CN113683748A - 一种氟改性超支化水性聚氨酯树脂及使用其的水性纳米防腐自洁面漆 - Google Patents

一种氟改性超支化水性聚氨酯树脂及使用其的水性纳米防腐自洁面漆 Download PDF

Info

Publication number
CN113683748A
CN113683748A CN202110837016.8A CN202110837016A CN113683748A CN 113683748 A CN113683748 A CN 113683748A CN 202110837016 A CN202110837016 A CN 202110837016A CN 113683748 A CN113683748 A CN 113683748A
Authority
CN
China
Prior art keywords
fluorine
polyurethane resin
modified hyperbranched
self
waterborne polyurethane
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
Application number
CN202110837016.8A
Other languages
English (en)
Inventor
孙德文
卢立群
张小冬
沈志明
冉千平
侯平平
马英杰
亓帅
王中华
朱剑南
李波
刘畅
刘加平
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.)
Jiangsu Fengcai Building Materials Group Co ltd
Sobute New Materials Co Ltd
Original Assignee
Jiangsu Fengcai Building Materials Group Co ltd
Sobute New Materials 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 Jiangsu Fengcai Building Materials Group Co ltd, Sobute New Materials Co Ltd filed Critical Jiangsu Fengcai Building Materials Group Co ltd
Priority to CN202110837016.8A priority Critical patent/CN113683748A/zh
Publication of CN113683748A publication Critical patent/CN113683748A/zh
Pending legal-status Critical Current

Links

Images

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
    • C08G18/08—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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
    • C08G18/3804—Polyhydroxy compounds
    • C08G18/3812—Polyhydroxy compounds having fluorine atoms
    • 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
    • C08G18/4825—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
    • C08G18/4854—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
    • 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
    • C08G18/6677—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 having at least three 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
    • C08G18/65—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
    • C08G18/6685—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 C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
    • 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
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—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)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

本发明公开了一种氟改性超支化水性聚氨酯树脂及使用其的水性纳米防腐自洁面漆。本发明所述氟改性超支化水性聚氨酯树脂采用多官能度聚醚为起始原料，脂肪族异氰酸酯为硬段，与亲水扩链剂、氟疏水链段合成超支化的自乳化氟改性水性聚氨酯树脂，并通过自乳化，得到所述氟改性超支化水性聚氨酯树脂；将所述氟改性超支化水性聚氨酯树脂应用于水性纳米防腐自洁面漆中。本发明所述水性纳米防腐自洁面漆中包含的氟改性超支化水性聚氨酯树脂乳液，粒径＜200nm，氟链段引入提升涂层的疏水性，自洁性，从而显著提升耐腐蚀性能；同时，超细的乳液粒径赋予涂层快速的干燥速度，提升涂层的施工效率。

