CN106674513A - 一种含磷与相变储能链段的改性聚醚多元醇及其制备方法 - Google Patents
一种含磷与相变储能链段的改性聚醚多元醇及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种含磷与相变储能链段的改性聚醚多元醇及其制备方法。该改性聚醚多元醇以三氯氧磷为偶联剂,通过其P‑Cl键与OH的充分反应,将相变储能物质聚乙二醇键接到聚醚多元醇上制得。本发明提供的含磷与相变储能链段的改性聚醚多元醇原料廉价易得、不含卤素、环保无毒,含有2个以上的活性端羟基可以与多亚甲基多苯基多异氰酸酯反应制备阻燃聚氨酯相变储能材料,既可克服物理添加型阻燃剂在聚氨酯体系中分散性差、容易降低材料物理性能的缺陷,又可同时赋予聚氨酯阻燃性能和相变储能性能。
Description
技术领域
本发明涉及阻燃聚合物以及保温隔热材料领域,具体涉及一种含磷与相变储能链段的改性聚醚多元醇及其制备方法。
背景技术
聚氨酯泡沫塑料因其性能优越、成型加工简单等特点得到快速发展,已成为世界主要的合成材料之一,被广泛应用于交通运输、家具、家电、日用品、建筑业等众多领域;按硬度聚氨酯泡沫塑料可分为软质和硬质两类,软质聚氨酯泡沫塑料广泛应用于垫材(如座椅、沙发、床垫等)和织物复合材料(如垫肩、文胸海绵、化妆棉和玩具等);硬质聚氨酯泡沫塑料最常被用做保温隔热材料,如何提高聚氨酯泡沫塑料的阻燃性能和软质聚氨酯的热舒适度以及硬质聚氨酯的保温隔热性能一直是人们所思考的问题。
利用物质在相变过程中吸收或放出相变潜热的相变储能技术也逐渐进入了人们的视野,所谓相变储能材料,就是可以在特定温度范围内,维持自身的温度不变,通过改变自身物理状态储存或释放热量的材料;合适的相变储能温度范围,不仅可以提高软质聚氨酯泡沫塑料的热舒适度,而且可以提高硬质聚氨酯泡沫塑料的保温隔热效果。
反应型磷系阻燃剂由于具有阻燃效率高、燃烧时不产生腐蚀性气体、阻燃持久稳定的特点,成为阻燃聚氨酯泡沫塑料的理想选择。然而,磷元素的引入,或多或少会增加材料的导热系数,从而使得聚氨酯材料的保温隔热性能降低,影响其节能效果,因此,提供一种具有良好的阻燃性能同时不降低保温隔热性能的聚氨酯材料对中国的节能领域具有重要意义。
聚醚多元醇是合成聚氨酯泡沫塑料的主要原料之一,广泛应用于制备聚氨酯泡沫、弹性体、涂料和纤维等产品,由含活性氢基团的低分子化合物如多元醇等作起始剂,在催化作用下与环氧化合物进行开环聚合反应而成;由于聚氨酯材料的性能主要取决于其原料聚醚多元醇的特性,通过对聚醚多元醇进行改性可以获得具有不同特性的聚氨酯材料,因此,亟需一种具有阻燃与相变储能功能于一体的聚醚多元醇材料。
发明内容
本发明的目的是提供一种含磷与相变储能链段的改性聚醚多元醇及其制备方法,其通过嵌段的方式在聚醚多元醇中嵌入聚乙二醇,使得其结晶性能保持独立性,从而具有良好的相变储能功能,同时,再在其中引入磷元素,使其同时具有良好的阻燃性能。
本发明解决上述技术问题的技术方案如下:提供一种含磷与相变储能链段的改性聚醚多元醇的制备方法,包括:
(1)在四氢呋喃中加入聚乙二醇,搅拌使聚乙二醇完全溶解,得到溶液A;
(2)在正己烷中加入三氯氧磷,搅拌使三氯氧磷完全溶解,得到溶液B;
(3)在40-50℃下,将溶液B加入到溶液A中,反应1.5小时,旋蒸,得到液态产物C;
