CN105622891B - 一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法 - Google Patents

一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法 Download PDF

Info

Publication number
CN105622891B
CN105622891B CN201510962796.3A CN201510962796A CN105622891B CN 105622891 B CN105622891 B CN 105622891B CN 201510962796 A CN201510962796 A CN 201510962796A CN 105622891 B CN105622891 B CN 105622891B
Authority
CN
China
Prior art keywords
emulsion
polysiloxane
aqueous polyurethane
glycol
polysiloxane emulsion
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
CN201510962796.3A
Other languages
English (en)
Other versions
CN105622891A (zh
Inventor
张胜文
王亚东
赵杰
徐子墨
白绘宇
刘晓亚
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.)
Ruentex chemical (Taixing) Co. Ltd.
Original Assignee
Jiangnan 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 Jiangnan University filed Critical Jiangnan University
Priority to CN201510962796.3A priority Critical patent/CN105622891B/zh
Publication of CN105622891A publication Critical patent/CN105622891A/zh
Application granted granted Critical
Publication of CN105622891B publication Critical patent/CN105622891B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752Polyisocyanates 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
    • C08G18/753Polyisocyanates 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
    • C08G18/755Polyisocyanates 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F130/00Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F130/04Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F130/08Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/22Emulsion polymerisation
    • C08F2/24Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26Emulsion polymerisation with the aid of emulsifying agents anionic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12Prepolymer 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/34Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348Hydroxycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44Polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/62Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6295Polymers of silicium containing compounds having carbon-to-carbon double bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6541Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633Compounds of group C08G18/42
    • C08G18/6659Compounds of group C08G18/42 with compounds of group C08G18/34
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • C08J2375/06Polyurethanes from polyesters

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)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

本发明具体涉及一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法。本发明以低聚物二元醇为软段,异氰酸酯化合物为硬段,并在乳化过程中引入聚硅氧烷乳液,制得基于聚硅氧烷乳液改性的水性聚氨酯杂化乳液。聚有机硅氧烷的引入有效提高了水性聚氨酯乳胶膜的拉伸强度和模量,膜表面疏水性增强,吸水率降低且膜具有较高透明性。用该方法制备的水性聚氨酯杂化乳液可广泛用于高性能涂层材料、油墨、胶粘剂和密封材料等领域。

