CN108484869A - 一种耐水性密封聚氨酯及其制备方法和应用 - Google Patents
一种耐水性密封聚氨酯及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种耐水性密封聚氨酯,其可以实现优异柔韧性、力学性能和耐水性的平衡,其组成为:聚醚多元醇30‑80重量份碳酸酯多元醇1‑5重量份,芳香族异氰酸酯20‑50重量份,异氰酸酯修饰活化二氧化硅5‑20重量份,催化剂0.1‑5重量份,复合交联剂1‑5重量份,功能助剂0‑20重量份,所述复合交联剂为三羟甲基丙烷和蓖麻油的混合物,质量比为1‑3.5:1,该聚氨酯适合制备浴室移门密封条和阳台门窗密封条。
Description
技术领域
本发明涉及聚氨酯领域,具体涉及一种耐水性密封聚氨酯领域,还涉及其具体的制备方法及其应用。
背景技术
聚氨酯又名聚氨基甲酸酯,其结构为主链上含有重复氨基甲酸酯基团的大分子化合物的统称。它是由有机二异氰酸酯或多异氰酸酯与二羟基或多羟基化合物加聚而成。聚氨酯材料,用途非常广,可以代替橡胶,塑料,尼龙等,用于机场、酒店、教材等领域。,在我们生活中的各方面应用十分广泛。
密封条广泛的应用于各个领域,在日常生活中,密封条用于门窗方面,发挥着重要作用,提高了门窗的密封性。由于聚氨酯材料自身强度稍有不足通常会加入一些补强填料提高材料的强度,但由于补强填料分散不均匀、填料自身空隙和孔隙的存在,会降低聚合物材料的强度以及耐水性,由于要保持良好的柔韧性、抗折性等,如何平衡上述性能成为实际研发和生产中亟待解决的问题。
针对上述问题,本人进行了系统的研究,得到了合适的配方,得到了优异的效果。
发明内容
发明目的:针对背景技术中介绍的技术问题,本发明通过对多元醇、交联剂的复配选择,通过对填料种类以及处理方式的选择,得到了一种具有柔韧性好、强度大且耐水性优异的密封聚氨酯。
本发明还提供了一种耐水性密封聚氨酯的制备方法。
本发明还进一步提供了一种耐水性密封聚氨酯的应用。
发明概述
本发明核心在于保护一种耐水性密封聚氨酯,其组成包括:聚醚多元醇30-80重量份,聚碳酸酯多元醇1-5重量份,芳香族异氰酸酯20-50重量份,异氰酸酯修饰活化二氧化硅5-20重量份,催化剂0.1-5重量份,复合交联剂1-5重量份,功能助剂0-20重量份。
作为优选技术方案,所述异氰酸酯修饰活化二氧化硅中的活性二氧化硅为微米二氧化硅在0.01-0.03mol/L的醋酸浸泡10-50分钟,清水洗至中性即可。
作为优选技术方案,所述异氰酸酯修饰活化二氧化硅为活性二氧化硅与异氰酸酯以质量比1:0.5-2混合,搅拌1-3小时即可。
作为优选技术方案,所述复合交联剂为三羟甲基丙烷和蓖麻油的混合物,质量比为1-3.5:1。
作为优选技术方案,所述芳香族二异氰酸酯为甲苯二异氰酸酯或二苯基甲烷二异氰酸酯。
作为优选技术方案,所述催化剂为有机锡类或有机胺类催化剂,所述功能助剂为抗氧剂、耐老化剂、紫外吸收剂等。
本发明还要求保护一种耐水性密封聚氨酯的制备方法,其包括如下步骤:
(1)将聚醚多元醇、聚碳酸酯多元醇和芳香族异氰酸酯分别进行真空干燥;
(2)将上述干燥后组分与异氰酸酯修饰活化二氧化硅、催化剂、复合交联剂和功能助剂通过一步反应反应1-3小时,得到耐水性密封聚氨酯。
本发明还提供了耐水性密封聚氨酯在制备密封条中的应用。
作为优选技术方案,所述密封条为浴室移门密封条。
作为另外一个优选技术方案,所述密封条为还可以用于阳台门窗密封条。
发明详述
