CN114835872A - 一种高阻燃低导热聚氨酯泡沫材料及其制备方法 - Google Patents
一种高阻燃低导热聚氨酯泡沫材料及其制备方法 Download PDFInfo
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- CN114835872A CN114835872A CN202210633283.8A CN202210633283A CN114835872A CN 114835872 A CN114835872 A CN 114835872A CN 202210633283 A CN202210633283 A CN 202210633283A CN 114835872 A CN114835872 A CN 114835872A
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Abstract
本发明提供一种高阻燃低导热聚氨酯泡沫材料,其中,按重量份数计,由如下成分组成:聚醚多元醇A:20‑30份;聚醚多元醇B:5‑25份;聚酯多元醇C:10‑30份;阻燃剂A:10‑15份;阻燃剂B:3‑8份;泡沫稳定剂:1‑3份;催化剂:2‑4份;蒸馏水:1‑5份;发泡剂:8‑15份;异氰酸酯:110‑180份。本发明通过聚酯多元醇的刚性基团,能够提高泡沫强度的同时避免泡沫收缩。能够通过直接镶嵌在分子链中的阻燃结构,来提高泡沫阻燃的持久性和尺寸稳定性,从而提高了泡沫材料的阻燃性能,能够通过降低泡沫的密度,来降低泡沫的成本以及导热系数。
Description
技术领域
本发明涉及高分子材料领域,特别是一种高阻燃低导热聚氨酯泡沫材料及其制备方法。
背景技术
聚氨酯泡沫密度小,导热系数低,广泛用于保温隔热行业,如冰箱,中央空调等行业。但是,聚氨酯泡沫材料作为一种有机物,为易燃材料,比表面积大,燃烧时会以极快的速度蔓延,同时产生大量有毒气体和烟雾,在施工及使用过程中存在着安全隐患。这极大的限制了聚氨酯泡沫塑料的应用。因而,研制具有良好阻燃功能的聚氨酯泡沫材料,将会大大提升其应用价值。按照目前GB8624-2012来划分的燃烧性能等级,我国聚氨酯泡沫在市场上面,多为B2阻燃等级,并且工艺技术趋于成熟化,随着近几年对保温材料阻燃要求的提高,B2级己不能满足高阻燃场合的使用需求,B1级聚氨酯保温板将成为未来市场重要的需求产品,比如在较高层的建筑上需要防火等级高的发泡板绝热板,处理器终端要求低温隔热场合和人流多场合如地铁里都需要使用高阻燃低导热绝热板。
但是,市场上现有的多数B1级阻燃发泡板使用的聚醚多元醇为组合物,需要添加的阻燃剂的量通常达到30-60wt%,过高的添加比例严重提高固体部分传热效率,影响了泡沫的物理性能,从而保温效果下降、间接导致保温层厚度增加,成本增加。
发明内容
为了克服现有技术的上述缺点,本发明的目的是提供一种高阻燃低导热聚氨酯泡沫材料及其制备方法,以解决上述技术问题。
本发明解决其技术问题所采用的技术方案是:
一种高阻燃低导热聚氨酯泡沫材料,其中,按重量份数计,由如下成分反应合成:
聚醚多元醇A:20-30份;
聚醚多元醇B:5-25份;
聚酯多元醇C:10-30份;
阻燃剂A:10-15份;
阻燃剂B:3-8份;
泡沫稳定剂:1-3份;
催化剂:2-4份;
蒸馏水:1-5份;
发泡剂:8-15份;
异氰酸酯:110-180份。
作为本发明的进一步改进:所述聚醚多元醇A为含磷、氯、溴阻燃基团的阻燃聚醚多元醇;所述聚醚多元醇B为具有伯羟基柔性长链结构的聚醚多元醇;所述聚酯多元醇C为含氮杂环多元醇;所述阻燃剂A为磷酸酯或磷酸酯的混合物;所述阻燃剂B为气凝胶粉末。
作为本发明的进一步改进:所述催化剂为三乙醇胺和有机锡T-20。
作为本发明的进一步改进:所述发泡剂为二氯一氟乙烷((HCFC-141b)、二氯三氟乙烷((HCFC-123)、1,1,1-三氟乙烷、1,1,1,4,4,4-六氟丁烷(HFC-356mffm)、1,1,1,3,3-五氟丁烷(HFC-365mfc)、1,1,1,4,4-五氟丁烷(HFC-245fa)、正戊烷、异戊烷、环戊烷中任意一种或多种的混合物。
