CN106634549B - 一种增韧涂料及其制备方法 - Google Patents
一种增韧涂料及其制备方法 Download PDFInfo
- Publication number
- CN106634549B CN106634549B CN201611189267.5A CN201611189267A CN106634549B CN 106634549 B CN106634549 B CN 106634549B CN 201611189267 A CN201611189267 A CN 201611189267A CN 106634549 B CN106634549 B CN 106634549B
- Authority
- CN
- China
- Prior art keywords
- parts
- solution
- unsaturated polyester
- glass flake
- coating
- 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
Links
Classifications
-
- 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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C08G18/36—Hydroxylated esters of higher fatty 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
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- 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
- C08G18/6547—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/40—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
本发明公开了一种增韧涂料及其制备方法,属于化工涂料加工技术领域。所述增韧涂料由如下重量份数的组分溶解在溶剂中制成:环氧树脂100‑120份、端异氰酸酯基不饱和聚酯溶液20‑30份、填料10‑20份、玻璃鳞片15‑20份、颜料5‑20份、酸酐固化剂10‑20份、过氧化二苯甲酰0.5‑1份、N,N‑二甲基苯胺0.5‑1份和促进剂0.05‑0.1份,本发明通过制备韧性极佳的端异氰酸酯基不饱和聚酯改性剂,加入过氧化二苯甲酰和环氧固化剂,并对玻璃鳞片进行表面处理,添加到涂料中,制备的涂料可在低温条件下快速固化,固化后的涂层粘接性能好,具有良好的韧性,在温湿度频繁变化的环境中长期使用不开裂也不脱落。
Description
【技术领域】
本发明涉及化工涂料加工技术领域,具体涉及一种增韧涂料及其制备方法。
【背景技术】
材料在使用过程中经常会因为材料本身的吸湿性或温度的变化膨胀或收缩,导致材料老化或变形,为了保护材料,往往要在材料表面喷涂保护层涂层。涂层一般是先将基体树脂、填充材料和固化剂等制备成涂料,将涂料涂布或喷涂在材料表层,在一定条件下固化后形成一层胶膜黏附在材料表面,将材料与大气隔绝,防止材料吸水或被酸碱腐蚀而老化。
以环氧树脂作为基体树脂制备的涂料粘接性好、收缩率低、尺寸稳定、电性能优良、耐化学介质、配置容易、工艺简单、使用温度宽广、适应性较强、毒性很低、危害也小、不污染环境等,对多种材料都具有良好的胶粘能力,还有密封、绝缘、防漏、固定、防腐、装饰等多种功用,被称为万能胶,但是环氧树脂固化后韧性不足,限制其使用范围。
