CN115449051B - 一种温敏型水性聚氨酯及其制备方法 - Google Patents

一种温敏型水性聚氨酯及其制备方法 Download PDF

Info

Publication number
CN115449051B
CN115449051B CN202211228262.4A CN202211228262A CN115449051B CN 115449051 B CN115449051 B CN 115449051B CN 202211228262 A CN202211228262 A CN 202211228262A CN 115449051 B CN115449051 B CN 115449051B
Authority
CN
China
Prior art keywords
temperature
sensitive
stirring
hours
parts
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.)
Active
Application number
CN202211228262.4A
Other languages
English (en)
Other versions
CN115449051A (zh
Inventor
易序扬
许修棋
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.)
Anhui Shengda Biopharmaceutical Co ltd
Original Assignee
Anhui Shengda Biopharmaceutical Co ltd
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 Anhui Shengda Biopharmaceutical Co ltd filed Critical Anhui Shengda Biopharmaceutical Co ltd
Priority to CN202211228262.4A priority Critical patent/CN115449051B/zh
Publication of CN115449051A publication Critical patent/CN115449051A/zh
Application granted granted Critical
Publication of CN115449051B publication Critical patent/CN115449051B/zh
Active 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
    • C08G18/70—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
    • 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
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/6688—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 C08G18/3271
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C08G18/677—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
    • C08G18/6785—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups containing phosphorus
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
    • D06N3/148—(cyclo)aliphatic polyisocyanates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/02—Synthetic macromolecular fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/068—Polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/06—Properties of the materials having thermal properties
    • D06N2209/067—Flame resistant, fire resistant
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/12—Permeability or impermeability properties
    • D06N2209/126—Permeability to liquids, absorption
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/142—Hydrophobic

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

本发明涉及一种温敏型水性聚氨酯及其制备方法，属于聚氨酯技术领域，包括如下重量份原料：聚四氢呋喃二醇15‑20份、二异氰酸酯9‑12份、催化剂0.06‑0.07份、添加剂3‑4份、温敏型二元醇0.6‑0.7份、交联剂0.6‑0.8份、1,4‑丁二醇0.4‑0.6份和纳米填料1.2‑2份，本发明中利用加入的添加剂配合交联剂等促进形成具有网状结构的聚氨酯树脂，使水分子渗入和扩散的难度增大，提高了耐静水压性能，同时添加剂的结构中含量磷酸酯和羧基等结构，不仅赋予了聚氨酯优异的阻燃性能，且改善乳液稳定性，提高成膜后的致密性，进而改善成膜效果，同时对于透湿性的提高具有促进作用。