为了使公众更加详细的了解本发明的技术方案以及原理,下面进一步对发明进行了详细的介绍。
本发明旨在提供的耐水性密封聚氨酯,其具体组成包括:聚醚多元醇30-80重量份,聚碳酸酯多元醇1-5重量份,芳香族异氰酸酯20-50重量份,异氰酸酯修饰活化二氧化硅5-20重量份,催化剂0.1-5重量份,复合交联剂1-5重量份,功能助剂0-20重量份。其中采用了聚醚多元醇和聚碳酸酯多元醇的配合使用,聚醚多元醇具有较好的耐水性,比常规的聚酯类要好很多,不存在酸碱性水解的问题,提高了密封胶的使用范围。由于聚醚链段很好的柔韧性,得到的密封条强度不足,传统有使用大量的添加剂或填料,优选添加剂或填料自身性能的限制,大量使用带来诸多问题,如添加剂迁移或填料导致的耐水性变差、脆性的提高、柔韧性下降。故本发明使用了可以缩聚到体系内的聚碳酸酯多元醇,进一步提高了硬链段的比例,强度提升,同时,聚碳酸酯的水解效率比常规聚酯小很多,不会降低耐水性,但可以提高强度。
对于用量的选择,具体选择参见上部分的具体范围,聚碳酸酯比例不宜过少,过少则无法有效的起到提高强度的效果;如果过多,也柔韧性下降明显,使用效果变差,难以满足实际使用中柔韧性的核心需求。
上部分提及填料的使用会降低耐水性,本发明采用了二氧化硅,为了减少由于二氧化硅表面空隙以及分散性导致的不利后果,本发明通过对二氧化硅进行活化,与异氰酸酯反应,得到异氰酸酯修饰的活化二氧化硅,其在后续反应中,由于活化中清洗,有微腐蚀形成小的孔隙,聚合物封闭了二氧化硅的孔隙,避免了孔隙的透水,也提高了分散性和填料的增强稳定性。
作为优选活化方式,所述异氰酸酯修饰活化二氧化硅中的活性二氧化硅为微米二氧化硅在0.01-0.03mol/L的醋酸浸泡10-50分钟,清水洗至中性即可。此处处理不宜使用强酸以及浓度过大,避免原料杂质过多,导致填料表面孔隙过深或过多,导致后续聚合物包裹不到位,影响耐水和分散效果。
作为进一步优选,所述异氰酸酯修饰活化二氧化硅为活化二氧化硅与异氰酸酯以质量比1:0.5-2混合,搅拌1-3小时即可,其比例可以根据实际原料选择可以调整,如果过多浪费,也会造成后续原料难以准确控制,如果过少,接触效果不佳。
同时,交联剂的选择也是重要发明,其可以提高体系的交联程度,但常规的单一小分子交联剂会导致脆性提高,实际使用效果较差,单一的交联剂选择难以实现优异的综合性能。本发明选择了一种复合交联剂,采用小分子交联剂和生物质长链交联剂复合,综合了小分子交联剂的高效交联和长链交联剂的柔韧性。所述复合交联剂为三羟甲基丙烷和蓖麻油的混合物,质量比为1-3.5:1,如果蓖麻油含量过小,小分子交联剂比例较高,交联程度高,柔韧性降低、脆性升高;如果蓖麻油含量过高,小分子交联小,硬度和强度大幅度降低,不满足实际使用需要。
其他组分的具体选择无特别限制,具体选择参见发明概述部分。
有益的技术效果
本发明提供一种耐水性密封聚氨酯,其通过多元醇的选择、交联剂的选择以及补强填料的处理,实现了强度与柔韧性的平衡,得到了一种具有柔韧性好、强度大且耐水性优异的密封聚氨酯,最终性能优于市售产品。
具体实施方式
为了使技术人员更加直观的了解本发明的技术方案,下面选择几个典型实施例进行介绍,这些实施例不构成对本发明保护范围的限制,今后任何不背离本发明基本构思的实施方案都在本发明保护范围内。
制备例1
将8微米的二氧化硅在0.02mol/L的醋酸浸泡20分钟,清水洗至中性,得到活化二氧化硅,按照活化二氧化硅与TDI以质量比1:0.8混合,搅拌2小时即得异氰酸酯修饰活化二氧化硅A。
制备例2