玻璃鳞片是由1200℃以上的熔融中碱玻璃,经吹泡、冷却、粉碎、筛选及碾磨等工艺步骤所制得,横纵比高达30-120,玻璃鳞片在树脂中呈平行重叠排列的宫式结构,形成致密的防渗层结构,水分在固化后的树脂中的渗透必须经过无数条曲折的途径,因此在一定厚度的涂层中,水分渗透的距离大大的延长,相当于有效地增加了玻璃鳞片防水层的厚度。玻璃鳞片为无机材料且表面光滑,直接将玻璃鳞片与有机树脂基体混合后其在界面间的相容性差,容易在界面间形成缝隙,液体和气体可通过界面间的缝隙渗透到涂层内部,影响涂层的性能及防水效果。
另外,现有的涂料中,为了获得较好的性能需要在较高温度下固化,在低温下固化不仅固化效率低,且固化后的涂层性能达不到要求,而材料因为温度变化或吸湿引起变形,涂布在材料表层的保护涂层由于粘接性差,韧性不足经常会开裂甚至脱落,影响保护涂层的保护效果。
【发明内容】
本发明的目的在于:针对上述存在的问题,提供一种增韧涂料及其制备方法,本发明的涂料可在低温条件下快速固化,固化后的涂层粘接性能好,具有良好的韧性,在温湿度频繁变化的环境中长期使用不开裂也不脱落。
为了实现上述目的,本发明采用的技术方案如下:
一种增韧涂料,由如下重量份数的组分溶解在溶剂中制成:环氧树脂100-120份、端异氰酸酯基不饱和聚酯溶液20-30份、填料10-20份、玻璃鳞片15-20份、颜料5-20份、酸酐固化剂10-20份、过氧化二苯甲酰0.5-1份、N,N-二甲基苯胺0.5-1份和促进剂0.05-1份,所述涂料的固形份为60-70%;
所述端异氰酸酯基不饱和聚酯溶液为由蓖麻油和二异氰酸酯按羟基与异氰酸酯基摩尔比为1:2-2.2的比例混合溶解在丙酮中并反应后,再加入经苯乙烯稀释后的端羟基不饱和聚酯,使端羟基不饱和聚酯中的羟基与剩余异氰酸酯基的摩尔比为0.8-0.9:1;
所述玻璃鳞片为经过砂磨处理后,获得表面粗糙度为1-2μm,厚度为5-8μm的片状材料,再浸泡在5-10重量倍的偶联剂溶液中,最后烘干制成。
所述环氧树脂为缩水甘油醚型环氧树脂和脂环族环氧树脂中的任意一种或两种;所述二异氰酸酯为甲苯二异氰酸酯、二苯甲烷二异氰酸酯、对苯二亚甲基二异氰酸酯、己二异氰酸酯或异佛尔酮二异氰酸酯。
所述填料为珍珠岩和/或氢氧化铝;所述颜料为二氧化钛、炭黑、酞菁蓝或氧化铁。
所述偶联剂溶液为硅烷偶联剂或钛酸酯偶联剂溶解在无水乙醇中制备而成,所述偶联剂溶液质量浓度为20-30%。
所述溶剂为苯乙烯、二丁酯、甲乙酮中的一种或两种以上的组合物。
所述酸酐固化剂为甲基四氢苯酐、马来酸酐、甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐和3,3’,4,4’-二苯酮四酸二酐中的一种或两种以上的组合物;所述促进剂为咪唑促进剂。
本发明还提供一种所述的增韧涂料的制备方法,包括如下步骤:
(1)将玻璃鳞片放入表面黏附有研磨砂粒的磨砂滚筒中,调节滚筒内气压为1-2MPa,在转速为1000-1500r/min的条件下砂磨30-60分钟,得表面粗糙度为1-2μm,厚度为5-8μm的片状材料;将经砂磨处理后的玻璃鳞片浸泡在5-10重量倍的偶联剂溶液中,边搅拌边升高温度至30-60℃后继续搅拌30-40分钟,再将浸泡在偶联剂溶液中的玻璃鳞片放入60-90℃的烘箱中烘烤1-1.5小时;
(2)将蓖麻油用重量为其3-4倍的丙酮稀释;将端羟基不饱和聚酯用重量为其2-3倍的苯乙烯稀释;将二异氰酸酯溶解在2-3重量倍的丙酮中,在60-80℃的油浴中边搅拌边缓慢滴加经丙酮稀释后的蓖麻油溶液,使蓖麻油与二异氰酸酯中的羟基与异氰酸酯基的摩尔比为1:2-2.2,滴加完成后继续搅拌反应40-60分钟,再缓慢滴入经苯乙烯稀释的端羟基不饱和聚酯,使端羟基不饱和聚酯中的羟基与剩余异氰酸酯基的摩尔比为0.8-0.9:1,滴加完成后继续搅拌40-60分钟,得端异氰酸酯基不饱和聚酯溶液,密封冷却后待用;