Description

一种温敏型水性聚氨酯及其制备方法
技术领域
本发明属于聚氨酯技术领域，具体地，涉及一种温敏型水性聚氨酯及其制备方法。
背景技术
温敏型聚氨酯将聚氨酯优异的机械性能和温敏物质的温度敏感性结合在一起，具有良好的水溶性、环境污染小、粘黏性好、较高的强度和耐磨性等优点，将其应用到织物涂层剂，中提高织物涂层剂的温度响应性。水性聚氨酯以水为分散介质，以含少量或不含有机溶剂的聚氨酯聚合物为分散相，常用作织物涂层剂，用于提高织物表面性能，然而单一的水性聚氨酯往往在纺织品的应用上存在很多缺陷，如易燃、耐静水压能力差等。
随着纺织品的发展和人们生活的需要，对材料综合性能的要求也越来越高，因此，开展水性聚氨酯的功能化改性研究，使水性聚氨酯同时具备耐静水压和阻燃等功能，既符合织物涂层最新发展趋势，也顺应市场需求的方向。
发明内容
为了解决背景技术中提到的技术问题，本发明提供一种温敏型水性聚氨酯及其制备方法。
本发明的目的可以通过以下技术方案实现：
一种温敏型水性聚氨酯，包括如下重量份原料：
聚四氢呋喃二醇15-20份、二异氰酸酯9-12份、催化剂0.06-0.07份、添加剂3-4份、温敏型二元醇0.6-0.7份、交联剂0.6-0.8份、1,4-丁二醇0.4-0.6份和纳米填料1.2-2份；
所述添加剂通过如下步骤制备：
步骤一、将氯化偏苯三酸酐和吡啶混合，然后加入阻燃剂和四氢呋喃，在温度为20℃条件下搅拌反应12h后，停止反应，抽滤取滤液，用旋蒸仪旋蒸，用甲苯和乙酸酐重结晶，得到的助剂；
步骤二、减压蒸馏除去蓖麻油中的水，约48h后将温度降至80℃，将蓖麻油和助剂混合，升温至110℃搅拌反应3h，即得添加剂。氯化偏苯三酸酐与阻燃剂反应制备得到的助剂，助剂中的酸酐结构与蓖麻油中的结构(部分羟基)反应，得到助剂。助剂的主体结构为蓖麻油，蓖麻油可参与聚氨酯的合成，一般的可取代多元醇作为软段，而且蓖麻油中结构中的双键在聚氨酯固化成膜时能发生自交联，提高聚氨酯成膜后的力学性能，常用于聚氨酯的改性，但直接引入蓖麻油后会造成疏水性过强，导致聚氨酯乳液的分散效果差，进而影响成膜效果，本发明中的助剂中通过将蓖麻油和助剂反应，在消耗部分羟基的同时引入了羧基，引入了亲水基团，改善乳液稳定性，提高成膜后的致密性，进而改善成膜效果。
进一步地，步骤一中氯化偏苯三酸酐和吡啶的用量质量比为3：1；氯化偏苯三酸酐、阻燃剂和四氢呋喃的用量比为2g：1.8-1.9g：50mL；步骤二中蓖麻油和助剂的用量质量比为10：3。
进一步地，阻燃剂通过如下步骤制备：
将亚磷酸二甲酯、四氯化碳和四氢呋喃混合，在冰水浴条件下加入三乙胺和乙醇胺，加完后设置温度为20℃，搅拌反应10-11h，抽滤，将得到的滤液旋蒸，除去溶剂，得到阻燃剂。阻燃剂为氨基磷酸酯阻燃剂，高效阻燃且低毒，具有良好的促进成炭能力，并且符合市场需要的无卤无甲醛的环保阻燃剂。阻燃剂的结构中保留了乙醇胺结构中的羟基，制备得到的阻燃剂与氯化偏苯三酸酐反应后，通过化学反应的方式引入添加剂的结构中，参与聚氨酯的合成，在保留了阻燃剂良好的阻燃性能的前提下，提高了阻燃剂的耐水洗性。
进一步地，亚磷酸二甲酯、四氯化碳、四氢呋喃、三乙胺和乙醇胺的用量摩尔比为1：1：1：1：1；所述乙醇胺为N-甲基单乙醇胺和N-乙基乙醇胺中的一种。
进一步地，所述纳米填料通过如下步骤制备：
将纳米二氧化硅、Tris-HCL缓冲液和无水乙醇混合，超声分散得到分散液，向分散液中加入盐酸多巴胺，超声分散10min，用质量分数10％的氢氧化钠溶液调节pH值为8.5，继续搅拌2h，搅拌结束后经过离心、洗涤、60℃干燥，得到纳米填料。Tris-HCL缓冲液的浓度为0.01mol/L，纳米二氧化硅、Tris-HCL缓冲液、无水乙醇、盐酸多巴胺的用量比为0.8g：100mL：30mL：0.2g。多巴胺在纳米二氧化硅表面发生自聚合形成聚多巴胺，使纳米二氧化硅具有更好的分散性，提高涂层的理化性能，尤其是耐磨、耐热等性能，良好分散的纳米无机填料可以大幅度增强水性涂层的力学性能，改性后得到的纳米填料在涂层中的团聚情况改善，且聚多巴胺在纳米二氧化硅表面形成的膜可以吸收部分紫外光，降低光老化对产品的影响。
进一步地，温敏型二元醇通过如下步骤制备：
