CN113072852A - 一种木器漆用含氟硅水性聚氨酯丙烯酸酯复合涂料的制备方法 - Google Patents

一种木器漆用含氟硅水性聚氨酯丙烯酸酯复合涂料的制备方法 Download PDF

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CN113072852A
CN113072852A CN202110347243.2A CN202110347243A CN113072852A CN 113072852 A CN113072852 A CN 113072852A CN 202110347243 A CN202110347243 A CN 202110347243A CN 113072852 A CN113072852 A CN 113072852A
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杨建军
朱建新
吴庆云
张建安
吴明元
刘久逸
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Abstract

本发明公开了一种木器漆用含氟硅水性聚氨酯丙烯酸酯复合涂料的制备方法,首先将单羟基封端的聚二甲基硅氧烷依次与二异氰酸酯、三甲基丙烷反应得到双羟基封端的侧链有机硅S‑TMP,接着将其与二异氰酸酯反应,并通过扩链、引入亲水剂、加入封端剂合成出双键封端的聚氨酯预聚体,加入含氟丙烯酸酯和丙烯酸酯混合单体稀释降低粘度,加三乙胺中和,再加水分散制成乳液,然后推入钴60源室进行辐照聚合并加入助剂,最后合成出含氟硅水性聚氨酯丙烯酸酯复合涂料。本发明方法制得的复合涂料具有附着力好、光泽高、疏水性能突出等优点,可以在木器漆等领域发挥作用。