(3)将100-120份环氧树脂、10-20份填料、5-20份颜料和适量溶剂投入分散机中,在800-1000r/min的转速下搅拌30-40分钟后,转入砂磨机中砂磨40-60分钟,得均质的溶液,然后将20-30份步骤(2)中制得的端异氰酸酯基不饱聚酯溶液、15-20份步骤(1)处理后的玻璃鳞片与上述均质溶液投入分散机中,在800-1000r/min的转速下分散30-40分钟,最后加入10-20份酸酐固化剂、0.5-1份过氧化二苯甲酰、0.5-1份N,N-二甲基苯胺和0.05-0.1份促进剂并搅拌20-30分钟,获得固形份为60-70%的混合液,即为本发明的增韧涂料。
蓖麻油是脂肪酸的三甘油酯,羟基平均官能度为2.7,分子中还含有不饱和双键,蓖麻油能够通过所具有的羟基、双键以及酯键进行多种化学反应,具有良好的柔韧性和反应性。
综上所述,由于采用了上述技术方案,本发明的有益效果是:本发明通以二异氰酸酯、蓖麻油和不饱和聚酯制备端羟基不饱和聚酯改性剂,将改性剂添加到以环氧树脂为基体的涂料中,改性剂中的异氰酸酯基可与环氧树脂反应,将柔性蓖麻油分子和双键接枝到环氧树脂上,以酸酐作为环氧的固化剂,以N,N-二甲基苯胺作为酸酐的催化剂,以咪唑作为促进剂,同时加入的过氧化二本甲酰既可引发双键聚合还可降低环氧固化的温度,改善环氧树脂的柔韧性,降低反应温度,提高反应速率;同时以防渗透性能极佳的玻璃鳞片作为填充材料,在使用前对玻璃鳞片表面进行砂磨使表面具有一定的粗糙度,再利用偶联剂对玻璃鳞片表面进行化学处理,通过对玻璃鳞片同时进行机械处理和化学处理,可提高玻璃鳞片与树脂之间界面的机械结合力和相容性,使环氧树脂与玻璃鳞片之间形成紧密的界面,防止液体和气体通过界面间的缝隙渗透到到涂层内部,制备的涂料涂覆性能佳,可在低温下快速固化,固化后具有良好的粘接性能,涂层韧性佳,可在温湿度变化大的环境中长期使用。
【具体实施方式】
下面结合具体实施例对本发明的技术方案作进一步进行的说明。
实施例1
(1)将玻璃鳞片放入表面黏附有研磨砂粒的磨砂滚筒中,调节滚筒内气压为1MPa,在转速为1500r/min的条件下砂磨30分钟,得表面粗糙度为1-2μm,厚度为5-8μm的玻璃鳞片;将经砂磨处理后的玻璃鳞片浸泡在5重量倍,质量浓度为20%的硅烷偶联剂乙醇溶液中,边搅拌边升高温度至30℃后继续搅拌40分钟,再将浸泡在硅烷偶联剂溶液中的玻璃鳞片放入60℃的烘箱中烘烤1.5小时;
(2)将蓖麻油用重量为其3倍的丙酮稀释;将端羟基不饱和聚酯用重量为其3倍的苯乙烯稀释;将甲苯二异氰酸酯溶解在2重量倍的丙酮中,在60℃的油浴中边搅拌边缓慢滴加经丙酮稀释后的蓖麻油溶液,使蓖麻油与甲苯二异氰酸酯中的羟基与异氰酸酯基的摩尔比为1:2,滴加完成后继续搅拌反应60分钟,再缓慢滴入经苯乙烯稀释的端羟基不饱和聚酯,使端羟基不饱和聚酯中的羟基与剩余异氰酸酯基的摩尔比为0.8:1,滴加完成后继续搅拌60分钟,得端异氰酸酯基不饱和聚酯溶液,密封冷却后待用;
(3)将100份双酚A型环氧树脂、10份珍珠岩、20份二氧化钛和适量甲乙酮投入分散机中,在800r/min的转速下搅拌40分钟后,转入砂磨机中砂磨40分钟,得均质的溶液,然后将20份由步骤(2)中制得的端异氰酸酯基不饱聚酯溶液、15份经步骤(1)处理过的玻璃鳞片与上述均质溶液投入分散机中,在800r/min的转速下分散40分钟,最后加入10份甲基四氢苯酐固化剂、0.5份过氧化二苯甲酰、0.5份N,N-二甲基苯胺和0.05份促进剂并搅拌20分钟,获得固形份为60%的混合液,即为本发明实施例1的增韧涂料。
对比例1
(1)将玻璃鳞片放入表面黏附有研磨砂粒的磨砂滚筒中,调节滚筒内气压为1MPa,在转速为1500r/min的条件下砂磨30分钟,得表面粗糙度为1-2μm,厚度为5-8μm的玻璃鳞片;将经砂磨处理后的玻璃鳞片浸泡在5重量倍,质量浓度为20%的硅烷偶联剂乙醇溶液中,边搅拌边升高温度至30℃后继续搅拌40分钟,再将浸泡在硅烷偶联剂溶液中的玻璃鳞片放入60℃的烘箱中烘烤1.5小时;
