CN117362574A - 一种保温阻燃聚氨酯材料及其制备方法 - Google Patents
一种保温阻燃聚氨酯材料及其制备方法 Download PDFInfo
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000003063 flame retardant Substances 0.000 title claims abstract description 65
- 239000004814 polyurethane Substances 0.000 title claims abstract description 38
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- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 15
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Abstract
本发明属于高分子材料技术领域,提供了一种保温阻燃聚氨酯材料及其制备方法,由包含下列质量份数的原料制备得到:多元醇40~60份、异氰酸酯40~50份、发泡剂1~3份、阻燃剂8~10份、催化剂4~6份、扩链剂2~4份、1~3水。通过添加自制的阻燃剂实现了聚氨酯材料阻燃性能的提升。本发明通过亚磷酸二甲酯和丙烯酰胺分别引入氮元素和磷元素;环糊精本身具有优异的阻燃性能,在燃烧开始时脱除内部的结晶水降低周围的温度,燃烧进一步进展后可以释放出二氧化碳气体阻止燃烧;将水解得到的中间体和环糊精进行反应,通过羟基接枝到环糊精的表面从而得到了复合型的阻燃剂。本发明中原料易得,工艺要求低,适合大规模制备。
Description
技术领域
本发明涉及高分子材料技术领域,尤其涉及一种保温阻燃聚氨酯材料及其制备方法。
背景技术
聚氨酯是一种常见的塑料制品,随着社会的进步聚氨酯的应用也越来越广泛。其中的一种产品是聚氨酯泡沫材料,泡沫材料主要分为硬质聚氨酯泡沫、半硬质聚氨酯泡沫和软质聚氨酯泡沫材料。硬质聚氨酯泡沫主要用于建筑隔热材料,保温材料和生活用品等。但是在生产生活中发现,聚氨酯泡沫的保温性能虽然优异但是不耐高温,在火焰的作用下,聚氨酯的燃烧速度非常快,此时反而成为了助燃物,造成巨大的损失。因此如何提高聚氨酯材料的阻燃性能,成为了亟需解决的问题。
发明内容
本发明的目的在于克服现有技术中的缺陷,提供了一种保温阻燃聚氨酯材料,由包含下列质量份数的原料制备得到:
多元醇40~60份、异氰酸酯40~50份、发泡剂1~3份、阻燃剂8~10份、催化剂4~6份、扩链剂2~4份、水1~3份。
作为优选,所述多元醇包含聚丙二醇、聚四氢呋喃二醇和四氢呋喃氧化丙烯共聚二醇中的一种或几种。
作为优选,所述异氰酸酯包含甲苯二异氰酸酯、异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯中的一种或几种。
作为优选,所述发泡剂包含环己烷和四氟乙烷;
所述环己烷和四氟乙烷的质量比为1:1~1.3。
作为优选,所述阻燃剂的制备方法包含下列步骤:
(1)将亚磷酸二甲酯、丙烯酰胺和甲醇钠混合进行水解反应,得到中间体;
(2)将中间体、环糊精和氢氧化钠混合进行反应,即得所述阻燃剂。作为优选,步骤(1)所述亚磷酸二甲酯和丙烯酰胺的摩尔比为0.5~1.5:0.5~1.5,
步骤(1)中混合后体系的pH值为7.2~7.5;
步骤(1)中所述水解反应的温度为60~80℃,时间为4~6h;
步骤(2)中所述环糊精和步骤(1)中所述丙烯酰胺的摩尔比为0.8~1.2:1~1.2;
步骤(2)中混合后体系的pH值为6.5~7.0;
步骤(2)中所述反应的温度为45~55℃,时间为0.5~0.8h。
作为优选,所述催化剂包含辛酸亚锡和五甲基二乙烯三胺;
所述辛酸亚锡和五甲基二乙烯三胺的质量比为1:0.5~0.8。
作为优选,所述扩链剂包含1,4-丁二醇和/或季戊四醇。
本发明还提供了所述保温阻燃聚氨酯材料的制备方法,包含下列步骤:
(1)将多元醇、阻燃剂、催化剂和水混合,得到醇体系;
