[go: up one dir, main page]

CN104448206A - 一种环保型可剥离水性聚氨酯树脂及其制备方法和应用 - Google Patents

一种环保型可剥离水性聚氨酯树脂及其制备方法和应用 Download PDF

Info

Publication number
CN104448206A
CN104448206A CN201410826926.6A CN201410826926A CN104448206A CN 104448206 A CN104448206 A CN 104448206A CN 201410826926 A CN201410826926 A CN 201410826926A CN 104448206 A CN104448206 A CN 104448206A
Authority
CN
China
Prior art keywords
environment
preparation
urethane resin
friendly type
soluble urethane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410826926.6A
Other languages
English (en)
Other versions
CN104448206B (zh
Inventor
龙志云
欧阳娇
李俊梅
欧阳洁
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 GUANZHI NEW MATERIAL TECHNOLOGY Co Ltd
Original Assignee
GUANGZHOU GUANZHI NEW MATERIAL TECHNOLOGY 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 GUANGZHOU GUANZHI NEW MATERIAL TECHNOLOGY Co Ltd filed Critical GUANGZHOU GUANZHI NEW MATERIAL TECHNOLOGY Co Ltd
Priority to CN201410826926.6A priority Critical patent/CN104448206B/zh
Publication of CN104448206A publication Critical patent/CN104448206A/zh
Application granted granted Critical
Publication of CN104448206B publication Critical patent/CN104448206B/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
    • C08G18/08—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
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—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
    • C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—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
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—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
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

本发明属于水性聚氨酯制备技术领域，公开了一种环保型可剥离水性聚氨酯树脂及其制备方法和应用。该制备方法包括以下具体步骤：将脱水后的低聚物二元醇与二异氰酸酯混合加热反应；加入小分子扩链剂、亲水扩链剂，加热反应；搅拌下依次加入中和剂、潜固化剂、水、后扩链剂，搅拌均匀，即得到环保型可剥离水性聚氨酯树脂；所述的潜固化剂包括封闭型异氰酸酯类和含环氧基的硅氧烷中的至少一种。本发明体系中加入了潜固化剂，在乳液成膜的过程中与树脂体系中存在的亲水性基团反应从而去除亲水基团，赋予树脂极佳的耐水性，且潜固化剂在成膜过程中再次交联固化，进一步提高树脂的综合性能，延长涂膜的使用寿命，提供长期有效的保护性能。