(4)将液态产物C加热至90-100℃,滴加聚醚多元醇,反应1.5小时,即得含磷与相变储能链段的改性聚醚多元醇。
本发明的有效效果为:将三氯氧磷滴加到聚乙二醇溶液中时,P-Cl键会迅速与聚乙二醇末端的羟基发生反应生成P-O-C键和副产物HCl气体,当三氯氧磷的某个P-Cl键键接上聚乙二醇分子后,剩余P-Cl的反应活性会因空间位阻效应而降低,本发明通过控制聚乙二醇的添加量,进而制得含P-Cl键的三氯氧磷-聚乙二醇化合物。
在制备含磷与相变储能链段的聚醚多元醇的过程中,聚乙二醇和POCl3的反应十分剧烈,很容易生成其它产物,引入四氢呋喃作为聚乙二醇的溶剂、正己烷作为POCl3的稀释剂,一方面可以有效控制反应速率,另一方面正己烷和四氢呋喃共沸,旋蒸大概50℃左右就能一起蒸出;
同时,由于含磷与相变储能链段的聚醚多元醇中通过嵌段的方式嵌入了聚乙二醇,根据嵌段高分子理论,嵌段高分子中的嵌段在结晶性能上能够保持独立性,因此,聚乙二醇的结晶性能够保持独立性,从而赋予聚醚多元醇相变储能的功能,并且,聚醚多元醇结构单元和MDI结构单元的骨架作用以及聚氨酯三维网络结构的网络限域作用,使得即使聚乙二醇发生熔融相变也不流动;同时,由于偶联剂三氯氧磷引入了无卤阻燃元素磷元素,在受热时其可以催化化合物中的叔炭、苯环等成炭结构单元成炭,起隔热隔氧以及阻碍凝聚相和气相的物质传递而发挥阻燃作用。
在上述技术方案的基础上,本发明还可以做如下改进。
进一步,所述聚醚多元醇为丙二醇基聚氧化丙烯醚、乙二醇基聚氧化丙烯醚、丙三醇基聚氧化丙烯醚、三羟甲基丙烷聚氧化丙烯醚以及季戊四醇聚氧化丙烯醚中的任一种。
进一步,所述聚乙二醇、三氯氧磷和聚醚多元醇的重量比为1~3:1~1.15:2~7;
所述聚乙二醇与四氢呋喃的质量体积比为1.5~3:2~7;
所述三氯氧磷与正己烷的质量体积比为1~1.15:2~4。
进一步,所述聚乙二醇为聚乙二醇-600、聚乙二醇-800或聚乙二醇-1000。
进一步,步骤(3)中,在45℃下,将溶液B缓慢滴加到溶液A中,反应1小时,得到液态产物C。
进一步,步骤(4)中,将液态产物C加热至90℃,快速搅拌下滴加聚聚醚多元醇,反应1小时,得到含磷与相变储能链段的改性聚醚多元醇。
本发明的有益效果为:
1)本发明将通过嵌段的方式在聚醚多元醇中嵌入聚乙二醇,使得其结晶性能保持独立性,从而具有良好的相变储能功能,同时,再在其中引入磷元素,使其同时具有良好的持续阻燃性能。
2)本发明提供的含磷与相变储能链段的改性聚醚多元醇原料廉价易得、不含卤素、环保无毒,含有2个以上的活性端羟基可以与多亚甲基多苯基多异氰酸酯反应制备阻燃聚氨酯相变储能材料,既克服了物理添加型阻燃剂在聚氨酯体系中分散性差、容易降低材料物理性能的缺陷,又通过相变储能材料的加入解决了磷元素的加入导致的保温隔热性能降低的问题。
3)本发明的含磷与相变储能功能的改性聚醚多元醇对聚氨酯材料具有相变储能功能同时具有阻燃性能,使得聚氨酯材料可保持低导热系数有机高分子泡沫体的本质,其相变储能功能使得其可作为一种“智能”保温隔热材料的特征,当室内温度高于人体的舒适温度时发生相变吸收热量,储存的能量在室内温度较低时释放出来,而使室内温度较长时间恒定在人体最佳舒适温度范围内。
附图说明
图1为本发明含磷与相变储能链段的改性聚醚多元醇的红外光谱图;
具体实施方式
以下结合附图对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。
