CN112812262A - 用于木器漆的无溶剂羟基水性聚氨酯及其制备方法和木器漆 - Google Patents
用于木器漆的无溶剂羟基水性聚氨酯及其制备方法和木器漆 Download PDFInfo
- Publication number
- CN112812262A CN112812262A CN202011636579.2A CN202011636579A CN112812262A CN 112812262 A CN112812262 A CN 112812262A CN 202011636579 A CN202011636579 A CN 202011636579A CN 112812262 A CN112812262 A CN 112812262A
- Authority
- CN
- China
- Prior art keywords
- solvent
- waterborne polyurethane
- parts
- free hydroxyl
- diol
- 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
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
- C08G18/28—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
- 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
- C08G18/4236—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
-
- 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
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—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 C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6622—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 C08G18/3225 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
- C08G18/65—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
- C08G18/6666—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
- C08G18/6688—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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种用于木器漆的无溶剂羟基水性聚氨酯及其制备方法和木器漆,所述聚氨酯先用聚醚多元醇或聚酯多元醇、非离子二元醇或非离子型聚醚多元醇、二异氰酸酯,生成NCO封端的聚预体,然后用二羟甲基丙酸及小分子二元醇进行扩链,再用三乙胺中和后在高速搅拌下分散于水中,最后用醇胺进行后扩链。无溶剂羟基水性聚氨酯与水性异氰酸酯固化后,硬度高,光泽度及丰满度高,所制备的木器漆耐水性、耐酒精等性能良好。本发明公开的羟基水性聚氨酯在合成制备过程中,无需添加DMF、DMAC、NMP、NEP或AC等溶剂,在施工过程中无任何有机溶剂释放,是一种高性能环保型羟基水性聚氨酯树脂。
Description
技术领域
本发明涉及水性聚氨酯及其制备技术领域,特别涉及一种用于木器漆的无溶剂羟基水性聚氨酯及其制备方法和木器漆。
背景技术
目前,随着人们对于室内环境空气质量问题越来越重视,在木器家具制造过程中人们越来越多地追求使用低VOC排放,无毒,环保型的木器漆。羟基丙烯酸乳液则是木器漆中关键的组分。
