CN111560204A - 一种可自修复聚碳酸酯表面防雾涂层及其制备方法 - Google Patents
一种可自修复聚碳酸酯表面防雾涂层及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种聚碳酸酯表面防雾涂层及其制备方法,包括:1)制备醇的低聚物反应单体与丙烯酸类单体、丙烯酸酯类单体、乙烯基硅烷单体共聚,作为成膜树脂;2)加入硅溶胶与成膜树脂进行水解交联;3)加入无机金属盐,形成丙烯酸离聚体,经涂覆干燥后,即得到一种可自修复聚碳酸酯表面防雾涂层;该涂层材料具有亲水的聚醇链段以及丙烯酸离聚体,在聚碳酸酯板材上能够形成超亲水表面;另外该涂层材料为共价与非共价键杂交体系,使得涂层具有优异的机械强度和耐磨性的同时,兼具良好的自愈合性能,具有综合性能优势。
Description
技术领域
本发明属于涂料领域,具体涉及一种聚碳酸酯表面防雾涂层及其制备方法。
背景技术
芳香族聚碳酸酯具有良好的透明性、强度和韧性,广泛应用于光学材料的制备,特别是作为交通工具的透光材料,如飞机座舱窗户、汽车挡风玻璃等。当聚碳酸酯板两面处于较大温差时,会产生雾气,从而造成视线模糊,因此制备聚碳酸酯的表面防雾涂层有一定的现实需要。
CN110281613公布了一种表面防雾化聚碳酸酯板,发明人通过乳胶粘合剂将增强层复合在聚碳酸酯板材上,然后将具有防雾化功能的防雾层涂覆在增强层表面,改善了聚碳酸酯板材的耐磨性的同时赋予其防雾性能。但该方法步骤繁杂,且未考虑到乳胶粘合剂的失效问题。
CN201501141U公布了一种具有防雾性的聚碳酸酯薄膜或片材,发明人通过在聚碳酸酯薄膜或片材本体的表面直接喷涂、辊涂、浸渍或旋涂防雾剂,防雾剂的主要有效成分是表面活性剂,再经加热固化后制得具有防雾的表面。该方法形成的防雾表面不具有耐久性,且其耐磨性没有得到改善。
CN 108485326A公布了一种有机-无机杂化聚碳酸酯表面涂层,无机硅溶胶的添加有效提高了有机涂层的硬度、耐磨性和热稳定性,但该涂层不具有自修复性,表面刮伤时将受到了不可逆的损坏,且不具有防雾性能。
发明内容
针对现有技术的以上不足之处,本发明提供一种可自修复的聚碳酸酯表面防雾涂层及其制备方法,该涂层是以有机硅改性丙烯酸离聚体作为成膜树脂,能够形成超亲水表面,改善现有聚碳酸酯表面涂层的防雾性能;另外,无机金属盐作为体系非共价交联的固化剂,能够赋予涂层自修复性能。
本发明提供一种可自修复的聚碳酸酯表面防雾涂层及其制备方法,该涂层按以下步骤制备:
(1)柔性反应单体的制备:在氮气环境下,将二元醇聚合物、二官能度异氰酸酯、二月桂酸二丁基锡投入反应釜中混合均匀,在70~80℃下搅拌反应1h后加入丙烯酸羟乙酯,继续保温反应1h,得到柔性反应单体。
所述二官能度异氰酸酯可以是异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯中的一种或两种。
所述二元醇聚合物可以是聚丁二醇、聚丙二醇、聚己二酸丁二醇酯二元醇、聚四氢呋喃二元醇中的一种或两种(分子量为200~1000g/mol)。
所述二元醇聚合物、二官能度异氰酸酯、丙烯酸羟乙酯的投料摩尔比为1:2.2:2.5,二月桂酸二丁基锡投入量为二官能度异氰酸酯质量的2%。
(2)硅溶胶改性丙烯酸树脂溶液的制备:按比例称取各原料,将柔性反应单体、不饱和酸、不饱和酯、有机硅反应单体放入反应釜中,加入无水乙醇,充分搅拌10min后加入引发剂,升温至60~70℃反应3h;待反应物冷却至40-50℃,加入固含量34%的酸性硅溶胶、用盐酸将体系pH调至2~4,搅拌下缓慢滴入硅烷偶联剂,滴完后搅拌水解3h;按GB/T1725-2007测量硅溶胶改性丙烯酸树脂的的固含量C;
所述的不饱和酸是指丙烯酸、甲基丙烯酸中的至少一种。
所述的不饱和酯是指丙烯酸酯类、甲基丙烯酸酯类中的至少一种;
所述的有机硅反应单体是指γ-甲基丙烯酰氧丙基三甲氧基硅烷。
所述的引发剂是指过氧化二苯甲酰或偶氮二异丁腈。
所述的硅烷偶联剂是指具有结构式为RnSi(OR’)4-n,0≤n≤2的硅氧烷及其组合物。