Description

一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法
技术领域
本发明涉及一种水性聚氨酯杂化乳液的制备方法,特别涉及有机硅氧烷乳液及水性聚氨酯乳液的制备方法。
背景技术
水性聚氨酯(WPU)以水为分散介质,具有高分子量、低粘度、容易施工、环保、安全、卫生等优点,在涂料、胶粘剂、油墨、密封剂等领域得到很好的应用。但是水性聚氨酯乳胶膜的力学性能(强度、模量)、粘附力、耐水性等性能还不能与传统的溶剂型聚氨酯相媲美,因此限制了该涂膜的进一步广泛应用。将无机纳米材料如二氧化硅、粘土、碳纳米管等引入WPU体系可以有效提高体系的力学性能,但是体系耐水性和表面疏水性能提高不明显甚至下降。聚二甲基硅氧烷(PDMS)具有低表面自由能、疏水性强、柔性好等优点,PDMS改性WPU可以有效提高体系的耐水性和表面疏水性,但是体系力学性能提高不明显甚至下降。将氨基硅氧烷引入WPU体系得到自交联WPU乳液,聚氨酯膜的力学性能和耐水性等得到改善,但是乳液的胶体稳定性和膜的微结构不太容易控制。为进一步有效提高聚氨酯膜的力学性能和耐水性,本发明通过细乳液聚合制备聚有机硅氧烷乳液,在水性聚氨酯乳化过程中原位引入聚有机硅氧烷乳液,制得聚有机硅氧烷乳液改性水性聚氨酯复合乳液。聚有机硅氧烷的引入可有效提高水性聚氨酯乳胶膜的力学性能、耐水性和表面疏水性。该分散体可应用于高性能涂料、粘合剂、密封剂、油墨等功能材料领域。
发明内容
本发明目的是提供一种聚硅氧烷乳液改性水性聚氨酯复合乳液的制备方法。本发明制备的水性聚氨酯在乳化过程中引入聚硅氧烷微球乳液。聚有机硅氧烷的引入有效提高了水性聚氨酯乳胶膜的拉伸强度和模量,膜表面疏水性增强,吸水率降低且膜具有较高透明性。
本发明的技术方案:
1、一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法,其特征在于组成包括:30wt%-50wt%的低聚物多元醇,20wt%-40wt%的二异氰酸酯化合物,3wt%-8wt%的亲水单体,2wt%-5wt%的胺类化合物,1wt%-5wt%胺类扩链剂,5wt%-20wt%的聚硅氧烷乳液,具体制备方法如下:
(1)聚硅氧烷乳液的合成:按配比将十二烷基磺酸钠、碳酸氢钠和磷酸二氢钠溶解于去离子水并混合均匀形成水相;另外按配比将有机硅氧烷单体、十六碳烷和偶氮二异丁腈混合并分散均匀形成油相,将油相组份滴加到水相组份中,边滴加边搅拌乳化,搅拌0.5h进行粗乳化,再细乳化10min,细乳化后在70℃条件下聚合5h,制得聚硅氧烷乳液;
(2)聚硅氧烷乳液改性水性聚氨酯乳液的合成:按配比在二异氰酸酯化合物中,滴加低聚物多元醇和催化剂,滴加完毕后在50℃反应1-2h,然后逐渐升温至65℃,加入亲水单体多羟基羧酸化合物粉末,在此温度下进行反应4-5h,用甲苯-二正丁胺法测定生成预聚体的异氰酸酯基(NCO)含量,当接近NCO理论值时,将反应温度降低到30℃,滴加胺类化合物反应1h,然后在乳化过程中引入聚硅氧烷乳液,最后加入胺类扩链剂对聚氨酯预聚体进行扩链得到聚硅氧烷乳液水性聚氨酯乳液;
所述的有机硅氧烷单体选用甲基丙烯酰氧基丙基三甲氧基硅烷、甲基丙烯酰氧基丙基三乙氧基硅烷、甲基丙烯酰氧基甲基二甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷之一种。
所述的低聚物多元醇选用聚乙二醇、聚丙二醇、聚四氢呋喃二醇、聚己内酯多元醇、聚碳酸酯二醇、聚氧乙烯-聚氧丙烯-聚氧乙烯二醇、聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇、聚对苯二甲酸乙二醇酯二醇、聚对苯二甲酸丁二醇酯二醇、α,ω-二羟基聚二甲基硅氧烷、二羟基聚二苯基硅氧烷、二羟基聚三氟丙基甲基硅氧烷之一种或几种,其分子量范围为400-10000。
所述的二异氰酸酯化合物选用2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷4,4’-二异氰酸酯、甲基环己基二异氰酸酯、2,2,4-三甲基己二异氰酸酯中之一种。
所述的亲水单体选用二羟甲基丙酸,二羟甲基丁酸,1,2-二羟基-3-丙磺酸钠中之一种。
所述的胺类化合物选用三乙胺、三乙醇胺、N-甲基二乙醇胺、N,N-二甲胺基对苯甲酸异辛酯、氨水中之一种。
所述胺类扩链剂选用乙二胺、己二胺、二乙烯三胺、异佛尔酮二胺、2-甲基戊二胺之一种
所述的聚硅氧烷乳液的粒径范围为10-1000nm,pH范围为6.0-8.0,固含量为10-50%。
附图说明
图1聚硅氧烷微球乳液改性水性聚氨酯复合膜的拉伸性能
图2聚硅氧烷微球乳液改性水性聚氨酯复合膜的水接触角
图3聚硅氧烷微球乳液改性水性聚氨酯复合膜的扫描电镜图
具体实施方式
为了更好的解释本发明,下面结合具体实施例对本发明进行进一步详细解释。
实施例1
聚硅氧烷微球乳液:按配比称量0.2g十二烷基磺酸钠,0.1g碳酸氢钠和0.1g磷酸二氢钠溶解于40.0g去离子水并混合均匀形成水相,并加入到250mL四颈烧瓶中。另外按配比称量9.0g乙烯基三甲氧基硅烷单体、0.5g十六碳烷和0.2g偶氮二异丁腈混合并分散均匀形成油相,将油相组份滴加到水相组份中,边滴加边搅拌乳化,搅拌0.5h进行粗乳化,再细乳化10min,细乳化后在70℃条件下聚合5h,制得聚有机硅氧烷乳液
实施例2
制备水性聚氨酯膜:在装有搅拌器、温度计和回流冷凝管的250mL四颈烧瓶中加入17.4g异佛尔酮二异氰酸酯(IPDI),室温下一边搅拌一边用滴液漏斗滴加57.1g聚碳酸酯多元醇(PCD2000)和0.05g催化剂二月桂酸二丁基锡(DBTDL),滴加速度控制在1.5h内,滴加完毕后在45±5℃反应1-2h;然后升温至60℃,加入3.75g二羟甲基丙酸(DMPA),反应3-4h,通过甲苯-二正丁胺反滴定法测定反应程度,直到测定NCO基团含量达到理论值;然后向树脂中加入2.83g的三乙胺,反应0.5-1h;向体系中滴加198.3g的去离子水进行乳化;最后制得水性聚氨酯膜。
实施例3
制备有机硅改性水性聚氨酯膜:在装有搅拌器、温度计和回流冷凝管的250mL四颈烧瓶中加入17.4g异佛尔酮二异氰酸酯(IPDI),室温下一边搅拌一边用滴液漏斗滴加51.3g聚碳酸酯多元醇(PCD2000)和0.05g催化剂二月桂酸二丁基锡(DBTDL),滴加速度控制在1.5h内,滴加完毕后在45±5℃反应1-2h;向其中加入6.85g有机硅化合物(PDMS),反应0.5-1h;然后升温至60℃,加入3.75g二羟甲基丙酸(DMPA),反应3-4h,通过甲苯-二正丁胺反滴定法测定反应程度,直到测定NCO基团含量达到理论值;然后向树脂中加入2.83g的三乙胺,反应0.5-1h;向体系中滴加198.3g的去离子水进行乳化;最后制得水性聚氨酯膜。
实施例4
制备聚硅氧烷微球乳液改性水性聚氨酯-有机硅膜:在装有搅拌器、温度计和回流冷凝管的250mL四颈烧瓶中加入17.4g异佛尔酮二异氰酸酯(IPDI),室温下一边搅拌一边用滴液漏斗滴加51.3g聚碳酸酯多元醇(PCD2000)和0.05g催化剂二月桂酸二丁基锡(DBTDL),滴加速度控制在1.5h内,滴加完毕后在45±5℃反应1-2h;向其中加入6.85g有机硅化合物(PDMS),反应0.5-1h;然后升温至60℃,加入3.75g二羟甲基丙酸(DMPA),反应3-4h,通过甲苯-二正丁胺反滴定法测定反应程度,直到测定NCO基团含量达到理论值;然后向树脂中加入2.83g的三乙胺,反应0.5-1h;加入14.91g的聚硅氧烷微球乳液,反应0.5-1h;向体系中滴加198.3g的去离子水进行乳化;最后制得二氧化硅改性的水性聚氨酯膜。