Description

一种氟改性超支化水性聚氨酯树脂及使用其的水性纳米防腐 自洁面漆
技术领域
本发明涉及一种氟改性超支化水性聚氨酯树脂及使用其的水性纳米防腐自洁面漆，属于涂料技术领域。
背景技术
聚氨酯防腐涂料，具有优异的基材粘附力、低收缩性、耐化学品性和灵活多样的可设计性能，在防腐蚀领域有着极其广泛的应用，尤其是在高耐候防护面漆领域。但随着环保法规愈加严厉，高耐候、低VOC聚氨酯防护涂料成为发展重点，而作为低VOC涂料，水性聚氨酯在木器漆、轻腐蚀防护领域应用广泛。然而，水性聚氨酯的合成目前多集中在线性聚氨酯水性化的研究和应用，由于聚氨酯合成中对水分要求严苛，所以水性聚氨酯合成发展缓慢。水性聚氨酯无法合成过大的分子量，且水分挥发成膜后，无法像水性环氧树脂一样进一步反应交联，从而导致涂层干燥速度慢，交联密度不够，粘结力不足，抗冲刷性和耐腐蚀性能低，从而导致水性聚氨酯在防腐领域不能大规模应用。
超支化聚合物为解决低溶剂、无溶剂环氧涂料存在的问题提供新的解决思路。研究表明超支化聚合物或引入超支化结构可以显著提高聚合物的溶解性，降低体系黏度，降低结晶性提升成膜性和韧性。此外，由于超支化聚合物的分子量大，破乳后失水速度增加，显著缩短表实干时间，提升固化速度和施工速度。
专利CN 111647120 A以丁四醇为枝化点，甲基丙烯酸羟乙酯为亲水链段和活性链段，与二异氰酸酯进行聚合合成了超支化的水性聚氨酯低聚物，拟用于 UV固化领域，所合成的聚合物为只是作为一个超支化的低分子量聚氨酯原料使用，而不能直接用于防护涂层。专利CN 111944392 A以超支化聚硫醚与环氧丙烯酸酯树脂反应制备得到低粘度、低内应力和固化收缩率，高附着力的可光固化的环氧丙烯酸酯涂料。专利CN 111848924 A选用含氟二酚类单体作为起始原料，利用分子上的酚羟基与多官能度缩水甘油醚单体上的环氧基通过质子转移聚合一锅法合成含氟超支化聚醚型环氧树脂，来制备无溶剂涂料，提升成膜树脂的疏水性和耐介质性能。
然而，目前超支化研究大部分仍然是简单的单一低聚物体系超支化合成，或有溶剂/无溶剂超支化聚合物合成，且大部分都是在环氧基树脂的超支化改性和光固化领域。
发明内容
为了解决涂层水性化及快干、耐水防腐及自洁性不足的技术瓶颈，本发明利用嵌段改性的技术途径，提供了一种氟改性超支化水性聚氨酯树脂及使用其水性纳米防腐自洁面漆防腐涂料。
本发明的技术方案如下：
本发明提供了一种氟改性超支化水性聚氨酯树脂，采用多官能度聚醚为起始原料，脂肪族异氰酸酯为硬段，与亲水扩链剂、氟疏水链段合成超支化的自乳化氟改性水性聚氨酯树脂，并通过自乳化，得到所述氟改性超支化水性聚氨酯树脂；
所述多官能度聚醚利用双官能度多元醇及多官能度多元醇混合得到。
本发明选用多官能度聚醚为起始原料，即利用混合聚醚得到的多官能度聚醚为原料来一步合成，脂肪族异氰酸酯为硬段，与亲水扩链剂、氟疏水链段合成超支化的自乳化氟改性水性聚氨酯树脂，并通过自乳化，得到水性防腐涂料专用的氟改性超支化水性聚氨酯树脂。由于亲水链段和疏水链段的合理设计及改性氟链段的引入，自乳化得到的乳胶粒子粒径为纳米级(粒径＜200nm)，赋予体系优异的干燥速度；将得到的超支化纳米乳液按照通用的水性面漆调漆工艺得到的涂层具有优异的疏水自洁性能和耐介质性，从而得到一种可应用于防护领域的水性纳米防腐自洁面漆。
进一步地，本发明所述一种氟改性超支化水性聚氨酯树脂由以下原料按质量份制备得到：
Figure BDA0003177571760000021
Figure BDA0003177571760000031
其中混合多羟基化合物是由以下原料按质量份搅拌混合得到：
Figure BDA0003177571760000032
本发明提供了上述一种氟改性超支化水性聚氨酯树脂的制备方法，包括：
(1)在机械搅拌、N2保护、有回流装置的条件下，依次加入氨酯级溶剂和脂肪族异氰酸酯，控制温度60-80℃下滴加混合多羟基化合物进行反应；
步骤(1)中滴加时间为0.5-1h，反应时间为3-5h；
(2)步骤(1)反应之后降温至30-50℃，加入成盐助剂进行反应；
步骤(2)中反应时间为1-2h；
(3)步骤(2)反应之后降温至10-30℃，加入去离子水，2000-5000r/min 高速分散一段时间后，加入胺类扩链剂继续扩链反应后，减压蒸馏，回收溶剂，得到所述氟改性超支化水性聚氨酯树脂乳液；
步骤(3)中分散时间为0.5-1h，反应时间为2-3h。
所述脂肪族异氰酸酯选自异佛尔酮二异氰酸酯、1,6-己二异氰酸酯、二环己基甲烷二异氰酸酯、甲基环己基二异氰酸酯中任意一种以上混合，合成聚合物的主链架构，为聚合物的主要硬段链段。
所述氨酯级溶剂的含水率＜0.5‰，选自丙酮、丁酮、环己酮中的任意一种以上混合，用于降低体系粘度。
所述双官能度多元醇为数均分子量≤1000的聚四氢呋喃醚多元醇(PTMG)、聚环氧丙烷多元醇(PPG)中的任意一种或多种，合成聚合物的主链架构，为聚合物的主要软段链段。
