CN113307937A - 原位阻燃增强聚氨酯泡棉及其制备方法 - Google Patents
原位阻燃增强聚氨酯泡棉及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种原位阻燃增强聚氨酯泡棉及其制备方法,所述聚氨酯泡棉为两层结构,是将混合料涂覆于PET薄膜表面形成上层的混合层和下层的PET薄膜,本发明的泡棉材料,不同于常规简单的将阻燃剂加到聚氨酯原材料体系中,利用原材料对阻燃剂的包裹进行加工成型,而是在微观分子层次进行设计,首先构造了酸源、气源、碳源的阻燃剂模型,即利用天然纤维分子富含羟基这一特性,将硝酸、磷酸与纤维素分子上的羟基进行酯化反应,获得硝酸磷酸酯纤维,再利用其上残留的羟基与异氰酸酯基继续反应,最终成为聚氨酯大分子的一部分,从而实现原位阻燃、增强聚氨酯泡棉。
Description
技术领域
本发明涉及发泡材料领域,具体涉及一种原位阻燃增强聚氨酯泡棉及其制备方法。
背景技术
聚氨酯自问世以来,在许多方面都获得了大范围应用。胶黏剂、保温板、隔热板、鞋底、沙发、服装等工业、家居、生活领域均可以看到相关的聚氨酯产品。但作为一种人工合成的高分子材料,与通用塑料、橡胶类似,都不具备阻燃性。
目前在电子产品,诸如手机、笔记本电脑、平板电脑、智能音响、扫地机、打印机、电视机、数码影音设备等所使用的泡棉,因为电子产品均需要配备电池或充电,面临着着火或爆炸的风险,因此大多数电子产品都对原材料阻燃有一定要求。
常规的聚氨酯发泡材料,做到阻燃一般都会添加阻燃剂,阻燃剂主要是无机和有机阻燃剂两大类。
1.无机阻燃剂主要涉及金属的氢氧化物,如氢氧化镁、氢氧化铝、碱式碳酸镁、膨胀石墨等,由于添加量大、阻燃效果差,难以单独使用;
2.有机阻燃剂主要分为有卤和无卤,有卤阻燃剂涉及溴系的较多,与三氧化二锑会配合使用,但燃烧过程会释放出大量的有毒气体,逐渐在环保要求高的领域被弃用。
无卤有机阻燃剂是近些年发展起来的新型阻燃剂,主要有磷酸三聚氰胺、聚磷酸三聚氰胺等氮磷系阻燃剂,有些会配合成炭剂如季戊四醇、淀粉使用,形成三元膨胀体系,即酸源、气源、碳源的协同作用。聚氨酯阻燃,一般会选择膨胀石墨,但膨胀石墨添加量较大,且在挥发过程中会释放出大量的石墨燃烧后的絮状物,烟密度超标。而降低石墨的添加量并与有机阻燃剂共用,虽可降低挥发物,但整体的添加量仍然较高,对聚氨酯特别是聚氨酯发泡材料的力学性能会产生影响。
发明内容
本发明的目的在于克服现有技术的不足,提供了一种原位阻燃增强聚氨酯泡棉及其制备方法,本发明通过化学方法在聚氨酯分子上引入含有氮、磷元素的天然纤维大分子,最终得到原位阻燃与增强的聚氨酯泡棉。
为实现上述目的,本发明所设计一种原位阻燃增强聚氨酯泡棉,所述聚氨酯泡棉为两层结构,是将混合料涂覆于PET薄膜表面形成上层的混合层和下层的PET薄膜,所述混合料的原料按重量份数比计包括100份的聚二元醇、1~3份的扩链剂、1.0~1.5份的水、0.2~0.3份的催化剂、19.15~63.77份的二异氰酸酯、0.5~1.0份的聚硅氧烷和5~15份的酯化纤维/酯化纤维混合物。
进一步地,所述混合料的原料按重量份数比计包括100份的聚二元醇、2~3份的扩链剂、1.0~1.5份的水、0.2~0.3份的催化剂、23.14~63.77份的二异氰酸酯、0.5~1.0份的聚硅氧烷和10~15份的酯化纤维/酯化纤维混合物。
再进一步地,所述酯化纤维的由以下方法制备而成:
a.按重量比100:10~15将天然纤维与混合酸反应;反应过程中加入浓硫酸,其中,所述混合酸为硝酸和磷酸按重量比1:1混合而成;