(2)将120份双酚A型环氧树脂、10份珍珠岩、20份二氧化钛和适量甲乙酮投入分散机中,在800r/min的转速下搅拌40分钟后,转入砂磨机中砂磨40分钟,得均质的溶液,然后将15份经步骤(1)处理过的玻璃鳞片和上述均质溶液投入分散机中,在800r/min的转速下分散40分钟,最后加入15份甲基四氢苯酐固化剂、0.5份过氧化二苯甲酰、0.5份N,N-二甲基苯胺和0.05份促进剂并搅拌20分钟,获得固形份为60%的混合液,即为本发明对比例1的增韧涂料。
实施例2
(1)将玻璃鳞片放入表面黏附有研磨砂粒的磨砂滚筒中,调节滚筒内气压为2MPa,在转速为1000r/min的条件下砂磨60分钟,得表面粗糙度为1-2μm,厚度为5-8μm的玻璃鳞片;将经砂磨处理后的玻璃鳞片浸泡在10重量倍,质量浓度为30%的钛酸酯偶联剂的乙醇溶液中,边搅拌边升高温度至60℃后继续搅拌35分钟,再将浸泡在钛酸酯偶联剂溶液中的玻璃鳞片放入90℃的烘箱中烘烤1小时;
(2)将蓖麻油用重量为其4倍的丙酮稀释;将端羟基不饱和聚酯用重量为其2倍的苯乙烯稀释;将对苯二亚甲基二异氰酸酯溶解在3重量倍的丙酮中,在80℃的油浴中边搅拌边缓慢滴加经丙酮稀释后的蓖麻油溶液,使蓖麻油与对苯二亚甲基二异氰酸酯中的羟基与异氰酸酯基的摩尔比为1:2.2,滴加完成后继续搅拌反应40分钟,再缓慢滴入经苯乙烯稀释的端羟基不饱和聚酯,使端羟基不饱和聚酯中的羟基与剩余异氰酸酯基的摩尔比为0.9:1,滴加完成后继续搅拌40分钟,得端异氰酸酯基不饱和聚酯溶液,密封冷却后待用;
(3)将120份由缩水甘油醚型环氧树脂和脂环族环氧树脂按重量比为2:1的比例混合的环氧树脂、20份由珍珠岩和氢氧化铝按重量比为1:1的比例混合的填料、5份炭黑和适量苯乙烯投入分散机中,在1000r/min的转速下搅拌30分钟后,转入砂磨机中砂磨60分钟,得均质的溶液,然后将30份由步骤(2)中制得的端异氰酸酯基不饱聚酯溶液、20份经步骤(1)中处理后的玻璃鳞片与上述均质溶液投入分散机中,在1000r/min的转速下分散30分钟,最后加入20份由甲基四氢邻苯二甲酸酐和马来酸酐按摩尔比为2:1的比例混合的固化剂、1份过氧化二苯甲酰、1份N,N-二甲基苯胺和0.1份咪唑促进剂并搅拌30分钟,获得固形份为70%的混合液,即为本发明实施例2的增韧涂料。
对比例2
与实施例2不同的是,对比例2中没有加入过氧化二苯甲酰。
实施例3
(1)将玻璃鳞片放入表面黏附有研磨砂粒的磨砂滚筒中,调节滚筒内气压为1.5MPa,在转速为900r/min的条件下砂磨50分钟,得表面粗糙度为1-2μm,厚度为5-8μm的玻璃鳞片;将经砂磨处理后的玻璃鳞片浸泡在8重量倍,质量浓度为25%的钛酸酯偶联剂的乙醇溶液中,边搅拌边升高温度至60℃后继续搅拌30分钟,再将浸泡在钛酸酯偶联剂溶液中的玻璃鳞片放入80℃的烘箱中烘烤1.3小时;
(2)将蓖麻油用重量为其2.5倍的丙酮稀释;将端羟基不饱和聚酯用重量为其2.5倍的苯乙烯稀释;将异佛尔酮二异氰酸酯溶解在2.5重量倍的丙酮中,在70℃的油浴中边搅拌边缓慢滴加经丙酮稀释后的蓖麻油溶液,使蓖麻油与异佛尔酮二异氰酸酯中的羟基与异氰酸酯基的摩尔比为1:2.1,滴加完成后继续搅拌反应50分钟,再缓慢滴入经苯乙烯稀释的端羟基不饱和聚酯,使端羟基不饱和聚酯中的羟基与剩余异氰酸酯基的摩尔比为0.85:1,滴加完成后继续搅拌50分钟,得端异氰酸酯基不饱和聚酯溶液,密封冷却后待用;