传统用于木器漆的羟基丙烯酸乳液在制备过程中,羟基丙烯酸分散体需要在140℃下反应,并加入醇醚溶剂作为溶剂,但是醇醚溶剂难以除去,会保留在羟基丙烯酸分散体中,在施工过程中会释放,产生气味,不环保。若羟基丙烯酸乳液在制备过程中不加入溶剂,则制备的乳液成膜透明性、丰满度、光泽度、硬度等性能会比较差。
可见,现有技术还有待改进和提高。
发明内容
鉴于上述现有技术的不足之处,本发明的目的在于提供用于木器漆的无溶剂羟基水性聚氨酯及其制备方法,旨在解决现有技术中传统的用于木器漆的乳液释放挥发性有机物,不环保的问题。
为了达到上述目的,本发明采取了以下技术方案:
一种用于木器漆的无溶剂羟基水性聚氨酯,包括以下按重量份数计算的原料:聚醚二元醇或聚酯二元醇15-20份,非离子二元醇或非离子型聚醚多元醇4-6份,二异氰酸酯50-60份,二羟甲基丙酸4-6份,小分子二元醇1-3份,三乙胺3-5份,醇胺5-15份。
所述的一种用于木器漆的无溶剂羟基水性聚氨酯中,所述聚醚二元醇为聚丙二醇或聚四氢呋喃醇中的一种或多种。
所述的一种用于木器漆的无溶剂羟基水性聚氨酯中,所述聚酯二元醇为聚己二酸辛戊二醇酯、聚己内酯或聚碳酸酯的一种或多种。
所述的一种用于木器漆的无溶剂羟基水性聚氨酯,所述非离子二元醇为聚乙二醇。
所述的一种用于木器漆的无溶剂羟基水性聚氨酯中,所述异氰酸酯为异氟尔酮二异氰酸酯、六亚甲基二异氰酸酯或氢化MDI的一种或多种。
所述的一种用于木器漆的无溶剂羟基水性聚氨酯中,所述小分子二元醇为乙二醇、1,4-丁二醇或三羟甲基丙烷的一种或多种。
所述的一种用于木器漆的无溶剂羟基水性聚氨酯中,所述醇胺为一乙醇胺或二乙醇胺的一种或多种。
一种用于木器漆的无溶剂羟基水性聚氨酯的制备方法,包括以下步骤:
A.往反应器中加入聚醚二元醇或聚酯二元醇,非离子二元醇或非离子型聚醚多元醇,二异氰酸酯,在80-85℃反应2-3h;
B.完成步骤A后往反应器加入二羟甲基丙酸,小分子二元醇,在80-85℃继续反应3-5h;
C.降温至50℃,往反应器加入三乙胺中和,反应20min;
D.中和反应结束后,将步骤C得到的反应体系在高速搅拌下分散于水中,再加入醇胺,反应0.5-1h,得到无溶剂羟基水性聚氨酯。
一种木器漆,包括:上述的无溶剂羟基水性聚氨酯,增稠剂,润湿剂,流平剂,消泡剂和水。
所述的一种木器漆,包括以下按重量份数计算的原料:所述的无溶剂羟基水性聚氨酯60份,增稠剂0.15-0.3份,润湿剂0.3份,流平剂0.2份,消泡剂0.2份,水39-39.15份。
有益效果:
本发明提供了一种用于木器漆的无溶剂羟基水性聚氨酯及其制备方法和木器漆。所述羟基水性聚氨酯制备过程中无需加入溶剂,产品水性无毒,气味小。以上述羟基水性聚氨酯制备的木器漆在施工过程中对环境无污染,而且具有较好的漆膜透明性、丰满度,光泽度、硬度和耐磨性。
具体实施方式
本发明提供一种用于木器漆的无溶剂羟基水性聚氨酯,为使本发明的目的、技术方案及效果更加清楚、明确,以下举实施例对本发明进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
本发明提供一种用于木器漆的无溶剂羟基水性聚氨酯,包括包括以下按重量份数计算的原料:聚醚二元醇或聚酯二元醇15-20份,非离子二元醇或非离子型聚醚多元醇4-6份,二异氰酸酯50-60份,二羟甲基丙酸4-6份,小分子二元醇1-3份,三乙胺3-5份,醇胺5-15份。
反应体系的粘度大小会影响聚合反应的进行,因此,通过调整扩链剂,非离子二元醇或非离子型聚醚多元醇,二异氰酸酯,二羟甲基丙酸和小分子二元醇的比例使预聚液的粘度满足聚合反应要求,且各组分之间在体系中相容性好,可以充分地相互接触反应。后扩链使用醇胺作为羟基化功能性单体,进一步赋予水性聚氨酯不同的性能,使得制备的水性聚氨酯满足木器漆对于水性聚氨酯的漆膜透明性,丰满度,以及光泽度等要求。水性聚氨酯是一种软硬段交互连接的聚合物,其中,扩链剂聚酯二元醇和聚醚二元醇构成软段,其中聚醚二元醇的醚键能够与水形成氢键,与水形成的氢键数的相对比例会影响水性聚氨酯的耐水性。硬段主要由二异氰酸酯,二羟甲基丙酸以及醇胺等构成。