将N-异丙基丙烯酰胺和二乙醇胺按照摩尔比1.2：1混合，在避光条件下，通入氮气保护，65℃条件下反应120h，得到温敏型二元醇。N-异丙基丙烯酰胺是一类典型的温度响应性聚合物，其温敏机制在于其分子链上同时含有亲水性氨基和疏水性链段，随着温度的变化链段形态发生改变，但温度低于临界温度时分子链舒展，呈现亲水性，当温度高于临界温度时，表现为疏水性。
一种温敏型水性聚氨酯的制备方法，包括如下步骤：
将聚四氢呋喃二醇、二异氰酸酯混合，在温度为20℃条件下搅拌分散，然后升温至70℃搅拌2h，加入催化剂、添加剂和温敏型二元醇，继续升高温度至80℃并搅拌2h，反应过程中可加入适量丙酮以降低体系黏度，然后加交联剂和1,4-丁二醇，升温至85℃，继续反应2h，自然冷却至40℃，滴加三乙胺中和，加入纳米填料搅拌30min，加入去离子水分散，得到一种温敏型水性聚氨酯。
进一步地，二异氰酸酯为异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯中的一种；交联剂为三羟甲基丙烷和季戊四醇中的一种；催化剂为二丁基锡二月桂酸。
本发明的有益效果：
本发明中利用加入的添加剂配合交联剂等促进形成具有网状结构的聚氨酯树脂，使水分子渗入和扩散的难度增大，提高了耐静水压性能，同时添加剂的结构中含量磷酸酯和羧基等结构，不仅赋予了聚氨酯优异的阻燃性能，且改善乳液稳定性，提高成膜后的致密性，进而改善成膜效果，同时对于透湿性的提高具有促进作用。
此外，在制备添加剂的过程中，将蓖麻油和阻燃剂结合，利用了二者的优势，提高了产品整体的性能，在阻燃过程中阻燃剂中的磷酸结构缩聚成聚磷酸包覆在聚合物表面，催化聚氨酯链段的分解，并形成绝热隔氧并且难燃的炭层，产品中的氮元素受热分解后释放出不燃气体，并带走热量，形成协同阻燃体系，可以有效地抑制材料的燃烧。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，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作出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
实施例1
制备阻燃剂：
将亚磷酸二甲酯、四氯化碳和四氢呋喃混合，在冰水浴条件下加入三乙胺和N-甲基单乙醇胺，加完后设置温度为20℃，搅拌反应10-11h，抽滤，将得到的滤液旋蒸，除去溶剂，得到阻燃剂。其中，亚磷酸二甲酯、四氯化碳、四氢呋喃、三乙胺和N-甲基单乙醇胺的用量摩尔比为1：1：1：1：1。
实施例2
制备阻燃剂：
将亚磷酸二甲酯、四氯化碳和四氢呋喃混合，在冰水浴条件下加入三乙胺和N-乙基乙醇胺，加完后设置温度为20℃，搅拌反应10-11h，抽滤，将得到的滤液旋蒸，除去溶剂，得到阻燃剂。其中，亚磷酸二甲酯、四氯化碳、四氢呋喃、三乙胺和N-乙基乙醇胺的用量摩尔比为1：1：1：1：1。
实施例3
制备添加剂：
步骤一、将氯化偏苯三酸酐和吡啶混合，然后加入实施例1制备的阻燃剂和四氢呋喃，在温度为20℃条件下搅拌反应12h后，停止反应，抽滤取滤液，用旋蒸仪旋蒸，用甲苯和乙酸酐重结晶，得到的助剂；氯化偏苯三酸酐和吡啶的用量质量比为3：1；氯化偏苯三酸酐、阻燃剂和四氢呋喃的用量比为2g：1.8g：50mL；
步骤二、减压蒸馏除去蓖麻油中的水，约48h后将温度降至80℃，将蓖麻油和助剂混合，升温至110℃搅拌反应3h，即得添加剂；蓖麻油和助剂的用量质量比为10：3。
实施例4
制备添加剂：
步骤一、将氯化偏苯三酸酐和吡啶混合，然后加入实施例2制备的阻燃剂和四氢呋喃，在温度为20℃条件下搅拌反应12h后，停止反应，抽滤取滤液，用旋蒸仪旋蒸，用甲苯和乙酸酐重结晶，得到的助剂；氯化偏苯三酸酐和吡啶的用量质量比为3：1；氯化偏苯三酸酐、阻燃剂和四氢呋喃的用量比为2g：1.9g：50mL；
步骤二、减压蒸馏除去蓖麻油中的水，约48h后将温度降至80℃，将蓖麻油和助剂混合，升温至110℃搅拌反应3h，即得添加剂。蓖麻油和助剂的用量质量比为10：3。
实施例5
制备纳米填料：
将纳米二氧化硅、Tris-HCL缓冲液和无水乙醇混合，超声分散得到分散液，向分散液中加入盐酸多巴胺，超声分散10min，用氢氧化钠溶液调节pH值为8.5，继续搅拌2h，搅拌结束后经过离心、洗涤、60℃干燥，得到纳米填料。Tris-HCL缓冲液的浓度为0.01mol/L，纳米二氧化硅、Tris-HCL缓冲液、无水乙醇、盐酸多巴胺的用量比为0.8g：100mL：30mL：0.2g。
实施例6