作为本发明的进一步改进:所述发泡剂为365mfc(五氟丁烷)和环戊烷的混合物。
作为本发明的进一步改进:所述异氰酸酯为2,4-二苯基甲烷二异氰酸酯与4,4’-二苯基甲烷二异氰酸酯的混合物。
一种高阻燃低导热聚氨酯泡沫材料的制备方法,其中,包括:
(1)称取聚醚多元醇A、聚醚多元醇B和聚酯多元醇C混合均匀;加入泡沫稳定剂搅拌均匀;加入催化剂搅拌均匀;加入蒸馏水搅拌混合;加入阻燃剂A和阻燃剂B搅拌均匀;加入发泡剂搅拌混合形成白料,并保持在18℃-20℃;
(2)将异氰酸酯作为黑料保持在18℃-20℃;
(3)将模具的温度保持在35℃;
(4)将黑料和白料在3000r/min下搅拌8-10s,得到混合料;
(5)将混合料倒入模具中,盖好模具,熟化1h,得到成品。
作为本发明的进一步改进:所述聚酯多元醇C的制备方法包括:
(1)将摩尔比为2:1的偏苯三酐和二元胺与催化剂混合,加入催化剂和反应溶剂,在75-90℃中进行氨化、环化、脱水反应,得到二元含氮杂环二元羧酸;
(2)将摩尔比为1:1-2的二元含氮杂环二元羧酸与二元醇混合,加入酯化反应催化剂进行酯化,至12-16h后得到所述聚酯多元醇C。
9.根据权利要求7所述的一种高阻燃低导热聚氨酯泡沫材料的制备方法,其特征在于,所述阻燃剂B的制备方法包括:
将正硅酸四乙酯、水和乙醇按照1:4:7的比例与酸水解24h,再加入摩尔比为0.8-1的二甲基甲酰胺混合,最后加入氨水,在PH值为7.5下快速凝胶,过滤干燥后得到阻燃剂B。
作为本发明的进一步改进:所述阻燃剂B的制备方法包括:
将硅酸钠与强酸按1.26:1混合得到正硅酸,将正硅酸脱水缩合得到气凝胶,将气凝胶陈化48h后,加入20%体积分数的蒸馏水/无水乙醇,老化12h;再加入20%体积分数的正硅酸乙酯/无水乙醇老化24h,得到老化液;倒出老化液,常压60℃干燥8小时后,打碎形成粉末,得到阻燃剂B。
与现有技术相比,本发明的有益效果是:
通过聚酯多元醇的刚性基团,能够提高泡沫强度的同时避免泡沫收缩。能够通过直接镶嵌在分子链中的阻燃结构,来提高泡沫阻燃的持久性和尺寸稳定性,从而提高了泡沫材料的阻燃性能,能够通过降低泡沫的密度,来降低泡沫的导热性能。
附图说明
图1为本发明的聚酯多元醇C制备反应示意图。
图2为本发明的阻燃剂B制备反应示意图。
图3为本发明的阻燃剂B制备反应示意图。
具体实施方式
现结合附图说明与实施例对本发明进一步说明:
实施例一:
本发明提供一种高阻燃低导热聚氨酯泡沫材料,其特征在于,按重量份数计,由如下成分组成:
聚醚多元醇A:20-30份;聚醚多元醇B:5-25份;聚酯多元醇C:10-30份;阻燃剂A:10-15份;阻燃剂B:3-8份;泡沫稳定剂:1-3份;催化剂:2-4份;蒸馏水:1-5份;发泡剂:8-15份;异氰酸酯:110-180份。
配方表格如下:
名称 | 份数 |
聚醚多元醇A | 20-30 |
聚醚多元醇B | 5-25 |
聚酯多元醇C | 10-30 |
阻燃剂A | 10-15 |
阻燃剂B | 3-8 |
泡沫稳定剂 | 1-3 |
催化剂 | 2-4 |
蒸馏水 | 1-5 |
发泡剂 | 8-15 |
异氰酸酯 | 110-180 |
在本发明中,所述聚醚多元醇A为含磷、氯、溴阻燃基团的阻燃聚醚多元醇;卤素可以阻燃,以氯化甘油为起始剂,引发环氧乙烷反应生成含氯多元醇,引发剂越多,含氯元素越多,阻燃性能越高。
所述聚醚多元醇B为具有伯羟基柔性长链结构的聚醚多元醇;在本发明中,聚醚多元醇B以水起始剂与环氧乙烷经加成反应聚合制得;反应比例为水比环氧=1:4-5,优选1:4.5;羟值250-400mgKOH/g。该多元醇具有伯羟基柔性长链结构,可明显改善泡沫表面脆性,从而达到提高聚氨酯泡沫粘结性的作用。
所述聚酯多元醇C为含氮杂环多元醇;即具有苯环及苯酞亚胺结构的聚酯二元醇。
所述阻燃剂A为磷酸酯或磷酸酯的混合物;在本发明的其中一个实施例中,阻燃剂A为磷元素含量为8-30wt%的磷酸酯,如TCPP、TCEP、TEP、DMMP。优选为磷酸三(2-氯丙基)酯TCPP和磷酸三乙酯TEP混合物,比例1:1。
所述阻燃剂B为气凝胶粉末;其密度低,阻燃性能高,导热系数低。为多孔二氧化硅材料,表面带有羟基。多孔材料,密度低,导热系数低,羟基与异氰酸酯基团反应,增强力学性能。