b.将步骤a得到反应产物经水洗、过滤、烘干、研磨得到酯化纤维;
所述酯化纤维混合物由上述方法制备的两个酯化纤维组合而成。
再进一步地,所述步骤a中,硝酸和磷酸为浓度98%以上的高纯酸;所述天然纤维为木浆纤维、棉纤维、亚麻、苎麻、亚麻、大麻和黄麻纤维中的任意一种。
再进一步地,所述步骤a中,所述浓硫酸的添加量为天然纤维的0.1~0.15%。
再进一步地,所述聚二元醇为常规分子量1000~3000的聚醚二元醇(POG)、聚酯二元醇(PEG)、聚碳二元醇(PCG)中任意一种或二种;
所述二异氰酸酯为甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、苯二亚甲基二异氰酸酯(XDI)和异佛尔酮二异氰酸酯(IPDI)中的任意一种;
所述扩链剂为乙二醇(EG)、1,3-丙二醇(1,3-PG)、1,4-丁二醇(1,4-BG)中的任意一种;
所述催化剂为新葵酸铋、异辛酸铋、新葵酸锌和异辛酸锌中的任意一种;
所述聚硅氧烷的分子量为1000。
再进一步地,所述混合层的厚度为0.3~1.0mm;所述PET薄膜的厚度为0.2mm~1.0mm。
再进一步地,所述聚氨酯泡棉为两层结构,混合料涂覆于PET薄膜表面形成上层的混合层和下层的PET薄膜,所述混合料的原料按重量份数比计包括1100份的分子量1000聚醚二元醇(POG)和聚碳二元醇(PCG)混合的聚二元醇、3份的乙二醇(EG)、1.5份的水、0.3份的异辛酸铋、1.0份的分子量1000的聚硅氧烷、15份的酯化黄麻纤维和63.77份的二苯基甲烷二异氰酸酯。
本发明还提供了一种上述原位阻燃增强聚氨酯泡棉的制备方法,包括以下步骤:
1)酯化纤维的由以下方法制备而成:
a.按重量比100:10~15将天然纤维与混合酸反应;反应过程中加入浓硫酸,其中,所述混合酸为硝酸和磷酸按重量比1:1混合而成;
b.将步骤a得到反应产物经水洗、过滤、烘干、研磨得到酯化纤维。
2)按重量份数比称取包括100份的聚多元醇、1~3份的扩链剂、1.0~1.5份的水、0.2~0.3份的催化剂、0.5~1.0份的表面活性剂、5~15份的酯化纤维和19.15~63.77份的二异氰酸酯;
3)将酯化纤维与聚多元醇、扩链剂、水、催化剂、表面活性剂混合均匀;
4)将二异氰酸酯加入步骤3)步中的混合物中,混合完毕后涂覆于PET薄膜上;在温度为90℃~110℃加热固化10min~15min;即得到原位阻燃增强聚氨酯泡棉。
再进一步地,所述混合层的厚度为0.3~1.0mm;所述PET薄膜的厚度为0.2mm~1.0mm。
本发明的原理:
本发明创造通过硝酸、磷酸与天然纤维大分子的酯化反应,将氮磷元素引入到天然纤维分子上,再通过纤维分子中残留的过量羟基,参与聚氨酯固化的过程,即与过量的异氰酸酯基发生化学反应,最终成为聚氨酯大分子的一部分。引入到分子链上的氮、磷元素与纤维分子起到了酸源、气源、碳源的三元协同阻燃功效,且纤维本身的长径比优势可以较大幅度增强聚氨酯泡棉的剥离强度;在分子层次同时结局了阻燃、增强聚氨酯泡棉的目的。
本发明的有益效果:
本发明的泡棉材料,不同于常规简单的将阻燃剂加到聚氨酯原材料体系中,利用原材料对阻燃剂的包裹进行加工成型,而是在微观分子层次进行设计,首先构造了酸源、气源、碳源的阻燃剂模型,即利用天然纤维分子富含羟基这一特性,将硝酸、磷酸与纤维素分子上的羟基进行酯化反应,获得硝酸磷酸酯纤维,再利用其上残留的羟基与异氰酸酯基继续反应,最终成为聚氨酯大分子的一部分,从而实现原位阻燃、增强聚氨酯泡棉。
具体实施方式
下面结合具体实施例对本发明作进一步的详细描述,以便本领域技术人员理解。
实施例1