Claims (4)

1.一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法,其特征在于组成包括:30wt%-50wt%的低聚物多元醇,20wt%-40wt%的二异氰酸酯化合物,3wt%-8wt%的亲水单体,2wt%-5wt%的胺类化合物,1wt%-5wt%的胺类扩链剂,5wt%-20wt%的聚硅氧烷乳液,具体制备方法如下:
(1)聚硅氧烷乳液的合成:按配比称量0.2g十二烷基磺酸钠,0.1g碳酸氢钠和0.1g磷酸二氢钠溶解于40.0g去离子水并混合均匀形成水相,并加入到250mL四颈烧瓶中;另外按配比称量9.0g乙烯基三甲氧基硅烷单体、0.5g十六碳烷和0.2g偶氮二异丁腈混合并分散均匀形成油相,将油相组分滴加到水相组分中,边滴加边搅拌乳化,搅拌0.5h进行粗乳化,再细乳化10min,细乳化后在70℃条件下聚合5h,制得聚硅氧烷乳液;
(2)聚硅氧烷乳液改性水性聚氨酯乳液的合成:按配比在二异氰酸酯化合物中,滴加低聚物多元醇和催化剂,滴加完毕后在50℃反应1-2h,然后逐渐升温至65℃,加入亲水单体多羟基羧酸化合物粉末,在此温度下进行反应4-5h,用甲苯-二正丁胺法测定生成预聚体的异氰酸酯基(NCO)含量,当接近NCO理论值时,将反应温度降低到30℃,滴加胺类化合物反应1h,然后在乳化过程中引入聚硅氧烷乳液,最后加入胺类扩链剂对聚氨酯预聚体进行扩链得到聚硅氧烷乳液改性水性聚氨酯乳液;
所述的亲水单体选用二羟甲基丙酸,二羟甲基丁酸中之一种;
所述的胺类化合物选用三乙胺、三乙醇胺、N-甲基二乙醇胺、氨水中之一种;
所述的胺类扩链剂选用乙二胺、己二胺、二乙烯三胺、异佛尔酮二胺、2-甲基戊二胺中之一种。
2.根据权利要求1所述一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法,其特征在于:所述的低聚物多元醇选用聚乙二醇、聚丙二醇、聚四氢呋喃二醇、聚己内酯多元醇、聚碳酸酯二醇、聚氧乙烯-聚氧丙烯-聚氧乙烯二醇、聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇、聚对苯二甲酸乙二醇酯二醇、聚对苯二甲酸丁二醇酯二醇、α,ω-二羟基聚二甲基硅氧烷、二羟基聚二苯基硅氧烷、二羟基聚三氟丙基甲基硅氧烷之一种或几种,其分子量范围为400-2000。
3.根据权利要求1所述一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法,其特征在于:所述的二异氰酸酯化合物选用2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷4,4’-二异氰酸酯、甲基环己基二异氰酸酯、2,2,4-三甲基己二异氰酸酯中之一种。
4.根据权利要求1所述一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法,其特征在于:所述的聚硅氧烷乳液的粒径范围为10-1000nm,pH范围为6.0-8.0,固含量为10-50%。
CN201510962796.3A 2015-12-21 2015-12-21 一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法 Active CN105622891B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510962796.3A CN105622891B (zh) 2015-12-21 2015-12-21 一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510962796.3A CN105622891B (zh) 2015-12-21 2015-12-21 一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法