(3)将110份脂环族环氧树脂、15份氢氧化铝、10份酞菁蓝和适量由苯乙烯及丁酮按重量比为3:1的比例混合的溶剂投入分散机中,在900r/min的转速下搅拌35分钟后,转入砂磨机中砂磨50分钟,得均质的溶液,然后将25份由步骤(2)中制得的端异氰酸酯基不饱聚酯溶液、17份经步骤(1)处理过的玻璃鳞片与上述均质溶液投入分散机中,在900r/min的转速下分散35分钟,最后加入15份由甲基四氢苯酐和3,3’,4,4’-二苯酮四酸二酐按摩尔比为2:1的比例混合的固化剂、0.8份过氧化二苯甲酰、0.7份N,N-二甲基苯胺和0.08份咪唑促进剂并搅拌25分钟,获得固形份为65%的混合液,即为本发明实施例3的增韧涂料。
对比例3
与实施例3不同的是,对比例3没有对玻璃鳞片表面进行砂磨处理。
对比例4
与实施例3不同的是,对比例4没有对玻璃鳞片表面进行化学处理。
分别测试本发明各实施例和对比例制备的涂料的达到最优性能时的固化温度和固化时间进行对比测试,同时将涂料在最优固化条件下固化后制备样品测试其性能,测试结果如表1所示。
性能测试包括粘接性能测试、耐湿热性能测试、柔韧性测试,
测试方法分别如下:
(1)粘接性能测试为将涂料涂覆在基材上固化完全后,在涂层上50×100毫米的范围内用划15×15毫米的格子,然后将胶布贴在划格子的涂层上,给胶布施加500g的力压紧,在垂直涂层表面的方向上,快速撕开胶带,查看格子完整为合格,各种涂层剥落即不合格;
(2)耐湿热老化性能为按粘接性能测试方法制备样品后,将样品放入温度分别为40℃、60℃和80℃,湿度为90%RH的恒温恒湿机中,分别测试不同时间间隔的粘接性,测试期限为1年,评价涂层耐湿热老化性能的极限时间;
(3)柔韧性测试方法为将涂料制备成薄膜,固化完全后测试其断裂伸长率。
表1:本发明实施例和对比例制备的增韧涂料性能测试结果
经过上述对比测试结果表明,通过在环氧树脂中加入以蓖麻油、二异氰酸酯和不饱和聚酯按一定的比例制备分子中同时含有双键和端异氰酸酯基的改性剂,改性剂通过端异氰酸酯基将包含韧性蓖麻油分子的改性剂接枝到环氧树脂分子上,提高环氧树脂的韧性,还加入过氧化二本甲酰作为不饱和聚酯的固化剂,同时还对环氧固化具有促进作用,可提高环氧树脂的固化效率,提高涂层固化后的交联密度,同时对玻璃鳞片表面进行磨砂处理增加玻璃鳞片的表面粗糙度,再对玻璃鳞片表面进行化学处理,提高玻璃鳞片与基体树脂之间界面结合的紧密程度,有效提高涂层的耐湿热老化性能;对比例1中没有加入改性剂,涂层的韧性和耐湿热老化性能明显降低,固化温度和固化时间也有所增加;对比例2中没有加入过氧化二苯甲酰,固化温度和固化时间均提高一倍左右,涂层韧性和耐湿热老化性能也降低;对比例3和对比例4仅单独对玻璃鳞片进行砂磨处理或化学处理,对固化效率没有影响,但是韧性和耐湿热老化性能变差。
上述说明是针对本发明较佳可行实施例的详细说明,但实施例并非用以限定本发明的专利申请范围,凡本发明所提示的技术精神下所完成的同等变化或修饰变更,均应属于本发明所涵盖专利范围。
Claims (7)
1.一种增韧涂料,其特征在于,由如下重量份数的组分溶解在溶剂中制成:环氧树脂100-120份、端异氰酸酯基不饱和聚酯溶液20-30份、填料10-20份、玻璃鳞片15-20份、颜料5-20份、酸酐固化剂10-20份、过氧化二苯甲酰0.5-1份、N,N-二甲基苯胺0.5-1份和促进剂0.05-0.1份,所述涂料的固形份为60-70%;
所述端异氰酸酯基不饱和聚酯溶液为由蓖麻油和二异氰酸酯按羟基与异氰酸酯基摩尔比为1:2-2.2的比例混合溶解在丙酮中并反应完成后,再加入经苯乙烯稀释后的端羟基不饱和聚酯,使端羟基不饱和聚酯中的羟基与剩余异氰酸酯基的摩尔比为0.8-0.9:1;
所述玻璃鳞片为经过砂磨处理后,获得表面粗糙度为1-2μm,厚度为5-8μm的片状材料,再浸泡在5-10重量倍的偶联剂溶液中,最后烘干制成。
2.根据权利要求1所述的增韧涂料,其特征在于,所述环氧树脂为缩水甘油醚型环氧树脂和脂环族环氧树脂中的任意一种或两种;所述二异氰酸酯为甲苯二异氰酸酯、二苯甲烷二异氰酸酯、对苯二亚甲基二异氰酸酯、己二异氰酸酯或异佛尔酮二异氰酸酯。