原位阻燃增强聚氨酯泡棉1的制备方法,包括以下步骤:
1)酯化木浆纤维的由以下方法制备而成:
a.按重量比100:10将木浆纤维与混合酸反应;反应过程中加入木浆纤维的0.1%的浓硫酸,其中,所述混合酸为硝酸和磷酸按重量比1:1混合而成;
b.将步骤a得到反应产物经水洗、过滤、烘干、研磨得到酯化木浆纤维;
2)按重量份数比称取包括100份的分子量为3000的聚醚二元醇(POG)、1份的1,4-丁二醇(1,4-BG)、1.0份的水、0.2份的异辛酸铋、0.5份的分子量1000的聚硅氧烷、5份的酯化木浆纤维和19.15份的甲苯二异氰酸酯(TDI);
3)将酯化木浆纤维与聚醚二元醇(POG)、1,4-丁二醇(1,4-BG)、水、异辛酸铋和聚硅氧烷混合均匀;
4)将甲苯二异氰酸酯加入步骤3)步中的混合物中,混合完毕后涂覆于PET薄膜上;在温度为90℃加热固化15min;即得到原位阻燃增强聚氨酯泡棉1;其中,所述混合层的厚度为0.3mm;所述PET薄膜的厚度为1.0mm。
实施例2
原位阻燃增强聚氨酯泡棉2的制备方法,包括以下步骤:
1)酯化棉纤维的由以下方法制备而成:
a.按重量比100:11将棉纤维与混合酸反应;反应过程中按加入棉纤维的0.11%的浓硫酸,其中,所述混合酸为硝酸和磷酸按重量比1:1混合而成;
b.将步骤a得到反应产物经水洗、过滤、烘干、研磨得到酯化棉纤维。
2)按重量份数比称取包括100份的分子量2500的聚酯二元醇(PEG)、1.5份的1,3-丙二醇(1,3-PG)、1.1份的水、0.25份的新葵酸铋、0.6份的分子量1000的聚硅氧烷、8份的酯化棉纤维和23.14份的甲苯二异氰酸酯(TDI);
3)将酯化棉纤维与聚酯二元醇(PEG)、1,3-丙二醇(1,3-PG)、水、新葵酸铋和聚硅氧烷混合均匀;
4)将甲苯二异氰酸酯(TDI)加入步骤3)步中的混合物中,混合完毕后涂覆于PET薄膜上;在温度为95℃加热固化14min;即得到原位阻燃增强聚氨酯泡棉2;其中,所述混合层的厚度为0.5mm;所述PET薄膜的厚度为0.8mm。
实施例3
原位阻燃增强聚氨酯泡棉3的制备方法,包括以下步骤:
1)酯化亚麻纤维的由以下方法制备而成:
a.按重量比100:12将亚麻纤维与混合酸反应;反应过程中按加入亚麻纤维的0.12%的浓硫酸,其中,所述混合酸为硝酸和磷酸按重量比1:1混合而成;
b.将步骤a得到反应产物经水洗、过滤、烘干、研磨得到酯化亚麻纤维;
2)按重量份数比称取包括100份的分子量2000的聚碳二元醇(PCG)、2份的乙二醇(EG)、1.2份的水、0.25份的异辛酸铋、0.7份的分子量1000的聚硅氧烷、10份的酯化亚麻纤维和30.82份的苯二亚甲基二异氰酸酯(XDI);
3)将酯化亚麻纤维与聚碳二元醇(PCG)、乙二醇(EG)、水、异辛酸铋、聚硅氧烷混合均匀;
4)将苯二亚甲基二异氰酸酯(XDI)加入步骤3)步中的混合物中,混合完毕后涂覆于PET薄膜上;在温度为100℃加热固化12min;即得到原位阻燃增强聚氨酯泡棉3;其中,所述混合层的厚度为0.6mm;所述PET薄膜的厚度为0.6mm。
实施例4
原位阻燃增强聚氨酯泡棉4的制备方法,包括以下步骤:
1)酯化纤维的由以下方法制备而成:
a.按重量比100:13将苎麻纤维与混合酸反应;反应过程中按加入苎麻纤维的0.13%的浓硫酸,其中,所述混合酸为硝酸和磷酸按重量比1:1混合而成;
b.将步骤a得到反应产物经水洗、过滤、烘干、研磨得到酯化苎麻纤维;
或者,a.按重量比100:14将大麻纤维与混合酸反应;反应过程中按加入大麻纤维的0.14%的浓硫酸,其中,所述混合酸为硝酸和磷酸按重量比1:1混合而成;
