CN111217984A - 一种可循环利用的低粘附聚氨酯材料及其制备方法 - Google Patents

一种可循环利用的低粘附聚氨酯材料及其制备方法 Download PDF

Info

Publication number
CN111217984A
CN111217984A CN202010035474.5A CN202010035474A CN111217984A CN 111217984 A CN111217984 A CN 111217984A CN 202010035474 A CN202010035474 A CN 202010035474A CN 111217984 A CN111217984 A CN 111217984A
Authority
CN
China
Prior art keywords
polyurethane material
compound
surface energy
recyclable
low
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
CN202010035474.5A
Other languages
English (en)
Inventor
吴旭
刘敏换
郭玉良
徐秀彬
于丹凤
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.)
Guangzhou University
Original Assignee
Guangzhou 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 Guangzhou University filed Critical Guangzhou University
Priority to CN202010035474.5A priority Critical patent/CN111217984A/zh
Publication of CN111217984A publication Critical patent/CN111217984A/zh
Priority to JP2020152295A priority patent/JP7270983B2/ja
Pending legal-status Critical Current

Links

Images

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
    • C08G18/70—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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
    • 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
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • C08G18/4825—Polyethers containing two 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
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
    • C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
    • 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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 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
    • C08G18/28—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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group 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
    • C08G18/28—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
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • 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
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

本发明提供一种可循环利用的低粘附聚氨酯材料及其制备方法，该可循环利用的低粘附聚氨酯材料包括以下重量百分数的原料：硬单体25％～40％；软单体45％～65％；低面能化合物1％～25％；扩链剂和催化剂；所述低表面能化合物选自有机氟化合物或有机硅化合物。本发明通过在软单体和硬单体聚合形成预聚体后加入具有低表面能的有机氟化合物、有机硅化合物，有机氟化合物、有机硅化合物与预聚体发生缩聚反应形成含有低表面能链段的聚氨酯材料，且低表面能链段在聚合物中仅以物理交联的形式存在，而不存在化学交联，使得聚氨酯材料能够溶解于常见的溶剂，或者在低温下熔化，从而实现可循环利用；同时可有效降低聚氨酯材料的表面能，从而降低聚氨酯材料的粘附性能。