3.根据权利要求1所述的增韧涂料,其特征在于,所述填料为珍珠岩和/或氢氧化铝;所述颜料为二氧化钛、炭黑、酞菁蓝或氧化铁。
4.根据权利要求1所述的增韧涂料,其特征在于,所述偶联剂溶液为硅烷偶联剂或钛酸酯偶联剂溶解在乙醇中制备而成,所述偶联剂溶液质量浓度为20-30%。
5.根据权利要求1所述的增韧涂料,其特征在于,所述溶剂为苯乙烯、二丁酯、甲乙酮中的一种或两种以上的组合物。
6.根据权利要求1所述的增韧涂料,其特征在于,所述酸酐固化剂为甲基四氢苯酐、马来酸酐、甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐和3,3’,4,4’-二苯酮四酸二酐中的一种或两种以上的组合物;所述促进剂为咪唑促进剂。
7.一种权利要求1至6任一项所述的增韧涂料的制备方法,其特征在于,包括如下步骤:
(1)将玻璃鳞片放入表面黏附有研磨砂粒的磨砂滚筒中,调节滚筒内气压为1-2MPa,在转速为1000-1500r/min的条件下砂磨30-60分钟,得表面粗糙度为1-2μm,厚度为5-8μm的片状材料;将经砂磨处理后的玻璃鳞片浸泡在5-10重量倍的偶联剂溶液中,边搅拌边升高温度至30-60℃后继续搅拌30-40分钟,再将浸泡在偶联剂溶液中的玻璃鳞片放入60-90℃的烘箱中烘烤1-1.5小时;
(2)将蓖麻油用重量为其3-4倍的丙酮稀释;将端羟基不饱和聚酯用重量为其2-3倍的苯乙烯稀释;将二异氰酸酯溶解在2-3重量倍的丙酮中,在60-80℃的油浴中边搅拌边缓慢滴加经丙酮稀释后的蓖麻油溶液,使蓖麻油与二异氰酸酯中的羟基与异氰酸酯基的摩尔比为1:2-2.2,滴加完成后继续搅拌反应40-60分钟,再缓慢滴入经苯乙烯稀释的端羟基不饱和聚酯,使端羟基不饱和聚酯中的羟基与剩余异氰酸酯基的摩尔比为0.8-0.9:1,滴加完成后继续搅拌40-60分钟,得端异氰酸酯基不饱和聚酯溶液,密封冷却后待用;
(3)将100-120份环氧树脂、10-20份填料、5-20份颜料和适量溶剂投入分散机中,在800-1000r/min的转速下搅拌30-40分钟后,转入砂磨机中砂磨40-60分钟,得均质的溶液,然后将20-30份步骤(2)中制得的端异氰酸酯基不饱聚酯溶液、15-20份步骤(1)中处理的玻璃鳞片与上述均质溶液投入分散机中,在800-1000r/min的转速下分散30-40分钟,最后加入10-20份酸酐固化剂、0.5-1份过氧化二苯甲酰、0.5-1份N,N-二甲基苯胺和0.05-0.1份促进剂并搅拌20-30分钟,获得固形份为60-70%的混合液,即为所述增韧涂料。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611189267.5A CN106634549B (zh) | 2016-12-21 | 2016-12-21 | 一种增韧涂料及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611189267.5A CN106634549B (zh) | 2016-12-21 | 2016-12-21 | 一种增韧涂料及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106634549A CN106634549A (zh) | 2017-05-10 |
CN106634549B true CN106634549B (zh) | 2019-03-05 |
Family
ID=58834884
