CN112592514A - 磷氮阻燃剂及其制备方法与应用 - Google Patents
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Abstract
本发明涉及一种磷氮阻燃剂及其制备方法与应用，主要解决现有技术中存在的常用阻燃剂通常不能同时含磷氮元素，而同时含磷氮元素的阻燃剂制备工艺复杂的问题，本发明通过提供一种磷氮阻燃剂，其制备方法包括以下步骤：(1)在装有挥发气体冷凝管的反应容器中按摩尔比1：1～3加入六甲氧基甲基三聚氰胺和亚磷酸二甲酯，得到物料Ⅰ；(2)物料Ⅰ在搅拌条件下反应，反应温度为90～130℃，反应压力为常压，反应时间为10～24h，得到物料Ⅱ；(3)在压力‑0.085～‑0.1Mpa下对物料Ⅱ减压蒸馏脱除挥发性物质后得到物料Ⅲ；(4)物料Ⅲ温度降至室温，得到磷氮阻燃剂及其应用的技术方案，较好地解决了该问题，可用于聚氨酯泡沫制品的工业应用中。
Description
技术领域
本发明涉及阻燃剂领域，尤其涉及一种磷氮阻燃剂及其制备方法与应用。
背景技术
聚氨酯材料因其优异的性能而被广泛使用，聚氨酯泡沫可用于家居用品、汽车座椅领域，也可以在建筑保温、冷藏保温领域作为保温材料使用。聚氨酯是由异氰酸酯组分和聚酯多元醇或聚醚多元醇组分反应制备而成的多孔性有机材质，属于易燃物质，对此，各应用领域都对聚氨酯材料的阻燃性能提出了要求，如，美国联邦制定了关于汽车内饰件防火测试的标准FMVSS302，在软体家具防火测试标准CAL TB117的A部分中也通过对海绵的明火燃烧测试来判断产品是否合格；我国国家强制标准GB 8410-2006中也对汽车内饰材料的燃烧特性进行了说明，可见材料的阻燃性能越来越受到人们的关注。
目前用于聚氨酯泡沫的阻燃剂主要有两类：添加型阻燃剂和反应型阻燃剂；常用的添加型阻燃剂有粒径为30～60μm的三聚氰胺、磷酸三(1,3-二氯异丙基)酯，三聚氰胺添加量达到10份以上时，虽然能达到阻燃效果，但三聚氰胺是固体粉末，在组合料使用中稳定性不好；磷酸三(1,3-二氯异丙基)酯，俗称TCPP，含有氯元素且气味大，已不允许用于家居和汽车内饰领域；反应型阻燃剂主要有Clariant公司的无卤阻燃剂Exolit OP550、ICLIndustrial公司的阻燃剂Fyrol 6等产品，但这些产品售价很高，如Emerald Innovation的NH-1磷氮阻燃剂价格在10万元/吨，极大的影响了其在聚氨酯泡沫中的广泛应用；所以制备出成本低、阻燃效果好的无卤阻燃剂成为研究人员的研发方向。
中国专利CN111004364A公开了一种反应型无卤氮磷阻燃剂的制备方法，通过将研磨成粉的多聚甲醛加入到熔融的醇胺中搅拌反应1～2h，得中间体溶液，加热减压脱水后得到中间体；再将得到的中间体与亚磷酸酯反应2～4h，得黄色透明液体；在黄色透明液体中加入Ca(OH)2，常温搅拌2～4h后过滤的方法制得反应型无卤氮磷阻燃剂，消除了水对抑制中间体生成和磷酸酯水解的不利影响，优化了工艺流程，提高了产品收率和纯度，但其制备工艺复杂，且将其应用于聚氨酯发泡中时易出现塌泡现象，不适合作为聚氨酯泡沫的阻燃剂使用。