进一步地,所述聚醚二元醇为聚丙二醇或聚四氢呋喃醇的一种或多种。聚醚二元醇的内聚能较低、易于旋转,可以提高水性聚氨酯的耐水性能,柔顺性。聚四氢呋喃醇分子量的提高,可以使柔性链段长度的增大,增强材料的机械性能。聚醚型水性聚氨酯的耐低温性能好,软化温度低,柔顺性好,耐水解。
进一步地,所述聚酯二元醇为聚己二酸新戊二醇酯、聚己内酯或聚碳酸酯的一种或多种。聚酯二元醇的结晶性好,可以提高水性聚氨酯的拉伸强度和粘接强度,耐水解性强的聚酯二醇。含有碳酸酯型的聚酯二元醇,内聚能高,所制备得水性聚氨酯机械强度高,耐油性、耐热性好。
进一步地,所述非离子二元醇为聚乙二醇。聚乙二醇无毒、无刺激性,具有良好的水溶性,与许多有机物有良好的相容性。使用非非离子二元醇或非离子型聚醚多元醇可以有效降低反应体系的粘度,无需再加入溶剂以及高温预融,提高了环保性和降低能耗。
进一步地,所述异氰酸酯为异氟尔酮二异氰酸酯、六亚甲基二异氰酸酯或氢化MDI的一种或多种。六亚甲基二异氰酸酯与二醇类反应生成聚氨酯,可以使制备得聚氨酯不泛黄,且提高耐磨和耐油性能。氢化MDI的结晶性好,粘度低,可以提高水性聚氨酯的光稳定性、耐候性和机械性能。
进一步地,所述小分子二元醇为乙二醇、1,4-丁二醇或三羟甲基丙烷的一种或多种。小分子二元醇可以增加水性聚氨酯硬段,提高性能。
二羟甲基丙酸是阴离子型亲水性扩链剂,其分子量小,较少的用量就能够提供足够多的羧酸量,制备的水性聚氨酯中离子浓度高,具有强乳化能力,形成的乳液微粒粒径比较小,稳定性高。二羟甲基丙酸对粒径的影响主要表现在两个方面,一是羧基导致分子链间产生静电斥力,减弱分子链间聚集,二是羧基会影响分子链的离子化程度,进而影响分子链间的静电斥力。小分子二元醇作为扩链剂,可以使分子链扩展、分子量增大,提高聚氨酯的力学性能。
三乙胺是阴离子型水性聚氨酯中和剂,能和羧基、磺酸基或叔胺基形成盐,使水性聚氨酯在水中具有分散性。中和度为三乙胺用量与二羟甲基丙酸中羧基含量的摩尔分数,对最终产品的外观透明度,粒径,粘度有很大影响。中和度低,水性聚氨酯的粘度会更小,但是外观的透明度会很差。中和度高,外观的透明度会更好,但是粘度也会随之增多。因此,应控制中和度,即三乙胺与二羟甲基丙酸的用量比例,满足使用要求。
进一步地,所述醇胺为一乙醇胺或二乙醇胺的一种或多种。醇胺用于在水性聚氨酯中引入羟基,可以提高耐水性。
一种用于木器漆的无溶剂羟基水性聚氨酯的制备方法,包括以下步骤:
A.往反应器中加入聚醚二元醇或聚酯二元醇,非离子二元醇或非离子型聚醚多元醇,二异氰酸酯,在80-85℃反应2-3h;
B.完成步骤A后往反应器加入二羟甲基丙酸,小分子二元醇,在80-85℃继续反应3-5h;
C.降温至50℃,往反应器加入三乙胺中和,反应20min;
D.中和反应结束后,将步骤C得到的反应体系在高速搅拌下分散于水中,再加入醇胺,反应0.5-1h,得到无溶剂羟基水性聚氨酯。
步骤A中用聚醚或聚酯多元醇、非离子二元醇、二异氰酸酯、生成NCO封端的聚预体,在制备预聚体时加入非离子二元醇,可以降低反应体系的粘度,无需太高温度进行预融,除此之外,使得步骤B加入二羟甲基丙酸及小分子二元醇后可以在较低温度下进行扩链,由于反应体系的粘度较低,各反应组分的分布均匀,反应可以充分地进行,转化率高,无需加入有机溶剂。在分散步骤时,预聚物的高温会不利于得到稳定的微细粒径乳液。步骤C中反应体系加入三乙胺中和后形成盐。步骤D采用醇胺进行扩链,增加体系中羟基的含量,可以提高水性聚氨酯的力学性能,同时满足木器漆所需的漆膜透明性,丰满度,光泽度。反应结束后,使用300目滤膜进行过滤,去除杂质和未充分反应的聚团颗粒,包装成品。
一种木器漆,包括:上述的无溶剂羟基水性聚氨酯,增稠剂,润湿剂,流平剂,消泡剂和水。在使用前,先往所述的木器漆添加4.5%的水性异氰酸酯固化剂,喷涂于木器上,喷涂两遍或以上,放置7天晾干。
进一步的,所述的木器漆,包括包括以下按重量份数计算的原料:无溶剂羟基水性聚氨酯60份,增稠剂0.15-0.3份,润湿剂0.3份,流平剂0.2份,消泡剂0.2份,水39-39.15份。
