CN110283307A - 阳离子聚合磷酸为起始剂制作阻燃聚醚 - Google Patents

阳离子聚合磷酸为起始剂制作阻燃聚醚 Download PDF

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CN110283307A
CN110283307A CN201910540883.8A CN201910540883A CN110283307A CN 110283307 A CN110283307 A CN 110283307A CN 201910540883 A CN201910540883 A CN 201910540883A CN 110283307 A CN110283307 A CN 110283307A
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phosphoric acid
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张格亮
马慧
刘晓会
刘涛
曹德健
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Aviation Brocade Polytron Technologies Inc
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Abstract

本发明提出的是阳离子聚合磷酸为起始剂制作阻燃聚醚。通过以磷酸为起始剂进行自催化聚合反应制得磷酸聚醚，再经阳离子催化剂或DMC催化剂催化聚合，从而得到阳离子聚合阻燃聚醚多元醇。在反应釜中加入磷酸起始剂，连续加入环氧乙烷EO或环氧丙烷PO，在搅拌下，在40～50℃进行聚合反应，熟化后制得磷酸聚醚；将磷酸聚醚加入反应釜中，加入催化剂，连续加入环氧乙烷EO或PO环氧丙烷中的一种，在搅拌下，于50～100℃下反应；聚合完成后在真空度≤‑0.096MPa下，脱除小分子物质，成为阳离子聚合阻燃聚醚多元醇。磷酸成本低，合成过程简单，工艺流程短，其聚氨酯制品的阻燃性较好，具有难燃性。适宜作为聚合阻燃聚醚多元醇应用。

Description

阳离子聚合磷酸为起始剂制作阻燃聚醚
技术领域
本发明涉及聚醚多元醇，特别是涉及制作聚醚多元醇的磷酸聚醚。
背景技术
目前，聚氨酯制品的阻燃技术主要分为添加型和反应型两大类。所谓添加型，即将含磷或含磷和卤素的阻燃型添加剂添加到原料聚醚多元醇中，使其产品具有阻燃效果，但这种技术存在很大缺点，例如聚合物与阻燃添加剂相容性不好，易沉降等。另一类反应型则是在聚氨酯制品的原料聚醚多元醇、聚酯多元醇、聚合物多元醇的聚合过程中将磷、卤素等阻燃元素聚合到链段中，从而具有阻燃性，但反应型阻燃技术制作的聚醚原料，一般生产成本较高，经济效益低。
发明内容
为了能够解决聚醚多元醇的含磷量和发泡性能、提高其阻燃性，本发明提出了阳离子聚合磷酸为起始剂制作阻燃聚醚。通过以磷酸为起始剂进行自催化聚合反应制得磷酸聚醚，再经阳离子催化剂或DMC催化剂催化聚合，从而得到阳离子聚合阻燃聚醚多元醇，解决的技术问题。
本发明解决技术问题所采用的方案是：
通过以磷酸为起始剂进行自催化聚合反应制得磷酸聚醚，再经阳离子催化剂或DMC催化剂催化聚合，得到阳离子聚合阻燃聚醚多元醇：
1、起始剂选择与反应物比例配比：
选择磷酸为起始剂，阳离子催化剂或DMC催化剂进行催化聚合，磷酸与PO的摩尔比为1:2，磷酸聚醚与EO或PO的摩尔比分别为1:1或1:1。
2、聚合反应：
第一步，在反应釜中加入磷酸起始剂，升温至40℃左右，连续加入环氧乙烷EO或环氧丙烷PO，在搅拌下，在40～50℃进行聚合反应，熟化后制得磷酸聚醚无色粘稠状液体；
第二步，将磷酸聚醚加入反应釜中，加入催化剂进行活化，升温至50℃，连续加入环氧乙烷EO或PO环氧丙烷中的一种，在搅拌下，于50～100℃下反应，控制聚合反应速度；
所述催化剂为阳离子催化剂或DMC双金属催化剂，其中阳离子催化剂为三氟化硼、氯化铁或氯化铝与亚硫酰二氯的复合酸。
第三步，聚合完成后，在真空度≤-0.096MPa下，脱除小分子物质，成为阳离子聚合阻燃聚醚多元醇。
制备的阳离子聚合阻燃聚醚多元醇的羟值为450，酸值小于1，官能度2.9～3，含磷量8～12%。可直接发泡，泡沫性能良好，离火自熄，氧指数大于26。
积极效果，由于本发明采用阳离子聚合磷酸为起始剂制作得阻燃聚醚多元醇，经过磷酸起始剂与阳离子催化剂的选择与PO或EO进行聚合反应，成为阻燃性聚醚多元醇产品，含磷量在8～12%，可直接发泡，其泡沫制品性能良好；其产品原料为磷酸，成本低，合成过程简单，工艺流程短，其聚氨酯制品的阻燃性较好，具有难燃性，离火自熄，具有较高的经济效益和社会效益。适宜作为聚合阻燃聚醚多元醇应用。
具体实施方式
实施例步骤1：
在5L反应釜中，加入磷酸75%（重量比）起始剂2000g，搅拌下升温至40℃，连续缓慢加入环氧乙烷EO或环氧丙烷PO至2400g，在搅拌下，在40～50℃进行聚合反应，熟化后制得磷酸聚醚无色粘稠状液体。
实施例步骤2：
在5L反应釜中，加入磷酸聚醚2000g，阳离子催化剂或DMC双金属催化剂0.12g，搅拌升温至50℃，连续加入环氧乙烷EO或环氧丙烷PO至550g，在搅拌下，于50～100℃下反应，控制聚合反应速度，熟化后在真空度≤-0.096MPa下，脱除小分子物质，得到阳离子聚合阻燃聚醚多元醇无色粘稠状液体。
产品指标：
粘度：5146mpa*s/25℃，
羟值：450mgKOH/g，
酸值：0.089，
官能度：2.9～3，
含磷量：8～12%
PH值：8.1，
水份：0.03。
实施例步骤3：
阻燃泡沫制备：
阳离子聚合阻燃聚醚多元醇 100份
硅油 1.5份
水 1.2份
催化剂 0.5～1.5份
异氰酸酯PAPI 1:1
将以上物料充分混合，倒入模具发泡，熟化72小时，成为阻燃聚氨酯泡沫体。
阻燃泡沫指标：
密度：25Kg/m3
硬度：100KPa
氧指数：＞26
本发明的工作原理：本发明采用阳离子聚合磷酸为起始剂制作得阻燃聚醚多元醇，经过磷酸起始剂与阳离子催化剂的选择与PO或EO进行聚合反应，成为阻燃性聚醚多元醇产品，含磷量在8～12%，可直接发泡，具有阻燃性。