Description

一种木器漆用含氟硅水性聚氨酯丙烯酸酯复合涂料的制备 方法
技术领域
本发明属于功能高分子材料领域,具体涉及一种木器漆用含氟硅水性聚氨酯丙烯酸酯复合涂料的制备方法。
背景技术
由于木器漆的发展,现有的木器相较于以往外观更加美观。木器漆需要涂膜具有优异的耐水性能、光泽度和机械性能等,在提升美观度的同时也对木器进行保护。
聚氨酯类涂料作为木器漆由来已久,但传统的溶剂型聚氨酯容易变黄且含有较多的挥发性有机化合物(VOCs),存在着对环境不友好、对人体健康有害等问题。水性聚氨酯(WPU)以水为溶剂,对环境十分友好,可以作为溶剂型聚氨酯良好的替代品。丙烯酸树脂具有优异的耐候性、耐化学性和较好的颜料润湿性和机器稳定性。有机氟、硅优异的耐化学品和低表面能等性能,但水性聚氨酯聚氨酯、丙烯酸酯和有机硅混合乳液相容性差和化学稳定性差。
因此,如何将水性聚氨酯、丙烯酸酯和有机氟硅结合制成复合涂料以提升产品的环保性和防水性能是当前急需解决的关键技术问题。
发明内容
本发明提供了一种木器漆用含氟硅水性聚氨酯丙烯酸酯复合涂料的制备方法,以解决现有木器漆的环保性不佳和耐水性差等技术问题。
本发明木器漆用含氟硅水性聚氨酯丙烯酸酯复合涂料的制备方法,包括如下步骤:
步骤1:在氮气氛围下,将脱水后的单羟基封端的聚二甲基硅氧烷10~20份、二异氰酸酯10~20份、溶剂20~30份、催化剂0.1~0.5份加入反应釜中,在40~45℃下反应5~6h,随后将三甲基丙烷(TMP)10~20份缓慢加入,在75~80℃下反应4~5h,蒸发除去溶剂,得到双羟基封端的侧链有机硅(S-TMP);
步骤2:在氮气氛围下,将脱水后的多元醇10~30份和步骤1获得的S-TMP 5~10份加入反应釜中,再加入二异氰酸酯20~60份,升温至85~90℃反应2~3h,随后加入小分子二元醇5~10份、亲水扩链剂5~15份、催化剂0.1~0.5份,在50~70℃下反应5~6h,加入封端剂5~15份,在70~75℃反应1~2h,即得到双键封端的水性聚氨酯预聚体;
步骤3:向步骤2获得的水性聚氨酯预聚体中加入丙烯酸酯混合单体1~5份、含氟丙烯酸酯5~10份、引发剂1~5份、有机交联剂1~5份和甲基丙烯酸缩水甘油醚10~15份混合均匀,再加入中和剂5~15份,在40~45℃下反应8~10min成盐,在强烈搅拌下加入去离子水进行乳化,接着在钴60源室中进行辐照聚合2~3h,再依次加入分散剂1~5份、消泡剂1~5份、增粘剂1~5份并在机械搅拌下混合均匀,得到氟硅改性的水性聚氨酯丙烯酸酯复合涂料(FSWPUA)。
步骤1、2中,所述二异氰酸酯为4,4'-二苯基甲烷二异氛酸酯(MDI)、甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、二环已基甲烷二异氰酸酷(HMDI)、1,6-己二异氰酸酯(HDI)中的至少一种;所述催化剂为二月桂酸二丁基锡、辛酸亚锡中的至少一种;所述溶剂为乙酸乙酯、醋酸丁酯、甲苯、二甲苯中的至少一种。
步骤2中,所述多元醇为聚氧化丙烯二元醇、聚四氢呋喃二元醇、聚氧化乙烯二元醇中的至少一种;所述小分子二元醇为1,4-丁二醇、乙二醇、丙二醇中的至少一种;所述亲水扩链剂为二羟甲基丁酸(DMBA)、二羟甲基丙酸(DMPA)中的一种;所述封端剂为甲基丙烯酸羟乙酯、甲基丙烯酸羟加酯中的一种。
步骤3中,所述丙烯酸酯混合单体为甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸中的至少一种;所述含氟丙烯酸酯为甲基丙烯酸六氟丁酯、全氟辛基丙烯酸酯、八氟戊基丙烯酸酯中的至少一种;所述引发剂为过硫酸铵、过硫酸钾、偶氮二异丁氰中的一种;所述有机交联剂为二酸二酰肼、乙二胺、己二胺中的一种;所述中和剂为三乙胺(TEA);所述分散剂为聚丙烯酸钠;所述消泡剂为聚丙烯聚氧乙烯甘油醚;所述增粘剂为松香树脂、氢化松香树脂、萜烯树脂中的至少一种。
有机硅类材料具有稳定性高和憎水性能好等优点,但传统的物理混合会造成有机硅与聚合物的相容性不佳;在聚合物主链原位聚合引入有机硅的添加方法会造成有机硅受主链刚性作用和约束不能发挥明显改性效果。本发明通过原位聚合法引入侧链有机硅(S-TMP)更加有利于发挥有机硅材料的性能。有机氟类聚合物以其独有的耐溶剂性和高疏水性,有机氟中C-F键具有键长短,键能高的特点,同时在成膜的过程中氟原子向表面迁移、富集,赋予有机氟聚合物材料优良的耐水性、耐溶剂性等优点。S-TMP和含氟丙烯酸酯协同改性能够显著提高聚合物的综合性能。
与现有技术相比,本发明的有益效果体现在:
1、本发明公布的一种木器漆用含氟硅水性聚氨酯丙烯酸酯复合涂料,相比现有木器漆干燥迅速,对底材润湿性好,硬度、光泽高,耐水性和耐热烫性优异,并具有良好耐候性。
2、本发明公布的一种木器漆用含氟硅水性聚氨酯丙烯酸酯复合涂料,相比现有木器漆施工灵活,可喷涂、手刷和淋涂等方式。
3、本发明公布的一种木器漆用含氟硅水性聚氨酯丙烯酸酯复合涂料,相比现有木器漆不含游离异氰酸酯以及甲醛、重金属等有害物质更加环保。
具体实施方式
下面结合具体的实施例对本发明技术方案作进一步分析说明,但本实验实施方式不限于此。
实施例1:
1、在氮气氛围下,将脱水后的单羟基封端的聚二甲基硅氧烷10g、异佛尔酮二异氰酸酯10g、乙酸乙酯20g、二月桂酸二丁基锡0.1g份加入反应釜中,在40℃反应6h,将三甲基丙烷(TMP)10g缓慢加入反应釜,在75℃反应5h,蒸发除去溶剂,得到双羟基封端的侧链有机硅(S-TMP)。
2、在氮气氛围下,将脱水后的聚氧化丙烯二元醇15g和步骤(1)中的S-TMP 5g份加入反应釜中,再加入异佛尔酮二异氰酸酯25g,升温到85℃反应2h,加入1,4-丁二醇5g、二羟甲基丁酸5g、二月桂酸二丁基锡0.1g,在70℃下反应6h,加入甲基丙烯酸羟乙酯10g,在75℃反应1h,即得到双键封端的水性聚氨酯预聚体;
3、向水性聚氨酯预聚体中,加入甲基丙烯酸甲酯2g、丙烯酸丁酯3g、甲基丙烯酸六氟丁酯6g、过硫酸钾5g、乙二胺5g和甲基丙烯酸缩水甘油醚10g,再加入三乙胺5g,在45℃反应8min成盐,在强烈搅拌下加入去离子水进行乳化,接着在钴60源室中进行辐照聚合2h,再依次加入聚丙烯酸钠1g、聚丙烯聚氧乙烯甘油醚3g、氢化松香树脂2g并在机械搅拌下混合均匀,得到氟硅改性的水性聚氨酯丙烯酸酯复合涂料。
实施例2:
1、在氮气氛围下,将脱水后的单羟基封端的聚二甲基硅氧烷12g、二环已基甲烷二异氰酸酯12g、醋酸丁酯25g、辛酸亚锡0.2g份加入反应釜中,在40℃反应6h,将三甲基丙烷(TMP)12g缓慢加入反应釜,在75℃反应5h,蒸发除去溶剂,得到双羟基封端的侧链有机硅(S-TMP)。
2、在氮气氛围下,将脱水后的聚四氢呋喃二元醇18g和步骤(1)中的S-TMP 6g份加入反应釜中,再加入二环已基甲烷二异氰酸酯30g,升温到85℃反应3h,加入乙二醇6g、二羟甲基丙酸7g、辛酸亚锡0.2g,在70℃下反应6h,加入甲基丙烯酸羟甲酯12g,即得到双键封端的水性聚氨酯预聚体;
3、向水性聚氨酯预聚体中,加入甲基丙烯酸甲酯3g、丙烯酸2g、全氟辛基丙烯酸酯7g、过硫酸铵5g、己二胺5g和甲基丙烯酸缩水甘油醚12g,再加入三乙胺7g,在45℃反应8min成盐,在强烈搅拌下加入去离子水进行乳化,接着在钴60源室中进行辐照聚合2h,再依次加入聚丙烯酸钠2g、聚丙烯聚氧乙烯甘油醚2g、松香树脂3g并在机械搅拌下混合均匀,得到氟硅改性的水性聚氨酯丙烯酸酯复合涂料。
实施例3:
1、在氮气氛围下,将脱水后的单羟基封端的聚二甲基硅氧烷20g、1,6-己二异氰酸酯20g、甲苯40g、辛酸亚锡0.4g加入反应釜中,在40℃反应6h,将三甲基丙烷(TMP)20g缓慢加入,在75℃反应5h,蒸发除去溶剂,得到双羟基封端的侧链有机硅(S-TMP)。
2、在氮气氛围下,将脱水后的聚氧化乙烯二元醇20g和步骤(1)中的S-TMP 10g份加入反应釜中,再加入1,6-己二异氰酸酯35g,升温到85℃反应3h,加入丙二醇6g、二羟甲基丁酸8g、辛酸亚锡0.1g,在70℃下反应6h,加入甲基丙烯酸羟甲酯15g,即得到双键封端的水性聚氨酯预聚体;
3、向水性聚氨酯预聚体中,加入丙烯酸丁酯3g、丙烯酸2g、八氟戊基丙烯酸酯8g、过硫酸钾6g、乙二胺5g和甲基丙烯酸缩水甘油醚15g,在75℃反应1h,再加入三乙胺8g,在45℃反应8min成盐,在强烈搅拌下加入去离子水进行乳化,接着在钴60源室中进行辐照聚合2h,再依次加入聚丙烯酸钠3g、聚丙烯聚氧乙烯甘油醚1g、萜烯树脂4g并在机械搅拌下混合均匀,得到氟硅改性的水性聚氨酯丙烯酸酯复合涂料。
对照例1:
本对照例是参照实施实例1,只是未添加S-TMP和含氟丙烯酸酯,其他的原料比例和种类不变,可以得到水性聚氨酯丙烯酸酯复合涂料。
对照例2:
本对照例是参照实施实例2,只是未添加S-TMP和含氟丙烯酸酯,其他的原料比例和种类不变,可以得到水性聚氨酯丙烯酸酯复合涂料。
对照例3:
本对照例是参照实施实例3,只是未添加S-TMP和含氟丙烯酸酯,其他的原料比例和种类不变,可以得到水性聚氨酯丙烯酸酯复合涂料。
表1是实施例1~3和对照例1~3制得的水性聚氨酯丙烯酸酯复合涂料的性能测试,可以看出相较与对照例,改性后的复合涂料在不影响光泽度和机械稳定性的同时冻融稳定性、附着力和耐水性能都有显著提高。
表1本发明中木器漆用含氟硅水性聚氨酯丙烯酸酯复合涂料测试结果
Figure BDA0003001133110000051