本发明通过两种常见原料六甲氧基甲基三聚氰胺与磷酸酯反应制备磷氮阻燃剂的方法，操作步骤简单，且可用于聚氨酯硬泡、半硬泡和软泡中，获得较好的阻燃效果。
发明内容
本发明所要解决的技术问题之一是，现有技术中存在的常用阻燃剂通常不能同时含磷氮元素，而同时含磷氮元素的阻燃剂制备工艺复杂的问题，提供一种磷氮阻燃剂，该磷氮阻燃剂具有同时含有磷氮元素，且制备工艺简单的优点。
本发明所要解决的技术问题之二是提供一种与解决技术问题之一相对应的制备方法。
本发明所要解决的技术问题之三是提供一种与解决技术问题之一相对应的用途。
为解决上述技术问题之一，本发明采用的技术方案如下：一种磷氮阻燃剂，其特征在于分子结构通式为：
其中，R1，R2均选自-O-CH3或
中的一种。
上述技术方案中，优选地，所述的磷氮阻燃剂中磷氮总量以质量百分比计为24～30％。
为解决上述技术问题之二，本发明采用的技术方案如下：一种磷氮阻燃剂的制备方法，包括以下步骤：
(1)在安装有挥发气体冷凝管的反应容器中按摩尔比1：1～3加入六甲氧基甲基三聚氰胺和亚磷酸二甲酯，得到物料Ⅰ；
(2)物料Ⅰ在搅拌条件下进行反应，反应温度为90～130℃，反应压力为常压，反应时间为10～24h，得到反应后的混合物料Ⅱ；
(3)对物料Ⅱ进行减压蒸馏，减压蒸馏的压力为-0.085～-0.1Mpa，脱除挥发性物质后得到物料Ⅲ；
(4)将物料Ⅲ温度降至室温，即得到目标产品磷氮阻燃剂。
上述技术方案中，优选地，所述的反应温度为90～110℃。
为解决上述技术问题之三，本发明采用的技术方案为：将制备的磷氮阻燃剂添加到聚氨酯泡沫的配方中，用于制备聚氨酯泡沫。
上述技术方案中，优选地，所述的磷氮阻燃剂用于聚氨酯泡沫的制备中时，添加量以整个配方质量百分比计为磷氮总质量百分含量为1～10％。
上述技术方案中，优选地，所述的磷氮阻燃剂用于聚氨酯泡沫的制备中时，添加量以整个配方质量百分比计为磷氮总质量百分含量为2～5％。
本发明提供一种磷氮阻燃剂及其制备方法，该磷氮阻燃剂同时含有磷氮元素，对阻燃性能具有协同作用，磷氮总含量高，在24～30％之间；其制备方法中不使用催化剂、不添加溶剂、反应在常压下进行，操作简单、环保友好，其采用的反应原料为常见的六甲氧基甲基三聚氰胺和亚磷酸二甲酯，成本低；将制备的磷氮阻燃剂用于聚氨酯发泡时未出现塌泡现象，且制备的聚氨酯泡沫的氧指数可达27.8％(实施例3)，高于将两种分别含磷、含氮阻燃剂混合添加的氧指数25.6％(比较例1)，阻燃性能好，所以本发明制备的阻燃剂具有同时含有磷氮元素，且制备工艺简单，用于聚氨酯泡沫时阻燃效果好的优点，取得了较好的技术效果。
具体实施方式
以下只是本发明的优选实施方式，并非是对本发明保护范围的限制，凡属于本发明思路下的技术方案应当落入本发明的保护范围之内，对于本技术领域内的专业技术人员，在不脱离本发明原理前提下对本发明进行的细微改进和润饰也应当落入本发明的保护范围内。
【实施例1】
(1)在安装有挥发气体冷凝管的反应容器中加入1mol的六甲氧基甲基三聚氰胺和1mol的亚磷酸二甲酯，得到物料Ⅰ；
(2)物料Ⅰ在搅拌条件下进行反应，反应温度为90℃，反应压力为常压，反应时间为10h，得到反应后的混合物料Ⅱ；
(3)对物料Ⅱ进行减压蒸馏，减压蒸馏的压力为-0.085Mpa，脱除挥发性物质后得到物料Ⅲ；
