CN109467671B - 水性聚异氰酸酯固化剂的制备 - Google Patents

水性聚异氰酸酯固化剂的制备 Download PDF

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CN109467671B
CN109467671B CN201710806062.5A CN201710806062A CN109467671B CN 109467671 B CN109467671 B CN 109467671B CN 201710806062 A CN201710806062 A CN 201710806062A CN 109467671 B CN109467671 B CN 109467671B
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curing agent
polyisocyanate
weight
polyisocyanate curing
monohydric alcohol
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CN109467671A (zh
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韦子遨
韦雨春
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Leling Sisheng Polymer Material Co ltd
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    • 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
    • C08G18/77Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78Nitrogen
    • C08G18/79Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G18/46Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4676Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
    • 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
    • C08G18/48Polyethers
    • C08G18/4833Polyethers containing oxyethylene units
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes

Abstract

本发明涉及一种水性聚异氰酸酯固化剂的制备。该水性聚异氰酸酯固化剂,按重量份计包括以下组分:聚异氰酸酯80~92重量份;多乙二醇单烷基醚4~16重量份;含磺酸盐基团的聚酯一元醇4~16重量份;催化剂0.01~0.05重量份。所述的聚异氰酸酯的平均异氰酸官能度为3‑6,所述的多乙二醇单烷基醚的分子量为300‑800,所述含磺酸盐基团的聚酯一元醇的分子量为600~1500。

Description

水性聚异氰酸酯固化剂的制备
技术领域
本发明涉及高分子材料领域,尤其是一种水性聚异氰酸酯固化剂的制备方法。
背景技术
随着环保意识的增强和环保法规的建立,开发无污染环保型的高性能水性涂料已成为涂料开发的重要方向之一。
水性涂料已在很多方面得到应用,但是,只有在其涂膜进行交联固化后,才能具备与溶剂型涂料相当的涂膜性能,如耐水性、耐溶剂性、耐化学品性、耐磨性等,故其所使用固化剂的交联特性的优劣直接影响涂料的质量。溶剂型双组份聚氨酯涂料中使用的聚异氰酸酯固化剂,不论是芳香族还是脂肪族聚异氰酸酯都很难直接乳化或分散于水中。在水性双组份聚氨酯涂料中要对其进行化学改性,通过引入亲水性官能团来改善聚异氰酸酯的亲水性,以使其易于在水中乳化或分散,从而保持一定的稳定性。
目前国内外市场上的产品,大都是利用异氰酸官能团和多乙二醇单烷基醚进行化学反应改性,或通过接入磺酸盐基团改性而保持其亲水性。前者形成的产物与水性羟基树脂相容性差,且由于其粘度较大,分散于水中较困难;后者方法中,使用通常的小分子磺酸盐化合物和聚异氰酸酯很难进行均相反应,且由于磺酸盐基团很强的亲水性,使其和水性羟基树脂形成的涂膜耐水性较差。
针对以上问题,本发明在充分考虑多乙二醇单烷基醚和磺酸盐化合物改性聚异氰酸酯的优缺点基础上,发明了一种适用于水性双组份聚氨酯涂料的优质水性聚异氰酸酯固化剂。
发明内容
本发明所要解决的技术问题在于提供上述水性聚异氰酸酯固化剂的制备方法。
本发明解决上述技术问题所采取的技术方案是:水性聚异氰酸酯固化剂,按重量百分比计,由以下各组分组成:
聚异氰酸酯 80~92%
多乙二醇单烷基醚 4~16%
含磺酸盐基团的聚酯一元醇 4~16%
催化剂 0.01-0.05%;
其中,所述的聚异氰酸酯的平均异氰酸官能度为3-6;
其中,所述的多乙二醇单烷基醚的分子量为300-800,烷基可以是甲基、乙基、丙基、丁基或其异构体;
具体的,聚异氰酸酯的含量可以为80,82,85,88,90,或92%重量份;
多乙二醇单烷基醚的含量可以为4,6,8,10,12,14,或16%重量份;
含磺酸盐基团的聚酯一元醇的含量可以为4,6,8,10,12,14,或16%重量份;
催化剂的含量可以为0.01,0.02,0.03,0.04,或0.05%重量份;
在上述方案的基础上,所述的含磺酸盐基团的聚酯一元醇由按重量百分比计的下述组分制备得到:
己二酸 25~35%
苯二甲酸-5-磺酸钠 10~20%
二元醇 40~50%
乙酸 2~10%;
其中,二元醇为乙二醇、1,4-丁二醇、1,3-丁二醇、2-甲基1,3-丙二醇、1,6-己二醇中的一种或几种的混合物。所述含磺酸盐基团的聚酯一元醇的分子量为600~1500。
具体的,己二酸含量可以为25,27,29,32,或35%重量份;
苯二甲酸-5-磺酸钠含量可以为,10,12,15,18,或20%重量份;
二元醇含量可以为40,42,,45,48,或50%重量份;
乙酸含量可以为2,4,6,8,或10%重量份;
在上述方案的基础上,所述的聚异氰酸酯为已二异氰酸酯、异佛尔酮二异氰酸酯、二环已基甲烷二异氰酸酯、四甲基苯二亚甲基二异氰酸酯的缩二脲、二聚体、三聚体、加成物等,或其中任意一种的相互混合物。
在上述方案的基础上,所述的催化剂为有机铋或有机锡。
针对上述的水性聚异氰酸酯固化剂的制备方法,将聚异氰酸酯与多乙二醇单烷基醚、含磺酸盐基团的聚酯一元醇、催化剂按配方加入反应釜中,在50-100℃条件下进行化学反应至异氰酸含量不再发生变化为止,制得水性聚异氰酸酯固化剂。
本发明的有益效果是:
本发明获得了水性聚异氰酸酯固化剂。
具体实施方式
实施例
水性聚异氰酸酯固化剂按重量百分比计包括下述组分:
(1)HDI三聚体(聚异氰酸酯),85%
(2)多乙二醇单烷基醚(分子量600),9.98%
(3)含磺酸盐基团的聚酯一元醇(分子量800),5%
(4)有机铋(催化剂),0.02%
制备方法为,将HDI三聚体与多乙二醇单烷基醚、含磺酸盐基团的聚酯一元醇和有机铋按配方加入反应釜中,在80℃条件下进行化学反应至异氰酸含量不再发生变化为止,制得水性聚异氰酸酯固化剂。
实测NCO含量为18.6%。