(2)将醇体系、异氰酸酯、发泡剂和扩链剂混合后顺次进行熟化和固化,即得所述保温阻燃聚氨酯材料。
作为优选,步骤(1)中所述混合的转速为100~150rpm,时间为10~20min;
步骤(2)中所述混合的转速为100~150rpm,温度为50~60℃,时间为1~2h;
所述熟化的时间为30~40min;
所述固化的温度为60~65℃,时间为1~2h。
本发明提供了一种保温阻燃聚氨酯材料,由包含下列质量份数的原料制备得到:多元醇40~60份、异氰酸酯40~50份、发泡剂1~3份、阻燃剂8~10份、催化剂4~6份、扩链剂2~4份、1~3水。在本发明中,通过添加自制的阻燃剂实现了聚氨酯材料阻燃性能的提升。本发明通过亚磷酸二甲酯和丙烯酰胺分别引入氮元素和磷元素;环糊精本身具有优异的阻燃性能,在燃烧开始时脱除内部的结晶水降低周围的温度,燃烧进一步进展后可以释放出二氧化碳气体阻止燃烧;在本发明中,将水解得到的中间体和环糊精进行反应,通过羟基接枝到环糊精的表面从而得到了复合型的阻燃剂。本发明通过各原料的配合得到了具有保温阻燃性能的聚氨酯材料,扩大了使用范围和场景。并且本发明中原料易得,工艺要求低,适合大规模制备以及各场所的推广使用。
具体实施方式
本发明提供了一种保温阻燃聚氨酯材料,由包含下列质量份数的原料制备得到:
多元醇40~60份、异氰酸酯40~50份、发泡剂1~3份、阻燃剂8~10份、催化剂4~6份、扩链剂2~4份、水1~3份。
在本发明中,所述多元醇的质量份数优选为42~58份,进一步优选为44~56份,更优选为48~52份。
在本发明中,所述多元醇优选包含聚丙二醇、聚四氢呋喃二醇和四氢呋喃氧化丙烯共聚二醇中的一种或几种。
在本发明中,所述异氰酸酯的质量份数优选为42~48份,进一步优选为43~47份,更优选为44~45份。
在本发明中,所述异氰酸酯优选包含甲苯二异氰酸酯、异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯中的一种或几种。
在本发明中,所述发泡剂的质量份数优选为1.2~2.8份,进一步优选为1.4~2.6份,更优选为1.8~2.2份。
在本发明中,所述发泡剂优选包含环己烷和四氟乙烷。
在本发明中,所述环己烷和四氟乙烷的质量比优选为1:1~1.3,进一步优选为1:1.1~1.2,更优选为1:1.14~1.15。
在本发明中,所述阻燃剂的质量份数优选为8.5~9.5份,进一步优选为8.6~9.4份,更优选为8.8~9.2份。
在本发明中,所述阻燃剂的制备方法优选包含下列步骤:
(1)将亚磷酸二甲酯、丙烯酰胺和甲醇钠混合进行水解反应,得到中间体;
(2)将中间体、环糊精和氢氧化钠混合进行反应,即得所述阻燃剂。
在本发明中,步骤(1)所述亚磷酸二甲酯和丙烯酰胺的摩尔比优选为0.5~1.5:0.5~1.5,进一步优选为0.6~1.4:0.6~1.4,更优选为0.8~1.2:0.8~1.2。
在本发明中,步骤(1)中混合后体系的pH值优选为7.2~7.5,更优选为7.3~7.4。
在本发明中,步骤(1)中所述水解反应的温度优选为60~80℃,进一步优选为65~75℃,更优选为68~72℃;时间优选为4~6h,进一步优选为4.5~5.5h,更优选为4.8~5.2h。
在本发明中,步骤(2)中所述环糊精和步骤(1)中所述丙烯酰胺的摩尔比优选为0.8~1.2:1~1.2,进一步优选为0.9~1.1:1.05~1.15,更优选为0.95~1.05:1.08~1.12。
在本发明中,步骤(2)中混合后体系的pH值优选为6.5~7.0,进一步优选为6.6~6.9,更优选为6.7~6.8。
在本发明中,步骤(2)中所述反应的温度优选为45~55℃,进一步优选为46~54℃,更优选为48~52℃;时间优选为0.5~0.8h,进一步优选为0.6~0.7h,更优选为0.64~0.65h。
在本发明中,所述催化剂的质量份数优选为4.5~5.5份,进一步优选为4.6~5.4份,更优选为4.8~5.2份。
在本发明中,所述催化剂优选包含辛酸亚锡和五甲基二乙烯三胺。