(4)将物料Ⅲ温度降至室温，即得到磷氮阻燃剂S1，S1中磷氮的质量百分含量为24.3％。
将得到的磷氮阻燃剂S1按表2的质量份数添加到聚氨酯泡沫的发泡配方中制备聚氨酯泡沫，制得的聚氨酯泡沫的性能指标见表3所示。
【实施例2～3】
实施例2～3按照实施例1中的各个步骤进行，唯一的区别为反应原料、原料配比、反应时间、反应温度不同，具体见表1；将制备得到的磷氮阻燃剂按表2的添加量添加到的聚氨酯泡沫的发泡配方中进行发泡，制得的聚氨酯泡沫的性能指标数据见表3所示。
表1实施例1～3磷氮阻燃剂制备中所用原料摩尔数及反应条件
【比较例1】
将市售的甲基磷酸二甲酯和六甲氧基甲基三聚氰胺按表2的质量份数同时添加到聚氨酯泡沫的发泡配方中制备聚氨酯泡沫，制得的聚氨酯泡沫的性能指标见表3所示。
【比较例2】
将市售的甲基磷酸二甲酯按表2的质量份数添加到聚氨酯泡沫的发泡配方中制备聚氨酯泡沫，制得的聚氨酯泡沫的性能指标见表3所示。
【比较例3】
将市售的六甲氧基甲基三聚氰胺按表2的质量份数添加到聚氨酯泡沫的发泡配方中制备聚氨酯泡沫，制得的聚氨酯泡沫的性能指标见表3所示。
表2中聚氨酯发泡配方中所用原料如下：
1、HT5100：聚酯多元醇，羟值280～305mgKOH/g，生产厂家为INVISTA；
2、R-425-X：聚醚多元醇，羟值410～440mgKOH/g，生产厂家为亨斯曼；
3、DMMP：甲基磷酸二甲酯，阻燃剂，生产厂家为青岛邦立精细化工；
4、HMMM：六甲氧基甲基三聚氰胺，阻燃剂，生产厂家为江苏长丰化工；
5、POLYCAT 77：N,N,N',N″,N″五甲基二亚丙基三胺，催化剂，生产厂家为新典化学；
6、DABCO BL-11：催化剂，由70％双(二甲胺基乙基)醚及30％二丙二醇组成的溶液，生产厂家为新典化学；
7、DC193：聚二甲基硅氧烷共聚多元醇，硅油，生产厂家为道康宁；
8、DMCHA：N,N-二甲基环己胺，催化剂，生产厂家为新典化学；
9、HFC-245fa：1,1,1,3,3-五氟丙烷，发泡剂，生产厂家为霍尼韦尔；
10、Desmodur 44V20L：4，4’-二苯基甲烷二异氰酸酯(MDI)及其异构体和同系物的多官能异氰酸酯的混合物，生产厂家为科思创。
表2实施例1～3及比较例1～3中制备聚氨酯泡沫配方的质量份数
| 原料 | 实施例1 | 实施例2 | 实施例3 | 比较例1 | 比较例2 | 比较例3 |
| HT5100 | 48 | 48 | 48 | 48 | 48 | 48 |
| R-425-X | 25 | 25 | 25 | 25 | 25 | 25 |
| S<sub>1</sub> | 29.1 | |||||
| S<sub>2</sub> | 26.8 | |||||
| S<sub>3</sub> | 25 | |||||
| DMMP | 15 | 28.3 | ||||
| HMMM | 16 | 33.4 | ||||
| POLYCAT 77 | 1 | 1 | 1 | 1 | 1 | 1 |
| DABCO BL-11 | 1 | 1 | 1 | 1 | 1 | 1 |
| DC193 | 1 | 1 | 1 | 1 | 1 | 1 |