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611189267.5A Active CN106634549B (zh) | 2016-12-21 | 2016-12-21 | 一种增韧涂料及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106634549B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021128250A1 (en) * | 2019-12-27 | 2021-07-01 | 3M Innovative Properties Company | High temperature resistant b-stageable epoxy adhesive and article manufactured therefrom |
CN112401488B (zh) * | 2020-12-16 | 2023-01-10 | 朱粒萍 | 一种多功能防水课桌 |
CN113801504B (zh) * | 2021-10-25 | 2022-04-08 | 华麟海(海南)新材料科技有限公司 | 海水潮差区用强韧抗渗防污水性硅酸盐涂层及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1075734A (zh) * | 1993-04-12 | 1993-09-01 | 哈尔滨玻璃钢制品厂 | 无毒环氧增韧涂料 |
CN102181218A (zh) * | 2011-03-18 | 2011-09-14 | 西北矿冶研究院 | 一种新型聚合物防腐涂层材料 |
CN104231694A (zh) * | 2014-09-29 | 2014-12-24 | 无锡康柏斯机械科技有限公司 | 一种海船用的防污增韧涂料 |
CN105273599A (zh) * | 2015-12-02 | 2016-01-27 | 青岛爱尔家佳新材料有限公司 | 一种舰船专用复合阻尼涂料及其制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05179196A (ja) * | 1991-12-26 | 1993-07-20 | Toyobo Co Ltd | 保存安定性に優れた塗料および塗装金属板 |
-
2016
- 2016-12-21 CN CN201611189267.5A patent/CN106634549B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1075734A (zh) * | 1993-04-12 | 1993-09-01 | 哈尔滨玻璃钢制品厂 | 无毒环氧增韧涂料 |
CN102181218A (zh) * | 2011-03-18 | 2011-09-14 | 西北矿冶研究院 | 一种新型聚合物防腐涂层材料 |
CN104231694A (zh) * | 2014-09-29 | 2014-12-24 | 无锡康柏斯机械科技有限公司 | 一种海船用的防污增韧涂料 |
CN105273599A (zh) * | 2015-12-02 | 2016-01-27 | 青岛爱尔家佳新材料有限公司 | 一种舰船专用复合阻尼涂料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN106634549A (zh) | 2017-05-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106634549B (zh) | 一种增韧涂料及其制备方法 | |
CN110951385B (zh) | 一种环氧树脂改性的聚氨酯防水涂料及其制备方法 | |
CN114456386B (zh) | 一种反应型环氧改性有机硅树脂及无溶剂耐高温涂料 | |