水性聚氨酯的粘度较低,在立面使用时,容易发生流挂,加入增稠剂可以增加施工膜厚,提高丰满度,改进刷涂施工性。
水性木器漆涂料中含有大量的水,有机溶剂含量很低,润湿性差,容易产生缩孔。加入润湿剂和平流剂能降低体系表面张力,改善涂料对木器的润湿性和渗透性,提高附着力,并且能提高整个体系的相容性,避免在使用时产生缩孔。
增稠剂,润湿剂以及流平剂的使用,会有助于气泡的产生和稳定,施工时容易留下气泡,影响木器漆的使用效果。消泡剂颗粒在体系中以微粒存在,可以破坏气泡的弹性膜,抑制泡沫的产生。
实施例1
无溶剂羟基水性聚氨酯的组成(按重量分数计算),包括:
聚醚二元醇或聚酯二元醇20份,非离子二元醇或非离子型聚醚多元醇4份,二异氰酸酯50份,二羟甲基丙酸4份,小分子二元醇3份,三乙胺3份,一乙醇胺5份。
所述聚氨酯的制备方法包括:
A.往反应器中加入聚醚二元醇或聚酯二元醇,非离子二元醇或非离子型聚醚多元醇,二异氰酸酯,在80-85℃反应2.5h;
B.完成步骤A后往反应器加入二羟甲基丙酸,小分子二元醇,在80-85℃继续反应4h;
C.降温至50℃,往反应器加入三乙胺中和,反应20min;
D.中和反应结束后,将步骤C得到的反应体系在高速搅拌下分散于水中,再加入一乙醇胺,反应1h,得到无溶剂羟基水性聚氨酯,用300目滤膜进行过滤后包装。
上述无溶剂羟基水性聚氨酯的性能参数如下表所示:
外观 | 半透明乳液 |
固含量(%) | 38 |
粘度(cps/25℃) | 260 |
PH | 7.2 |
-OH含量(%) | 1.2 |
DMF含量(%) | 0 |
DMAC含量(%) | 0 |
NMP含量(%) | 0 |
NEP含量(%) | 0 |
AC含量(%) | 0 |
取上述制备的无溶剂羟基水性聚氨酯制备木器漆,所述木器漆按重量分数计算,包括:
无溶剂羟基水性聚氨酯60份,增稠剂0.3份,润湿剂0.3份,流平剂0.2份,消泡剂0.2份,水39份。
上述无溶剂羟基水性聚氨酯制备的木器漆的性能检测:
往上述制备的木器漆添加4.5%的水性异氰酸酯固化剂后,喷涂于木器和玻璃底材上,喷涂两遍,放置7天后进行检测,检测结果如下:
实施例2
无溶剂羟基水性聚氨酯的组成(按重量分数计算),包括:
聚醚二元醇或聚酯二元醇20份,非离子二元醇或非离子型聚醚多元醇4份,二异氰酸酯50份,二羟甲基丙酸4份,小分子二元醇3份,三乙胺3份,二乙醇胺8.6份。
所述聚氨酯的制备方法包括:
A.往反应器中加入聚醚二元醇或聚酯二元醇,非离子二元醇或非离子型聚醚多元醇,二异氰酸酯,在80-85℃反应2.5h;
B.完成步骤A后往反应器加入二羟甲基丙酸,小分子二元醇,在80-85℃继续反应4h;
C.降温至50℃,往反应器加入三乙胺中和,反应20min;
D.中和反应结束后,将步骤C得到的反应体系在高速搅拌下分散于水中,再加入二乙醇胺,反应1h,得到无溶剂羟基水性聚氨酯,用300目滤膜进行过滤后包装。
上述无溶剂羟基水性聚氨酯的性能参数如下表所示:
取上述制备的无溶剂羟基水性聚氨酯制备木器漆,所述木器漆按重量分数计算,包括:
无溶剂羟基水性聚氨酯60份,增稠剂0.25份,润湿剂0.3份,流平剂0.2份,消泡剂0.2份,水39.05份。
基于上述无溶剂羟基水性聚氨酯制备的木器漆的性能检测:
往上述制备的木器漆添加4.5%的水性异氰酸酯固化剂后,喷涂于木器和玻璃底材上,喷涂两遍,放置7天后进行检测,检测结果如下:
检测项目 | 结果 |
铅笔硬度(玻璃板) | 2-3H |
漆膜透明性 | 好 |
光泽度 | 98 |
耐水性 | 无异常 |
耐沸水 | 无异常 |
耐酒精 | 无异常 |
耐咖啡 | 无异常 |
耐红酒 | 无异常 |
耐醋 | 无异常 |
抗回粘 | 通过 |
实施例3
无溶剂羟基水性聚氨酯的组成(按重量分数计算),包括:
聚醚二元醇或聚酯二元醇18份,非离子二元醇或非离子型聚醚多元醇5份,二异氰酸酯54份,二羟甲基丙酸5份,小分子二元醇2份,三乙胺4份,一乙醇胺6份。
所述聚氨酯的制备方法包括:
A.往反应器中加入聚醚二元醇或聚酯二元醇,非离子二元醇或非离子型聚醚多元醇,二异氰酸酯,在80-85℃反应2.5h;