所述多官能度多元醇选自丙三醇、丁四醇中的任意一种或两种，提高体系超支化节点。
所述亲水扩链剂选自二羟甲基丙酸、二羟甲基丁酸、二羟甲基戊酸和二羟基甲基辛酸中的任意一种以上混合，实现聚合物链段的自乳化。
所述含氟二羟基单体选自全氟聚醚二元醇、2,2-双(4-羟基苯基)六氟丙烷、 2,2-双(3-烯丙基-4-羟基苯基)六氟丙烷、八氟-4,4'-联苯酚中的任意一种以上混合，超低表面能链段，赋予最终涂层耐候耐污性能。
所述成盐助剂为三乙胺；
所述胺类扩链剂选自乙二胺、丙二胺、异佛尔酮二胺、己二胺中的任意一种以上混合，主要用于提升体系交联度，赋予更有防腐性能。
进一步的将上述氟改性超支化水性聚氨酯树脂乳液应用于水性纳米防腐自洁面漆中，具体按照行业公知的防护面漆制备方法加入滑石粉、硫酸钡、钛白粉、颜填料、pH调节剂、润湿剂、聚氨酯增稠剂、杀菌剂、防霉剂、消泡剂、流平剂等在500-2000r/min高速分散得到水性纳米防腐自洁面漆。
本发明所述面漆涂料制备方法和所用的其他原料为行业内公知的技术方案。
本发明有益效果为
本发明所述水性纳米防腐自洁面漆中包含的氟改性超支化水性聚氨酯树脂乳液，粒径＜200nm，氟链段引入提升涂层的疏水性，自洁性，从而显著提升耐腐蚀性能；同时，超细的乳液粒径赋予涂层快速的干燥速度，提升涂层的施工效率。
附图说明
图1为通过超支化自乳化技术制备得到的氟改性超支化水性聚氨酯树脂乳液粒径电镜照片(粒径尺寸＜200nm)。
具体实施方式
为了更好的理解本发明，下面结合具体实施例进行阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例中。凡是根据本发明精神实质所作的等效变化或修饰，都应该涵盖在本发明的保护范围之内。
实施例中用到的全氟聚醚二元醇Fluorolink D10为Solvay Solexis公司的，其余原料皆为行业内常规易得的原料。
各实施例及对比例中的份数为质量份。
(一)混合多羟基化合物的制备：
实施例1-3为混合多羟基化合物的制备，其原料组成见表1，实施例1-3的多羟基化合物由表1中各组原料混合而成。
表1混合多羟基化合物R-OH制备原料
Figure BDA0003177571760000051
(二)氟改性超支化聚氨酯树脂乳液PUF制备的制备：
实施例4-6为氟改性超支化聚氨酯树脂乳液PUF的制备，其原料组成见表2，具体制备方法如下：
在机械搅拌、N2保护、有回流装置的条件下，依次加入氨酯级溶剂和脂肪族异氰酸酯，控制温度60-80℃下滴加混合多羟基化合物，滴加完毕继续反应 3-5h；降温至30-50℃，加入成盐助剂，反应1-2h；降温至10-30℃，加入去离子水，2000-5000r/min高速分散0.5-1h，加入胺类扩链剂继续扩链反应2-3h，减压蒸馏，回收溶剂，得到所述氟改性超支化聚氨酯树脂乳液。
表2实施例4-6氟改性超支化聚氨酯树脂乳液PUF制备原料
Figure BDA0003177571760000052
Figure BDA0003177571760000061
性能测试：
将实施例4-6得到的氟改性超支化聚氨酯树脂乳液，基本性能指标检测如下表3所示，图1为通过超支化自乳化技术制备得到的氟改性超支化水性聚氨酯树脂乳液粒径电镜照片(粒径尺寸＜200nm)：
表3氟改性超支化聚氨酯树脂乳液性能参数
Figure BDA0003177571760000062
Figure BDA0003177571760000071
由表3可以看出，通过本方法制备得到的氟改性超支化聚氨酯树脂乳液为粒径＜200nm，固含量达到50％以上的低粘度纳米级高固含量水性功能树脂，为制备快速干燥、高固含、低粘度高性能防腐材料提供原料支持。
应用实施例
将市售进口聚氨酯乳液Bayhydrol XP 2427及上述实施例4-6制备的氟改性超支化聚氨酯树脂乳液PUF应用于水性纳米防腐自洁面漆制备中，其水性纳米防腐自洁面漆原料组分见表4所示，
表4水性纳米防腐自洁面漆C制备原料
Figure BDA0003177571760000072
将上述得到的水性纳米防腐自洁面漆进行刮涂施工，基本性能检测结果如下表5所示：
表5水性纳米防腐自洁面漆性能测试
Figure BDA0003177571760000073
Figure BDA0003177571760000081
由表5中数据可以发现，采用本发明制得的氟改性超支化聚氨酯树脂乳液制备得到的防腐自洁面漆，具有0.5h的快速干燥性能，优异的耐水、耐腐蚀和耐洗刷性能，同时，由于改性氟链段引入，赋予涂层优异的耐污性能和疏水性能，实现涂层自清洁和超过5000h的高耐候性能，与采用作为对比例的国外树脂配制的(C0)自洁面漆在干燥时间、疏水性、耐污等级、耐洗刷性、耐候性和耐碱性相比具有显著的优势。