Description

一种环保型可剥离水性聚氨酯树脂及其制备方法和应用
技术领域
本发明属于水性聚氨酯制备技术领域，特别涉及一种环保型可剥离水性聚氨酯树脂及其制备方法和应用。
背景技术
随着生活水平的不断提高，人们对产品的外观、环保性及其使用性能等要求也在日益增加。制造商会在玻璃、陶瓷、金属建材等材料表面附加一层保护涂料，以避免其在加工、运输以及组装等过程中被刮伤，以至影响其美观度，甚至降低其性能。
目前市场上大部分可剥离涂料使用的基础树脂仍是溶剂型的，其在生产、施工及使用过程中均会对环境及人体造成污染和伤害，有悖于绿色环保的发展理念。虽有小部分水性产品在使用，但是也暴露出不少的问题：(1)在使用过程中，涂层与基材不能始终粘合在一起，易脱落；(2)涂层强度不够，不易整片剥离；(3)亲水扩链剂作为内乳化剂，对乳液的稳定性起着至关重要的作用，但是涂膜干燥后，其极易吸水，使得涂层耐水性较差，吸水后易泛白，大大降低了涂膜对基材的保护效果；(4)涂层耐酸碱以及耐高低温性能差等。
发明内容
为了克服上述现有技术的缺点与不足，本发明的首要目的在于提供一种环保型可剥离水性聚氨酯树脂的制备方法。
本发明另一目的在于提供上述方法制备的环保型可剥离水性聚氨酯树脂。
本发明再一目的在于提供上述环保型可剥离水性聚氨酯树脂在表面防护领域中的应用，特别适用于玻璃、陶瓷及金属建材表面保护中。
本发明的目的通过下述方案实现：
一种环保型可剥离水性聚氨酯树脂的制备方法，包括以下具体步骤：
(1)将脱水后的低聚物二元醇与二异氰酸酯混合加热反应；
(2)加入小分子扩链剂、亲水扩链剂，加热反应；
(3)搅拌下依次加入中和剂、潜固化剂、水、后扩链剂，搅拌均匀，即得到环保型可剥离水性聚氨酯树脂。
所述的潜固化剂包括封闭型异氰酸酯类和含环氧基的硅氧烷中的至少一种。优选地，所用潜固化剂与低聚物二元醇的质量比为(0.5～1.5):(20～60)。
为了更好地实现本发明，所述的含环氧基的硅氧烷不含氨基、羟基或者硫醇基等带有活泼氢的基团。
本发明所述的低聚物多元醇优选为分子量为400～4000的聚酯型或者聚醚型二元醇，可包括聚己二酸丁二醇酯二醇、聚己内酯二醇、聚碳酸酯二醇、聚四氢呋喃醚二醇和聚丙二醇等中的至少一种，其中包括至少一种的聚醚多元醇。
优选地，本发明所述的二异氰酸酯并无特别限制，已知使用的二异氰酸酯均可，可为异佛尔酮二异氰酸酯(IPDI)、六次甲基二异氰酸酯(HDI)、甲苯二异氰酸酯(TDI)和4,4-二环己基甲烷二异氰酸酯(H12-MDI)等中的至少一种。
优选地，本发明所述的小分子扩链剂并无特别限制，已知使用的小分子扩链剂均可，为了更好地实现本发明，所述的小分子扩链剂优选为1,4-丁二醇(BDO)、新戊二醇(NPG)、1,6-己二醇(HEG)和一缩二乙二醇中的至少一种，其用量为催化量即可。
优选地，本发明所述的亲水扩链剂并无特别限制，已知使用的亲水扩链剂均可，为了更好地实现本发明，所述的亲水扩链剂优选为二羟甲基丙酸、二羟甲基丁酸和双羟基磺酸盐中的至少一种，其用量为催化量即可。
本发明所述的中和剂用于调节反应体系的pH值至弱碱性，可为本领域任意常用的碱液，如三甲胺、三乙胺、氨水等。
本发明所述的后扩链剂并无特别限制，已知使用的后扩链剂均可，为了更好地实现本发明，所述的后扩链剂优选为乙二胺、丙二胺、1,6-己二胺、二亚乙基三胺、异氟尔酮二胺和三亚乙基四胺中的至少一种。
为了进一步更好地实现本发明，上述制备方法过程中各组分的用量优选为：
上述制备方法优选在惰性气体保护下进行。
步骤(1)中所述的加热反应优选在60～90℃下，搅拌反应1.5～2.5 h。
步骤(1)中所述的脱水优选在80～140℃下脱水2 h。
步骤(2)中的试剂添加前优选降低反应体系的温度至40～60℃。
步骤(2)中所述的加热反应优选加热至70～85℃，反应2.5～4.5 h。
步骤(3)中的试剂添加前优选降低反应体系的温度至50℃以下。
步骤(3)中所述依次加入中和剂、潜固化剂、水、后扩链剂，优选每次加入一种试剂后进行充分搅拌再加入下一种试剂，优选加入中和剂、潜固化剂后分别搅拌1～5 min，加入水、后扩链剂后分别高速搅拌10～30 min，加入水后进行高速搅拌可使体系充分乳化。
步骤(3)中添加水主要用于调节体系的固含，可根据实际生产需要进行任意的条件，因此其用量可根据需要调整，适量即可，优选使用120～280重量份。
优选地，上述所用小分子扩链剂和亲水扩链剂的总量为2.5～7.5重量份。
上述制备方法得到的环保型可剥离水性聚氨酯树脂，具有环保易剥离、稳定性好、持久可剥、强度高、耐水性极佳、良好的耐酸碱性以及耐高低温性能、产品成本低等优点，为环保型可剥涂料提供了高性价比的基础树脂，可广泛的用于表面防护领域中，特别适用于玻璃、陶瓷及金属建材表面保护中。
本发明的机理为：