Description

一种可循环利用的低粘附聚氨酯材料及其制备方法
技术领域
本发明属于聚合物材料技术领域，尤其涉及一种可循环利用的低粘附聚氨酯材料及其制备方法。
背景技术
可循环利用是材料的重要属性之一，可帮助提高资源的利用效率并减轻材料制备造成的环境污染。近年来，大量研究工作投入到不沾水/油的低粘附材料的设计与制备之中，低粘附材料在自清洁、防污、防冰、防雾、防腐、液体输送和减阻等领域具有广阔的应用前景。材料的低粘附性能受材料表面化学组成和形貌影响，现有设计低粘附材料的方法严重制约着实现材料的可循环利用，甚至低粘附性能和可循环利用似乎成为材料不可兼得的两个性质。
现有的低粘附材料可根据组成大体分为均质材料和复合材料两大类。均质低粘附材料可进一步分为单分子层、特氟龙等线性分子结构的热塑性材料和具有化学交联的热固性材料。这些均质材料的平整表面可不粘附水油，表现出不高于120度的接触角。如果进一步采用刻蚀或制纤赋予平整表面微纳粗糙结构，接触角可提升至150度进而达到超疏液性能。复合材料典型的例子有表面微纳粗糙度的荷叶仿生超疏液材料和内部微纳结构的猪笼草仿生超润滑材料。复合超疏液材料组成上可使用含氟化合物配以SiO2、TiO2、ZnO、碳纳米管等纳米粒子。超润滑材料通过将润滑油锁在多孔基材之中，形成的润滑表面同样表现出不沾水/油的性能和不高于120度的接触角。低表面能和的氟醚或硅油与待测液体不相溶，可作为灌注润滑油，特氟龙纤维、硅球、或氧化铝凝胶等可作为多孔基材的材料。复合材料难以分离与重制，尤其是复合材料精细纳米结构，以及特氟龙和热固性体系在多数溶剂中不溶解和高沸点等问题严重制约了现有低粘附材料的可循环利用。
发明内容
本发明的目的在于解决现有低粘附材料难以循环利用的问题，提供一种可循环利用的低粘附聚氨酯材料及其制备方法，该聚氨酯材料的各原料可通过溶解于良性溶剂或低温加热实现再加工和自修复，同时具有优异的透明性和可拉伸性，对水性和油性液体都表现出抗粘附性。
本发明提供的一种可循环利用的低粘附聚氨酯材料包括以下重量百分数的原料
硬单体25％～40％；
软单体45％～65％；
低表面能化合物1％～25％；
扩链剂和催化剂；
所述低表面能化合物选自有机氟化合物或有机硅化合物。
进一步，所述有机氟化合物选自全氟聚醚醇(如聚全氟环氧丙烷二醇)、十三氟正辛醇和六氟丁醇中的至少一种。
进一步，所述有机硅化合物选自氨基硅油(如氨丙基聚二甲基硅氧烷、氨基聚二甲基硅氧烷)、羟基硅油(如羟基聚二甲基硅氧烷)中的至少一种。
进一步，所述硬单体选自甲苯-2,4-二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)、1,4-环己烷二异氰酸酯、异氟尔酮二异氰酸酯(IPDI)中的至少一种。
进一步，所述软单体选自聚酯二醇和/或聚醚二醇。
进一步，扩链剂选自1,4-丁二醇、乙二醇、一缩二乙二醇、乙二胺、水中的至少一种。
进一步，所述扩链剂在聚氨酯材料的原料中的重量百分比为0～5％。
进一步，所述催化剂选自有机锡催化剂，如二月桂酸二丁基锡。
进一步，所述催化剂在聚氨酯材料的原料中的重量百分比为0～0.05％。
本发明提供的上述可循环利用的低粘附聚氨酯材料的制备方法包括以下步骤：
(1)将软单体、扩链剂、硬单体和催化剂分散于溶剂中，反应形成预聚体；
(2)在预聚体中加入低表面能化合物，进行缩聚反应；
(3)最后再加入扩链剂进行反应，反应结束后固化即得聚氨酯材料。
进一步，步骤(1)，软单体、扩链剂、硬单体、催化剂和溶剂的混合顺序为：先向软单体和扩链剂的混合物中加入硬单体，再加入催化剂和溶剂。
进一步，步骤(2)所述缩聚反应温度为70～80℃，反应时间为1～2h。
进一步，步骤(3)的反应时间为10～12h，优选12h。步骤(3)在缩聚反应结束后，还加入扩链剂。此时加入扩链剂可将硬单体中未反应的-NCO消耗掉。例如以水作为扩链剂时，水与硬单体中异氰酸酯的-NCO反应，可形成极性较大的脲键，将预聚体连接起来，生成大分子，同时赋予材料更强的物理交联作用。
进一步，步骤(1)中的溶剂选自丁酮、丙酮、N,N-二甲基甲酰胺和N,N-二甲基乙酰胺中的至少一种，用量20％～60％(质量比)。
相对于现有技术，本发明通过在软单体和硬单体聚合形成预聚体后加入具有低表面能的有机氟化合物、有机硅化合物，有机氟化合物、有机硅化合物与预聚体发生缩聚反应形成含有低表面能链段的聚氨酯材料，且低表面能链段在聚合物中仅以物理交联的形式存在，而不存在化学交联，使得聚氨酯材料能够溶解于常见的溶剂，或者在低温下熔化，从而实现可循环利用；同时可有效降低聚氨酯材料的表面能，从而降低聚氨酯材料的粘附性能，提高其抗污能力。
附图说明
图1为聚氨酯材料表面的元素地图；
图2为聚氨酯薄膜对(a)水(经蓝墨水染色以便观察)、(b)十六烷、(c)植物油、(d)泵油的粘附性能测试结果；
图3为聚氨酯材料在(a)聚四氟乙烯、(b)金属、(c)玻璃、(d)木材、(e)聚对苯二甲酸乙二醇基材上形成的涂层；
图4为聚氨酯材料在聚四氟乙烯上形成的基材的弯曲测试结果；
图5为聚氨酯材料涂层的透光率曲线；
图6表示聚氨酯材料再成型过程；
图7表示聚氨酯材料的自修复过程。
具体实施方式
以下通过具体实施例详细说明本发明的技术方案。
本发明的可循环利用的低粘附聚氨酯材料由硬单体、软单体、低表面能化合物、扩链剂和催化剂制成，具体包括以下重量百分数的原料：
硬单体25％～40％；
软单体45％～65％；
低表面能化合物1％～25％；
扩链剂0～5％；
催化剂0～0.05％。