所述催化剂为三乙醇胺和有机锡T-20;三乙醇胺能有效催化三聚反应,提高交联度,提高泡沫的强度。有机锡T-20可以有效的催化凝胶,用量为多元醇的2-4%,优选3%。
在本发明中,所述发泡剂为二氯一氟乙烷((HCFC-141b)、二氯三氟乙烷((HCFC-123)、1,1,1-三氟乙烷、1,1,1,4,4,4-六氟丁烷(HFC-356mff)、1,1,1,3,3-五氟丁烷(HFC-365mfc)、1,1,1,4,4-五氟丁烷(HFC-245fa)、正戊烷、异戊烷、环戊烷中任意一种或多种的混合物。另外,发泡剂优选选用365mfc(五氟丁烷)和环戊烷的混合物,其环保性能好,沸点低,能有效提高发泡反应速率。环戊烷占比四分之三。另外水也可以与异氰酸酯反应生成气体二氧化碳,充当发泡剂,水含量为多元醇的1-5%,优选2%。
所述异氰酸酯为2,4-二苯基甲烷二异氰酸酯与4,4’-二苯基甲烷二异氰酸酯的混合物。该混合物含有苯环结构,能够通过刚性基团来增加强度,其混合比例为1:3。异氰酸酯用量与多元醇用量比1.3-2:1,优选1.45。并通过发泡机混合发泡。
在本发明中,B1级阻燃聚氨酯硬质泡沫制备工艺中,所用高压发泡的混合压力(表压)为120-150MPa,原料温度为18-20℃。所述发泡保温温度为35-45℃。
实施例二:
本发明还提供一种高阻燃低导热聚氨酯泡沫材料的制备方法,其特征在于,包括:
(1)称取聚醚多元醇A、聚醚多元醇B和聚酯多元醇C混合均匀;加入泡沫稳定剂搅拌均匀;加入催化剂搅拌均匀;加入蒸馏水搅拌混合;加入阻燃剂A和阻燃剂B搅拌均匀;加入发泡剂搅拌混合形成白料,并保持在18℃-20℃;
(2)将异氰酸酯作为黑料保持在18℃-20℃;
(3)将模具的温度保持在35℃;
(4)将黑料和白料在3000r/min下搅拌8-10s,得到混合料;
(5)将混合料倒入模具中,盖好模具,熟化1h,得到成品。
如附图1所示,在本实施例中,所述聚酯多元醇C的制备方法包括:
(1)将摩尔比为2:1的偏苯三酐和二元胺与催化剂混合,加入催化剂和反应溶剂,在75-90℃中进行氨化、环化、脱水反应,得到二元含氮杂环二元羧酸;
(2)将摩尔比为1:1-2的二元含氮杂环二元羧酸与二元醇混合,加入酯化反应催化剂进行酯化,至12-16h后得到所述聚酯多元醇C。所述聚酯多元醇C具有芳基及含氮杂环刚性结构,即具有苯环及苯酞亚胺结构的聚酯二元醇。反应过程如附图1所示。
其中,二元胺可以也可以为丙二胺、丁二胺,最佳为乙二胺。所述用于偏苯三酐与乙二胺氨化、环化反应的催化剂为无水醋酸钠,催化剂用量为反应原料的2%-4%,反应溶剂为丙酮;所二元醇可以为乙二醇,丙二醇、丁二醇,缩二乙二醇或其混合物,最佳为缩二乙二醇,所述氨化和环化脱水的反应温度为75-90℃;二元醇与二元含氮杂环二元竣酸采用熔融酯化反应,两者摩尔比为1-2:1,以H3BO3-ZnO(1:1(摩尔比))作为酯化反应催化剂,其添加量为基于所述二元醇与含氮杂环总量的0.2%-0.3%,反应时间12-16h。
在本实施例中,所述阻燃剂B的制备方法包括:
如附图2-3所示,将正硅酸四乙酯、水和乙醇按照1:4:7的比例与酸水解24h,再加入摩尔比为0.8-1的二甲基甲酰胺混合,最后加入氨水,在PH值为7.5下快速凝胶得到阻燃剂B。即正硅酸四乙酯水解生成正硅酸,正硅酸进一步脱水缩合,最后形成气凝胶骨架。
或者:
将硅酸钠与强酸按1.26:1混合反应得到正硅酸,将正硅酸脱水缩合得到气凝胶,将气凝胶陈化48h后,加入20%体积分数的蒸馏水/无水乙醇,老化12h;再加入20%体积分数的正硅酸乙酯/无水乙醇老化24h,得到老化液;倒出老化液,常压60℃干燥8小时后,打碎形成粉末,得到阻燃剂B。例如,将硅酸钠在酸性条件下形成硅酸,进一步形成正硅酸,然后脱水缩合形成气凝胶。酸为强酸,可为盐酸和硫酸,已硫酸为例,硫酸用量与硅酸钠用量比为1.26:1,形成凝胶后,将凝胶陈化两天后,加入20%体积分数的蒸馏水/无水乙醇,老化12小时;再加入20%体积分数的正硅酸乙酯/无水乙醇老化24小时。倒出老化液,进行干燥。常压60℃干燥8小时,将其打碎形成粉末,得到阻燃剂B。
实施例三:
称取上70g的聚醚多元醇并混合,25g的聚醚多元醇A,20g的聚醚多元醇B,25g的聚醚多元醇C;主要的作用是与异氰酸酯反应,羟基与异氰酸酯反应放热,并交联反应,形成骨架。
另外提供阻燃元素,聚醚多元醇A提供阻燃元素氯;聚醚多元醇C提供阻燃元素氮。
加入1.5g泡沫稳定剂,并搅拌;作用是保证泡孔大小稳定,导热慢,导热系数低;
加入3g的催化剂,搅拌混合;控制发泡反应速率,使反应平稳;
加入2.5g的水,搅拌混合;一方面与异氰酸酯反应放出气体形成泡孔,另一方面可以起控制反应速率作用。
加入14份阻燃剂A,3份阻燃剂B,搅拌均匀;阻燃剂A提供阻燃元素磷;阻燃剂B提供阻燃元素硅,另外表面含有羟基,可以与异氰酸酯反应,充当交联骨架,另外其密度低,降低整体密度。
最后加入11份的发泡剂,搅拌混合形成白料,作用为在多元醇和异氰酸酯反应过程中吸收反应热量从液态转换为气体,形成泡孔,降低泡沫密度。
称取135g异氰酸酯,为黑料;将白料和黑料温度控制在20℃,防止发泡剂吸收热量提前挥发;
取300*300*50mm大的模具保温35℃,该温度控制发泡料反应速率和熟化时间;
将白料和黑料放在3000r/min搅拌装置下搅拌8-10s,得到混合料,使白料和黑料充分混合,羟基与异氰酸基团充分接触反应。
将搅拌完的混合料立刻倒入模具中,盖好模具,熟化1h后及得到硬质泡沫材料样品。
熟化作用是使羟基与异氰酸酯充分反应交联形成泡沫骨架,发泡剂挥发形成泡孔。
试验验证:
1.制备组分:
(1)将摩尔比为2:1的偏苯三酐与对乙二胺、500ml乙酸乙酯溶剂加入到反应釜中,待完全溶解再加入1.5wt%的无水醋酸钠催化剂于80-90℃进行氨化脱水环化反应,形成二元含氮杂环二元羧酸。该二元酸再与乙二醇(摩尔比=1:2)在0.2wt%H3BO3-ZnO(摩尔比=1:1)的催化作用于200-230℃下进行真空酚化脱水反应,得到官能度为2的聚酯多元醇C。
(2)配置1mol/L的硅酸钠溶液,像其中滴加1mol/L的硫酸,当滴加到PH=6.8时,会产生凝胶。将凝胶陈化两天后,用蒸馏水置换气凝胶中的水,除去硫酸钠等盐分以及未反应残留物。再干燥4小时得到气凝胶,得到阻燃剂B。
2.聚氨酯硬质泡沫的制备如下:
按下表配方比例称取聚醚/聚酯多元醇、阻燃剂、泡沫稳定剂、催化剂、水及发泡剂置于高速搅拌机内将其混合均匀,形成组合多元醇,之后与多异氰酸分别加入到高压机发泡剂,启动发泡剂,通循环水,控制黑白料罐中物料温度在上18-20℃。两者按照比例混合后从高压机喷嘴射打出,分别打自由泡和硬泡。
试验配方表:
名称 | 配方1 | 配方2 | 配方3 | 配方4 | 配方5 |
聚醚多元醇A | 30 | 30 | 25 | 20 | 30 |
聚醚多元醇B | 15 | 20 | 20 | 25 | 25 |
聚酯多元醇C | 25 | 20 | 25 | 25 | 15 |
阻燃剂A | 12 | 10 | 14 | 11 | 13 |
阻燃剂B | 5 | 7 | 3 | 6 | 4 |
泡沫稳定剂 | 1.5 | 2 | 1.5 | 2 | 1.5 |
催化剂 | 2.5 | 3 | 3 | 3 | 2.5 |
蒸馏水 | 3 | 2 | 2.5 | 2 | 3 |
发泡剂 | 10 | 8 | 11 | 9 | 9 |
异氰酸酯 | 135 | 135 | 135 | 135 | 135 |
3.性能测试结果如下表所示:
本发明的主要功能:
应用于各类泡沫材料及其材料的制备方法,特别是一种高阻燃低导热聚氨酯泡沫材料及其制备方法,也用于制造组合柜、矿井机泡沫保温材料等领域。通过采用含氮杂环的聚酯多元醇,与常用聚酯或聚醚多元醇相比,具有更优异的刚性基团,大幅度提高泡沫强度,泡沫强度高,不收缩。其分子链内部含有耐热阻燃的、苯酞亚胺杂环、卤素等阻燃结构,阻燃结构直接镶嵌在分子链当中,泡沫阻燃持久性和尺寸稳定性大幅度提高。而发泡料中含有大量阻燃元素,大大提高了发泡板的阻燃性能,主要元素有氯、磷、硅等。氧指数高达31。发泡料中掺杂有保温性能好密度轻的气凝胶,大大的降低泡沫的密度,提高其阻燃性。
综上所述,本领域的普通技术人员阅读本发明文件后,根据本发明的技术方案和技术构思无需创造性脑力劳动而作出其他各种相应的变换方案,均属于本发明所保护的范围。