一种温敏型水性聚氨酯的制备方法，包括如下步骤：
第一步、将N-异丙基丙烯酰胺和二乙醇胺按照摩尔比1.2：1混合，在避光条件下，通入氮气保护，65℃条件下反应120h，得到温敏型二元醇；
第二步、按重量份计，将15份聚四氢呋喃二醇、9份异佛尔酮二异氰酸酯混合，在温度为20℃条件下搅拌分散，然后升温至70℃搅拌2h，加入0.06份二丁基锡二月桂酸、3份实施例3制备的添加剂和0.6份温敏型二元醇，继续升高温度至80℃并搅拌2h，反应过程中可加入适量丙酮以降低体系黏度，然后加0.6份三羟甲基丙烷和0.4份1,4-丁二醇，升温至85℃，继续反应2h，自然冷却至40℃，滴加三乙胺中和，加入1.2份实施例5制备的纳米填料搅拌30min，加入去离子水分散，至固含量为30％，得到一种温敏型水性聚氨酯。
实施例7
一种温敏型水性聚氨酯的制备方法，包括如下步骤：
第一步、将N-异丙基丙烯酰胺和二乙醇胺按照摩尔比1.2：1混合，在避光条件下，通入氮气保护，65℃条件下反应120h，得到温敏型二元醇；
第二步、按重量份计，将20份聚四氢呋喃二醇、12份异佛尔酮二异氰酸酯混合，在温度为20℃条件下搅拌分散，然后升温至70℃搅拌2h，加入0.07份二丁基锡二月桂酸、4份实施例4制备的添加剂和0.7份温敏型二元醇，继续升高温度至80℃并搅拌2h，反应过程中可加入适量丙酮以降低体系黏度，然后加0.8份三羟甲基丙烷和0.6份1,4-丁二醇，升温至85℃，继续反应2h，自然冷却至40℃，滴加三乙胺中和，加入2份实施例5制备的纳米填料搅拌30min，加入去离子水分散，至固含量为30％，得到一种温敏型水性聚氨酯。
实施例8
一种温敏型水性聚氨酯的制备方法，包括如下步骤：
第一步、将N-异丙基丙烯酰胺和二乙醇胺按照摩尔比1.2：1混合，在避光条件下，通入氮气保护，65℃条件下反应120h，得到温敏型二元醇；
第二步、按重量份计，将20份聚四氢呋喃二醇、12份六亚甲基二异氰酸酯混合，在温度为20℃条件下搅拌分散，然后升温至70℃搅拌2h，加入0.07份二丁基锡二月桂酸、4份实施例4制备的添加剂和0.7份温敏型二元醇，继续升高温度至80℃并搅拌2h，反应过程中可加入适量丙酮以降低体系黏度，然后加0.8份季戊四醇和0.6份1,4-丁二醇，升温至85℃，继续反应2h，自然冷却至40℃，滴加三乙胺中和，加入2份实施例5制备的纳米填料搅拌30min，加入去离子水分散，至固含量为30％，得到一种温敏型水性聚氨酯。
对比例1
将实施例7中的添加剂换成蓖麻油，其余原料及制备过程与实施例7保持相同。
对比例2
将实施例7中的纳米填料换成纳米二氧化硅，其余原料及制备过程与实施例7保持相同。
对实施例6-实施例8和对比例1-对比例2制备的样品进行测试，在样品中加入质量分数为1％的TF601增稠剂进行增稠，得到乳液；使用涂层机涂布乳液，涂烘温度为170℃，涂烘时间为45s，涂膜厚度为80～100μm；极限氧指数按照极限氧指数测定仪进行测试；
将乳液刮涂在涤纶织物表面置入定型烘干机中170℃定型50s，涂烘3次，最终质量增加为28～32g/m2。按照GB/T4744—1997《纺织织物抗渗水性测定静水压试验》测试相关性能；
测试结果如下表1所示：
表1
实施例6 实施例7 实施例8 对比例1 对比例2
极限氧指数 28.7 28.9 29.0 24.8 28.5
静水压值/kPa 17.5 17.9 17.7 15.4 14.1
透湿量/(g·m-2·d-1) 3547 3534 3579 3125 3341
从测试数据可知，本发明制备的聚氨酯具有良好的阻燃、防水透湿性，对比例1与实施例7相比，因未添加阻燃剂阻燃效果差，对比例2相对于实施例7，因纳米填料表面具有聚多巴胺层而体现出一定的阻燃协同性，所以对比例2的阻燃性能略有下降。防水和透湿在一定程度上是矛盾的，本发明制备的聚氨酯利用引入的亲水基团提高透湿性，并通过原料之间形成稳定的互穿网络起到良好的防水效果。
在说明书的描述中，参考术语“一个实施例”、“示例”、“具体示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上内容仅仅是对本发明所作的举例和说明，所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代，只要不偏离发明或者超越本权利要求书所定义的范围，均应属于本发明的保护范围。

