CN109651549A - 一种用于聚合物多孔材料自修复的微胶囊的制备方法 - Google Patents

一种用于聚合物多孔材料自修复的微胶囊的制备方法 Download PDF

Info

Publication number
CN109651549A
CN109651549A CN201811387673.1A CN201811387673A CN109651549A CN 109651549 A CN109651549 A CN 109651549A CN 201811387673 A CN201811387673 A CN 201811387673A CN 109651549 A CN109651549 A CN 109651549A
Authority
CN
China
Prior art keywords
microcapsules
porous material
selfreparing
preparation
solution
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.)
Pending
Application number
CN201811387673.1A
Other languages
English (en)
Inventor
章圣苗
朱汉颍
张茂林
王彦华
朱芸
朱文潇
王梦
张晓宇
周策
殷正乔
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.)
East China University of Science and Technology
Original Assignee
East China University of Science and Technology
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 East China University of Science and Technology filed Critical East China University of Science and Technology
Priority to CN201811387673.1A priority Critical patent/CN109651549A/zh
Publication of CN109651549A publication Critical patent/CN109651549A/zh
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/009—Use of pretreated compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • C08J2325/14—Copolymers of styrene with unsaturated esters

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)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

本发明公开了一种用于聚合物多孔材料自修复的微胶囊的制备方法。发明以1,6‑双马来酰亚胺基己烷和乙酸苯酯为芯材，聚乙烯缩甲醛为壁材，采用细乳液和溶剂挥发相结合制备微胶囊，并将微胶囊植入高内相乳液得到苯乙烯和甲基丙烯酸糠醇酯共聚的多孔材料即得自修复多孔材料。步骤如下：将聚乙烯醇缩甲醛氯仿溶液和1,6‑双马来酰亚胺基己烷乙酸苯酯溶液混合，加入十二烷基硫酸钠水溶液，剧烈搅拌1小时，冰浴超声，40℃反应并蒸发溶剂，离心之后得到微胶囊，最后微胶囊分散于苯乙烯和甲基丙烯酸糠醇酯为连续相的高内相乳液中，聚合获得自修复多孔材料。本发明的制备方法新颖独特，所得材料产生裂纹时，微胶囊破裂释放出自修复剂，利用Diels‑Alder反应实现裂纹修复。