Claims (10)
1.一种高阻燃低导热聚氨酯泡沫材料,其特征在于,按重量份数计,由如下成分反应合成:
聚醚多元醇A:20-30份;
聚醚多元醇B:5-25份;
聚酯多元醇C:10-30份;
阻燃剂A:10-15份;
阻燃剂B:3-8份;
泡沫稳定剂:1-3份;
催化剂:2-4份;
蒸馏水:1-5份;
发泡剂:8-15份;
异氰酸酯:110-180份。
2.根据权利要求1所述的一种高阻燃低导热聚氨酯泡沫材料,其特征在于,所述聚醚多元醇A为含磷、氯、溴阻燃基团的阻燃聚醚多元醇;所述聚醚多元醇B为具有伯羟基柔性长链结构的聚醚多元醇;所述聚酯多元醇C为含氮杂环多元醇;所述阻燃剂A为磷酸酯或磷酸酯的混合物;所述阻燃剂B为气凝胶粉末。
3.根据权利要求1所述的一种高阻燃低导热聚氨酯泡沫材料,其特征在于,所述催化剂为三乙醇胺和有机锡T-20。
4.根据权利要求1所述的一种高阻燃低导热聚氨酯泡沫材料,其特征在于,所述发泡剂为二氯一氟乙烷((HCFC-141b)、二氯三氟乙烷((HCFC-123)、1,1,1-三氟乙烷、1,1,1,4,4,4-六氟丁烷(HFC-356mffm)、1,1,1,3,3-五氟丁烷(HFC-365mfc)、1,1,1,4,4-五氟丁烷(HFC-245fa)、正戊烷、异戊烷、环戊烷中任意一种或多种的混合物。
5.根据权利要求1所述的一种高阻燃低导热聚氨酯泡沫材料,其特征在于,所述发泡剂为365mfc(五氟丁烷)和环戊烷的混合物。
6.根据权利要求1所述的一种高阻燃低导热聚氨酯泡沫材料,其特征在于,所述异氰酸酯为2,4-二苯基甲烷二异氰酸酯与4,4’-二苯基甲烷二异氰酸酯的混合物。
7.一种高阻燃低导热聚氨酯泡沫材料的制备方法,其特征在于,包括:
(1)称取聚醚多元醇A、聚醚多元醇B和聚酯多元醇C混合均匀;加入泡沫稳定剂搅拌均匀;加入催化剂搅拌均匀;加入蒸馏水搅拌混合;加入阻燃剂A和阻燃剂B搅拌均匀;加入发泡剂搅拌混合形成白料,并保持在18℃-20℃;
(2)将异氰酸酯作为黑料保持在18℃-20℃;
(3)将模具的温度保持在35℃;
(4)将黑料和白料在3000r/min下搅拌8-10s,得到混合料;
(5)将混合料倒入模具中,盖好模具,熟化1h,得到成品。
8.根据权利要求7所述的一种高阻燃低导热聚氨酯泡沫材料的制备方法,其特征在于,所述聚酯多元醇C的制备方法包括:
(1)将摩尔比为2:1的偏苯三酐和二元胺与催化剂混合,加入催化剂和反应溶剂,在75-90℃中进行氨化、环化、脱水反应,得到二元含氮杂环二元羧酸;
(2)将摩尔比为1:1-2的二元含氮杂环二元羧酸与二元醇混合,加入酯化反应催化剂进行酯化,至12-16h后得到所述聚酯多元醇C。
9.根据权利要求7所述的一种高阻燃低导热聚氨酯泡沫材料的制备方法,其特征在于,所述阻燃剂B的制备方法包括:
将正硅酸四乙酯、水和乙醇按照1:4:7的比例与酸水解24h,再加入摩尔比为0.8-1的二甲基甲酰胺混合,最后加入氨水,在PH值为7.5下快速凝胶,过滤干燥后得到阻燃剂B。
10.根据权利要求7所述的一种高阻燃低导热聚氨酯泡沫材料的制备方法,其特征在于,所述阻燃剂B的制备方法包括:
将硅酸钠与强酸按1.26:1混合得到正硅酸,将正硅酸脱水缩合得到气凝胶,将气凝胶陈化48h后,加入20%体积分数的蒸馏水/无水乙醇,老化12h;再加入20%体积分数的正硅酸乙酯/无水乙醇老化24h,得到老化液;倒出老化液,常压60℃干燥8小时后,打碎形成粉末,得到阻燃剂B。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115651150A (zh) * | 2022-10-11 | 2023-01-31 | 华北理工大学 | 水玻璃填充改性阻燃聚氨酯泡沫及其制备方法 |
CN116751354A (zh) * | 2023-07-11 | 2023-09-15 | 苏州健能新材料科技有限公司 | 木质素生物基阻燃型聚氨酯泡沫填缝剂及其制备方法 |
WO2024091536A1 (en) * | 2022-10-25 | 2024-05-02 | Dow Global Technologies Llc | Imide-containing polyols, methods for making imide-containing polyols and methods for using imide-containing polyols |