Publications (2)

Publication Number Publication Date
CN105622891A CN105622891A (zh) 2016-06-01
CN105622891B true CN105622891B (zh) 2018-04-17

Family

ID=56038269

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510962796.3A Active CN105622891B (zh) 2015-12-21 2015-12-21 一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法

Country Status (1)

Country Link
CN (1) CN105622891B (zh)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106432679A (zh) * 2016-09-05 2017-02-22 华南理工大学 一种水性聚氨酯油墨连接料及其制备方法
CN106947050B (zh) * 2017-05-03 2020-02-18 湖北博天体育设施有限公司 一种环保无毒的水性聚氨酯材料及其制备方法
CN107011507B (zh) * 2017-05-15 2019-04-23 福建湄洲湾氯碱工业有限公司 一种有机硅改性聚醚多元醇的制备及其应用
CN109610230A (zh) * 2018-11-21 2019-04-12 山东同创精细化工股份有限公司 一种造纸用水性聚氨酯及其制备方法
CN109608587A (zh) * 2018-12-11 2019-04-12 成都杰晟蜀邦新材料科技有限公司 一种复合改性聚氨酯乳液及其制备方法
CN109575223A (zh) * 2018-12-28 2019-04-05 南京高正农用化工有限公司 一种温度和pH双重刺激响应性智能聚合物微囊及其制备方法
CN112940595A (zh) * 2019-12-11 2021-06-11 武汉惠帮地平工程有限公司 一种绝缘高电阻地坪及施工方法
CN111019507B (zh) * 2019-12-31 2021-06-25 江南大学 一种高强度水性聚氨酯/纤维素纳米复合乳液及制备方法
CN111187564A (zh) * 2020-03-05 2020-05-22 清远粤绿新材料技术有限公司 一种可加热聚氨酯类汽车装饰膜的导热涂料及其制造方法
CN113527614B (zh) * 2021-07-05 2022-09-23 重庆交通大学 一种具有自补偿疏水表面功能的水性高分子乳液及其制备方法
CN116948621A (zh) * 2022-04-19 2023-10-27 中国石油天然气集团有限公司 纳米双疏表面活性剂及低渗致密油气储层用纳米排驱压裂液

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101955613A (zh) * 2010-10-20 2011-01-26 江南大学 一种聚合物-氧化锌纳米复合微球的制备方法
CN102816274A (zh) * 2012-07-06 2012-12-12 安徽大学 二氧化硅/聚(甲基丙烯酸甲酯-苯乙烯)双壳层复合微球及其制备方法
CN103542696A (zh) * 2013-09-25 2014-01-29 开原圣意达木材干燥设备有限公司 一种木材真空干燥碳化一体窑
CN103819648A (zh) * 2014-03-12 2014-05-28 东华大学 一种聚硅氧烷改性聚氨酯水分散体的制备方法
CN103980451A (zh) * 2014-06-10 2014-08-13 山东省农业科学院农业质量标准与检测技术研究所 羟烃基封端聚硅氧烷改性阳离子水性聚氨酯的制备方法
CN104774397A (zh) * 2014-12-29 2015-07-15 江南大学 一种双亲性聚合物/Ag纳米复合微球的制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101955613A (zh) * 2010-10-20 2011-01-26 江南大学 一种聚合物-氧化锌纳米复合微球的制备方法
CN102816274A (zh) * 2012-07-06 2012-12-12 安徽大学 二氧化硅/聚(甲基丙烯酸甲酯-苯乙烯)双壳层复合微球及其制备方法
CN103542696A (zh) * 2013-09-25 2014-01-29 开原圣意达木材干燥设备有限公司 一种木材真空干燥碳化一体窑
CN103819648A (zh) * 2014-03-12 2014-05-28 东华大学 一种聚硅氧烷改性聚氨酯水分散体的制备方法
CN103980451A (zh) * 2014-06-10 2014-08-13 山东省农业科学院农业质量标准与检测技术研究所 羟烃基封端聚硅氧烷改性阳离子水性聚氨酯的制备方法
CN104774397A (zh) * 2014-12-29 2015-07-15 江南大学 一种双亲性聚合物/Ag纳米复合微球的制备方法