B.完成步骤A后往反应器加入二羟甲基丙酸,小分子二元醇,在80-85℃继续反应4h;
C.降温至50℃,往反应器加入三乙胺中和,反应20min;
D.中和反应结束后,将步骤C得到的反应体系在高速搅拌下分散于水中,再加入一乙醇胺,反应1h,得到无溶剂羟基水性聚氨酯,用300目滤膜进行过滤后包装。
上述无溶剂羟基水性聚氨酯的性能参数如下表所示:
外观 | 半透明乳液 |
固含量(%) | 38.2 |
粘度(cps/25℃) | 280 |
PH | 7.3 |
-OH含量(%) | 1.6 |
DMF含量(%) | 0 |
DMAC含量(%) | 0 |
NMP含量(%) | 0 |
NEP含量(%) | 0 |
AC含量(%) | 0 |
取上述制备的无溶剂羟基水性聚氨酯制备木器漆,所述木器漆按重量分数计算,包括:
无溶剂羟基水性聚氨酯60份,增稠剂0.3份,润湿剂0.3份,流平剂0.2份,消泡剂0.2份,水39份。
基于上述无溶剂羟基水性聚氨酯制备的木器漆的性能检测:
往上述制备的木器漆添加4.5%的水性异氰酸酯固化剂后,喷涂于木器和玻璃底材上,喷涂两遍,放置7天后进行检测,检测结果如下:
检测项目 | 结果 |
铅笔硬度(玻璃板) | 2H |
漆膜透明性 | 好 |
光泽度 | 98 |
耐水性 | 无异常 |
耐沸水 | 无异常 |
耐酒精 | 无异常 |
耐咖啡 | 无异常 |
耐红酒 | 无异常 |
耐醋 | 无异常 |
抗回粘 | 通过 |
实施例4
无溶剂羟基水性聚氨酯的组成(按重量分数计算),包括:
聚醚二元醇或聚酯二元醇18份,非离子二元醇或非离子型聚醚多元醇5份,二异氰酸酯54份,二羟甲基丙酸5份,小分子二元醇2份,三乙胺4份,二乙醇胺10.2份。
所述聚氨酯的制备方法包括:
A.往反应器中加入聚醚二元醇或聚酯二元醇,非离子二元醇或非离子型聚醚多元醇,二异氰酸酯,在80-85℃反应2.5h;
B.完成步骤A后往反应器加入二羟甲基丙酸,小分子二元醇,在80-85℃继续反应4h;
C.降温至50℃,往反应器加入三乙胺中和,反应20min;
D.中和反应结束后,将步骤C得到的反应体系在高速搅拌下分散于水中,再加入二乙醇胺,反应1h,得到无溶剂羟基水性聚氨酯,用300目滤膜进行过滤后包装。
上述无溶剂羟基水性聚氨酯的性能参数如下表所示:
外观 | 半透明乳液 |
固含量(%) | 38.8 |
粘度(cps/25℃) | 430 |
PH | 7.5 |
-OH含量(%) | 3.2 |
DMF含量(%) | 0 |
DMAC含量(%) | 0 |
NMP含量(%) | 0 |
NEP含量(%) | 0 |
AC含量(%) | 0 |
取上述制备的无溶剂羟基水性聚氨酯制备木器漆,所述木器漆按重量分数计算,包括:
无溶剂羟基水性聚氨酯60份,增稠剂0.2份,润湿剂0.3份,流平剂0.2份,消泡剂0.2份,水39.1份。
基于上述无溶剂羟基水性聚氨酯制备的木器漆的性能检测:
往上述制备的木器漆添加4.5%的水性异氰酸酯固化剂后,喷涂于木器和玻璃底材上,喷涂两遍,放置7天后进行检测,检测结果如下:
实施例5
无溶剂羟基水性聚氨酯的组成(按重量分数计算),包括:
聚醚二元醇或聚酯二元醇15份,非离子二元醇或非离子型聚醚多元醇6份,二异氰酸酯60份,二羟甲基丙酸6份,小分子二元醇1份,三乙胺5份,一乙醇胺8.8份。
所述聚氨酯的制备方法包括:
A.往反应器中加入聚醚二元醇或聚酯二元醇,非离子二元醇或非离子型聚醚多元醇,二异氰酸酯,在80-85℃反应2.5h;
B.完成步骤A后往反应器加入二羟甲基丙酸,小分子二元醇,在80-85℃继续反应4h;
C.降温至50℃,往反应器加入三乙胺中和,反应20min;
D.中和反应结束后,将步骤C得到的反应体系在高速搅拌下分散于水中,再加入一乙醇胺,反应1h,得到无溶剂羟基水性聚氨酯,用300目滤膜进行过滤后包装。
上述无溶剂羟基水性聚氨酯的性能参数如下表所示:
外观 | 半透明乳液 |
固含量(%) | 38.3 |
粘度(cps/25℃) | 370 |
PH | 7.5 |