b.将步骤a得到反应产物经水洗、过滤、烘干、研磨得到酯化大麻纤维;
2)按重量份数比称取包括100份的分子量1500的聚醚二元醇(POG)和聚酯二元醇(PEG)混合的聚二元醇、2.5份的1,4-丁二醇(1,4-BG)、1.3份的水、0.3份的新葵酸铋、0.8份的分子量1000的聚硅氧烷、6份的酯化苎麻纤维、6份的酯化大麻纤维和40.73份的异佛尔酮二异氰酸酯(IPDI);
3)将酯化苎麻纤维、酯化大麻纤维与聚二元醇、1,4-丁二醇(1,4-BG)、水、新葵酸铋、聚硅氧烷混合均匀;
4)将异佛尔酮二异氰酸酯(IPDI)加入步骤3)步中的混合物中,混合完毕后涂覆于PET薄膜上;在温度为105℃加热固化10min;即得到原位阻燃增强聚氨酯泡棉4;其中,所述混合层的厚度为0.4mm;所述PET薄膜的厚度为0.5mm。
实施例5
原位阻燃增强聚氨酯泡棉5的制备方法,包括以下步骤:
1)酯化黄麻纤维的由以下方法制备而成:
a.按重量比100:15将黄麻纤维与混合酸反应;反应过程中按加入黄麻纤维的0.15%的浓硫酸,其中,所述混合酸为硝酸和磷酸按重量比1:1混合而成;
b.将步骤a得到反应产物经水洗、过滤、烘干、研磨得到酯化黄麻纤维;
2)按重量份数比称取包括100份的分子量1000聚醚二元醇(POG)和聚碳二元醇(PCG)混合的聚二元醇、3份的乙二醇(EG)、1.5份的水、0.3份的异辛酸铋、1.0份的分子量1000的聚硅氧烷、15份的酯化黄麻纤维和63.77份的二苯基甲烷二异氰酸酯(MDI);
3)将酯化黄麻纤维与聚二元醇、乙二醇(EG)、水、异辛酸铋、聚硅氧烷混合均匀;
4)将二苯基甲烷二异氰酸酯(MDI)加入步骤3)步中的混合物中,混合完毕后涂覆于PET薄膜上;在温度为110℃加热固化10min;即得到原位阻燃增强聚氨酯泡棉5;其中,所述混合层的厚度为0.3mm;所述PET薄膜的厚度为0.2mm。
上述实施例中原料组分表如下:
表1酯化纤维的组分表
天然纤维种类 | a木浆纤维 | b棉纤维 | c亚麻纤维 | d苎麻纤维 | e大麻纤维 | f黄麻纤维 |
天然纤维份数 | 100 | 100 | 100 | 100 | 100 | 100 |
硝酸+磷酸(1:1) | 10 | 11 | 12 | 13 | 14 | 15 |
浓硫酸(%) | 0.1 | 0.11 | 0.12 | 0.13 | 0.14 | 0.15 |
表2原位阻燃增强聚氨酯泡棉的组分表
将上述实施例1~5制备的原位阻燃增强聚氨酯泡棉1~5与对比例比较:
注:对比例1:将种类1制备泡棉,不添加酯化纤维,异氰酸酯变为17.41份。
对比例2:将种类5制备泡棉,添加未酯化f纤维15份,异氰酸酯为63.77份。
通过以上测试数据可以看出,加入酯化纤维/酯化纤维混合物的样品,全部可以通过HBF水平燃烧测试,且随着添加量的增加,氧指数及剥离力不断提升,当添加量为15份时,氧指数高达20.6,剥离力为12.79N/25mm;实施例5效果最好。
其它未详细说明的部分均为现有技术。尽管上述实施例对本发明做出了详尽的描述,但它仅仅是本发明一部分实施例,而不是全部实施例,人们还可以根据本实施例在不经创造性前提下获得其他实施例,这些实施例都属于本发明保护范围。
Claims (10)
1.一种原位阻燃增强聚氨酯泡棉,其特征在于:所述聚氨酯泡棉为两层结构,是将混合料涂覆于PET薄膜表面形成上层的混合层和下层的PET薄膜,所述混合料的原料按重量份数比计包括100份的聚二元醇、1~3份的扩链剂、1.0~1.5份的水、0.2~0.3份的催化剂、19.15~63.77份的二异氰酸酯、0.5~1.0份的聚硅氧烷和5~15份的酯化纤维/酯化纤维混合物。