本发明的环保型可剥离水性聚氨酯树脂选材独具匠心，体系中加入了潜固化剂，在乳液成膜的过程中与树脂体系中存在的亲水性基团反应从而去除制备过程中引入的亲水基团，从而赋予树脂极佳的耐水性，并消除了现有水性聚氨酯体系中存在的大量游离亲水基团而导致树脂极易吸水，使得涂层耐水性较差，吸水后易泛白，大大降低了涂膜对基材的保护效果的影响，并且由于这些酸性亲水基团的存在，导致涂膜的耐水解性能下降，降低涂膜的使用寿命，使其不能提供长期有效的保护功能；且本发明的潜固化剂在成膜过程中会再次交联固化，从而进一步提高了环保型可剥离水性聚氨酯树脂的综合性能。同时，本发明优选使用聚醚多元醇和聚酯多元醇进行混合制备树脂，从而获得优异的各项性能。
本发明相对于现有技术，具有如下的优点及有益效果：
(1)本发明的环保型可剥离水性聚氨酯树脂中加入了潜固化剂，在乳液成膜过程中既消除体系中的亲水基团，又相互交联固化，从而提高树脂的各项性能。
(2)本发明的环保型可剥离水性聚氨酯树脂合成工艺简单，可控性强，对设备的要求明显降低，同时避免了多重改性产品在合成过程中所带来的诸多影响因素。
(3)本发明的环保型可剥离水性聚氨酯树脂分散介质为水，成本较低，为水性环保可剥离涂料的制备提供了高性价比的基础树脂。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1：环保型可剥离水性聚氨酯树脂的制备
在干燥氮气保护下，将120℃下真空脱水2 h后的聚四氢呋喃醚二醇80克，异佛尔酮二异氰酸酯26.7克，加入反应器中，在机械搅拌下控制温度在70～90℃进行反应2小时；加入一缩二乙二醇5.6克，二羟甲基丙酸3.5克，在70～85℃反应3小时；降至50℃以下，加入计量三乙胺2.45克调节体系pH为弱碱性，继续搅拌5分钟；加入封闭型异氰酸酯类潜固化剂(TPA-B80X)0.7克，继续搅拌5分钟；加入水200克，高速(转速优选≥1200 r/min)分散10分钟；加入乙二胺1.5克，继续高速分散30分钟，即可得到环保型可剥离水性聚氨酯树脂。
实施例2：环保型可剥离水性聚氨酯树脂的制备
在干燥氮气保护下，将120℃下真空脱水2 h后的聚四氢呋喃醚二醇40克，聚丙二醇40克，异佛尔酮二异氰酸酯44.4克，加入反应器中，在机械搅拌下控制温度在70～90℃进行反应2小时；加入一缩二乙二醇4.0克，二羟甲基丙酸5.0克，在70～85℃反应3小时；降至50℃以下，加入计量三乙胺2.45克，继续搅拌5分钟；加入封闭型异氰酸酯类潜固化剂(TPA-B80X)4.5克，继续搅拌5分钟；加入水200克，高速分散10分钟；加入乙二胺1.5克，继续高速分散30分钟，即可得到环保型可剥离水性聚氨酯树脂。
实施例3：环保型可剥离水性聚氨酯树脂的制备
在干燥氮气保护下，将120℃下真空脱水2 h后的聚己内酯二醇40克，聚己二酸丁二醇酯二醇40克，甲苯二异氰酸酯34.8克，加入反应器中，在机械搅拌下控制温度在70～90℃进行反应2小时；加入一缩二乙二醇5.6克，二羟甲基丙酸3.5克，在70～85℃反应3小时；降至50℃以下，加入计量三乙胺2.45克，继续搅拌5分钟；加入环氧基硅氧烷类潜固化剂(OS-9012)2.8克，继续搅拌5分钟；加入水200克，高速分散10分钟；加入乙二胺1.5克，继续高速分散30分钟，即可得到环保型可剥离水性聚氨酯树脂。
实施例4：环保型可剥离水性聚氨酯树脂的制备
在干燥氮气保护下，将120℃下真空脱水2 h后的聚碳酸酯二元醇40克，聚四氢呋喃醚二醇40克，异佛尔酮二异氰酸酯22.2克，六次甲基二异氰酸酯16.8克，加入反应器中，在机械搅拌下控制温度在70～90℃进行反应2小时；加入1,4-丁二醇4.75克，二羟甲基丙酸3.5克，在70～85℃反应3小时；降至50℃以下，加入计量三乙胺2.45克，继续搅拌5分钟；加入封闭型异氰酸酯类潜固化剂(TPA-B80X)6.0克，继续搅拌5分钟；加入水200克，高速分散10分钟；加入乙二胺1.5克，继续高速分散30分钟，即可得到环保型可剥离水性聚氨酯树脂。
实施例5：环保型可剥离水性聚氨酯树脂的制备
在干燥氮气保护下，将120℃下真空脱水2 h后的聚碳酸酯二元醇40克，聚四氢呋喃醚二醇40克，4,4-二环己基甲烷二异氰酸酯104.8克，六次甲基二异氰酸酯16.8克，加入反应器中，在机械搅拌下控制温度在70～90℃进行反应2小时；加入1,4-丁二醇17.5克，二羟甲基丙酸10.0克，在70～85℃反应3小时；降至50℃以下，加入计量三乙胺2.45克，继续搅拌5分钟；加入环氧基硅氧烷(OS-9012)1.8克，继续搅拌5分钟；加入水200克，高速分散10分钟；加入乙二胺1.5克，继续高速分散30分钟，即可得到环保型可剥离水性聚氨酯树脂。
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)