Claims (10)

1.一种氟改性超支化水性聚氨酯树脂，其特征在于，采用多官能度聚醚为起始原料，脂肪族异氰酸酯为硬段，与亲水扩链剂、氟疏水链段合成超支化的自乳化氟改性水性聚氨酯树脂，并通过自乳化，得到所述氟改性超支化水性聚氨酯树脂；
所述多官能度聚醚利用双官能度多元醇及多官能度多元醇混合得到。
2.根据权利要求1所述的一种氟改性超支化水性聚氨酯树脂，其特征在于，所述自乳化得到的氟改性超支化水性聚氨酯树脂乳胶粒子粒径为纳米级，粒径＜200nm。
3.根据权利要求2所述的一种氟改性超支化水性聚氨酯树脂，其特征在于，所述氟改性超支化水性聚氨酯树脂由以下原料按质量份制备得到：
Figure FDA0003177571750000011
其中混合多羟基化合物是由以下原料按质量份搅拌混合得到：
Figure FDA0003177571750000012
4.根据权利要求3所述的一种氟改性超支化水性聚氨酯树脂，其特征在于，所述氟改性超支化水性聚氨酯树脂由以下原料按质量份制备得到：
Figure FDA0003177571750000013
5.根据权利要求4所述的一种氟改性超支化水性聚氨酯树脂，其特征在于，所述混合多羟基化合物是由以下原料按质量份搅拌混合得到：
Figure FDA0003177571750000021
6.根据权利要求3至5任一项所述的一种氟改性超支化水性聚氨酯树脂，其特征在于，所述脂肪族异氰酸酯选自异佛尔酮二异氰酸酯、1,6-己二异氰酸酯、二环己基甲烷二异氰酸酯、甲基环己基二异氰酸酯中任意一种以上混合；
所述氨酯级溶剂的含水率＜0.5‰；
所述成盐助剂为三乙胺；
所述胺类扩链剂选自乙二胺、丙二胺、异佛尔酮二胺、己二胺中的任意一种以上混合。
7.根据权利要求6所述的一种氟改性超支化水性聚氨酯树脂，其特征在于，所述氨酯级溶剂选自丙酮、丁酮、环己酮中的任意一种以上混合。
8.根据权利要求7所述的一种氟改性超支化水性聚氨酯树脂，其特征在于，所述双官能度多元醇为数均分子量≤1000的聚四氢呋喃醚多元醇(PTMG)、聚环氧丙烷多元醇(PPG)中的任意一种或多种；
所述多官能度多元醇选自丙三醇、丁四醇中的任意一种或两种；
所述亲水扩链剂选自二羟甲基丙酸、二羟甲基丁酸、二羟甲基戊酸和二羟基甲基辛酸中的任意一种以上混合；
所述含氟二羟基单体选自全氟聚醚二元醇、2,2-双(4-羟基苯基)六氟丙烷、2,2-双(3-烯丙基-4-羟基苯基)六氟丙烷、八氟-4,4'-联苯酚中的任意一种以上混合。
9.权利要求7或8所述的一种氟改性超支化水性聚氨酯树脂的制备方法，其特征在于，包括：
(1)在机械搅拌、N2保护、有回流装置的条件下，依次加入氨酯级溶剂和脂肪族异氰酸酯，控制温度60-80℃下滴加混合多羟基化合物进行反应；
步骤(1)中滴加时间为0.5-1h，反应时间为3-5h；
(2)步骤(1)反应之后降温至30-50℃，加入成盐助剂进行反应；
步骤(2)中反应时间为1-2h；
(3)步骤(2)反应之后降温至10-30℃，加入去离子水，2000-5000r/min高速分散一段时间后，加入胺类扩链剂继续扩链反应后，减压蒸馏，回收溶剂，得到所述氟改性超支化水性聚氨酯树脂乳液；
步骤(3)中分散时间为0.5-1h，反应时间为2-3h。
10.一种包含权利要求1至2、7至8任一项所述的氟改性超支化水性聚氨酯树脂的水性纳米防腐自洁面漆，其特征在于，所述氟改性超支化水性聚氨酯树脂乳液应用于水性纳米防腐自洁面漆中，按照面漆制备方法加入滑石粉、硫酸钡、钛白粉、颜填料、pH调节剂、润湿剂、聚氨酯增稠剂、杀菌剂、防霉剂、消泡剂、流平剂等在500-2000r/min高速分散得到所述水性纳米防腐自洁面漆。
CN202110837016.8A 2021-07-23 2021-07-23 一种氟改性超支化水性聚氨酯树脂及使用其的水性纳米防腐自洁面漆 Pending CN113683748A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110837016.8A CN113683748A (zh) 2021-07-23 2021-07-23 一种氟改性超支化水性聚氨酯树脂及使用其的水性纳米防腐自洁面漆