Citations (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3637543A (en) * | 1964-12-23 | 1972-01-25 | Standard Oil Co | Fire resistant polyurethane foams from polyisocyanates polyols and carboxylic acid derivatives |
US5093382A (en) * | 1991-08-08 | 1992-03-03 | Texaco Chemical Company | Preparation of foams using polyfunctional organic acids |
JPH04136014A (ja) * | 1990-09-27 | 1992-05-11 | Hitachi Chem Co Ltd | 発泡用樹脂組成物,発泡体および難燃性構造体 |
CN101233166A (zh) * | 2005-08-03 | 2008-07-30 | 陶氏环球技术公司 | 由含有羟基的脂肪酸酰胺制备的聚氨酯 |
CN102115528A (zh) * | 2009-12-31 | 2011-07-06 | 浙江华峰新材料股份有限公司 | 一种提高烃发泡剂相容性的芳族聚酯多元醇及其制备方法 |
CN102432816A (zh) * | 2010-09-29 | 2012-05-02 | 株式会社日立制作所 | 聚氨酯分解物、聚氨酯及聚氨酯形成方法 |
JP2013023669A (ja) * | 2011-07-25 | 2013-02-04 | Sanyo Chem Ind Ltd | ポリウレタンフォーム製造用ポリオール組成物 |
CN102924686A (zh) * | 2012-11-22 | 2013-02-13 | 中国铁道科学研究院铁道建筑研究所 | 一种用于散粒体固结的软质聚氨酯泡沫材料 |
CN103242647A (zh) * | 2013-04-27 | 2013-08-14 | 大连理工大学 | 一种阻燃耐热聚氨酯泡沫塑料及其制备方法 |
CN103923294A (zh) * | 2013-01-10 | 2014-07-16 | 上海联合气雾制品灌装有限公司 | 单组份阻燃聚氨酯泡沫填缝剂的制备 |
CN103936956A (zh) * | 2014-03-21 | 2014-07-23 | 万华化学集团股份有限公司 | 生产硬质聚氨酯泡沫材料的组合料及低气味、高阻燃的硬质聚氨酯泡沫 |
CN104151517A (zh) * | 2014-08-08 | 2014-11-19 | 甘肃科正建筑科技有限责任公司 | 一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料及其制备方法 |
CN104387549A (zh) * | 2014-11-27 | 2015-03-04 | 山东一诺威新材料有限公司 | 阻燃大块聚氨酯硬质泡沫用组合聚醚及其应用方法 |
CN104628979A (zh) * | 2015-02-09 | 2015-05-20 | 万华化学(宁波)容威聚氨酯有限公司 | 一种连续线生产用b1级阻燃聚氨酯硬质泡沫及制备方法和用途 |
CN104672420A (zh) * | 2015-02-09 | 2015-06-03 | 万华化学(宁波)容威聚氨酯有限公司 | 一种高强度聚氨酯硬质泡沫及其制备方法和用途 |
CN108285523A (zh) * | 2017-10-09 | 2018-07-17 | 南京大学 | 多羟基苯环磷氮型阻燃剂及其制法和在阻燃聚氨酯硬泡材料中的应用 |
CN109232850A (zh) * | 2018-08-08 | 2019-01-18 | 山东新朗华科技有限公司 | 一种气凝胶改性耐热阻燃低导热系数硬质聚氨酯泡沫塑料及其制备方法 |