1.一种环保型可剥离水性聚氨酯树脂的制备方法，其特征在于包括以下具体步骤：
(1)将脱水后的低聚物二元醇与二异氰酸酯混合加热反应；
(2)加入小分子扩链剂、亲水扩链剂，加热反应；
(3)搅拌下依次加入中和剂、潜固化剂、水、后扩链剂，搅拌均匀，即得到环保型可剥离水性聚氨酯树脂；
所述的潜固化剂包括封闭型异氰酸酯类和含环氧基的硅氧烷中的至少一种。
2.根据权利要求1所述的环保型可剥离水性聚氨酯树脂的制备方法，其特征在于：所述的含环氧基的硅氧烷不含氨基、羟基或者硫醇基的带有活泼氢的基团。
3.根据权利要求1所述的环保型可剥离水性聚氨酯树脂的制备方法，其特征在于：所用潜固化剂与低聚物二元醇的质量比为(0.5～1.5):(20～60)。
4.根据权利要求1所述的环保型可剥离水性聚氨酯树脂的制备方法，其特征在于：所述的低聚物多元醇包括分子量为400～4000的聚酯型或者聚醚型二元醇。
5.根据权利要求1所述的环保型可剥离水性聚氨酯树脂的制备方法，其特征在于：所述的低聚物多元醇包括聚己二酸丁二醇酯二醇、聚己内酯二醇、聚碳酸酯二醇、聚四氢呋喃醚二醇和聚丙二醇中的至少一种，其中包括至少一种的聚醚多元醇。
6.根据权利要求1所述的环保型可剥离水性聚氨酯树脂的制备方法，其特征在于：所述的二异氰酸酯包括异佛尔酮二异氰酸酯、六次甲基二异氰酸酯、甲苯二异氰酸酯和4,4-二环己基甲烷二异氰酸酯中的至少一种；所述的小分子扩链剂包括1,4-丁二醇、新戊二醇、1,6-己二醇和一缩二乙二醇中的至少一种；所述的亲水扩链剂包括二羟甲基丙酸、二羟甲基丁酸和双羟基磺酸盐中的至少一种；所述的后扩链剂包括乙二胺、丙二胺、1,6-己二胺、二亚乙基三胺、异氟尔酮二胺和三亚乙基四胺中的至少一种。
7.根据权利要求1所述的环保型可剥离水性聚氨酯树脂的制备方法，其特征在于所述制备方法过程中各组分的用量为：
8.根据权利要求1所述的环保型可剥离水性聚氨酯树脂的制备方法，其特征在于：步骤(1)中所述的加热反应指在60～90℃下，搅拌反应1.5～2.5h；步骤(2)中所述的加热反应为加热至70～85℃，反应2.5～4.5h。
9.一种环保型可剥离水性聚氨酯树脂，其特征在于根据权利要求1～8任一项所述的环保型可剥离水性聚氨酯树脂的制备方法得到。
10.根据权利要求9所述的环保型可剥离水性聚氨酯树脂在表面防护领域中的应用。
CN201410826926.6A 2014-12-25 2014-12-25 一种环保型可剥离水性聚氨酯树脂及其制备方法和应用 Active CN104448206B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410826926.6A CN104448206B (zh) 2014-12-25 2014-12-25 一种环保型可剥离水性聚氨酯树脂及其制备方法和应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410826926.6A CN104448206B (zh) 2014-12-25 2014-12-25 一种环保型可剥离水性聚氨酯树脂及其制备方法和应用