各原料所用具体物质以及用量详见表1～6。
本发明的聚氨酯材料的制备方法如下：
(1)将软单体、扩链剂、硬单体和催化剂分散于溶剂中，反应形成预聚体。
具体地，按照表1的配比将软单体和扩链剂加入四口烧瓶中，混合均匀。然后在搅拌下加入硬单体，并加入催化剂和溶剂。将反应体系温度升至70～85℃，优选80℃，恒温反应2h形成预聚体。
(2)在预聚体中加入低表面能化合物，进行缩聚反应。
具体地，在步骤(1)的预聚体中加入低表面能化合物，继续反应2h，使低表面能化合物与步骤(1)的预聚体发生缩聚反应，产生低表面能链段。
(3)最后加入扩链剂进行反应，反应结束后固化即得聚氨酯材料。
在缩聚反应结束后，将反应体系降温至40℃，然后再加入一定量的扩链剂，在50℃反应12h。待反应完成，在20～70℃烘焙1～24h进行固化，即得最终聚氨酯材料。
在实际制备中，步骤(1)中所用溶剂选自丁酮、丙酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的至少一种，其用量至少能将软单体、扩链剂和硬单体分散均匀。步骤(3)中加入的扩链剂优选水。
作为对比，以下还提供了不加入低表面能化合物，仅由硬单体、软单体、扩链剂和催化剂制成的聚氨酯材料，原料详见表7对比例1，其制备方法同上。
表1.实施例1聚氨酯材料原料组成：
Figure BDA0002365681690000041
表2.实施例2聚氨酯材料原料组成：
Figure BDA0002365681690000042
表3.实施例3聚氨酯材料原料组成：
Figure BDA0002365681690000043
Figure BDA0002365681690000051
表4.实施例4聚氨酯材料原料组成：
Figure BDA0002365681690000052
表5.实施例5聚氨酯材料原料组成：
Figure BDA0002365681690000053
表6.实施例6聚氨酯材料原料组成：
Figure BDA0002365681690000054
表7.对比例1聚氨酯材料原料组成：
Figure BDA0002365681690000055
上述各实施例或对比例制得的聚氨酯材料均为液体形态，固含量为40％～80％，以下称聚氨酯溶液。
实施例1的聚氨酯材料表面的元素地图如图1所示。从图1可以看出，C、O、N、F等元素均匀分布在聚氨酯材料中，说明有机氟成功与聚氨酯的预聚体发生物理交联。
在室温或在20～70℃下将一定量实施例1的聚氨酯溶液倒入培养皿中，然后平放于50℃的恒温干燥箱里干燥24h，再将薄膜从培养皿中剥离下来，制成聚氨酯薄膜。然后将聚氨酯薄膜分别浸入水、十六烷、植物油、泵油中，取出后观察聚氨酯薄膜上水、十六烷、植物油、泵油的粘附情况，结果如图2所示。图2反映，水完全无法粘附在聚氨酯薄膜上；刚将聚氨酯薄膜从十六烷中取出时，聚氨酯薄膜表面轻微粘附有十六烷，但经过5s十六烷即完全脱离聚氨酯薄膜，无法继续粘附；聚氨酯薄膜对植物油的粘附性较十六烷稍强，不过经过将聚氨酯薄膜从植物油中取出25s后植物油即可完全脱离聚氨酯薄膜；而粘稠度更高的泵油，经过35s即可从聚氨酯薄膜中完全脱离。
将实施例1的聚氨酯溶液涂覆在聚四氟乙烯、金属、玻璃、木材和聚对苯二甲酸乙二醇等不同基材上，干燥后可形成光滑、透明的涂层，如图3所示。且将涂覆有聚氨酯材料涂层的聚四氟乙烯弯曲发现，涂层的最小弯曲半径可小于1mm，如图4所示，说明聚氨酯材料与聚四氟乙烯之间具有良好的附着性。
进一步，将实施例1的聚氨酯溶液涂覆在有二维码图案的基材上，干燥后形成涂层，对该涂层的透过率进行检测，结果如图5所示。图5反映，本发明的聚氨酯材料形成的涂层具有98％以上的透过率，透明性优良，不影响对二维码的识别。
将实施例1的聚氨酯溶液倒入模具中，干燥后得到成型品，再在室温下将其溶解于有机溶剂(如乙醇、丁酮、丙酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺)中形成溶液，倒入模具中，待有机溶剂挥发干燥后可得到重新成型的产品，如图6所示，说明本发明的聚氨酯材料可通过简单的溶解方法进行循环利用。且如图7所示，在聚氨酯材料形成的涂层上刻画形成划痕(图7a)后，再在120℃下加热10min，划痕即可消失(图7b)，说明本发明的聚氨酯材料具有自修复功能。
此外，经测试，实施例2～6所制得的聚氨酯材料与实施例1的聚氨酯材料具有相同的性能，在此不再赘述。
相比之下，对比例1没有加入低表面能化合物的聚氨酯材料透明度良好，透过率可达到95％以上，同时具有可回收性和可修复性，但对水/油性液体没有抗粘附性。
综上所述，本发明通过在软单体和硬单体聚合形成预聚体后加入具有低表面能的有机氟化合物、有机硅化合物，有机氟化合物、有机硅化合物与预聚体发生缩聚反应形成含有低表面能链段的聚氨酯材料，且低表面能链段在聚合物中仅以物理交联的形式存在，而不存在化学交联，使得聚氨酯材料能够溶解于常见的溶剂，或者在低温(80～120℃)下熔化，从而实现可循环利用；同时可有效降低聚氨酯材料的表面能，从而降低聚氨酯材料的粘附性能，所形成的薄膜完全不粘附水，且对粘稠度高的十六烷、植物油、泵油等液态有机物均具有很低的粘附性。而且，本发明的聚氨酯材料对玻璃、金属、陶瓷、聚合物、木材等固体基材均具有良好的粘附性，形成的薄膜或涂层透光率极高，可应用于柔性电子显示屏、可穿戴传感器等可穿戴设备、智能机器人或人体修复材料等领域。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

