CN111892694B - 一种水性聚氨酯用外交联剂及其制备方法与应用 - Google Patents
一种水性聚氨酯用外交联剂及其制备方法与应用 Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
本发明涉及一种水性聚氨酯用外交联剂的制备方法,采用咪唑离子液体改性的端羟基聚醚和多异氰酸酯作为原材料,在催化剂的作用下发生加聚反应,最终制得水性聚氨酯用外交联剂。本发明制备的水性聚氨酯用外交联剂,同时具备非离子与离子型亲水基团,水溶性好,可显著提高PU胶膜的耐水性、耐溶剂性以及力学强度,且交联后的涂层不发粘。
Description
技术领域
本发明涉及涂料技术领域,具体涉及一种水性聚氨酯用外交联剂及其制备方法与应用。
背景技术
聚氨酯(PU)既有橡胶的弹性,又有塑料优异的加工性能,在隔热、隔音、耐磨、耐油、弹性等方面有其它合成材料无法比拟的优点,是继聚乙烯、聚氯乙烯、聚丙烯、聚苯乙烯和ABS后第六大塑料。传统的溶剂型聚氨酯涂料性能虽高但在使用过程中向空气中散发挥发性有机物(VOC)污染空气且大部分会对人的健康造成危害。随着人们环保意识的提高和国家环境保护法规的日益严格,水性聚氨酯由于具有低的挥发性,越来越得到人们的青睐。
水性聚氨酯涂料分为单组份和双组分。单组分水性聚氨酯涂料中聚合物的相对分子量较大,依靠水分的挥发成膜,具有施工方便的优点。但是,单组分水性聚氨酯涂料的耐化学品性、耐溶剂性欠佳,硬度和光泽较低。因此需对水性PU体系进行交联改性,大致分为外交联和内交联,而对于大多数单组分水性聚氨酯体系,内交联程度如果太大,乳液将不稳定,仅仅通过内交联改性难以使涂膜的耐水、耐湿擦等性能有很大的改善。因此开发外交联剂成为研发的一个重要方向。
目前常见的外交联剂有环氧类交联剂、氮丙啶类交联剂、醛类交联剂、聚碳化二亚胺类交联剂和多异氰酸酯类交联剂五大类。其中,由于异氰酸酯(-NCO)基团对含有活泼氢原子的化合物具有非常高的反应性,以多异氰酸酯作为外交联剂,具有交联速度快、效率高,能够显著增强涂层的耐水性、耐溶剂性和力学性能等优良特点。然而普通的多异氰酸酯是亲油疏水的,难与水性体系均匀混合,容易在水性体系中发生相分离,也难以应用于水性PU中。因此开发可水分散多异氰酸酯作为水性PU的外交联剂成为了近年来国内外研究的热点。
水分散多异氰酸酯可以大致分为两类:非离子型和离子型。非离子型改性多异氰酸酯一般采用聚醚(如聚乙二醇单醚等)进行亲水改性,虽然这种交联剂在大多数应用领域得到了市场的广泛认可,但是其也存在很多缺点:由于聚醚带来的亲水性有限,需要使用大量的聚醚才能赋予聚异氰酸酯较好的水分散性能,这极大地降低了聚异氰酸酯体系中的-NCO浓度,致使产品的NCO含量太低达不到足够的交联度,并且大量的聚醚链段引入到聚氨酯胶膜中,还会对胶膜的耐水性造成一定的负面影响。虽然人们针对这些问题提出过一些解决方案,但非离子改性中起主要亲水作用的聚醚链段和离子基团在亲水作用上相比,还是有着本质上的劣势。
为了克服上述缺陷,研究人员通过引入亲水的离子基团来实现异氰酸酯的亲水改性,如羟基磺酸或盐、氨基磺酸盐等也被用来改性异氰酸酯,但磺酸盐会导致聚氨酯的颜色明显发黄,妨碍了这些产品作为交联组分应用于优质涂料体系。