Description

一种用于聚合物多孔材料自修复的微胶囊的制备方法
技术领域
本发明涉及一种用于聚合物多孔材料自修复的微胶囊的制备方法。
背景技术
聚合物材料在使用过程中，由于外力、环境等作用下的老化和失效问题严重，特别是在材料表面和内部不可避免会产生裂纹。针对表面裂纹，一般采用焊接法、补片法等方法修复。但是内部损伤和微裂纹难于检测，传统方法无法及时有效修复。受生物体自动修复损伤现象的启发，科学家提出了自修复概念，近年来自修复材料研究成为高分子材料的研究热点。
迄今为止，现有的愈合方法根据用于将愈合组分投放到目标材料中的部位分成本征型和埋伏型两大类。本征型自修复材料可利用材料中的可逆化学反应进行修复，而埋伏型自修复材料则利用微胶囊、玻璃纤维或脉管包裹的修复剂进行修复。其中，微胶囊自修复材料的修复过程为：基体中的裂纹扩展使微胶囊破裂，微胶囊中的修复剂在毛细作用下流到裂纹处，在催化剂的作用下修复剂发生聚合反应修复裂纹。自修复材料的修复效果一般用断裂韧性进行表征，其修复效率定义为修复后与修复前的断裂韧性的比值。由于微胶囊复合材料的制备工艺简单，可修复的基体广泛，对材料的多种损伤均可修复，成为自修复材料的热点和重点。
本发明采用溶剂蒸发与细乳液相结合的技术，设计合成了负载马来酰亚胺溶液的微胶囊，利用呋喃和马来酰亚胺的Diels-Alder反应，形成热可逆交联网络结构，对多孔材料产生的裂纹进行自动修复，在室温下修复一天的修复效率为70%。
发明内容
本发明需要解决的技术问题是一种用于聚合物多孔材料自修复的微胶囊的制备方法，包括以下步骤：
将聚乙烯醇缩甲醛溶于有机溶剂，和溶有1,6-双马来酰亚胺基己烷的乙酸苯酯组成混合溶液，以一定转速搅拌20分钟，加入表面活性剂，提高转速搅拌1小时，将溶液在冰浴环境下超声3分钟，再40℃油浴反应8小时蒸发溶剂，将得到的乳液离心之后冷冻干燥得到微胶囊，再将所得的微胶囊分散到由单体，司盘80组成的油相，加入引发剂，在搅拌下滴入水形成高内相乳液，70℃聚合48小时获得自修复多孔材料。将多孔材料裁成宽度为4毫米样条，在万能拉伸试验机上进行拉伸性能测试，拉伸速度为10毫米每分钟，标距为25毫米。样条断成两块后，沿裂缝合并，用少许力固定。放入40℃烘箱保温24小时，使其充分进行Diels-Alder反应，重新形成交联结构，再将样条取出重新测试拉伸性能。
所说的有机溶剂是氯仿；
所说的表面活性剂是十二烷基硫酸钠;
所说的引发剂是偶氮二异丁腈；
所说的单体是苯乙烯和甲基丙烯酸糠醇酯；
所说的司盘80占油相的质量分数为5%~10%；
所说的微胶囊占油相的质量分数为10%~15%。
采用扫描电镜(SEM)S-3400(日本JEOL公司)观测微胶囊的形貌；采用万能拉伸试验机CMT6104（深圳新三思技术有限公司）测定自修复聚合物多孔材料的拉伸性能。
本发明的制备方法操作简便，得到的聚合物多孔材料形貌良好，孔径在3~10微米之间，并具备高效的自修复能力，第一次拉伸断裂之后，在40℃烘箱中反应24小时，力学性能恢复到70%，延长了材料的使用寿命。
具体实施方式
实施例1
将0.25克聚乙烯醇缩甲醛溶于5毫升氯仿，和溶有0.125克1,6-双马来酰亚胺基己烷的0.25毫升乙酸苯酯组成混合溶液，以一定转速搅拌20分钟，加入15毫升十二烷基硫酸钠水溶液，提高转速搅拌1小时，随后将溶液在冰浴环境下超声3分钟，再40℃油浴反应8小时蒸发溶剂，制得的乳液离心之后冷冻干燥得到微胶囊。再将0.2克微胶囊分散到由1.2克苯乙烯，0.4克甲基丙烯酸糠醇酯，0.2克司盘80组成的油相中，加入0.2g偶氮二异丁腈，在搅拌下滴入8毫升水形成高内相乳液，70℃聚合48小时获得自修复多孔材料。
将多孔材料裁成宽度为4毫米样条，在万能拉伸试验机上进行拉伸性能测试，拉伸速度为10毫米每分钟，标距为25毫米。样条断成两块后，沿裂缝合并，用少许力固定。放入40℃烘箱保温24小时，使其充分进行Diels-Alder反应，重新形成交联结构，再将样条取出重新测试拉伸性能，修复效率达到55%。
实施例2
将0.25克聚乙烯醇缩甲醛溶于5毫升氯仿，和溶有0.125克1,6-双马来酰亚胺基己烷的0.25毫升乙酸苯酯组成混合溶液，以一定转速搅拌20分钟，加入15毫升十二烷基硫酸钠水溶液，提高转速搅拌1小时，随后将溶液在冰浴环境下超声3分钟，再40℃油浴反应8小时蒸发溶剂，制得的乳液离心之后冷冻干燥得到微胶囊。再将0.24克微胶囊分散到由1.2克苯乙烯，0.4克甲基丙烯酸糠醇酯，0.16克司盘80组成的油相中，加入0.2g偶氮二异丁腈，在搅拌下滴入8毫升水形成高内相乳液，70℃聚合48小时获得自修复多孔材料。
将多孔材料裁成宽度为4毫米样条，在万能拉伸试验机上进行拉伸性能测试，拉伸速度为10毫米每分钟，标距为25毫米。样条断成两块后，沿裂缝合并，用少许力固定。放入40℃烘箱保温24小时，使其充分进行Diels-Alder反应，重新形成交联结构，再将样条取出重新测试拉伸性能，修复效率达到60%。
实施例3
将0.25克聚乙烯醇缩甲醛溶于5毫升氯仿，和溶有0.125克1,6-双马来酰亚胺基己烷的0.25毫升乙酸苯酯组成混合溶液，以一定转速搅拌20分钟，加入15毫升十二烷基硫酸钠水溶液，提高转速搅拌1小时，随后将溶液在冰浴环境下超声3分钟，再40℃油浴反应8小时蒸发溶剂，制得的乳液离心之后冷冻干燥得到微胶囊。再将0.3克微胶囊分散到由1.2克苯乙烯，0.4克甲基丙烯酸糠醇酯，0.1克司盘80组成的油相中，加入0.2g偶氮二异丁腈，在搅拌下滴入8毫升水形成高内相乳液，70℃聚合48小时获得自修复多孔材料。
将多孔材料裁成宽度为4毫米样条，在万能拉伸试验机上进行拉伸性能测试，拉伸速度为10毫米每分钟，标距为25毫米。样条断成两块后，沿裂缝合并，用少许力固定。放入40℃烘箱保温24小时，使其充分进行Diels-Alder反应，重新形成交联结构，再将样条取出重新测试拉伸性能，修复效率达到70%。