1.一种可循环利用的低粘附聚氨酯材料，其特征在于：包括以下重量百分数的原料
硬单体25％～40％；
软单体45％～65％；
低表面能化合物1％～25％；
扩链剂和催化剂；
所述低表面能化合物选自有机氟化合物或有机硅化合物。
2.根据权利要求1所述可循环利用的低粘附聚氨酯材料，其特征在于：所述有机氟化合物选自全氟聚醚醇、十三氟正辛醇和六氟丁醇中的至少一种。
3.根据权利要求1所述可循环利用的低粘附聚氨酯材料，其特征在于：所述有机硅化合物选自氨基硅油和羟基硅油中的至少一种。
4.根据权利要求1所述可循环利用的低粘附聚氨酯材料，其特征在于：所述硬单体选自甲苯-2,4-二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、1,4-环己烷二异氰酸酯和异氟尔酮二异氰酸酯中的至少一种。
5.根据权利要求4所述可循环利用的低粘附聚氨酯材料，其特征在于：所述软单体选自聚酯二醇和/或聚醚二醇。
6.根据权利要求5所述可循环利用的低粘附聚氨酯材料，其特征在于：扩链剂选自1,4-丁二醇、乙二醇、一缩二乙二醇、乙二胺和水中的至少一种。
7.根据权利要求6所述可循环利用的低粘附聚氨酯材料，其特征在于：所述催化剂选自有机锡催化剂。
8.根据权利要求7所述可循环利用的低粘附聚氨酯材料，其特征在于：所述催化剂在聚氨酯材料的原料中的重量百分比为0～0.05％。
9.一种可循环利用的低粘附聚氨酯材料的制备方法，其特征在于：包括以下步骤：
(1)将软单体、扩链剂、硬单体和催化剂分散于溶剂中，反应形成预聚体；
(2)在预聚体中加入低表面能化合物，进行缩聚反应；
(3)最后再加入扩链剂进行反应，反应结束后固化即得聚氨酯材料。
10.根据权利要求9所述制备方法，其特征在于：步骤(2)所述缩聚反应温度为70～80℃。
CN202010035474.5A 2020-01-14 2020-01-14 一种可循环利用的低粘附聚氨酯材料及其制备方法 Pending CN111217984A (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202010035474.5A CN111217984A (zh) 2020-01-14 2020-01-14 一种可循环利用的低粘附聚氨酯材料及其制备方法
JP2020152295A JP7270983B2 (ja) 2020-01-14 2020-09-10 リサイクル可能な低付着性ポリウレタン材料