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
聚氨酯-聚硅氧烷自乳化复合乳液的研究;张洪涛等;《石油化工》;20021231;第31卷(第11期);第890-893页 *
聚硅氧烷与纳米SiO2复合改性光固化水性聚氨酯的制备与性能;陈子栋等;《功能高分子学报》;20140630;第27卷(第2期);第178-183,218页 *
聚硅氧烷改性光固化水性聚氨酯的制备与性能研究;陈子栋等;《涂料技术》;20131231(第12期);第22-26页 *
聚硅氧烷改性聚氨酯的研究进展;王全杰等;《中国皮革》;20100331;第39卷(第5期);第54-59页 *
聚硅氧烷聚氨酯的合成与性能;陈精华等;《精细化工》;20040731;第21卷(第7期);第557-560页 *

Also Published As

Publication number Publication date
CN105622891A (zh) 2016-06-01

Similar Documents

Publication Publication Date Title
CN105622891B (zh) 一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法
CN105732940A (zh) 一种水性聚氨酯-二氧化硅纳米复合乳液的制备方法
CN107828046A (zh) 一种水性聚氨酯/多巴胺改性石墨烯纳米复合乳液的制备方法
JP5531956B2 (ja) 水性ポリウレタン樹脂分散体、その製造方法、及びそれを含有する塗料組成物
CN101821318B (zh) 水性复合树脂组合物、含有其的涂布剂、以及使用其的层压体
CN101313020B (zh) 碳二亚胺化合物及包含它的水性可固化树脂组合物
Liang et al. Synthesis and properties of self-crosslinking waterborne polyurethane with side chain for water-based varnish
Zheng et al. The effect of polyether functional polydimethylsiloxane on surface and thermal properties of waterborne polyurethane
CN109762454B (zh) 一种汽车清漆用硅改性双组份水性聚氨酯复合涂料的制备方法
JP5668690B2 (ja) 水性ポリウレタン樹脂分散体、その製造方法及びその使用
JP5139730B2 (ja) 合成擬革の表皮層用塗料および合成擬革の製造方法
CN107383848A (zh) 一种水性聚氨酯/石墨烯纳米复合乳液的制备方法
JP5554426B2 (ja) 合成擬革および合成擬革の製造方法
JP5249631B2 (ja) 合成擬革の表皮層形成用塗料
Lee et al. Biodegradable sol–gel coatings of waterborne polyurethane/gelatin chemical hybrids
JP6187465B2 (ja) ゴム積層体及びその製造方法
CN105131806B (zh) 水性荧光聚氨酯涂料及其预聚体混合法制备方法
CN109810239B (zh) 一种水性聚氨酯/改性氧化石墨烯复合乳液及其制备方法
JP6705445B2 (ja) 水性ポリウレタン樹脂分散体、その製造方法及びその使用
CN107011495A (zh) 水系聚氨酯分散体
CN103588951A (zh) 一种高强度疏水性光固化水性聚氨酯纳米复合乳液的制备
CN106939143A (zh) 光固化水性聚氨酯‑硅‑氧‑硅互穿网络结构涂层材料的制备方法
Park et al. Hyperbranched waterborne polyurethanes
Li et al. Synthesis and characterization of waterborne polyurethane-based ink binder modified via a silane coupling agent
JP2006022133A (ja) 水性ポリウレタンエマルジョン、並びにその製造方法及びその用途

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
TR01 Transfer of patent right

Effective date of registration: 20191125

Address after: 225300 No. 17 Cultural West Road, Taixing Economic Development Zone, Taizhou City, Jiangsu Province

Patentee after: Ruentex chemical (Taixing) Co. Ltd.

Address before: No. 1800 road 214122 Jiangsu Lihu Binhu District City of Wuxi Province

Patentee before: Jiangnan University

TR01 Transfer of patent right