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110837016.8A CN113683748A (zh) 2021-07-23 2021-07-23 一种氟改性超支化水性聚氨酯树脂及使用其的水性纳米防腐自洁面漆

Publications (1)

Publication Number Publication Date
CN113683748A true CN113683748A (zh) 2021-11-23

Family

ID=78577955

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110837016.8A Pending CN113683748A (zh) 2021-07-23 2021-07-23 一种氟改性超支化水性聚氨酯树脂及使用其的水性纳米防腐自洁面漆

Country Status (1)

Country Link
CN (1) CN113683748A (zh)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101935449A (zh) * 2010-07-28 2011-01-05 丽水市优耐克水性树脂科技有限公司 一种水性聚氨酯树脂的制备方法和水性聚氨酯树脂
CN104448211A (zh) * 2014-12-19 2015-03-25 江南大学 一种uv固化含氟超支化水性聚氨酯树脂的制备方法
CN104877099A (zh) * 2015-05-22 2015-09-02 安徽大学 一种有机氟改性超支化水性聚氨酯的制备方法
CN106883375A (zh) * 2017-03-21 2017-06-23 北京理工大学 一种超支化聚氨酯改性的水性聚氨酯、制备方法及应用
CN107880235A (zh) * 2017-12-19 2018-04-06 江南大学 一种高耐候性氟改性uv固化多臂型水性聚氨酯树脂的制备方法
CN111117213A (zh) * 2019-12-31 2020-05-08 合肥科天水性科技有限责任公司 一种超疏水轻质聚氨酯微纳米纤维海绵及其制备方法和用途
CN111333808A (zh) * 2020-02-18 2020-06-26 明新孟诺卡(辽宁)新材料有限公司 一种无溶剂水性聚氨酯的制备方法
CN112358593A (zh) * 2020-10-28 2021-02-12 上海华峰新材料研发科技有限公司 一种双组份水性聚氨酯及其制备方法和应用