实施例1:
一种含磷与相变储能链段的改性聚醚多元醇的制备方法,包括:以三氯氧磷为偶联剂,通过其P-Cl键与OH的充分反应,将相变储能物质聚乙二醇键接到丙三醇基聚氧化丙烯醚上;
具体包括以下步骤:
(1)在三口圆底烧瓶中加入30ml四氢呋喃,然后缓慢加入15g聚乙二醇-800,常温下快速搅拌,溶解后得到溶液A;
(2)常温下,将10.00g三氯氧磷加入到20ml正己烷中配制成溶液B,然后倒入恒压漏斗,在45℃下,快速搅拌,缓慢滴加到溶液A中,滴料完毕,反应1小时,旋蒸,得到液态产物C;
(3)将液态产物C缓慢升温至90℃,在快速搅拌下缓慢滴加85g丙三醇基聚氧化丙烯醚,滴料完毕,反应1小时,得到含磷与相变储能链段的改性聚醚多元醇。
实施例2:
一种含磷与相变储能链段的改性聚醚多元醇的制备方法,包括:以三氯氧磷为偶联剂,通过其P-Cl键与OH的充分反应,将相变储能物质聚乙二醇键接到三羟甲基丙烷聚氧化丙烯醚上;
具体包括以下步骤:
(1)在三口圆底烧瓶中加入50ml四氢呋喃,然后缓慢加入25g聚乙二醇-800,常温下快速搅拌,溶解后得到溶液A;
(2)常温下,将11.50g三氯氧磷加入到40ml正己烷中配制成溶液B,然后倒入恒压漏斗,在50℃下,快速搅拌,缓慢滴加到溶液A中,滴料完毕,反应1.5小时,旋蒸,得到液态产物C;
(3)将液态产物C缓慢升温至100℃,在快速搅拌下缓慢滴加75g三羟甲基丙烷基聚氧化丙烯醚,滴料完毕,反应1.5小时,得到含磷与相变储能链段的改性聚醚多元醇。
实施例3:
一种含磷与相变储能链段的改性聚醚多元醇的制备方法,包括:以三氯氧磷为偶联剂,通过其P-Cl键与OH的充分反应,将相变储能物质聚乙二醇键接到季戊四醇基聚氧化丙烯醚上;
具体包括以下步骤:
(1)在三口圆底烧瓶中加入70ml四氢呋喃,然后缓慢加入30g聚乙二醇-600,常温下快速搅拌,溶解后得到溶液A;
(2)常温下,将11.50g三氯氧磷加入到40ml正己烷中配制成溶液B,然后倒入恒压漏斗,在40℃下,快速搅拌,缓慢滴加到溶液A中,滴料完毕,反应1.5小时,旋蒸,得到液态产物C;
(3)将液态产物C缓慢升温至95℃,在快速搅拌下缓慢滴加70g季戊四醇基聚氧化丙烯醚,滴料完毕,反应1小时,得到含磷与相变储能链段的改性聚醚多元醇。
实施例4:
一种含磷与相变储能链段的改性聚醚多元醇的制备方法,包括:以三氯氧磷为偶联剂,通过其P-Cl键与OH的充分反应,将相变储能物质聚乙二醇键接到丙二醇基聚氧化丙烯醚上;
具体包括以下步骤:
(1)在三口圆底烧瓶中加入70ml四氢呋喃,然后缓慢加入30g聚乙二醇-800,常温下快速搅拌,溶解后得到溶液A;
(2)常温下,将11.50g三氯氧磷加入到40ml正己烷中配制成溶液B,然后倒入恒压漏斗,在50℃下,快速搅拌,缓慢滴加到溶液A中,滴料完毕,反应1小时,旋蒸,得到液态产物C;
(3)将液态产物C缓慢升温至95℃,在快速搅拌下缓慢滴加70g丙二醇基聚氧化丙烯醚,滴料完毕,反应1.5小时,得到含磷与相变储能链段的改性聚醚多元醇。
实施例5:
一种含磷与相变储能链段的改性聚醚多元醇的制备方法,包括:以三氯氧磷为偶联剂,通过其P-Cl键与OH的充分反应,将相变储能物质聚乙二醇键接到乙二醇基聚氧化丙烯醚上;
具体包括以下步骤:
(1)在三口圆底烧瓶中加入70ml四氢呋喃,然后缓慢加入30g聚乙二醇-1000,常温下快速搅拌,溶解后得到溶液A;
(2)常温下,将11.50g三氯氧磷加入到40ml正己烷中配制成溶液B,然后倒入恒压漏斗,在45℃下,快速搅拌,缓慢滴加到溶液A中,滴料完毕,反应1小时,旋蒸,得到液态产物C;
(3)将液态产物C缓慢升温至90℃,在快速搅拌下缓慢滴加70g乙二醇基聚氧化丙烯醚,滴料完毕,反应1小时,得到含磷与相变储能链段的改性聚醚多元醇。
试验例
将本发明实施例2制得的含磷与相变储能链段的改性聚醚多元醇采用红外光谱测定其性能,具体如下:
图1为本发明含磷与相变储能链段的改性聚醚多元醇的红外光谱分析图,从图上可以看出,有旧的吸收峰消失和偏移,新的吸收峰产生,产生了新的化学键C-O-P=O,均说明了聚乙二醇经由三氯氧磷偶联后,成功接枝到了聚醚多元醇上,使得聚醚多元醇的分子结构发生变化,聚氨酯材料会因此含有P元素而具有阻燃性能。
Claims (7)
1.一种含磷与相变储能链段的改性聚醚多元醇的制备方法,其特征是,包括:
(1)在四氢呋喃中加入聚乙二醇,搅拌使聚乙二醇完全溶解得到溶液A;
(2)在正己烷中加入三氯氧磷,搅拌使三氯氧磷完全溶解得到溶液B;
(3)在40-50℃下,将溶液B加入到溶液A中,反应1~1.5小时,旋蒸,得到液态产物C;
(4)将液态产物C加热至90-100℃,滴加聚醚多元醇,反应1~1.5小时,即得含磷与相变储能链段的改性聚醚多元醇。
2.根据权利要求1所述的含磷与相变储能链段的改性聚醚多元醇的制备方法,其特征是,所述聚醚多元醇为丙二醇基聚氧化丙烯醚、乙二醇基聚氧化丙烯醚、丙三醇基聚氧化丙烯醚、三羟甲基丙烷聚氧化丙烯醚以及季戊四醇聚氧化丙烯醚中的任一种。
3.根据权利要求1所述的含磷与相变储能链段的改性聚醚多元醇的制备方法,其特征是:
所述聚乙二醇、三氯氧磷和聚醚多元醇的重量比为1~3:1~1.15:2~7;
所述聚乙二醇与四氢呋喃的质量体积比为1.5~3:3~7;
所述三氯氧磷与正己烷的质量体积比为1~1.15:2~4。
4.根据权利要求1所述的含磷与相变储能链段的改性聚醚多元醇的制备方法,其特征是,所述聚乙二醇为聚乙二醇-600、聚乙二醇-800或聚乙二醇-1000。
5.根据权利要求1所述的含磷与相变储能链段的改性聚醚多元醇的制备方法,其特征是,步骤(3)中,在45℃下,将溶液B缓慢滴加到溶液A中,反应1小时,得到液态产物C。
6.根据权利要求1所述的含磷与相变储能链段的改性聚醚多元醇的制备方法,其特征是,步骤(4)中,将液体产物C加热至90℃,快速搅拌下滴加聚醚多元醇,反应1小时,得到含磷与相变储能链段的改性聚醚多元醇。
7.权利要求1-6任一项所述的含磷与相变储能链段的改性聚醚多元醇的制备方法制备得到的改性聚醚多元醇。
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CN117511514A (zh) * | 2024-01-04 | 2024-02-06 | 西南石油大学 | 一种阻燃型聚乙烯醇气凝胶相变材料及其制备方法 |
CN117511514B (zh) * | 2024-01-04 | 2024-04-30 | 西南石油大学 | 一种阻燃型聚乙烯醇气凝胶相变材料及其制备方法 |
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