Claims (4)

1.一种温敏型水性聚氨酯，其特征在于，包括如下重量份原料：
聚四氢呋喃二醇15-20份、二异氰酸酯9-12份、催化剂0.06-0.07份、添加剂3-4份、温敏型二元醇0.6-0.7份、交联剂0.6-0.8份、1,4-丁二醇0.4-0.6份和纳米填料1.2-2份；
所述添加剂通过如下步骤制备：
步骤一、将亚磷酸二甲酯、四氯化碳和四氢呋喃混合，在冰水浴条件下加入三乙胺和乙醇胺，加完后设置温度为20℃，搅拌反应10-11h，得到阻燃剂；将氯化偏苯三酸酐和吡啶混合，然后加入阻燃剂和四氢呋喃，在温度为20℃条件下搅拌反应12h后，得到的助剂；亚磷酸二甲酯、四氯化碳、四氢呋喃、三乙胺和乙醇胺的用量摩尔比为1：1：1：1：1；所述乙醇胺为N-甲基单乙醇胺和N-乙基乙醇胺中的一种；
步骤二、将蓖麻油和助剂混合，升温至110℃搅拌反应3h，即得添加剂；
所述纳米填料通过如下步骤制备：
将纳米二氧化硅、Tris-HCL缓冲液和无水乙醇混合，超声分散得到分散液，向分散液中加入盐酸多巴胺，超声分散10min，用氢氧化钠溶液调节pH值为8.5，继续搅拌2h，得到纳米填料；
所述温敏型二元醇通过如下步骤制备：
将N-异丙基丙烯酰胺和二乙醇胺按照摩尔比1.2：1混合，在避光条件下，通入氮气保护，65℃条件下反应120h，得到温敏型二元醇。
2.根据权利要求1所述的一种温敏型水性聚氨酯，其特征在于，步骤一中氯化偏苯三酸酐和吡啶的用量质量比为3：1；氯化偏苯三酸酐、阻燃剂和四氢呋喃的用量比为2g：1.8-1.9g：50mL；步骤二中蓖麻油和助剂的用量质量比为10：3。
3.根据权利要求1所述的一种温敏型水性聚氨酯，其特征在于，二异氰酸酯为异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯中的一种；交联剂为三羟甲基丙烷和季戊四醇中的一种；催化剂为二丁基锡二月桂酸。
4.根据权利要求1所述的一种温敏型水性聚氨酯的制备方法，其特征在于，包括如下步骤：
将聚四氢呋喃二醇、二异氰酸酯混合，在温度为20℃条件下搅拌分散，然后升温至70℃搅拌2h，加入催化剂、添加剂和温敏型二元醇，继续升温度至80℃并搅拌2h，然后加交联剂和1,4-丁二醇，升温至85℃，继续反应2h，自然冷却至40℃，滴加三乙胺中和，加入纳米填料搅拌30min，加入去离子水分散，得到一种温敏型水性聚氨酯。
CN202211228262.4A 2022-10-09 2022-10-09 一种温敏型水性聚氨酯及其制备方法 Active CN115449051B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211228262.4A CN115449051B (zh) 2022-10-09 2022-10-09 一种温敏型水性聚氨酯及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211228262.4A CN115449051B (zh) 2022-10-09 2022-10-09 一种温敏型水性聚氨酯及其制备方法