Publications (2)

Publication Number Publication Date
CN104448206A true CN104448206A (zh) 2015-03-25
CN104448206B CN104448206B (zh) 2017-10-10

Family

ID=52895005

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410826926.6A Active CN104448206B (zh) 2014-12-25 2014-12-25 一种环保型可剥离水性聚氨酯树脂及其制备方法和应用

Country Status (1)

Country Link
CN (1) CN104448206B (zh)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106085188A (zh) * 2016-06-16 2016-11-09 南昌航空大学 两种水性可剥聚氨酯分散体的制备方法
CN106519170A (zh) * 2016-10-25 2017-03-22 广州冠志新材料科技有限公司 一种木器漆修色用水性聚氨酯树脂及其制备方法
CN107142003A (zh) * 2017-07-05 2017-09-08 北京科技大学 一种用于连接部位可剥离增强防护涂料体系的制备方法
CN107501497A (zh) * 2017-08-28 2017-12-22 同光（江苏）新材料科技有限公司 一种车衣用可剥离水性聚氨酯树脂合成方法
CN107722687A (zh) * 2017-09-19 2018-02-23 河北晨阳工贸集团有限公司 水性可剥离树脂及其制备方法
CN109207049A (zh) * 2018-08-22 2019-01-15 青岛汇智领先新材料科技有限公司 一种双组份改性聚氨酯可剥离涂料及其制备方法
CN109486402A (zh) * 2018-11-19 2019-03-19 山东天庆科技发展有限公司 一种水性可剥离树脂及其制备方法
CN109554102A (zh) * 2018-12-03 2019-04-02 宁夏银珠蓝箭建材科技有限公司 一种用于建筑物防水的防水涂料及其制备方法
CN112250818A (zh) * 2020-09-27 2021-01-22 长春一汽富维东阳汽车塑料零部件有限公司 一种可重复利用水性聚氨酯遮蔽材料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070129488A1 (en) * 2005-12-01 2007-06-07 Bayer Materialscience Ag Preparation of a polyurethane dispersion with blocked isocyanate groups
CN101914343A (zh) * 2010-08-26 2010-12-15 合肥工业大学 一种有机硅氧烷改性水性聚氨酯涂料的制备方法
CN102358777A (zh) * 2011-07-28 2012-02-22 上海华明高技术（集团）有限公司 水性聚氨酯弹性体乳液及制备方法和应用
CN103450437A (zh) * 2013-08-28 2013-12-18 桐乡市濮院毛针织技术服务中心 一种有机硅氧烷改性水性聚氨酯制备羊毛柔软剂的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070129488A1 (en) * 2005-12-01 2007-06-07 Bayer Materialscience Ag Preparation of a polyurethane dispersion with blocked isocyanate groups
CN101914343A (zh) * 2010-08-26 2010-12-15 合肥工业大学 一种有机硅氧烷改性水性聚氨酯涂料的制备方法
CN102358777A (zh) * 2011-07-28 2012-02-22 上海华明高技术（集团）有限公司 水性聚氨酯弹性体乳液及制备方法和应用
CN103450437A (zh) * 2013-08-28 2013-12-18 桐乡市濮院毛针织技术服务中心 一种有机硅氧烷改性水性聚氨酯制备羊毛柔软剂的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
吕贻胜等: "封闭型水性多异氰酸酯固化剂的制备及其性能研究", 《涂料工业》 *
罗建光等: "水性聚氨酯涂料的交联改性研究进展", 《合成材料老化与应用》 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106085188A (zh) * 2016-06-16 2016-11-09 南昌航空大学 两种水性可剥聚氨酯分散体的制备方法
CN106519170A (zh) * 2016-10-25 2017-03-22 广州冠志新材料科技有限公司 一种木器漆修色用水性聚氨酯树脂及其制备方法
CN106519170B (zh) * 2016-10-25 2019-02-26 广州冠志新材料科技有限公司 一种木器漆修色用水性聚氨酯树脂及其制备方法
CN107142003A (zh) * 2017-07-05 2017-09-08 北京科技大学 一种用于连接部位可剥离增强防护涂料体系的制备方法
CN107142003B (zh) * 2017-07-05 2019-11-12 北京科技大学 一种用于连接部位可剥离增强防护涂料体系的制备方法
CN107501497A (zh) * 2017-08-28 2017-12-22 同光（江苏）新材料科技有限公司 一种车衣用可剥离水性聚氨酯树脂合成方法
CN107722687A (zh) * 2017-09-19 2018-02-23 河北晨阳工贸集团有限公司 水性可剥离树脂及其制备方法
CN107722687B (zh) * 2017-09-19 2020-02-07 河北晨阳工贸集团有限公司 水性可剥离树脂及其制备方法
CN109207049A (zh) * 2018-08-22 2019-01-15 青岛汇智领先新材料科技有限公司 一种双组份改性聚氨酯可剥离涂料及其制备方法
CN109486402A (zh) * 2018-11-19 2019-03-19 山东天庆科技发展有限公司 一种水性可剥离树脂及其制备方法
CN109554102A (zh) * 2018-12-03 2019-04-02 宁夏银珠蓝箭建材科技有限公司 一种用于建筑物防水的防水涂料及其制备方法
CN112250818A (zh) * 2020-09-27 2021-01-22 长春一汽富维东阳汽车塑料零部件有限公司 一种可重复利用水性聚氨酯遮蔽材料及其制备方法