-OH含量(%) | 2.15 |
DMF含量(%) | 0 |
DMAC含量(%) | 0 |
NMP含量(%) | 0 |
NEP含量(%) | 0 |
AC含量(%) | 0 |
取上述制备的无溶剂羟基水性聚氨酯制备木器漆,所述木器漆按重量分数计算,包括:
无溶剂羟基水性聚氨酯60份,增稠剂0.25份,润湿剂0.3份,流平剂0.2份,消泡剂0.2份,水39.05份。
基于上述无溶剂羟基水性聚氨酯制备的木器漆的性能检测:
往上述制备的木器漆添加4.5%的水性异氰酸酯固化剂后,喷涂于木器和玻璃底材上,喷涂两遍,放置7天后进行检测,检测结果如下:
实施例6
无溶剂羟基水性聚氨酯的组成(按重量分数计算),包括:
聚醚二元醇或聚酯二元醇15份,非离子二元醇或非离子型聚醚多元醇6份,二异氰酸酯60份,二羟甲基丙酸6份,小分子二元醇1份,三乙胺5份,二乙醇胺15份。
所述聚氨酯的制备方法包括:
A.往反应器中加入聚醚二元醇或聚酯二元醇,非离子二元醇或非离子型聚醚多元醇,二异氰酸酯,在80-85℃反应2.5h;
B.完成步骤A后往反应器加入二羟甲基丙酸,小分子二元醇,在80-85℃继续反应4h;
C.降温至50℃,往反应器加入三乙胺中和,反应20min;
D.中和反应结束后,将步骤C得到的反应体系在高速搅拌下分散于水中,再加入二乙醇胺,反应1h,得到无溶剂羟基水性聚氨酯,用300目滤膜进行过滤后包装。
上述无溶剂羟基水性聚氨酯的性能参数如下表所示:
取上述制备的无溶剂羟基水性聚氨酯制备木器漆,所述木器漆按重量分数计算,包括:
无溶剂羟基水性聚氨酯60份,增稠剂0.15份,润湿剂0.3份,流平剂0.2份,消泡剂0.2份,水39.15份。
基于上述无溶剂羟基水性聚氨酯制备的木器漆的性能检测:
往上述制备的木器漆添加4.5%的水性异氰酸酯固化剂后,喷涂于木器和玻璃底材上,喷涂两遍,放置7天后进行检测,检测结果如下:
检测项目 | 结果 |
铅笔硬度(玻璃板) | 4-5H |
漆膜透明性 | 好 |
光泽度 | 98 |
耐水性 | 无异常 |
耐沸水 | 无异常 |
耐酒精 | 无异常 |
耐咖啡 | 无异常 |
耐红酒 | 无异常 |
耐醋 | 无异常 |
抗回粘 | 通过 |
从上述实施例可以看出,本发明制备的无溶剂羟基水性聚氨酯环保性好,无有机物挥发。用本发明的无溶剂羟基水性聚氨酯制备的木器漆,经过添加水性异氰酸酯固化剂,硬度最高可达5H,其漆膜透明性好,光泽度高,耐水性好,耐酒精、咖啡等介质,是一种高性能环保型水性木器漆。
可以理解的是,对本领域普通技术人员来说,可以根据本发明的技术方案及其发明构思加以等同替换或改变,而所有这些改变或替换都应属于本发明所附的权利要求的保护范围。
Claims (10)
1.一种用于木器漆的无溶剂羟基水性聚氨酯,其特征在于,包括以下按重量份数计算的原料:聚醚二元醇或聚酯二元醇15-20份,非离子二元醇或非离子型聚醚多元醇4-6份,二异氰酸酯50-60份,二羟甲基丙酸4-6份,小分子二元醇1-3份,三乙胺3-5份,醇胺5-15份。
2.根据权利要求1所述的一种用于木器漆的无溶剂羟基水性聚氨酯,其特征在于,所述聚醚二元醇为聚丙二醇或聚四氢呋喃醇。
3.根据权利要求1所述的一种用于木器漆的无溶剂羟基水性聚氨酯,其特征在于,所述聚酯二元醇为聚己二酸辛戊二醇酯、聚己内酯或聚碳酸酯中的一种或多种。
4.根据权利要求1所述的一种用于木器漆的无溶剂羟基水性聚氨酯,其特征在于,所述非离子二元醇为聚乙二醇。
5.根据权利要求1所述的一种用于木器漆的无溶剂羟基水性聚氨酯,其特征在于,所述异氰酸酯为异氟尔酮二异氰酸酯、六亚甲基二异氰酸酯或氢化MDI中的一种或多种。
6.根据权利要求1所述的一种用于木器漆的无溶剂羟基水性聚氨酯,其特征在于,所述小分子二元醇为乙二醇、1,4-丁二醇或三羟甲基丙烷中的一种或多种。
7.根据权利要求1所述的一种用于木器漆的无溶剂羟基水性聚氨酯,其特征在于,所述醇胺为一乙醇胺、二乙醇胺中的一种或多种。
8.根据权利要求1-7任一项中的用于木器漆的无溶剂羟基水性聚氨酯的制备方法,其特征在于,包括以下步骤:
A.往反应器中加入聚醚二元醇或聚酯二元醇,非离子二元醇或非离子型聚醚多元醇,二异氰酸酯,在80-85℃反应2-3h;
B.完成步骤A后往反应器加入二羟甲基丙酸,小分子二元醇,在80-85℃继续反应3-5h;
C.降温至50℃,往反应器加入三乙胺中和,反应20min;
D.中和反应结束后,将步骤C得到的反应体系在高速搅拌下分散于水中,再加入醇胺,反应0.5-1h,得到无溶剂羟基水性聚氨酯。
9.一种木器漆,其特征在于,包括:权利要求8中制备的所述的无溶剂羟基水性聚氨酯,还包括增稠剂,润湿剂,流平剂,消泡剂和水。
10.根据权利要求9所述的一种木器漆,其特征在于,包括以下按重量份数计算的原料:权利要求8中制备的所述的无溶剂羟基水性聚氨酯60份,增稠剂0.15-0.3份,润湿剂0.3份,流平剂0.2份,消泡剂0.2份,水39-39.15份。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011636579.2A CN112812262A (zh) | 2020-12-31 | 2020-12-31 | 用于木器漆的无溶剂羟基水性聚氨酯及其制备方法和木器漆 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011636579.2A CN112812262A (zh) | 2020-12-31 | 2020-12-31 | 用于木器漆的无溶剂羟基水性聚氨酯及其制备方法和木器漆 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112812262A true CN112812262A (zh) | 2021-05-18 |
Family
ID=75857177
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011636579.2A Pending CN112812262A (zh) | 2020-12-31 | 2020-12-31 | 用于木器漆的无溶剂羟基水性聚氨酯及其制备方法和木器漆 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112812262A (zh) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103483539A (zh) * | 2013-08-27 | 2014-01-01 | 中国科学院长春应用化学研究所 | 聚(碳酸酯-醚)型水性聚氨酯、水性聚氨酯胶粘剂及其制备方法 |
CN104212330A (zh) * | 2014-09-28 | 2014-12-17 | 中国科学技术大学 | 一种烤漆型水性聚氨酯/氨基树脂复合乳液的制备方法 |
CN104387547A (zh) * | 2014-11-19 | 2015-03-04 | 上海华峰新材料研发科技有限公司 | 水性聚氨酯树脂及其制备方法和应用 |
CN106496485A (zh) * | 2016-11-09 | 2017-03-15 | 广州慧谷化学有限公司 | 一种环氧改性阴/非离子水性聚氨酯树脂及其制备方法 |
CN109456459A (zh) * | 2018-09-30 | 2019-03-12 | 中国科学院山西煤炭化学研究所 | 一种提高水性聚氨酯耐水或耐溶剂性的方法 |
-
2020
- 2020-12-31 CN CN202011636579.2A patent/CN112812262A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103483539A (zh) * | 2013-08-27 | 2014-01-01 | 中国科学院长春应用化学研究所 | 聚(碳酸酯-醚)型水性聚氨酯、水性聚氨酯胶粘剂及其制备方法 |
CN104212330A (zh) * | 2014-09-28 | 2014-12-17 | 中国科学技术大学 | 一种烤漆型水性聚氨酯/氨基树脂复合乳液的制备方法 |