Claims (4)

1.一种水性聚异氰酸酯固化剂,其特征在于:按重量百分比计,由以下各组份组成:
聚异氰酸酯 80~92%
多乙二醇单烷基醚 4~16%
含磺酸盐基团的聚酯一元醇 4~16%
催化剂 0.01-0.05%;
上述各组份总量为100%;
其中,所述的聚异氰酸酯的平均异氰酸酯 基官能度为3-6;
其中,所述的多乙二醇单烷基醚的分子量为300-800,烷基是甲基、乙基、丙基、丁基或其异构体;
其中,所述的含磺酸盐基团的聚酯一元醇由按重量百分比计的下述组份制备得到:
己二酸 25~35%
苯二甲酸-5-磺酸钠 10~20%
二元醇 40~50%
乙酸 2~10%;
其中,二元醇为乙二醇、1,4-丁二醇、1,3-丁二醇、2-甲基1,3-丙二醇、1,6-己二醇中的一种或几种的混合物,所述含磺酸盐基团的聚酯一元醇的分子量为600~1500。
2.根据权利要求1所述的水性聚异氰酸酯固化剂,其特征在于:所述聚异氰酸酯为已二异氰酸酯、异佛尔酮二异氰酸酯、二环已基甲烷二异氰酸酯、四甲基苯二亚甲基二异氰酸酯的缩二脲、二聚体或三聚体。
3.根据权利要求1所述的水性聚异氰酸酯固化剂,其特征在于:所述的催化剂为有机铋或有机锡。
4.根据权利要求1或2所述的水性聚异氰酸酯固化剂的制备方法,其特征在于:将聚异氰酸酯与多乙二醇单烷基醚、含磺酸盐基团的聚酯一元醇、催化剂按配方加入反应釜中,在50-100℃条件下进行化学反应至异氰酸酯 基含量不再发生变化为止,制得水性聚异氰酸酯固化剂。
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