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010035474.5A CN111217984A (zh) 2020-01-14 2020-01-14 一种可循环利用的低粘附聚氨酯材料及其制备方法

Publications (1)

Publication Number Publication Date
CN111217984A true CN111217984A (zh) 2020-06-02

Family

ID=70808327

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010035474.5A Pending CN111217984A (zh) 2020-01-14 2020-01-14 一种可循环利用的低粘附聚氨酯材料及其制备方法

Country Status (2)

Country Link
JP (1) JP7270983B2 (zh)
CN (1) CN111217984A (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116515379B (zh) * 2023-05-16 2024-03-15 江苏晨光涂料有限公司 一种生物基超疏水导电防腐聚氨酯涂层及其制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2829561A1 (en) * 2013-07-24 2015-01-28 Centre National De La Recherche Scientifique Self-healing polymers
EP3110877A1 (en) * 2014-02-28 2017-01-04 Fundación Cidetec Self-healing elastomer and process for its preparation
CN107216440A (zh) * 2017-06-16 2017-09-29 徐州佑季化工材料有限公司 一种可逆氢键自修复聚合物及其制备方法
CN107814937A (zh) * 2017-11-17 2018-03-20 四川大学 一种自修复可重复加工的聚硅氧烷弹性体及制备方法和应用
CN108559045A (zh) * 2018-04-23 2018-09-21 四川大学 自修复可重复加工的聚脲材料及制备方法和应用
CN108559052A (zh) * 2018-04-19 2018-09-21 清华大学 具有自修复性能的交联聚脲弹性体及其制备方法
CN108659188A (zh) * 2018-06-01 2018-10-16 南京理工大学 一种聚脲自修复热塑性弹性体及其制备方法
CN109627946A (zh) * 2018-12-06 2019-04-16 中国科学院海洋研究所 一种制备室温下具有自修复性能的仿生超滑表面的方法
CN110423454A (zh) * 2019-07-19 2019-11-08 广州大学 一种高弹高透的防污聚氨酯薄膜及其制备方法和应用

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0320376A (ja) * 1989-06-15 1991-01-29 Toyoda Gosei Co Ltd 塗料組成物
JP2007169411A (ja) 2005-12-21 2007-07-05 Toyobo Co Ltd ポリウレタン樹脂およびそれを用いた導電性ロール
EP2719713B1 (en) 2011-06-13 2018-10-03 DIC Corporation Polyurethane composition, water repellent agent, polyurethane resin composition for forming surface skin layer of leather-like sheet, and leather-like sheet
US20140170917A1 (en) * 2012-12-19 2014-06-19 3M Innovative Properties Company Polyurethane polymer, synthetic leather, and method
JP6105510B2 (ja) 2013-04-12 2017-03-29 ヤマウチ株式会社 紙送りローラおよびその製造方法
US10414859B2 (en) * 2014-08-20 2019-09-17 Resinate Materials Group, Inc. High recycle content polyester polyols
JP6710975B2 (ja) * 2015-07-29 2020-06-17 東ソー株式会社 耐紫外線吸収剤性ポリウレタン組成物、該組成物を用いたコーティング材