CN109385204A (zh) * | 2018-10-12 | 2019-02-26 | 湖北长海新能源科技有限公司 | 一种水溶性聚酯酰亚胺绝缘漆及其制备方法 |
CN109912764A (zh) * | 2019-02-25 | 2019-06-21 | 广州立泰新材料科技有限公司 | 一种高阻燃硬质聚氨酯泡沫及其制备方法 |
CN110591042A (zh) * | 2019-10-25 | 2019-12-20 | 中国林业科学研究院林产化学工业研究所 | 一种阻燃型聚氨酯硬质泡沫的制备方法 |
CN111471208A (zh) * | 2020-06-04 | 2020-07-31 | 周玉 | 一种阻燃型聚氨酯建筑保温板的制备工艺 |
CN114341222A (zh) * | 2019-08-09 | 2022-04-12 | 亨斯迈国际有限责任公司 | 含芳族聚酯多元醇化合物的聚氨酯泡沫组合物及由其制备的产品 |
-
2022
- 2022-06-07 CN CN202210633283.8A patent/CN114835872B/zh active Active
Patent Citations (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3637543A (en) * | 1964-12-23 | 1972-01-25 | Standard Oil Co | Fire resistant polyurethane foams from polyisocyanates polyols and carboxylic acid derivatives |
JPH04136014A (ja) * | 1990-09-27 | 1992-05-11 | Hitachi Chem Co Ltd | 発泡用樹脂組成物,発泡体および難燃性構造体 |
US5093382A (en) * | 1991-08-08 | 1992-03-03 | Texaco Chemical Company | Preparation of foams using polyfunctional organic acids |
CN101233166A (zh) * | 2005-08-03 | 2008-07-30 | 陶氏环球技术公司 | 由含有羟基的脂肪酸酰胺制备的聚氨酯 |
CN102115528A (zh) * | 2009-12-31 | 2011-07-06 | 浙江华峰新材料股份有限公司 | 一种提高烃发泡剂相容性的芳族聚酯多元醇及其制备方法 |
CN102432816A (zh) * | 2010-09-29 | 2012-05-02 | 株式会社日立制作所 | 聚氨酯分解物、聚氨酯及聚氨酯形成方法 |
JP2013023669A (ja) * | 2011-07-25 | 2013-02-04 | Sanyo Chem Ind Ltd | ポリウレタンフォーム製造用ポリオール組成物 |
CN102924686A (zh) * | 2012-11-22 | 2013-02-13 | 中国铁道科学研究院铁道建筑研究所 | 一种用于散粒体固结的软质聚氨酯泡沫材料 |
CN103923294A (zh) * | 2013-01-10 | 2014-07-16 | 上海联合气雾制品灌装有限公司 | 单组份阻燃聚氨酯泡沫填缝剂的制备 |
CN103242647A (zh) * | 2013-04-27 | 2013-08-14 | 大连理工大学 | 一种阻燃耐热聚氨酯泡沫塑料及其制备方法 |
CN103936956A (zh) * | 2014-03-21 | 2014-07-23 | 万华化学集团股份有限公司 | 生产硬质聚氨酯泡沫材料的组合料及低气味、高阻燃的硬质聚氨酯泡沫 |
CN104151517A (zh) * | 2014-08-08 | 2014-11-19 | 甘肃科正建筑科技有限责任公司 | 一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料及其制备方法 |