Claims (7)

1.一种木器漆用含氟硅水性聚氨酯丙烯酸酯复合涂料的制备方法,其特征在于包括如下步骤:
步骤1:在氮气氛围下,将脱水后的单羟基封端的聚二甲基硅氧烷、二异氰酸酯、溶剂、催化剂加入反应釜中,在40~45℃下反应5~6h,随后将三甲基丙烷缓慢加入,在75~80℃下反应4~5h,蒸发除去溶剂,得到双羟基封端的侧链有机硅S-TMP;
步骤2:在氮气氛围下,将脱水后的多元醇和步骤1获得的S-TMP加入反应釜中,再加入二异氰酸酯,升温至85~90℃反应2~3h,随后加入小分子二元醇、亲水扩链剂、催化剂,在50~70℃下反应5~6h,加入封端剂,在70~75℃反应1~2h,即得到双键封端的水性聚氨酯预聚体;
步骤3:向步骤2获得的水性聚氨酯预聚体中加入丙烯酸酯混合单体1~5份、含氟丙烯酸酯5~10份、引发剂1~5份、有机交联剂1~5份和甲基丙烯酸缩水甘油醚10~15份混合均匀,再加入中和剂5~15份,在40~45℃下反应8~10min成盐,在强烈搅拌下加入去离子水进行乳化,接着在钴60源室中进行辐照聚合2~3h,再依次加入分散剂1~5份、消泡剂1~5份、增粘剂1~5份并在机械搅拌下混合均匀,得到氟硅改性的水性聚氨酯丙烯酸酯复合涂料FSWPUA。
2.根据权利要求1所述的制备方法,其特征在于:
步骤1、2中,所述二异氰酸酯为4,4'-二苯基甲烷二异氛酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二环已基甲烷二异氰酸酷、1,6-己二异氰酸酯中的至少一种;所述催化剂为二月桂酸二丁基锡、辛酸亚锡中的至少一种。
3.根据权利要求1或2所述的制备方法,其特征在于:
步骤1中,各组分的添加量按质量份数为:单羟基封端的聚二甲基硅氧烷10~20份,二异氰酸酯10~20份,溶剂20~30份,催化剂0.1~0.5份,三甲基丙烷10~20份。
4.根据权利要求1所述的制备方法,其特征在于:
步骤2中,所述多元醇为聚氧化丙烯二元醇、聚四氢呋喃二元醇、聚氧化乙烯二元醇中的至少一种;所述小分子二元醇为1,4-丁二醇、乙二醇、丙二醇中的至少一种;所述亲水扩链剂为二羟甲基丁酸、二羟甲基丙酸中的一种;所述封端剂为甲基丙烯酸羟乙酯、甲基丙烯酸羟加酯中的一种。
5.根据权利要求1或4所述的制备方法,其特征在于:
步骤2中,各组分的添加量按质量份数为:多元醇10~30份,步骤1获得的S-TMP 5~10份,二异氰酸酯20~60份,小分子二元醇5~10份,亲水扩链剂5~15份,催化剂0.1~0.5份,封端剂5~15份。
6.根据权利要求1所述的制备方法,其特征在于:
步骤3中,所述丙烯酸酯混合单体为甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸中的至少一种;所述含氟丙烯酸酯为甲基丙烯酸六氟丁酯、全氟辛基丙烯酸酯、八氟戊基丙烯酸酯中的至少一种;所述引发剂为过硫酸铵、过硫酸钾、偶氮二异丁氰中的一种;所述有机交联剂为二酸二酰肼、乙二胺、己二胺中的一种;所述中和剂为三乙胺;所述分散剂为聚丙烯酸钠;所述消泡剂为聚丙烯聚氧乙烯甘油醚;所述增粘剂为松香树脂、氢化松香树脂、萜烯树脂中的至少一种。
7.根据权利要求1或6所述的制备方法,其特征在于:
步骤3中,各组分的添加量按质量份数为:丙烯酸酯混合单体1~5份,含氟丙烯酸酯5~10份,引发剂1~5份,有机交联剂1~5份,甲基丙烯酸缩水甘油醚10~15,中和剂5~15份,分散剂1~5份,消泡剂1~5份,增粘剂1~5份。
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