所述的柔性反应单体、不饱和酸、不饱和酯、有机硅反应单体、引发剂、酸性硅溶胶、硅烷偶联剂的投料比例,按质量比例计算为0~10%:15~25%:3~8%:2~3%:0.1~0.3%:10~15%:5~15%,余量为无水乙醇。
(3)硅溶胶改性丙烯酸离聚体的制备:将硅溶胶改性丙烯酸树脂溶液、无机金属盐的乙醇溶液放入反应釜中,室温搅拌10min使其充分混合,所得硅溶胶改性丙烯酸离聚体涂抹在聚碳酸酯板材上,在70~80℃下真空干燥24h,即制备得一种可自修复聚碳酸酯表面防雾涂层。
所述无机金属盐的投料摩尔量为n(COOH)的0.3~1倍。
硅溶胶改性丙烯酸树脂溶液中羧基的摩尔量按以下公式计算得到:
所述无机金属盐可以是氯化铁、氯化铝中的至少一种。
所述乙醇为无水乙醇,加入量为无机金属盐质量的1~2倍。
本发明具有如下的有益效果:
本发明提供一种可自修复的聚碳酸酯表面防雾涂层及其制备方法,组分中的聚醇链段和离聚体赋予涂层超亲水表面,起防雾作用;同时,聚醇链段具有很强的运动能力,当涂层因外力作用而撕裂、刮伤时,断面上的链段运动使得破坏过程中断裂的离子键重新接触成键,完成自修复。
附图说明
图1为实施例1硅溶胶改性丙烯酸树脂溶液加FeCl3前后FT-IR谱图。
图2为实施例2中A5~A8涂层的水接触角示意图。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
本发明测试:
耐磨性测试:按照ASTMD 1044《透明塑料耐磨试验方法》,采用Taber试验机以1kg载荷的石英砂以200冲程磨蚀试样后,通过测量雾度评估透明塑料耐磨性能。
铅笔硬度测试:按照GB/T6739-2006标准测定铅笔硬度。
水接触角测试:采用JGW-360A接触角测量仪测定。
自修复率测试:采用BYK微型光泽仪测量涂层的光泽度。将涂层置于水平桌面测量涂层初始光泽G0,然后使用钢丝绒(#0000)对涂层表面横竖摩擦各10次后,使用软刷将涂层表面清理干净后测量涂层受损时的光泽Gd,在50℃环境下静置2h后测量修复后的光泽度Gh。依据公式可算出涂层的修复效率为:(Gh-Gd)/(G0-Gd)×100%。
实施例1
(1)硅溶胶改性丙烯酸树脂溶液的制备:在装有温度计、搅拌桨的三口烧瓶中,将25.11g丙烯酸、4.86g甲基丙烯酸酯、3.09gγ-甲基丙烯酰氧丙基三甲氧基硅烷放入反应釜中,加入50.10g无水乙醇,充分搅拌10min后加入0.31g过氧化二苯甲酰,升温至60℃反应3h;待反应物冷却至50℃,加入23.62g酸性硅溶胶(固含量34%),用盐酸将体系pH调至3,搅拌下缓慢滴入20.08g甲基三乙氧基硅烷,滴完后搅拌水解3h,即得到硅溶胶改性丙烯酸树脂溶液。按GB/T1725-2007测量硅溶胶改性丙烯酸树脂溶液的固含量为C=46.11%。
(2)硅溶胶改性丙烯酸离聚体的制备:往硅溶胶改性丙烯酸树脂溶液中加入氯化铁的乙醇溶液,室温搅拌10min使其充分混合,所得硅溶胶改性丙烯酸离聚体涂抹在聚碳酸酯板材上,在80℃下真空干燥24h,即制备得一种可自修复聚碳酸酯表面防雾涂层。其中,不同的氯化铁的乙醇溶液和硅溶胶改性丙烯酸树脂溶液的投料量对应的涂层记号分别是:
参阅图1,硅溶胶改性丙烯酸树脂(加FeCl3前)硅溶胶改性丙烯酸离聚体(加FeCl3后)的FT-IR谱图如图1所示。
实施例2
(1)柔性反应单体的制备:在有氮气保护搅拌桨的三口烧瓶中,放入100g聚丙二醇(PPG-200)、244.25g异佛尔酮二异氰酸酯、4.89g二月桂酸二丁基锡搅拌均匀,升温至70℃反应1h。往烧瓶中加入145.05g丙烯酸羟乙酯,继续保温反应1h,得到柔性反应单体。
(2)硅溶胶改性丙烯酸树脂溶液的制备步骤与实施例1相同,区别为各原料投料量:柔性反应单体2.4g,丙烯酸25.11g,甲基丙烯酸酯5.08g,γ-甲基丙烯酰氧丙基三甲氧基硅烷3g,无水乙醇50g,过氧化二苯甲酰0.3g,固含量34%为酸性硅溶胶23.56g,甲基三乙氧基硅烷16.12g。按GB/T1725-2007测量硅溶胶改性丙烯酸树脂溶液的固含量为C=46.27%。