Publications (2)

Publication Number Publication Date
CN115449051A CN115449051A (zh) 2022-12-09
CN115449051B true CN115449051B (zh) 2023-09-26

Family

ID=84309531

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211228262.4A Active CN115449051B (zh) 2022-10-09 2022-10-09 一种温敏型水性聚氨酯及其制备方法

Country Status (1)

Country Link
CN (1) CN115449051B (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104017164A (zh) * 2014-06-24 2014-09-03 北京理工大学 一种温敏智能型防水透湿和阻燃水性聚氨酯涂层剂及其制备方法
CN110511349A (zh) * 2019-07-30 2019-11-29 湖北大学 一种新型超支化型温敏型水性聚氨酯的制备方法
CN110627967A (zh) * 2019-09-04 2019-12-31 湖北大学 一种新型梳形温敏型水性聚氨酯的制备方法
CN111270525A (zh) * 2020-04-14 2020-06-12 陕西科技大学 一种阻燃防污功能水性聚氨酯织物整理剂及其制备方法
CN113403018A (zh) * 2021-06-30 2021-09-17 湖南松井新材料股份有限公司 一种聚氨酯热熔胶及其制备方法和应用

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007054112A1 (de) * 2005-11-10 2007-05-18 Henkel Ag & Co. Kgaa Kleb-, dicht- und beschichtungsstoffe mit glaspartikeln als füllstoff