2.根据权利要求1所述原位阻燃增强聚氨酯泡棉,其特征在于:所述混合料的原料按重量份数比计包括100份的聚二元醇、2~3份的扩链剂、1.0~1.5份的水、0.2~0.3份的催化剂、23.14~63.77份的二异氰酸酯、0.5~1.0份的聚硅氧烷和10~15份的酯化纤维/酯化纤维混合物。
3.根据权利要求1或2所述原位阻燃增强聚氨酯泡棉,其特征在于:所述酯化纤维的由以下方法制备而成:
a.按重量比100:10~15将天然纤维与混合酸反应;反应过程中加入浓硫酸,其中,所述混合酸为硝酸和磷酸按重量比1:1混合而成;
b.将步骤a得到反应产物经水洗、过滤、烘干、研磨得到酯化纤维;
所述酯化纤维混合物由上述方法制备的两个酯化纤维组合而成。
4.根据权利要求3所述原位阻燃增强聚氨酯泡棉,其特征在于:所述步骤a中,硝酸和磷酸为浓度98%以上的高纯酸;所述天然纤维为木浆纤维、棉纤维、亚麻、苎麻、亚麻、大麻和黄麻纤维中的任意一种。
5.根据权利要求3所述原位阻燃增强聚氨酯泡棉,其特征在于:所述步骤a中,所述浓硫酸的添加量为天然纤维的0.1~0.15%。
6.根据权利要求1或2所述原位阻燃增强聚氨酯泡棉,其特征在于:所述聚二元醇为常规分子量1000~3000的聚醚二元醇、聚酯二元醇、聚碳二元醇中任意一种或二种;
所述二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯和异佛尔酮二异氰酸酯中的任意一种;
所述扩链剂为乙二醇、1,3-丙二醇、1,4-丁二醇中的任意一种;
所述催化剂为新葵酸铋、异辛酸铋、新葵酸锌和异辛酸锌中的任意一种;
所述聚硅氧烷的分子量为1000。
7.根据权利要求1或2所述原位阻燃增强聚氨酯泡棉,其特征在于:所述混合层的厚度为0.3~1.0mm;所述PET薄膜的厚度为0.2mm~1.0mm。
8.根据权利要求1或2所述原位阻燃增强聚氨酯泡棉,其特征在于:所述聚氨酯泡棉为两层结构,混合料涂覆于PET薄膜表面形成上层的混合层和下层的PET薄膜,所述混合料的原料按重量份数比计包括1100份的分子量1000聚醚二元醇和聚碳二元醇混合的聚二元醇、3份的乙二醇、1.5份的水、0.3份的异辛酸铋、1.0份的分子量1000的聚硅氧烷、15份的酯化黄麻纤维和63.77份的二苯基甲烷二异氰酸酯。
9.一种权利要求1所述原位阻燃增强聚氨酯泡棉的制备方法,其特征在于:包括以下步骤:
1)酯化纤维的由以下方法制备而成:
a.按重量比100:10~15将天然纤维与混合酸反应;反应过程中加入浓硫酸,其中,所述混合酸为硝酸和磷酸按重量比1:1混合而成;
b.将步骤a得到反应产物经水洗、过滤、烘干、研磨得到酯化纤维;
2)按重量份数比称取包括100份的聚多元醇、1~3份的扩链剂、1.0~1.5份的水、0.2~0.3份的催化剂、0.5~1.0份的表面活性剂、5~15份的酯化纤维和19.15~63.77份的二异氰酸酯;
3)将酯化纤维与聚多元醇、扩链剂、水、催化剂、表面活性剂混合均匀;
4)将二异氰酸酯加入步骤3)步中的混合物中,混合完毕后涂覆于PET薄膜上;在温度为90℃~110℃加热固化10min~15min;即得到原位阻燃增强聚氨酯泡棉。
10.根据权利要求9所述原位阻燃增强聚氨酯泡棉的制备方法,其特征在于:所述混合层的厚度为0.3~1.0mm;所述PET薄膜的厚度为0.2mm~1.0mm。
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