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2829561A1 (en) * 2013-07-24 2015-01-28 Centre National De La Recherche Scientifique Self-healing polymers
EP3110877A1 (en) * 2014-02-28 2017-01-04 Fundación Cidetec Self-healing elastomer and process for its preparation
CN107216440A (zh) * 2017-06-16 2017-09-29 徐州佑季化工材料有限公司 一种可逆氢键自修复聚合物及其制备方法
CN107814937A (zh) * 2017-11-17 2018-03-20 四川大学 一种自修复可重复加工的聚硅氧烷弹性体及制备方法和应用
CN108559052A (zh) * 2018-04-19 2018-09-21 清华大学 具有自修复性能的交联聚脲弹性体及其制备方法
CN108559045A (zh) * 2018-04-23 2018-09-21 四川大学 自修复可重复加工的聚脲材料及制备方法和应用
CN108659188A (zh) * 2018-06-01 2018-10-16 南京理工大学 一种聚脲自修复热塑性弹性体及其制备方法
CN109627946A (zh) * 2018-12-06 2019-04-16 中国科学院海洋研究所 一种制备室温下具有自修复性能的仿生超滑表面的方法
CN110423454A (zh) * 2019-07-19 2019-11-08 广州大学 一种高弹高透的防污聚氨酯薄膜及其制备方法和应用

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
MINHUAN LIU ET.AL: "Endowing recyclability to anti-adhesion materials via designing physically crosslinked polyurethane", 《JOURNAL OF MATERIALS CHEMISTRY A》 *
丁绍兰等主编: "《革制品材料学》", 31 January 2019, 中国轻工业出版社 *
刘敏换: "高拉伸透明聚氨酯防污材料的设计合成及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *
山西省化工研究所主编: "《聚氨酯弹性体手册》", 31 January 2001, 化学工业出版社 *
石建高主编: "《渔用网片与防污技术》", 31 October 2011, 东华大学出版社 *

Also Published As

Publication number Publication date
JP7270983B2 (ja) 2023-05-11
JP2021130804A (ja) 2021-09-09

Similar Documents

Publication Publication Date Title
Fu et al. Mechanically robust, self-healing superhydrophobic anti-icing coatings based on a novel fluorinated polyurethane synthesized by a two-step thiol click reaction
CN104098999B (zh) 一种uv‑热双固化聚氨酯涂料及其制备方法和应用
CN110845952B (zh) 一种氟化聚氨酯涂料及超疏水涂料的制备方法
CN103608160A (zh) 模内成形用转印膜及其制造方法
WO2022247035A1 (zh) 一种抗菌低粘附聚乙烯醇涂层
US20220127428A1 (en) Anti-fouling polyurethane thin film with high elasticity and high transparency, preparation method and use thereof
CN109575782A (zh) 氧化石墨烯改性聚氨酯电泳树脂、聚氨酯电泳漆及其制备方法
CN112457762A (zh) 一种高附着力的含氟疏水聚氨酯透明防护涂料及其制备、使用方法
CN114479665A (zh) 一种高透明的柔性耐刮擦涂层、功能化涂层及其制备方法
Shahrousvand et al. Preparation of polyurethane/poly (2-hydroxyethyl methacrylate) semi-IPNs containing cellulose nanocrystals for biomedical applications
CN111217984A (zh) 一种可循环利用的低粘附聚氨酯材料及其制备方法
CN113527995B (zh) 一种透明耐用防污涂料的制备方法与应用
CN118005888B (zh) 一种超强附着力的uv树脂及其制备方法、uv涂料
Yao et al. Improvement of mechanical and thermal properties of cationic waterborne polyurethane by using an amino-rich multifunctional macromolecular crosslinking agent
CN111548731B (zh) 一种室温自修复聚碳酸酯表面涂层及其制备方法
CN110452352B (zh) 一种水性聚氨酯树脂及其制备方法
CN117264165A (zh) 一种水性抗污聚氨酯及其形成的水性聚氨酯抗污涂层
WO2024045782A1 (zh) 一种超疏水自修复热固化pu胶膜制备方法及汽车保护膜
CN1451702A (zh) 有机硅改性环氧阴极电泳涂料及其制备方法
CN113462254B (zh) 一种低血液粘附抗菌琼脂糖基涂层制备方法
CN114806392A (zh) 超亲水抗脏污的自修复涂料、涂层的制备方法及涂层
CN110669404B (zh) 一种防石墨吸附复合卷材及其制备方法
CN112321842A (zh) 一种紫外光固化超支化丙烯酸酯树脂及其制造方法
CN113214731A (zh) 一种耐久性植物油基抗涂鸦、易清洁涂料及其制备方法和应用
TWI531467B (zh) 光學膜

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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200602