Claims (1)

1.一种用于聚合物多孔材料自修复的微胶囊的制备方法，其特征在于新颖独特，简单可行，主要包括如下步骤：将聚乙烯醇缩甲醛溶于有机溶剂，和溶有1,6-双马来酰亚胺基己烷的乙酸苯酯组成混合溶液，以一定的转速搅拌20分钟，加入表面活性剂，提高转速搅拌1小时，将溶液在冰浴环境下超声3分钟，再40℃油浴反应8小时蒸发溶剂，将得到的乳液离心之后冷冻干燥得到微胶囊，再将所得的微胶囊，单体，司盘80分散到油相中，加入引发剂，在搅拌下滴入水形成高内相乳液，70℃聚合48小时获得自修复多孔材料；
所说的有机溶剂是氯仿；
所说的表面活性剂是十二烷基硫酸钠;
所说的引发剂是偶氮二异丁腈；
所说的单体是苯乙烯和甲基丙烯酸糠醇酯；
所说的司盘80占油相的质量分数为5%~10%；
所说的微胶囊占油相的质量分数为10%~15%。
CN201811387673.1A 2018-11-21 2018-11-21 一种用于聚合物多孔材料自修复的微胶囊的制备方法 Pending CN109651549A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811387673.1A CN109651549A (zh) 2018-11-21 2018-11-21 一种用于聚合物多孔材料自修复的微胶囊的制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811387673.1A CN109651549A (zh) 2018-11-21 2018-11-21 一种用于聚合物多孔材料自修复的微胶囊的制备方法

Publications (1)

Publication Number Publication Date
CN109651549A true CN109651549A (zh) 2019-04-19

Family

ID=66111503

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811387673.1A Pending CN109651549A (zh) 2018-11-21 2018-11-21 一种用于聚合物多孔材料自修复的微胶囊的制备方法

Country Status (1)

Country Link
CN (1) CN109651549A (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111138945A (zh) * 2020-01-08 2020-05-12 长春顺风新材料有限公司 一种生物基自修复涂料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1372940A (en) * 1972-01-26 1974-11-06 Toyo Jozo Kk Process for preparing mecrocapsules
CN103539929A (zh) * 2013-10-10 2014-01-29 华东理工大学 一种基于高内相乳液中的双烯合成制备聚合物多孔材料的方法
CN107400247A (zh) * 2016-05-19 2017-11-28 北京化工大学 一种原位交联水凝胶
EP3335785A1 (en) * 2016-12-13 2018-06-20 Fundación Tecnalia Research & Innovation Self-healing microcapsules, process for the prepartion thereof, polymeric matrix and composite materials comprising the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1372940A (en) * 1972-01-26 1974-11-06 Toyo Jozo Kk Process for preparing mecrocapsules
US3891570A (en) * 1972-01-26 1975-06-24 Toyo Jozo Kk Process for preparing microcapsules
CN103539929A (zh) * 2013-10-10 2014-01-29 华东理工大学 一种基于高内相乳液中的双烯合成制备聚合物多孔材料的方法
CN107400247A (zh) * 2016-05-19 2017-11-28 北京化工大学 一种原位交联水凝胶
EP3335785A1 (en) * 2016-12-13 2018-06-20 Fundación Tecnalia Research & Innovation Self-healing microcapsules, process for the prepartion thereof, polymeric matrix and composite materials comprising the same
CN110087764A (zh) * 2016-12-13 2019-08-02 泰克纳里阿研究与创新基金 自修复微囊、其制备方法、包含其的聚合物基体和复合材料

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHENCHEN XIAO, ET AL.: "Synthesis of emulsion-templated macroporous materials via Diels-Alder polymerization", 《POLYMER》 *
PURNOMO A. PRATAMA, ET AL.: "Room Temperature Self-Healing Thermoset Based on the Diels–Alder Reaction", 《ACS APPLIED MATERIALS & INTERFACES》 *
贺子腾等: "微胶囊智能自修复材料研究进展", 《化工新型材料》 *
马万鹏等: "微胶囊自修复材料的修复反应", 《高分子通报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111138945A (zh) * 2020-01-08 2020-05-12 长春顺风新材料有限公司 一种生物基自修复涂料及其制备方法

Similar Documents

Publication Publication Date Title
Liu et al. Sustainable thermoplastic elastomers derived from renewable cellulose, rosin and fatty acids
Choi et al. Star-shaped poly (ether− ester) block copolymers: synthesis, characterization, and their physical properties
Yang et al. Two step extrusion process: from thermal recycling of PHB to plasticized PLA by reactive extrusion grafting of PHB degradation products onto PLA chains
Wang et al. Photo-crosslinked poly (ɛ-caprolactone fumarate) networks: roles of crystallinity and crosslinking density in determining mechanical properties
Silberberg et al. The effect of rubber particle size on the mechanical properties of high‐impact polystyrene
CN108504021B (zh) 一种基于酰腙键的聚二甲基硅氧烷自修复弹性体及其制备方法
CN104624132B (zh) 环氧树脂自修复微胶囊及其制备方法
CN105885693A (zh) 一种非固化橡胶沥青防水涂料及其制备方法、复合防水卷材
Yao et al. Self-healing of thermoplastics via reversible addition–fragmentation chain transfer polymerization
CN109651549A (zh) 一种用于聚合物多孔材料自修复的微胶囊的制备方法
Zheng et al. Polymer-enhanced enzymatic microalgal cell disruption for lipid and sugar recovery
CN108191282A (zh) 一种用于水泥混凝土裂缝自修复聚合物乳液微胶囊及其制备方法
CN106633555A (zh) 一种利用动态共价键实现自修复功能的聚乙烯醇膜及其制备方法
Sung et al. Cardanol modified fatty acids from camelina oils for flexible bio-based acrylates coatings
CN104558389B (zh) 一种具有自愈合能力的液晶共聚物材料及其制备方法
CN110092921A (zh) 一种力学性能可调控的高强度木质素水凝胶的制备方法
Malberg et al. Design of elastomeric homo-and copolymer networks of functional aliphatic polyester for use in biomedical applications
Wu et al. Preparation of aligned poly (glycerol sebacate) fibrous membranes for anisotropic tissue engineering
CN103804558A (zh) 宽温变范围的纳米相变材料乳液及其制备方法
CN102863597B (zh) 一种v型梯度共聚物及其制备方法
CN106810887A (zh) 一种基于uv固化行为的自修复沥青及其制备方法
CN106117632B (zh) 一种核壳型沥青自修复剂及其制备方法
Luo et al. Fabrication of well-defined lignin-derived elastomers by atom transfer radical polymerization and Diels-Alder reaction towards sustainable, super-tough and high temperature-resistant hot-melt adhesives
Capiel et al. Stress relaxation behavior of weldable crosslinked polymers based on methacrylated oleic and lauric acids
CN102093726A (zh) 废旧沥青混合料热再生专用添加剂及其制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20190419