(3)硅溶胶改性丙烯酸离聚体的制备步骤与实施例1相同,区别为各原料投料量,投料量及对应涂层记号如下:
参阅图2,A5~A8涂层的水接触角示意图如图2所示。
实施例3
(1)柔性反应单体的制备,与实施例2相同。
(2)硅溶胶改性丙烯酸树脂溶液的制备步骤与实施例1相同,区别为各原料投料量:柔性反应单体6.05g、丙烯酸24.98g、甲基丙烯酸酯5.1g、γ-甲基丙烯酰氧丙基三甲氧基硅烷3.08g,无水乙醇50g,过氧化二苯甲酰0.32g,固含量34%的酸性硅溶胶23.81g,甲基三乙氧基硅烷12.06g;按GB/T1725-2007测量硅溶胶改性丙烯酸树脂溶液的固含量为C=46.50%。
(3)硅溶胶改性丙烯酸离聚体的制备步骤与实施例1相同,区别为各原料投料量,投料量及对应涂层记号如下:
实施例4
(1)柔性反应单体的制备,与实施例2相同;
(2)硅溶胶改性丙烯酸树脂溶液的制备步骤与实施例1相同,区别为各原料投料量:柔性反应单体9.12g、丙烯酸25.05g、甲基丙烯酸酯5.03g、γ-甲基丙烯酰氧丙基三甲氧基硅烷2.99g,无水乙醇50.16g,过氧化二苯甲酰0.29g,固含量34%的酸性硅溶胶23.52g,甲基三乙氧基硅烷8.14g。按GB/T1725-2007测量硅溶胶改性丙烯酸树脂溶液的固含量为C=45.25%;
(3)硅溶胶改性丙烯酸离聚体的制备步骤与实施例1相同,区别为各原料投料量,投料量及对应涂层记号如下:
对实施例1-5的16份涂层材料固化后形成漆膜性能测试,测试结果列于表1。
表1
实施例1中的A1~A4具有不同的n(Fe3+):n(COOH),氯化铁与丙烯酸形成的离子键作为涂层的辅助交联,同时提高涂层材料的机械强度和表面亲水性。A2、A6、A10、A14涂层材料分别具有从小到大的聚醇组分/硅氧烷组分的比例,从表1可知,随着聚醇链段的增加,体系的自修复率增大,但硬度和耐磨性却随着硅氧烷组分的减小而降低。
Claims (4)
1.一种可自修复聚碳酸酯表面防雾涂层及制备方法,其特征在于,包括以下步骤:
(1)柔性反应单体的制备:二元醇聚合物、二官能度异氰酸酯、二月桂酸二丁基锡在70~80℃下混合反应1h后加入丙烯酸羟乙酯,继续反应1h;
(2)硅溶胶改性丙烯酸树脂溶液的制备:柔性反应单体、不饱和酸、不饱和酯、有机硅反应单体在引发剂的存在下进行自由基聚合,反应温度为60~70℃,反应时间为3h;待反应体系冷却至40~50℃,加入酸性硅溶胶、用盐酸将体系pH调至3,搅拌下缓慢滴入硅烷偶联剂,滴完后搅拌水解3h;按GB/T1725-2007测量硅溶胶改性丙烯酸树脂的的固含量C;
(3)硅溶胶改性丙烯酸离聚体的制备:将硅溶胶改性丙烯酸树脂溶液、无机金属盐的乙醇溶液放入反应釜中,室温搅拌10min使其充分混合,所得硅溶胶改性丙烯酸离聚体涂抹在聚碳酸酯板材上,在70~80℃下真空干燥24h,即制备得一种可自修复聚碳酸酯表面防雾涂层。
2.根据权利要求1所述的一种可自修复聚碳酸酯表面防雾涂层及制备方法,其特征在于:
所述步骤(1)的二官能度异氰酸酯可以是异佛尔酮二异氰酸酯或六亚甲基二异氰酸酯;
所述步骤(1)的二元醇聚合物可以是聚丁二醇、聚丙二醇、聚己二酸丁二醇酯二元醇、聚四氢呋喃二元醇(分子量为200~1000g/mol)中的至少一种;
所述步骤(2)的不饱和酸可以是丙烯酸、甲基丙烯酸中的至少一种;
所述步骤(2)的不饱和酯可以是丙烯酸酯类、甲基丙烯酸酯类中的至少一种;
所述步骤(2)的有机硅反应单体为γ-甲基丙烯酰氧丙基三甲氧基硅烷;
所述步骤(2)的引发剂是过氧化二苯甲酰或偶氮二异丁腈;
所述步骤(2)的酸性硅溶胶,为固含量34%的酸性硅溶胶;
所述步骤(2)的硅烷偶联剂是指具有结构式为RnSi(OR’)4-n,0≤n≤2的硅氧烷及其组合物;
所述步骤(2)的无机金属盐可以是氯化铁、氯化铝中的至少一种。
4.根据权利要求1所述的一种可自修复聚碳酸酯表面防雾涂层及制备方法,其特征在于无机金属盐与丙烯酸树脂螯合交联形成离聚体。
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