Also Published As

Publication number Publication date
CN104448206B (zh) 2017-10-10

Similar Documents

Publication Publication Date Title
CN104448206A (zh) 一种环保型可剥离水性聚氨酯树脂及其制备方法和应用
CN101696262B (zh) 多异氰酸酯固化剂改性聚氨酯水分散体的制备方法及应用
CN105400481B (zh) 一种水性聚氨酯胶黏剂的合成方法
CN103601867B (zh) 用作高分子材料的水性聚氨酯分散液及其制备方法
CN101225150B (zh) 水分散有机硅-聚氨酯嵌段共聚物的合成方法及应用
CN101851325B (zh) 湿法合成革用聚酯型高耐水解高剥离聚氨酯树脂及其制备方法
CN101225226B (zh) 水分散蒙脱土/有机硅嵌段聚氨酯纳米复合材料的制备方法及用途
WO2018184307A1 (zh) 水性聚氨酯分散体及其无溶剂制备方法
CN103130977B (zh) 一种双组分水性木器漆的聚氨酯多元醇分散体及其制备方法
CN110272705B (zh) 一种汽车内饰用双组分水性胶黏剂及其制备方法
CN107163217B (zh) 一种纳米金刚石改性水性聚氨酯的制备方法
CN103570915A (zh) 一种高固含羟基型水性聚氨酯树脂的制备方法
CN104194610A (zh) 一种自交联型单组份聚氨酯防水涂料
CN104448233A (zh) 合成革中间层用高耐候性无溶剂型聚氨酯树脂
CN110229301A (zh) 一种水性聚氨酯树脂及其合成革的制备方法
CN102504166A (zh) 超支化水性聚氨酯羟基组分的制备方法
CN107011495A (zh) 水系聚氨酯分散体
CN114276519B (zh) 一种自消光水性聚氨酯及其制备方法
CN107936212B (zh) 指甲油用水性聚氨酯树脂及其制备方法
CN109575228A (zh) 一种聚氨酯树脂及其制备方法和用途
CN104629606A (zh) 一种抗菌防水聚氨酯涂料及其制备方法
CN109293866A (zh) 一种腐植酸改性水性聚氨酯材料及其制备方法
CN104892891A (zh) 高耐醇性、耐黄变的水性聚氨酯分散乳液及其制备方法
CN105504214B (zh) 一种生物质聚氨酯电泳树脂及其电泳漆的制备方法
CN105482765A (zh) 一种水性聚氨酯胶粘剂组合物及其制备方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant