CN112266460A - 一种热固性聚氨酯及其制备方法 - Google Patents
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Abstract
本发明公开了一种热固性聚氨酯,其特征在于:包括以下成份,聚氧化丙烯二醇50‑100份,异佛尔酮二异氰酸酯10‑30份,二羟甲基丙酸1‑5份,1‑2丙二醇1‑5份,催化剂0.5份,三乙胺1‑5份,去离子水200‑250份以及酮肼交联单体5‑20份,并提供了该热固性聚氨酯的制备方法。靠分子交联形成网状结构,制备用于织物的产品具有刚性大、硬度高、耐温高、不易燃、制品尺寸稳定性好,耐水性能优异。
Description
技术领域
本发明属于聚氨酯技术领域,具体涉及一种热固性聚氨酯及其制备方法。
背景技术
热固性树脂其分子结构为体型,指在加热、加压下或在固化剂、紫外光作用下,进行化学反应,交联固化成为不溶不熔物质的一大类合成树脂。这种树脂在固化前一般为分子量不高的固体或粘稠液体;在成型过程中能软化或流动,具有可塑性,可制成一定形状,同时又发生化学反应而交联固化;有时放出一些副产物,如水等。此反应是不可逆的,一经固化,再加压加热也不可能再度软化或流动;温度过高,则分解或碳化。这也就是与热塑性树脂的基本区别。
聚氨酯是最重要的聚合材料之一,具有独特的优点,如密度低、导热系数小、透湿性好、力学性能优异、化学稳定性好等。自80年前,Bayer等人通过异氰酸酯与多元醇组分的聚合反应得到聚氨酯以来,聚氨酯工业迅猛发展。其产品家族贯穿热塑性材料和热固性材料,在日常生活中得到广泛应用,如泡沫、弹性体、胶黏剂和涂料等。
国内,水性聚氨酯树脂的热固性主要还是通过异氰酸酯基团的交联、氮丙啶与羧基的交联、硅氧烷基团的水解缩聚交联以及基于Michael加成反应的交联。异氰酸酯基团和氮丙啶的交联以双组份为主,用封闭型的异氰酸酯会使得交联所需的温度很高,不利于树脂的普遍推广。硅氧烷基团的水解缩聚的缺点是硅氧烷加入量不能太多,否则体系不稳定。
由于热固性塑料的优良特性,所以热固性聚氨酯也具有很大的工业和商业需求,随着工业生产的不断优化,对于热固性聚氨酯本身以及其生产工艺进行了优化设计。
发明内容
本发明的目的在于提供一种超高硬度丙烯酸树脂的制备方法投入使用,以解决上述背景技术中提出的问题。
为实现上述目的,本发明公开了一种热固性聚氨酯,包括以下成份,
聚氧化丙烯二醇50-100份,异佛尔酮二异氰酸酯10-30份,二羟甲基丙酸1-5份,1-2丙二醇1-5份,催化剂0.5份,三乙胺1-5份,去离子水200-250份以及酮肼交联单体5-20份。
还公开了热固性聚氨酯的制备方法,其特征在于:包括以下步骤,
S1、利用至少含一个胺基和至少一个羟基的物质和DAAM通过Michael加成反应制得酮肼交联单体,再添加计量的去离子水制得酮肼交联单体水溶液;
S2、按5:1的比例称取多元醇和异氰酸酯加入反应釜中,保持温度在85-100℃条件下反应2h;
S3、再加入适量的丙酮、DMPA(2,2-二羟甲基丙酸)、小分子扩链剂和/或内交联剂,保持在70-80度反应1h;
S4、控制反应釜温度在40-45摄氏度,加入磺酸盐,继续反应0.5h后加入三乙胺中和;
S5、再启动反应釜乳化机构,高速搅拌条件下加入去离子水120g分散乳化10min;
S6、最后滴加计量S1步骤中制备的酮肼交联单体水溶液,去丙酮后加入ADH即得。
优选的,所述S1步骤中的至少含一个胺基和至少一个羟基的物质为DETA(二乙烯三胺)。
优选的,所述小分子扩链剂和内交联剂为TMP(三羟甲基丙烷)、蓖麻油和N303的一种或多种。
优选的,所述的多元醇包括聚氧化丙烯二醇、聚己二酸乙二醇酯、聚己内酯、端羟基聚丁二烯、聚四亚甲基醚二醇、聚乙二醇、丙乙醇中的至少一种或多种。
优选的,所述S6步骤中去除丙酮的方法为减压蒸煮。
本发明的技术效果和优点:该热固性聚氨酯及其制备方法,
1、该热固性聚氨酯在固化后,由于分子间交联,形成网状结构,因此刚性大、硬度高、耐温高、不易燃、制品尺寸稳定性好,制品尺寸稳定性好,以及优异的耐水性能。
2、并公开了该热固性聚氨酯的制备方法,无需过高的交联反应温度,适用性更强,工艺优化相对简单,适合推广使用。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明公开了一种热固性聚氨酯,包括以下成份,
聚氧化丙烯二醇50-100份,异佛尔酮二异氰酸酯10-30份,二羟甲基丙酸1-5份,1-2丙二醇1-5份,催化剂0.5份,三乙胺1-5份,去离子水200-250份以及酮肼交联单体5-20份。
该热固性聚氨酯在固化后,由于分子间交联,形成网状结构,因此刚性大、硬度高、耐温高、不易燃、制品尺寸稳定性好。
还公开了热固性聚氨酯的制备方法,包括以下步骤,
S1、利用至少含一个胺基和至少一个羟基的物质和DAAM通过Michael加成反应制得酮肼交联单体,再添加计量的去离子水制得酮肼交联单体水溶液;
S2、按5:1的比例称取多元醇和异氰酸酯加入反应釜中,保持温度在85-100℃条件下反应2h;
S3、再加入适量的丙酮、DMPA(2,2-二羟甲基丙酸)、小分子扩链剂和/或内交联剂,保持在70-80度反应1h;
S4、控制反应釜温度在40-45摄氏度,加入磺酸盐,继续反应0.5h后加入三乙胺中和;
S5、再启动反应釜乳化机构,高速搅拌条件下加入去离子水120g分散乳化10min;
S6、最后滴加计量S1步骤中制备的酮肼交联单体水溶液,去丙酮后加入ADH即得。
现将20gDETA,32gDAAM加入三口烧瓶中,在45℃条件下反应5h后,加入计量的去离子水制得酮肼交联单体水溶液;
将100g聚氧化丙烯二醇、20g异氰酸酯加入反应釜中,在85-90℃条件下反应2h;
然后加入亲水性扩链剂二羟甲基丙酸2g及1-2丙二醇0.6g,反应1h;
然后加入辛酸亚锡0.3g并保温3.5h后,在45℃加入2g磺酸盐,继续反应0.5h;
再后加入2g三乙胺中和,高速搅拌条件下加入去离子水120g分散乳化10min,并滴加计量酮肼交联单体水溶液,减压脱丙酮,加入2gADH即得所需乳液
所述S1步骤中的至少含一个胺基和至少一个羟基的物质为DETA(二乙烯三胺)。
所述小分子扩链剂和内交联剂为TMP(三羟甲基丙烷)、蓖麻油和N303的一种或多种。
所述的多元醇包括聚氧化丙烯二醇、聚己二酸乙二醇酯、聚己内酯、端羟基聚丁二烯、聚四亚甲基醚二醇、聚乙二醇、丙乙醇中的至少一种或多种。
所述S6步骤中去除丙酮的方法为减压蒸煮。
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种热固性聚氨酯,其特征在于:包括以下成份,
聚氧化丙烯二醇50-100份,异佛尔酮二异氰酸酯10-30份,二羟甲基丙酸1-5份,1-2丙二醇1-5份,催化剂0.5份,三乙胺1-5份,去离子水200-250份以及酮肼交联单体5-20份。
2.一种如权利要求1所述的热固性聚氨酯的制备方法,其特征在于:包括以下步骤,
S1、利用至少含一个胺基和至少一个羟基的物质和DAAM通过Michael加成反应制得酮肼交联单体,再添加计量的去离子水制得酮肼交联单体水溶液;
S2、按5:1的比例称取多元醇和异氰酸酯加入反应釜中,保持温度在85-100℃条件下反应2h;
S3、再加入适量的丙酮、DMPA(2,2-二羟甲基丙酸)、小分子扩链剂和/或内交联剂,保持在70-80度反应1h;
S4、控制反应釜温度在40-45摄氏度,加入磺酸盐,继续反应0.5h后加入三乙胺中和;
S5、再启动反应釜乳化机构,高速搅拌条件下加入去离子水120g分散乳化10min;
S6、最后滴加计量S1步骤中制备的酮肼交联单体水溶液,去丙酮后加入ADH即得。
3.根据权利要求2所述的一种热固性聚氨酯的制备方法,其特征在于:所述S1步骤中的至少含一个胺基和至少一个羟基的物质为DETA(二乙烯三胺)。
4.根据权利要求2所述的一种热固性聚氨酯的制备方法,其特征在于:所述小分子扩链剂和内交联剂为TMP(三羟甲基丙烷)、蓖麻油和N303的一种或多种。
5.根据权利要求2所述的一种热固性聚氨酯的制备方法,其特征在于:所述的多元醇包括聚氧化丙烯二醇、聚己二酸乙二醇酯、聚己内酯、端羟基聚丁二烯、聚四亚甲基醚二醇、聚乙二醇、丙乙醇中的至少一种或多种。
6.根据权利要求2所述的一种热固性聚氨酯的制备方法,其特征在于:所述S6步骤中去除丙酮的方法为减压蒸煮。
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