth)acrylatbasis
CN107406745A (zh) 反应性热熔粘接剂组合物
CN103865088A (zh) 一种聚己内酯与聚乙二醇改进聚肽膜亲水性的方法
Ferris et al. Synthesis of functional sugar‐based polyurethanes
Buchmeiser et al. Co (acac) 2‐Mediated Radical Polymerization of Acrylonitrile: Control Over Molecular Weights and Copolymerization With Methyl Methacrylate
CN103044649A (zh) 一种含氟阳离子水性聚氨酯及其制备方法
CN103819909A (zh) 一种聚对二氧环己酮与聚氨酯改进聚肽膜柔顺性的方法
CN107903348B (zh) 一种聚乙二醇接枝聚甲基丙烯酸甲酯两亲性接枝共聚物的制备方法
Arslan et al. The synthesis and solution behaviors of novel amphiphilic block copolymers based on d-galactopyranose and 2-(dimethylamino) ethyl methacrylate
CN108250383A (zh) 多交联度聚氨酯弹性体及其制备方法
CN103739833B (zh) 一种制备聚丙交酯的方法
Jiang et al. Syntheses and self-assembly of novel polyurethane–itaconic acid copolymer hydrogels
Liu et al. Amphiphilic triblock terpolymers consisting of poly (n-hexyl isocyanate) and poly (ethylene glycol): Preparation and characterization
CN104559219B (zh) 一种聚己内酯与水性聚氨酯改进聚肽膜亲水性与柔顺性的方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180717

CF01 Termination of patent right due to non-payment of annual fee