另一方面,近年来,离子液体(IL)因可回收、高热稳定性、可设计性、强极性以及良好的生物相容性等独特性能,而广泛应用于电化学、有机合成、化工分离、材料制备等领域。IL是一种由离子组成的而且在低温(<100℃)下呈液态的盐,因此有时也称之为低温熔融盐。与一般的高温熔融态盐类化合物相似,通常是由有机阳离子和无机阴离子构成。与常规液体相比,由于液态和离子性的双重特点使IL 展现出独特的物理化学性质,是一类新型介质或“软”功能材料。利用离子液体改性的聚醚与多异氰酸酯亲核加聚反应制备的水基异氰酸酯交联剂,可在赋予多异氰酸酯交联剂良好亲水性的同时,带来离子强度方面的显著变化。
发明内容
为了改善传统水性聚氨酯涂饰材料因交联不足、亲水基团较多而在机械性能、耐水、耐溶剂性能等方面的缺陷。本发明提供了一种水性聚氨酯用外交联剂,采用含有咪唑离子液体的端羟基聚醚来改性多异氰酸酯,同时含有可解离的咪唑盐离子基团与聚乙二醇(EO)链段,降低交联剂分子中EO链段含量,同时赋予其较大的离子强度和良好的水溶性;同时还提供了该水性聚氨酯用外交联剂的制备方法,原料易寻成本低,工艺简单;最后该水性交联剂可作为环保水性PU树脂材料或其它丙烯酸等水性树脂涂层材料的外用交联剂。
本发明的技术方案如下:
一种水性聚氨酯用外交联剂,结构示意式如(I)所示:
(I)
式中X为氯或溴,n为1-20,R为多异氰酸酯。
上述水性聚氨酯用外交联剂,原料包括:多异氰酸酯、咪唑离子液体改性端羟基聚醚、催化剂、溶剂;
所述的多异氰酸酯为六亚甲基二异氰酸酯HDI缩二脲、HDI三聚体、异氟尔酮二异氰酸酯IPDI三聚体中的一种或几种的组合;
所述的多异氰酸酯的化学结构式如下:
HDI缩二脲
HDI三聚体
IPDI三聚体;
所述的咪唑离子液体改性端羟基聚醚的制备方法为:N-甲基咪唑、单卤代聚乙二醇、乙腈,在N2保护下反应,后洗涤获得。
所述的催化剂为辛酸亚锡、辛酸钴、辛酸铁、二月桂酸二丁基锡中的一种。
所述的溶剂为丙酮、N-甲基吡咯烷酮、二丙二醇二甲醚中的一种。
所述的咪唑离子液体改性端羟基聚醚,结构如式(II)所示:
(II)
式中X为氯或者溴,n为1-20。
所述的催化剂用量为多异氰酸酯和咪唑离子液体改性端羟基聚醚总质量的0.01%~0.2%。
所述的多异氰酸酯的异氰酸酯根(-NCO)与咪唑离子液体改性端羟基聚醚羟基(-OH)的摩尔比为70~10:1。
所述的水性聚氨酯用外交联剂,固含为50-90%,NCO含量为7-20 wt%。
上述水性聚氨酯用外交联剂的制备方法,包括以下步骤:
(1)咪唑离子液体改性端羟基聚醚干燥脱水;
(2)向步骤(1)的咪唑离子液体改性端羟基聚醚中加入多异氰酸酯,混合均匀;
(3)向步骤(2)中加入催化剂,反应,再继续保温反应,得到水性聚氨酯用外交联剂初品;
(4)初品冷却至40℃以下,加入溶剂稀释,即得水性聚氨酯用外交联剂。
所述的步骤(3)的反应温度为50~90℃;反应时间为2h;再保温反应时间为0.5~1h。
上述水性聚氨酯用外交联剂在PU膜上的应用。
上述应用的方法为:将水性聚氨酯用外交联剂加入到聚氨酯中搅拌均匀,室温晾晒后烘干。
本发明的有益效果:
(1)良好的水溶性
传统聚醚改性多异氰酸酯属于非离子亲水改性范畴,水分散性不足,耐水性不佳,与离子化亲水改性相比,存在本质上的劣性,因此为了获得良好水溶性,需要引入大量的聚醚(EO)链段,这样又会消耗多异氰酸酯中大量-NCO基团,导致聚醚改性多异氰酸酯-NCO含量偏低,交联效果不理想,且过多醚键链段进入PU涂膜中,易造成PU涂膜发粘,而现有氨基或羟基磺酸盐离子亲水化合物改性多异氰酸酯易导致涂层颜色变黄。本发明采用含有咪唑离子液体的端羟基聚醚来改性多异氰酸酯,兼具离子与非离子改性多异氰酸酯的优点,交联剂分子链中同时含有可解离的咪唑盐离子基团与聚乙二醇(EO)链段,咪唑盐离子基团的引入降低了交联剂分子中EO链段含量,同时又赋予其较大的离子强度和良好的水溶性。
(2)综合性能好
离子液体改性的聚醚-多异氰酸酯亲水交联剂,因具有较高的离子强度,良好的亲水性,较高的-NCO含量,使得其交联的水性聚氨酯涂层不发粘,并且较强离子键作用增强了PU分子链间的分子作用力,使得交联的PU具备较强的力学强度,良好的耐水、耐溶剂及耐热等综合性能。
附图说明
图1不同交联剂用量下制备的交联PU膜的外观图;
图2 空白及交联PU膜在水中浸泡24h后的外观图(交联剂用量从左至右:0、0.5%、1%,1.5%、2%、2.5%、3%);
图3 空白及交联PU膜在0.05M NaOH中浸泡24h后的外观图(交联剂用量从左至右:0、0.5%、1%,1.5%、2%、2.5%、3%);
图4 空白及交联PU膜在甲苯溶液中浸泡24后的外观图(交联剂用量从左至右:0、0.5%、1%,1.5%、2%、2.5%、3%);
图5 空白及交联PU膜的拉伸强度及断裂伸长率的变化趋势图。
具体实施方式
实施例1
向三口瓶中加入0.25mol的N-甲基咪唑,0.22mol单氯代一缩二乙二醇,50ml乙腈。氮气保护80℃下反应96h,停止反应后体系呈淡黄色液体。分别用丙酮,乙酸乙酯,乙醚洗涤。洗涤几次后真空干燥。得产物,密封保存(结构如下所示):
按-NCO/-OH摩尔比50:1,分别称取上面制备的咪唑离子液体改性端羟基聚醚,HDI三聚体;将改性聚醚加入洁净干燥的三口瓶中,装好搅拌器和温度计,并通氮气保护,加入HDI三聚体,搅拌均匀后,加入聚醚及多异氰酸酯总质量0.02%的辛酸亚锡,加热(加热速度≤5℃/min),升温至60℃,保温2h,再保温反应时间0.5h,冷却至40℃以下,加入适量丙酮溶剂稀释,即得一种固含量为80%、NCO含量为16%的离子-非离子型水性HDI聚氨酯用外交联剂。
其中制备的咪唑离子液体改性聚醚在使用前在90-95℃,真空度≥0.09 MPa 的条件下脱水3h;溶剂使用前已采用4A分子筛脱水处理。
实施例2
向三口瓶中加入0.25mol的N-甲基咪唑,0.21mol的单溴代聚乙二醇(M=300),100ml乙腈。氮气保护80℃下反应96小时,停止反应后体系呈淡黄色液体。分别用丙酮,乙酸乙酯,乙醚洗涤。洗涤几次后真空干燥,得产物,密封保存(结构如下所示):
按-NCO/-OH摩尔比20:1,分别称取上面制备的咪唑离子液体改性端羟基聚醚,HDI缩二脲,将改性聚醚加入洁净干燥的三口瓶中,装好搅拌器和温度计,并通氮气保护,加入HDI缩二脲,搅拌均匀后,加入聚醚及多异氰酸酯总质量0.05%的辛酸亚锡,加热(加热速度≤5℃/min),升温至80℃,保温2h,再保温反应时间0.5h,冷却至40℃以下,加入N-甲基吡咯烷酮溶剂稀释,即得一种固含量为70%、NCO含量为13%的离子-非离子型水性HDI聚氨酯用外交联剂。
其中制备的咪唑离子液体改性聚醚在使用前在90-95℃,真空度≥0.09 MPa 的条件下脱水3h;溶剂使用前已采用4A分子筛脱水处理。
实施例3
向三口瓶中加入0.25mol的N-甲基咪唑,0.2mol的单氯代聚乙二醇(M=400),100ml乙腈。氮气保护80℃下反应96小时,停止反应后体系呈淡黄色液体。分别用丙酮,乙酸乙酯,乙醚洗涤。洗涤几次后真空干燥,得产物,密封保存(结构如下所示):
按-NCO/-OH摩尔比60:1,分别称取上面制备的咪唑离子液体改性端羟基聚醚、HDI三聚体,将改性聚醚加入洁净干燥的三口瓶中,装好搅拌器和温度计,并通氮气保护,加入HDI三聚体,搅拌均匀后,加入聚醚及多异氰酸酯总质量0.1%的二月桂酸二丁基锡,加热(加热速度≤5℃/min),升温至70℃,保温2h, 再保温反应时间0.5h,冷却至40℃以下,加入丙酮溶剂稀释,即得一种固含量为90%、NCO含量为20%的离子-非离子型水性HDI聚氨酯用外交联剂。
其中制备的咪唑离子液体改性聚醚在使用前在90-95℃,真空度≥0.09 MPa 的条件下脱水3h;溶剂使用前已采用4A分子筛脱水处理。
实施例4
向三口瓶中加入0.25mol的N-甲基咪唑,0.2mol的单氯代聚乙二醇(M=600),100ml乙腈。氮气保护80℃下反应96小时,停止反应后体系呈淡黄色液体。分别用丙酮,乙酸乙酯,乙醚洗涤。洗涤几次后真空干燥,得产物,密封保存(结构如下所示):
按-NCO/-OH摩尔比10:1,分别称取上面制备的咪唑离子液体改性端羟基聚醚、HDI三聚体,将改性聚醚加入洁净干燥的三口瓶中,装好搅拌器和温度计,并通氮气保护,加入HDI三聚体,搅拌均匀后,加入聚醚及多异氰酸酯总质量0.1%的二月桂酸二丁基锡,加热(加热速度≤5℃/min),升温至70℃,保温2h, 再保温反应时间0.5h,冷却至40℃以下,加入丙酮溶剂稀释,即得一种固含量为90%、NCO含量为12%的离子-非离子型水性HDI聚氨酯用外交联剂。
其中制备的咪唑离子液体改性聚醚在使用前在90-95℃,,真空度≥0.09 MPa 的条件下脱水3h;溶剂使用前已采用4A分子筛脱水处理。
实施例5
向三口瓶中加入0.25mol的N-甲基咪唑,0.19mol单氯代聚乙二醇(M=700),100ml乙腈。氮气保护80℃下反应96小时,停止反应后体系呈淡黄色液体。分别用丙酮,乙酸乙酯,乙醚洗涤。真空干燥,得产物,密封保存(结构如下所示):
按-NCO/-OH摩尔比70:1,分别称取上面制备的咪唑离子液体改性端羟基聚醚、IPDI三聚体,将改性聚醚加入洁净干燥的三口瓶中,装好搅拌器和温度计,并通氮气保护,加入IPDI三聚体及HDI三聚体(摩尔比为1:1),搅拌均匀后,加入聚醚及多异氰酸酯总质量0.2%的辛酸铁,加热(加热速度≤5℃/min),升温至90℃,保温2h,再保温反应时间1h,冷却至40℃以下,加入二丙二醇二甲醚溶剂稀释,即得一种固含量为50%、-NCO含量为8%的离子-非离子型水性IPDI聚氨酯用外交联剂。
其中制备的咪唑离子液体改性聚醚在使用前在90-95℃,真空度≥0.09 MPa 的条件下脱水3h;溶剂使用前已采用4A分子筛脱水处理。
实施效果例
为了进一步说明本发明的有益效果,对实施例3制备的HDI型水性聚氨酯用外交联剂的交联效果进行评价,其中交联PU膜的制备,PU膜的耐水、耐碱、耐溶剂性及力学强度的测试方法如下:
①交联PU膜的制备
取7份相同质量的市售脂肪族水性聚氨酯,向其中分别加入聚氨酯重(wt%)0,0.5%,1%,1.5%,2%,2.5%,3%的交联剂,搅拌均匀,倒入四氟乙烯板中室温晾干2d后,再放入80℃烘箱烘干4h,取出干燥器中冷却至室温。
②力学性能测试
用哑铃型模具从交联PU膜上裁取,得到哑铃状试样,经过空气调节后,按照标准操作方法,用定重式测厚仪测量试样的厚度,测量点至少有三处并取平均值,并在XDL型多功能拉力机上进行测试,测试方法如下:
式中:
α—拉伸强度/Mpa;F—试样所受作用力/N;b—试样工作部分的厚度/mm;d—试样工作部分的宽度/mm。
断裂伸长率:
式中:β—扯断伸长率/%;L—试样扯断时的标距/mm;L0—试样初始标距/mm。
③耐水性测试
用直径为1.5 cm的打孔器在交联PU膜上进行打孔,得到直径为1.5 cm的圆形试样,将试样置于真空烘箱中烘干至恒重,称其质量m0;把试样放置蒸馏水中,浸泡24 h,到规定时间后取出并用滤纸快速拭干表面水分,称其质量m1,观察试样的溶胀情况。计算公式如下:
式中:δ—试样的吸水率;m0—试样吸水前的质量/g;m1—试样吸水后的质量/g。
④耐碱性测试
配置浓度为0.05 mol/L 的NaOH溶液,用直径为1.5 cm的打孔器在PU胶膜上进行打孔,得到直径为1.5 cm的圆形试样,将试样置于真空烘箱中烘干至恒重,称其质量m0;把试样放置0.05 mol/L的NaOH溶液中,浸泡24 h,到规定时间后取出并用滤纸快速拭干表面水分,称其质量m1,观察试样的溶胀情况。计算公式如下:
式中:ω—试样的吸碱率;m0—试样吸收0.05 mol/L NaOH 溶液前的质量/g;m1—试样吸收0.05 mol/L NaOH 溶液后的质量/g。
⑤耐有机溶剂测试
用直径为1.5 cm的打孔器在PU胶膜上进行打孔,得到直径为1.5 cm的圆形试样,置于真空干燥箱中烘干至恒重,称其质量m0,把试样放入甲苯中浸泡24 h,到规定时间后取出试样并用滤纸拭干表面甲苯后称其重量m1,观察试样的溶胀情况。
式中:Z—试样的吸甲苯率;m0—试样吸甲苯前的质量/g;m1—试样吸甲苯后的质量/g。
图1为不同交联剂用量下交联PU膜的外观,由图可知,交联前后PU膜的光泽度未发生明显变化,没有黄变现象,说明本发明制备的咪唑离子液体改性聚醚-多异氰酸酯类交联剂具有良好的保光性。
图2、图3、图4分别是交联前后交联PU膜分别在水、0.05M NaOH、甲苯等溶液中浸泡24h后的外观。由于水性聚氨酯自身含有亲水基团,分子链间缺乏交联,导致不耐水、碱、溶剂的固有缺陷,交联前后的水性PU膜均发生了一定程度的溶胀,其吸水率、吸碱率及吸甲苯率列于表1。由表1可知,未交联的水性PU胶膜吸水率较高在37%附近,当改性交联剂用量在2%时即可将PU胶膜吸水率控制在4%左右,同时吸减率、吸甲苯率分别从未交联前的260%、393%降低到3%、130%左右,再继续增加交联剂的用量,PU胶膜吸水率、吸碱率及吸甲苯率虽有所下降,但下降幅度并不明显,表明2%的交联剂即可显著改善水性PU胶膜的耐水、耐碱及耐溶剂性能。
表1 .交联前后PU膜的吸水率、吸碱率表、吸甲苯率
图5反映了交联前后PU胶膜的力学性能变化,由图可知未经交联的PU胶膜拉伸强度在3.5MPa,加入交联剂改性后,PU胶膜的拉伸强度均有不同程度的提升,在 3%时胶膜的拉伸强度接近于8MPa。这是因为本发明的交联剂中含有-NCO基团,在PU胶膜的固化过程中,进一步与PU分子链内及分子链间的氨基甲酸酯键上的活泼氢反应,形成次级交联,显著增加了PU膜的力学强度。
对比例1
按-NCO/-OH摩尔比60:1,分别称取聚乙二醇单甲醚(MPEG,M=350)、HDI三聚体,将聚醚加入洁净干燥的三口瓶中,装好搅拌器和温度计,并通氮气保护,加入HDI三聚体,搅拌均匀后,加入聚醚及多异氰酸酯总质量0.1%的二月桂酸二丁基锡,加热(加热速度≤5℃/min),升温至70℃,保温2h, 再保温反应时间0.5h,冷却至40℃以下,加入丙酮溶剂稀释,即得一种固含量为90%、NCO含量为19%的非离子型水性HDI聚氨酯用外交联剂。
对比例2
按-NCO/-OH摩尔比10:1,分别称取聚乙二醇单甲醚(MPEG,M=550)、HDI三聚体,将聚醚加入洁净干燥的三口瓶中,装好搅拌器和温度计,并通氮气保护,加入HDI三聚体,搅拌均匀后,加入聚醚及多异氰酸酯总质量0.1%的二月桂酸二丁基锡,加热(加热速度≤5℃/min),升温至70℃,保温2h, 再保温反应时间1h,冷却至40℃以下,加入丙酮溶剂稀释,即得一种固含量为90%、NCO含量为14%的非离子型水性HDI聚氨酯用外交联剂。
取2份相同质量的市售脂肪族水性聚氨酯,向其中分别加入聚氨酯重2wt%的对比例1及对比例2制备的交联剂, 其交联膜的制备、力学性能、耐水、耐碱及耐溶剂性能测试同效果例中的方法,其结果如表2所示。有表2可知,对比例交联后的PU膜拉伸强度、耐水、耐碱、耐溶剂性能均有明显提升,但是与效果例同样采用2%的改性交联剂相比,其拉伸强度、耐水、耐碱、耐溶剂性能提升有限,没有后者的交联效果突出(见图5及表1,2%改性交联剂用量下,PU膜的拉伸强度、断裂伸长率,吸水率、吸碱率、吸甲苯率分别为7.4MPa、480%、4.32%、3.66%、129.90%)。这可能是由于咪唑离子液体聚醚中阴阳离子对的强离子键作用力,增强了PU胶膜的分子链间作用力,导致膜的力学性能及其它耐水、耐碱、耐溶剂性能的提升。
表2. 对比例交联后PU膜的吸水率、吸碱率表、吸甲苯率
Claims (7)
3.根据权利要求1所述的水性聚氨酯用外交联剂,其特征在于,所述的水性聚氨酯用外交联剂,固含为50-90%,NCO含量为7-20 wt%。
4.权利要求1所述的水性聚氨酯用外交联剂的制备方法,其特征在于,包括以下步骤:
(1)咪唑离子液体改性端羟基聚醚干燥脱水;
(2)向步骤(1)的咪唑离子液体改性端羟基聚醚中加入多异氰酸酯,混合均匀;
(3)向步骤(2)中加入催化剂,反应,再继续保温反应,得到水性聚氨酯用外交联剂初品;
(4)初品冷却至40℃以下,加入溶剂稀释,即得水性聚氨酯用外交联剂。
5.根据权利要求4所述的水性聚氨酯用外交联剂的制备方法,其特征在于,所述的步骤(3)的反应温度为50~90℃;反应时间为2h;再保温反应时间为0.5~1h。
6.采用权利要求5所述的制备方法制备的水性聚氨酯用外交联剂在PU膜上的应用。
7.根据权要求6所述的应用,其特征在于,方法为:将水性聚氨酯用外交联剂加入到聚氨酯中搅拌均匀,室温晾晒后烘干。
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