CN104387547A (zh) * | 2014-11-19 | 2015-03-04 | 上海华峰新材料研发科技有限公司 | 水性聚氨酯树脂及其制备方法和应用 |
CN106496485A (zh) * | 2016-11-09 | 2017-03-15 | 广州慧谷化学有限公司 | 一种环氧改性阴/非离子水性聚氨酯树脂及其制备方法 |
CN109456459A (zh) * | 2018-09-30 | 2019-03-12 | 中国科学院山西煤炭化学研究所 | 一种提高水性聚氨酯耐水或耐溶剂性的方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107522841B (zh) | 一种无溶剂法制备羧酸/磺酸混合型高固含量水性聚氨酯的方法 | |
EP2945973B1 (en) | Radiation curable aqueous compositions with reversible drying | |
CN103087286B (zh) | 一种水性聚氨酯弹性分散体及其制备方法 | |
CN107163217B (zh) | 一种纳米金刚石改性水性聚氨酯的制备方法 | |
CN107141434B (zh) | 一种用于合成革面料的水性聚氨酯树脂及其制备方法 | |
CN105504215B (zh) | 一种耐黄变的水性聚氨酯乳液及其制备方法 | |
CN109517513B (zh) | 一种具有自消光效果的常温自修复型水性聚氨酯车衣的制作方法 | |
CN105482060A (zh) | 一种超支化水性聚氨酯丙烯酸酯乳液及其制备方法与应用 | |
EP3328912B1 (en) | Polyurethane (meth)acrylate oligomers and curable compositions comprising said oligomers | |
CN111269390B (zh) | 一种合成革面层用聚氨酯树脂及其制备方法 | |
CN112409564A (zh) | 一种免脱溶水性非离子聚氨酯及其制备方法 | |
TW202112890A (zh) | 聚醚聚碳酸酯二醇及其製造方法 | |
CN103805122A (zh) | 一种水性聚氨酯贴布胶及其制备方法 | |
CN107814895A (zh) | 一种稀土金属配位改性水性聚氨酯发光树脂及其制备方法 | |
CN109293871B (zh) | 一种自流平水性含氟聚氨酯丙烯酸树脂及其制备方法、水性光固化涂料 | |
CN108329342B (zh) | 一种有机硅偶联剂及其制备方法和应用 | |
CN109666122A (zh) | 环氧大豆油改性聚氨酯皮革涂饰剂及其制备方法 | |
CN113549392B (zh) | 聚氨酯分散体及其制备方法和应用 | |
CN112300386B (zh) | 壳聚糖改性胍盐聚合物及其制备方法、改性水性聚氨酯及其制备方法、改性水性聚氨酯涂料 | |
CN112322169A (zh) | 水性聚氨酯乳液及制备方法、涂层溶液、pvc功能膜 | |
CN109096468A (zh) | 一种无溶剂水性聚氨酯树脂及其制备方法 | |
CN112812262A (zh) | 用于木器漆的无溶剂羟基水性聚氨酯及其制备方法和木器漆 | |
CN107974190A (zh) | 一种水性聚氨酯涂料及其制备方法 | |
CN109355924B (zh) | 用于纺织物的包含纳米填料和黄连浸提物的聚氨酯涂料制备方法 | |
CN108864401B (zh) | 一种聚氨酯丙烯酸酯低聚物及其制备方法和一种水性涂料 |
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 |
Application publication date: 20210518 |
|
RJ01 | Rejection of invention patent application after publication |