将8微米的二氧化硅在0.06mol/L的醋酸浸泡20分钟,清水洗至中性,得到活化二氧化硅,按照活化二氧化硅与TDI以质量比1:0.8混合,搅拌2小时即得异氰酸酯修饰活化二氧化硅B。
制备例3
将8微米的二氧化硅在0.02mol/L的醋酸浸泡20分钟,清水洗至中性,得到活化二氧化硅,按照活化二氧化硅与TDI以质量比1:3混合,搅拌2小时即得异氰酸酯修饰活化二氧化硅C。
制备例4
将8微米的二氧化硅与TDI以质量比1:0.8混合,搅拌2小时即得异氰酸酯修饰二氧化硅D。
实施例部分
以下实施例采用相同的制备方法,仅在于组分选择和用量的区别,具体制备方法如下:
(1)将聚醚多元醇、聚碳酸酯多元醇和芳香族异氰酸酯分别进行真空干燥;
(2)将上述干燥后组分与异氰酸酯修饰活化二氧化硅、催化剂、复合交联剂和功能助剂通过一步反应反应2小时,得到耐水性密封聚氨酯。
各实施例的具体组分选择和用量如下(单位:重量份):
*江苏省化工研究所有限公司的聚碳酸酯二元醇材料。
#8微米的二氧化硅,未处理和修饰。
测试方法:
断裂伸长率(%)和50%定伸应力(MPa)测试采用GB/T528-1992,样品采用2型结构。
耐水性采用透水蒸汽性测试,参考GB1037-88进行测试,采用条件A,膜层厚度50微米,单位:g/m2.24h。
测试结果
由上述数据的比对可以发现,交联剂复配以及比例的选择对力学性能的柔韧性和强度进行了很好的平衡,耐水性的控制通过在填料二氧化硅的表面处理和修饰共同作用得到,这两个重要方面配合后,得到具有优异柔韧性、力学性能和耐水性的耐水性密封聚氨酯,性能在各方面表现优异。
Claims (10)
1.一种耐水性密封聚氨酯,其特征在于:其组成包括:聚醚多元醇30-80重量份,聚碳酸酯多元醇1-5重量份,芳香族异氰酸酯20-50重量份,异氰酸酯修饰活化二氧化硅5-20重量份,催化剂0.1-5重量份,复合交联剂1-5重量份,功能助剂0-20重量份。
2.根据权利要求1所述的耐水性密封聚氨酯,其特征在于:所述异氰酸酯修饰活化二氧化硅中的活性二氧化硅为微米二氧化硅在0.01-0.03mol/L的醋酸浸泡10-50分钟,清水洗至中性即可。
3.根据权利要求1或2所述的耐水性密封聚氨酯,其特征在于:所述异氰酸酯修饰活化二氧化硅为活性二氧化硅与异氰酸酯以质量比1:0.5-2混合,搅拌1-3小时即可。
4.根据权利要求1所述的耐水性密封聚氨酯,其特征在于:所述复合交联剂为三羟甲基丙烷和蓖麻油的混合物,质量比为1-3.5:1。
5.根据权利要求1所述的耐水性密封聚氨酯,其特征在于:所述芳香族二异氰酸酯为甲苯二异氰酸酯或二苯基甲烷二异氰酸酯。
6.根据权利要求1所述的耐水性密封聚氨酯,其特征在于:所述催化剂为有机锡类或有机胺类催化剂,所述功能助剂为抗氧剂、耐老化剂、紫外吸收剂等。
7.一种如权利要求1-6任一项所述耐水性密封聚氨酯的制备方法,其特征在于:包括如下步骤:
(1)将聚醚多元醇、聚碳酸酯多元醇和芳香族异氰酸酯分别进行真空干燥;
(2)将上述干燥后组分与异氰酸酯修饰活化二氧化硅、催化剂、复合交联剂和功能助剂通过一步反应反应1-3小时,得到耐水性密封聚氨酯。
8.权利要求1-6任一项所述耐水性密封聚氨酯在制备密封条中的应用。
9.根据权利要求8所述的应用,其特征在在于,所述密封条为浴室移门密封条。
10.根据权利要求8所述的应用,其特征在在于,所述密封条为阳台门窗密封条。
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