CN104387549A (zh) * | 2014-11-27 | 2015-03-04 | 山东一诺威新材料有限公司 | 阻燃大块聚氨酯硬质泡沫用组合聚醚及其应用方法 |
CN104628979A (zh) * | 2015-02-09 | 2015-05-20 | 万华化学(宁波)容威聚氨酯有限公司 | 一种连续线生产用b1级阻燃聚氨酯硬质泡沫及制备方法和用途 |
CN104672420A (zh) * | 2015-02-09 | 2015-06-03 | 万华化学(宁波)容威聚氨酯有限公司 | 一种高强度聚氨酯硬质泡沫及其制备方法和用途 |
CN108285523A (zh) * | 2017-10-09 | 2018-07-17 | 南京大学 | 多羟基苯环磷氮型阻燃剂及其制法和在阻燃聚氨酯硬泡材料中的应用 |
CN109232850A (zh) * | 2018-08-08 | 2019-01-18 | 山东新朗华科技有限公司 | 一种气凝胶改性耐热阻燃低导热系数硬质聚氨酯泡沫塑料及其制备方法 |
CN109385204A (zh) * | 2018-10-12 | 2019-02-26 | 湖北长海新能源科技有限公司 | 一种水溶性聚酯酰亚胺绝缘漆及其制备方法 |
CN109912764A (zh) * | 2019-02-25 | 2019-06-21 | 广州立泰新材料科技有限公司 | 一种高阻燃硬质聚氨酯泡沫及其制备方法 |
CN114341222A (zh) * | 2019-08-09 | 2022-04-12 | 亨斯迈国际有限责任公司 | 含芳族聚酯多元醇化合物的聚氨酯泡沫组合物及由其制备的产品 |
CN110591042A (zh) * | 2019-10-25 | 2019-12-20 | 中国林业科学研究院林产化学工业研究所 | 一种阻燃型聚氨酯硬质泡沫的制备方法 |
CN111471208A (zh) * | 2020-06-04 | 2020-07-31 | 周玉 | 一种阻燃型聚氨酯建筑保温板的制备工艺 |
Non-Patent Citations (5)
Title |
---|
刘德辉, 夏建峰, 刘学贵: "合成全芳香族聚酯酰亚胺新工艺研究", 现代化工, no. 04, pages 25 - 26 * |
周成飞: "聚(氨酯-酰亚胺)的合成与应用研究进展 Ⅰ.聚(氨酯-酰亚胺)的合成技术", 合成技术及应用, vol. 29, no. 03, pages 18 - 23 * |
左晓兵;倪亚洲;高坡;朱亚辉;杨昌正;: "乙醇胺改性酰亚胺聚酯聚氨酯的合成及性能", 高分子材料科学与工程, no. 06, pages 30 - 33 * |
廖贵红;谢光亮;吴方娟;宋才生;: "聚芳酰胺酰亚胺的合成与性能", 高分子材料科学与工程, no. 05, pages 48 - 51 * |
蒋文俊;姚其胜;范仲勇;侯一斌;陆企亭;: "偏苯三酸酐聚酯多元醇的合成及其在PU硬泡中的应用研究", 功能材料, no. 17, pages 2578 - 2582 * |
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---|---|---|---|---|
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CN115651150B (zh) * | 2022-10-11 | 2024-06-04 | 华北理工大学 | 水玻璃填充改性阻燃聚氨酯泡沫及其制备方法 |
WO2024091536A1 (en) * | 2022-10-25 | 2024-05-02 | Dow Global Technologies Llc | Imide-containing polyols, methods for making imide-containing polyols and methods for using imide-containing polyols |
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