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104017164A (zh) * 2014-06-24 2014-09-03 北京理工大学 一种温敏智能型防水透湿和阻燃水性聚氨酯涂层剂及其制备方法
CN110511349A (zh) * 2019-07-30 2019-11-29 湖北大学 一种新型超支化型温敏型水性聚氨酯的制备方法
CN110627967A (zh) * 2019-09-04 2019-12-31 湖北大学 一种新型梳形温敏型水性聚氨酯的制备方法
CN111270525A (zh) * 2020-04-14 2020-06-12 陕西科技大学 一种阻燃防污功能水性聚氨酯织物整理剂及其制备方法
CN113403018A (zh) * 2021-06-30 2021-09-17 湖南松井新材料股份有限公司 一种聚氨酯热熔胶及其制备方法和应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
单向导湿纺织品领域水性温敏聚氨酯研究进展;周亭;廖欢;张汇;陈建芳;;湖南工程学院学报(自然科学版)(02);全文 *
温敏聚氨酯膜开关温度阀值及其调控途径;周虎;石欢欢;范浩军;周建;;高分子材料科学与工程(03);全文 *

Also Published As

Publication number Publication date
CN115449051A (zh) 2022-12-09

Similar Documents

Publication Publication Date Title
JP7111402B2 (ja) 難燃性・耐摩耗性・低ｖｏｃポリウレタン塗料の調製及び応用方法
CN103524696B (zh) 一种硅烷改性的磺酸型水性聚氨酯乳液及其制备方法
CN112225865A (zh) 一种疏水阻燃型水性聚氨酯及其制备方法
CN104530371A (zh) 一种无卤持久型阻燃水基聚氨酯及其制备方法
CN104497050A (zh) 一种水基聚氨酯用反应性膨胀型阻燃剂及其制备方法
Feng et al. Synthesis of P, N and Si-containing waterborne polyurethane with excellent flame retardant, alkali resistance and flexibility via one-step synthetic approach
CN111040660A (zh) 一种纺织品用水性透湿、阻燃聚氨酯膜及制备方法
CN111019084A (zh) 一种纺织品用水性透湿、阻燃聚氨酯乳液及制备方法
CN111057209A (zh) 一种纺织品用水性透湿、阻燃聚氨酯涂层胶及制备方法
Xu et al. Durable and high-efficiency casein-derived phosphorus-nitrogen-rich flame retardants for cotton fabrics
CN115107322A (zh) 一种环保柔性皮革及其制备方法
CN115449051B (zh) 一种温敏型水性聚氨酯及其制备方法
CN114058051A (zh) 一种核壳结构无卤阻燃剂原位改性无溶剂聚氨酯树脂膜及其制备方法
CN117512986A (zh) 一种防火阻燃的涤纶面料及其制备工艺
CN113214539A (zh) 一种生物基阻燃剂微胶囊及其制备方法
CN115678407A (zh) 一种含氮化碳的阻燃改性水性聚氨酯及其制备方法与应用
CN116790138A (zh) 一种改性石墨烯及改性石墨烯浆料的制备方法
CN112375203B (zh) 丝胶蛋白改性水性聚氨酯防水透湿涂料及其制备方法
CN113667091B (zh) 一种石墨烯/水性聚氨酯复合材料及其制备方法和应用
CN115124721B (zh) 一种用于涂料印染粘合剂的改性明胶及其制备方法与应用
CN113386409A (zh) 一种防水耐腐蚀聚乙烯面料及其制备方法
CN111875774A (zh) 一种织物用水性阻燃耐水压聚氨酯乳液制备方法
CN113214632A (zh) 一种阻燃型三聚氯氰改性石墨烯/聚氨酯复合材料及其制备方法、应用
CN107163208B (zh) 一种耐久环保型含氟纳米三防整理剂及其制备方法和应用
CN112480649A (zh) 一种二氧化钛/tpu复合型亲水薄膜及其制备方法

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
GR01 Patent grant
GR01 Patent grant
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: A temperature sensitive waterborne polyurethane and its preparation method

Granted publication date: 20230926

Pledgee: Anhui Dongzhi Rural Commercial Bank Co.,Ltd.

Pledgor: Anhui Shengda Biopharmaceutical Co.,Ltd.

Registration number: Y2024980017998