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101935449A (zh) * 2010-07-28 2011-01-05 丽水市优耐克水性树脂科技有限公司 一种水性聚氨酯树脂的制备方法和水性聚氨酯树脂
CN104448211A (zh) * 2014-12-19 2015-03-25 江南大学 一种uv固化含氟超支化水性聚氨酯树脂的制备方法
CN104877099A (zh) * 2015-05-22 2015-09-02 安徽大学 一种有机氟改性超支化水性聚氨酯的制备方法
CN106883375A (zh) * 2017-03-21 2017-06-23 北京理工大学 一种超支化聚氨酯改性的水性聚氨酯、制备方法及应用
CN107880235A (zh) * 2017-12-19 2018-04-06 江南大学 一种高耐候性氟改性uv固化多臂型水性聚氨酯树脂的制备方法
CN111117213A (zh) * 2019-12-31 2020-05-08 合肥科天水性科技有限责任公司 一种超疏水轻质聚氨酯微纳米纤维海绵及其制备方法和用途
CN111333808A (zh) * 2020-02-18 2020-06-26 明新孟诺卡(辽宁)新材料有限公司 一种无溶剂水性聚氨酯的制备方法
CN112358593A (zh) * 2020-10-28 2021-02-12 上海华峰新材料研发科技有限公司 一种双组份水性聚氨酯及其制备方法和应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
O.B.李特文: "《国外合成橡胶生产现状》", 30 September 1959, 化学工业出版社 *
侯宝荣 主编: "《腐蚀研究与防护技术》", 31 December 1998, 海洋出版社 *

Similar Documents

Publication Publication Date Title
CN111393888B (zh) 一种水性dtm聚氨酯涂料及其制备方法
CN103555192B (zh) 一种有机硅改性的水性uv涂料及其制备方法
CN1324063C (zh) 水性聚氨酯的制备方法
CN111995943B (zh) 一种有机硅改性水性聚氨酯防水涂料及其制备方法
CN105255348A (zh) 一种单组份透明水性聚氨酯乳液防水涂料及其制备方法
CN113755064B (zh) 水性防结冰清漆及其制备方法
EP2834283A1 (en) Polyurethane/acrylic hybrid dispersions for roof coatings and their preparation
CN110845698A (zh) 一种聚醚胺改性水性聚氨酯树脂及其制备方法
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
CN112457762A (zh) 一种高附着力的含氟疏水聚氨酯透明防护涂料及其制备、使用方法
CN111171702B (zh) 双重固化的聚氨酯水分散体及水性uv涂料
EP1124871A1 (de) Polyurethan-polymer-hybrid-dispersion mit hoher filmhärte, verfahren zu ihrer herstellung sowie deren verwendung
CN103865377A (zh) 一种水性丙烯酸聚氨酯有机硅涂料
CN110746875B (zh) 一种水性聚氨酯面漆及其制备方法
CN115838463A (zh) 一种含三重动态键的水性室温自修复聚氨酯的制备方法
CN113683748A (zh) 一种氟改性超支化水性聚氨酯树脂及使用其的水性纳米防腐自洁面漆
JPH06136321A (ja) ポリウレタン・シリカハイブリット体の製造方法及びアルコールゾル溶液
CN112745732A (zh) 一种环保型除甲醛的聚合物胶乳的制备和在涂料中的应用
CN112322170A (zh) 一种双组份水性聚氨酯涂料及其制备方法和应用
CN100338111C (zh) 一种双疏性聚氨酯—聚丙烯酸酯微乳液及其制备方法
CN114045108A (zh) 一种sis衍生物改性聚氨酯-环氧树脂水性涂料
CN114539901A (zh) 一种水性聚氨酯涂料及其制备方法
CN113773468A (zh) 长链有机硅改性外露型水性聚氨酯乳液及其制备方法
DE10112390A1 (de) Polyurethan-Dispersion mit hoher Filmhärte, Verfahren zu ihrer Herstellung sowie deren Verwendung
JP6336690B1 (ja) シリコーン樹脂エマルションを含む水性塗料組成物の調製方法

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
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20211123

WD01 Invention patent application deemed withdrawn after publication