在本发明中,所述辛酸亚锡和五甲基二乙烯三胺的质量比优选为1:0.5~0.8,进一步优选为1:0.6~0.7,更优选为1:0.64~0.66。
在本发明中,所述扩链剂的质量份数优选为2.2~3.8份,进一步优选为2.5~3.5份,更优选为2.8~3.2份。
在本发明中,所述扩链剂优选包含1,4-丁二醇和/或季戊四醇。
在本发明中,所述水的质量份数优选为1.5~2.5份,进一步优选为1.6~2.4份,更优选为1.8~2份。
本发明还提供了所述保温阻燃聚氨酯材料的制备方法,包含下列步骤:
(1)将多元醇、阻燃剂、催化剂和水混合,得到醇体系;
(2)将醇体系、异氰酸酯、发泡剂和扩链剂混合后顺次进行熟化和固化,即得所述保温阻燃聚氨酯材料。
在本发明中,步骤(1)中所述混合的转速优选为100~150rpm,进一步优选为110~140rpm,更优选为120~130rpm;时间优选为10~20min,进一步优选为12~18min,更优选为14~16min。
在本发明中,步骤(2)中所述混合的转速优选为100~150rpm,进一步优选为110~140rpm,更优选为120~130rpm;温度优选为50~60℃,进一步优选为52~58℃,更优选为54~56℃;时间优选为1~2h,进一步优选为1.2~1.8h,更优选为1.4~1.6h。
在本发明中,所述熟化的时间优选为30~40min,进一步优选为32~38min,更优选为34~36min。
在本发明中,所述固化的温度优选为60~65℃,进一步优选为61~64℃,更优选为62~63℃;时间优选为1~2h,进一步优选为1.2~1.8h,更优选为1.4~1.6h。
下面结合实施例对本发明提供的技术方案进行详细的说明,但是不能把它们理解为对本发明保护范围的限定。
实施例1
取1mol的亚磷酸二甲酯和1.2mol的丙烯酰胺,加入甲醇钠后控制pH值为7.3,混合均匀后在70℃下水解5h得到混合体系即为中间体;将中间体、1.2mol的环糊精和氢氧化钠混合,控制pH值为6.8,然后在50℃下反应0.8h得到阻燃剂。
取50份聚丙二醇、50份甲苯二异氰酸酯、2份发泡剂(其中环己烷和四氟乙烷的质量比1:1.2)、10份阻燃剂、5份催化剂(其中辛酸亚锡和五甲基二乙烯三胺的质量比为1:0.6)、2份1,4-丁二醇和2份水。
将多元醇、阻燃剂、催化剂和水混合,在140rpm条件下搅拌20min得到醇体系;将醇体系、异氰酸酯、发泡剂和扩链剂混合,在100rpm、50℃条件下搅拌1.5h,熟化40min后,在60℃下固化1.5h得到保温阻燃聚氨酯材料。
实施例2
取0.8mol的亚磷酸二甲酯和1mol的丙烯酰胺,加入甲醇钠后控制pH值为7.5,混合均匀后在62℃下水解4.5h得到混合体系即为中间体;将中间体、1.1mol的环糊精和氢氧化钠混合,控制pH值为6.6,然后在45℃下反应0.6h得到阻燃剂。
取57份聚四氢呋喃二醇、48份异佛尔酮二异氰酸酯、3份发泡剂(其中环己烷和四氟乙烷的质量比1:1.1)、8.5份阻燃剂、5.8份催化剂(其中辛酸亚锡和五甲基二乙烯三胺的质量比为1:0.8)、4份季戊四醇和3份水。
将多元醇、阻燃剂、催化剂和水混合,在100rpm条件下搅拌15min得到醇体系;将醇体系、异氰酸酯、发泡剂和扩链剂混合,在130rpm、60℃条件下搅拌1h,熟化35min后,在63℃下固化1.8h得到保温阻燃聚氨酯材料。
实施例3
取1.2mol的亚磷酸二甲酯和0.9mol的丙烯酰胺,加入甲醇钠后控制pH值为7.2,混合均匀后在75℃下水解6h得到混合体系即为中间体;将中间体、1.2mol的环糊精和氢氧化钠混合,控制pH值为7,然后在53℃下反应0.8h得到阻燃剂。
取42份四氢呋喃氧化丙烯共聚二醇、50份六亚甲基二异氰酸酯、1.5份发泡剂(其中环己烷和四氟乙烷的质量比1:1.3)、9.6份阻燃剂、4.7份催化剂(其中辛酸亚锡和五甲基二乙烯三胺的质量比为1:0.5)、3.4份1,4-丁二醇和2份水。
将多元醇、阻燃剂、催化剂和水混合,在140rpm条件下搅拌20min得到醇体系;将醇体系、异氰酸酯、发泡剂和扩链剂混合,在150rpm、50℃条件下搅拌2h,熟化30min后,在60℃下固化1.2h得到保温阻燃聚氨酯材料。