Claims (5)

1.阳离子聚合磷酸为起始剂制作阻燃聚醚,其特征是：
通过以磷酸为起始剂进行自催化聚合反应制得磷酸聚醚，再经阳离子催化剂或DMC催化剂催化聚合，得到阳离子聚合阻燃聚醚多元醇：
1）、起始剂选择与反应物比例配比：
选择磷酸为起始剂，阳离子催化剂或DMC双金属催化剂进行催化聚合，磷酸与PO环氧丙烷的摩尔比为1:2，磷酸聚醚与环氧乙烷EO或环氧丙烷PO的摩尔比分别为1:1或1:1；
2）、聚合反应：
第一步，在反应釜中加入磷酸起始剂，升温至40℃左右，连续加入PO或EO，在搅拌下，于小于50℃进行聚合反应，熟化后制得磷酸聚醚；
第二步，将磷酸聚醚加入反应釜中，加入催化剂进行活化，升温至50℃，连续加入EO或PO中的一种，在搅拌下，于50～100℃下反应，控制聚合反应速度；
所述的催化剂为阳离子催化剂或双金属催化剂；
第三步，聚合完成后，在真空度≤-0.096MPa下，脱除小分子物质，成为阳离子聚合阻燃聚醚多元醇。
2.根据权利要求1所述的阳离子聚合磷酸为起始剂制作阻燃聚醚，其特征是：所述起始剂为磷酸起始剂，进行自催化聚合。
3.根据权利要求1所述的阳离子聚合磷酸为起始剂制作阻燃聚醚，其特征是：所述阳离子催化剂为三氟化硼、氯化铁或氯化铝与亚硫酰二氯的复合酸。
4.根据权利要求1所述的阳离子聚合磷酸为起始剂制作阻燃聚醚，其特征是：所述阳离子聚合阻燃聚醚多元醇的羟值为450，酸值小于1，官能度2.9～3，含磷量8～12%。
5.根据权利要求1所述的阳离子聚合磷酸为起始剂制作阻燃聚醚，其特征是：所述阳离子聚合阻燃聚醚多元醇可直接发泡，泡沫性能良好，离火自熄，氧指数大于26。
CN201910540883.8A 2019-06-21 2019-06-21 阳离子聚合磷酸为起始剂制作阻燃聚醚 Pending CN110283307A (zh)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04364196A (ja) * 1991-06-10 1992-12-16 Sanyo Chem Ind Ltd ホスフィン酸誘導体からなる反応性難燃剤およびこの誘導体の製法
CN1961024A (zh) * 2004-06-03 2007-05-09 国际壳牌研究有限公司 聚醚多元醇的制备方法
CN108779241A (zh) * 2016-03-21 2018-11-09 科思创德国股份有限公司 阻燃的醚软质泡沫材料

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04364196A (ja) * 1991-06-10 1992-12-16 Sanyo Chem Ind Ltd ホスフィン酸誘導体からなる反応性難燃剤およびこの誘導体の製法
CN1961024A (zh) * 2004-06-03 2007-05-09 国际壳牌研究有限公司 聚醚多元醇的制备方法
CN108779241A (zh) * 2016-03-21 2018-11-09 科思创德国股份有限公司 阻燃的醚软质泡沫材料

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