EP2644745B1 (en) | Metal protective coating, the use thereof, and hot-dip metallic material using the same | |
CN101397475B (zh) | 一种聚氨酯耐高温长效防腐涂料 | |
EP1765905B1 (en) | Flexible, impact resistant primer | |
David et al. | Development of anti-corrosive paint with improved toughness using carboxyl terminated modified epoxy resin | |
CN109439158A (zh) | 一种无溶剂聚脲耐候防腐涂料及制备方法 | |
CN109679556A (zh) | 一种环保型硅烷改性密封胶的制备方法 | |
CN105419421B (zh) | 一种水性碳纳米管散热涂料及其制备方法 | |
CN108841263A (zh) | 用于天线罩表面的疏水材料的制备方法及其应用 | |
CN107556701A (zh) | 一种传感器用环氧树脂制造工艺 | |
CN106634513B (zh) | 一种防腐涂料及其制备方法 | |
CN108048007B (zh) | 复合改性环氧树脂结构胶及复合改性剂和结构胶制备方法 | |
CN107227093B (zh) | 一种环氧聚吡咯金属防腐涂料及其制备方法 | |
CN106634434B (zh) | 一种阻燃涂料及其制备方法 | |
CN106939138B (zh) | 一种抗剥离低聚物水性环氧涂料的制备方法 | |
KR20080023885A (ko) | 고마찰 계수를 가지는 에폭시 징크계 도료조성물 | |
CN109181620B (zh) | 一种可粘接时间长室温固化耐候性聚氨酯胶黏剂 | |
CN108610922A (zh) | 一种涂料组合物及其制备方法和涂层以及保护永磁材料的方法 | |
CN103992721B (zh) | 一种用于金属表面处理的聚苯胺改性多羧基环氧树脂基料 | |
CN109321063A (zh) | 一种柔性抗辐射涂料及制备方法 | |
CN109929455A (zh) | 一种喷涂在smc板上的陶瓷涂料 | |
CN107011785A (zh) | 一种硬质抗磨聚酯镜面涂料及其制备方法 | |
CN109486398A (zh) | 一种汽车涂装用漆及其制备方法 |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right | ||
TR01 | Transfer of patent right |
Effective date of registration: 20220718 Address after: Room 101, building 4, 197 Fugang Road, Houjie Town, Dongguan City, Guangdong Province 523000 Patentee after: Dongguan Puqi sports facilities Co.,Ltd. Address before: 545021 No. 1-20, building 1, Henglong Plaza, No. 20, beique Road, Liubei District, Liuzhou City, Guangxi Zhuang Autonomous Region Patentee before: LIUZHOU CHANGQUAN TRADE CO.,LTD. |