| DMCHA | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| HFC-245fa | 6.8 | 6.8 | 6.8 | 6.8 | 6.8 | 6.8 |
| Desmodur 44V20L | 88 | 88 | 88 | 88 | 88 | 88 |
| MDI指数(％) | 102 | 102 | 102 | 102 | 102 | 102 |
表3实施例1～3及比较例1～3中制备的聚氨酯泡沫的性能数据
按表2的配方进行聚氨酯发泡，添加到发泡配方中的阻燃剂质量份数为基于整个配方中含有相同的磷氮质量百分含量换算而得，添加阻燃剂后实施例1～3及比较例1～3的发泡配方中磷氮质量百分含量相近，均在3.51～3.58％之间；从表3中聚氨酯泡沫的氧指数数据可知，比较例3中只采用含氮元素的阻燃剂六甲氧基甲基三聚氰胺，需添加的质量份数为33.4份，氧指数为22.5％，可见其用量最多，但阻燃性能最差；比较例2中只采用含磷元素的阻燃剂甲基磷酸二甲酯，氧指数为23.9％；比较例1中同时采用含磷的阻燃剂甲基磷酸二甲酯和含氮的阻燃剂六甲氧基甲基三聚氰胺，在配方中总的磷氮质量百分含量为3.56％的情况下，需要添加的总的阻燃剂的质量份数为31份，此时氧指数为25.6％，阻燃性能要优于比较例2～3中单独使用只含氮或只含磷阻燃剂的效果，可见磷-氮结合体的阻燃效果好，磷氮对聚氨酯阻燃性能具有协同作用。
由实施例1～3中阻燃剂的制备过程可知，本发明的阻燃剂制备方法中不使用催化剂、不添加溶剂、反应在常压下进行，操作简单、环保友好，其采用的反应原料为常见的六甲氧基甲基三聚氰胺和亚磷酸二甲酯，成本低；得到的阻燃剂中同时含有磷氮元素，将其添加到聚氨酯的发泡配方中，制得的聚氨酯泡沫的氧指数均高于比较例1～3，且需要在配方中添加的质量份数均小于比较例1；其中，实施例3中制备的磷氮阻燃剂中磷氮质量百分含量为28％，换算为整个配方中磷氮含量质量百分含量为3.57％后需要添加到聚氨酯发泡配方中的质量份数为25份，用量最少，但其氧指数最高，达27.8％，具有阻燃剂用量少、阻燃效果好的优点，取得了较好的技术效果，可用于聚氨酯泡沫的应用中。
Claims (5)
1.一种磷氮阻燃剂，其特征在于分子结构通式为：
其中，R1，R2均选自-O-CH3或
中的一种。
2.根据权利要求1所述的磷氮阻燃剂，其特征在于所述的磷氮阻燃剂中磷氮总量以质量百分比计为24～30％。
3.权利要求1所述的磷氮阻燃剂的制备方法，包括以下步骤：
(1)在安装有挥发气体冷凝管的反应容器中按摩尔比1：1～3加入六甲氧基甲基三聚氰胺和亚磷酸二甲酯，得到物料Ⅰ；
(2)物料Ⅰ在搅拌条件下进行反应，反应温度为90～130℃，反应压力为常压，反应时间为10～24h，得到反应后的混合物料Ⅱ；
(3)对物料Ⅱ进行减压蒸馏，减压蒸馏的压力为-0.085～-0.1Mpa，脱除挥发性物质后得到物料Ⅲ；
(4)将物料Ⅲ温度降至室温，即得到目标产品磷氮阻燃剂。
4.根据权利要求3所述的磷氮阻燃剂的制备方法，其特征在于所述的反应温度为90～110℃。
5.权利要求1所述的磷氮阻燃剂在聚氨酯泡沫中的应用。
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