将实施例1~3得到的保温阻燃聚氨酯材料进行性能检测,按照GB/T2406.2-2009进行极限氧指数测试;按照GB/T 10294-2008进行导热系数的测定;按照GB/T 8813-2008测试抗压强度;按照GB/T 8811-2008测试尺寸稳定性,测试结果记录在表1中。
表1实施例1~3保温阻燃聚氨酯材料测试结果
测试项目 | 实施例1 | 实施例2 | 实施例3 |
尺寸稳定性(-30℃,48h)% | -0.2 | -0.2 | -0.2 |
抗压强度(kPa) | 162 | 159 | 160 |
导热系数(W/m·K) | 0.02 | 0.021 | 0.021 |
极限氧指数(%) | 34.8 | 34.7 | 35.1 |
由以上实施例可知,本发明提供了一种保温阻燃聚氨酯材料,由包含下列质量份数的原料制备得到:多元醇40~60份、异氰酸酯40~50份、发泡剂1~3份、阻燃剂8~10份、催化剂4~6份、扩链剂2~4份、1~3水。在本发明中,通过添加自制的阻燃剂以及各原料的配合使用实现了聚氨酯材料阻燃性能的提升。根据实施例的结果可以看出,本发明提供的保温阻燃聚氨酯材料尺寸稳定性优秀,抗压强度达到162kPa,导热系数低至0.02W/m·K,极限氧指数高达35.1%,是一种综合性能优异的聚氨酯材料,可适用于多种场景。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种保温阻燃聚氨酯材料,其特征在于,由包含下列质量份数的原料制备得到:
多元醇40~60份、异氰酸酯40~50份、发泡剂1~3份、阻燃剂8~10份、催化剂4~6份、扩链剂2~4份、水1~3份。
2.如权利要求1所述的保温阻燃聚氨酯材料,其特征在于,所述多元醇包含聚丙二醇、聚四氢呋喃二醇和四氢呋喃氧化丙烯共聚二醇中的一种或几种。
3.如权利要求1或2所述的保温阻燃聚氨酯材料,其特征在于,所述异氰酸酯包含甲苯二异氰酸酯、异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯中的一种或几种。
4.如权利要求3所述的保温阻燃聚氨酯材料,其特征在于,所述发泡剂包含环己烷和四氟乙烷;
所述环己烷和四氟乙烷的质量比为1:1~1.3。
5.如权利要求1或4所述的保温阻燃聚氨酯材料,其特征在于,所述阻燃剂的制备方法包含下列步骤:
(1)将亚磷酸二甲酯、丙烯酰胺和甲醇钠混合进行水解反应,得到中间体;
(2)将中间体、环糊精和氢氧化钠混合进行反应,即得所述阻燃剂。
6.如权利要求5所述的保温阻燃聚氨酯材料,其特征在于,步骤(1)所述亚磷酸二甲酯和丙烯酰胺的摩尔比为0.5~1.5:0.5~1.5;
步骤(1)中混合后体系的pH值为7.2~7.5;
步骤(1)中所述水解反应的温度为60~80℃,时间为4~6h;
步骤(2)中所述环糊精和步骤(1)中所述丙烯酰胺的摩尔比为0.8~1.2:1~1.2;
步骤(2)中混合后体系的pH值为6.5~7.0;
步骤(2)中所述反应的温度为45~55℃,时间为0.5~0.8h。
7.如权利要求1或6所述的保温阻燃聚氨酯材料,其特征在于,所述催化剂包含辛酸亚锡和五甲基二乙烯三胺;
所述辛酸亚锡和五甲基二乙烯三胺的质量比为1:0.5~0.8。
8.如权利要求7所述的保温阻燃聚氨酯材料,其特征在于,所述扩链剂包含1,4-丁二醇和/或季戊四醇。
9.权利要求1~8任意一项所述保温阻燃聚氨酯材料的制备方法,其特征在于,包含下列步骤:
(1)将多元醇、阻燃剂、催化剂和水混合,得到醇体系;
(2)将醇体系、异氰酸酯、发泡剂和扩链剂混合后顺次进行熟化和固化,即得所述保温阻燃聚氨酯材料。
10.如权利要求9所述的制备方法,其特征在于,步骤(1)中所述混合的转速为100~150rpm,时间为10~20min;
步骤(2)中所述混合的转速为100~150rpm,温度为50~60℃,时间为1~2h;
所述熟化的时间为30~40min;
所述固化的温度为60~65℃,时间为1~2h。
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