CN106632461B - 一种间苯二酚四苯基二磷酸酯的制备方法 - Google Patents
一种间苯二酚四苯基二磷酸酯的制备方法 Download PDFInfo
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Abstract
本发明提供了一种间苯二酚四苯基二磷酸酯的制备方法：间苯二酚四苯基二磷酸酯使用骨架中含二氰基以及喹啉等杂环基团的固体催化剂，催化剂抗失活性能增强，可重复使用，提高了酯交换反应的收率。
Description
技术领域
本发明涉及一种磷酸酯的制备方法，特别是一种间苯二酚四苯基二磷酸酯的制备方法。
背景技术
随着人们环保意识的提高 , 无卤、低毒的阻燃剂倍受关注 , 与此同时 , 传统的卤系阻燃剂的使用范围也变得越来越小。所以 , 开发环境友好型、健康无害型阻燃剂已成为当今社会阻燃剂发展一个必然趋势。间苯二酚型磷酸酯齐聚物 (RDP) 阻燃剂是一种无卤添加型阻燃剂 , 因其具有独特的化学结构和力学性能 , 在高分子聚合物中显现出优异的热稳定性和超强的阻燃性能 , 而得到广泛应用。
CN100427494C提供阻燃剂间苯二酚四苯基二磷酸酯的制备方法，步骤如下：苯酚和三氯氧磷在催化剂、加热的条件下反应生成三苯基磷酸酯；三苯基磷酸酯和间苯二酚在催化剂、加热、减压的条件下进行酯交换反应，得到间苯二酚四苯基二磷酸酯，所述的反应温度为80～260℃；所述的催化剂，第一步反应为Lewis酸性催化剂；第二步反应为Lewis酸性催化剂或碱性催化剂，用量为苯酚或间苯二酚重量的0.05％～3％。酸性催化剂选自：MgCl2、ZnCl2、AlCl3、TiCl4；碱性催化剂选自：NaOH、KOH、Na2CO3、K2CO3、苯酚钠。本发明反应时间较短、能耗较低；所得产品的总产率大于92％，并能够减轻对环境的污染。
CN102942684B涉及一种热固性氰酸酯树脂组合物，包括如下成分：多官能氰酸酯、环氧树脂和阻燃剂。所述热固性氰酸酯树脂组合物还包括无机填料。本发明的热固性树脂组合物用于制备树脂片材、树脂复合物金属铜箔、预浸料、层压板、覆铜板层压板和印制线路板等。本发明的树脂组合物具有优良的耐热性、耐湿性、阻燃性和低热膨胀系数。所述磷系阻燃剂选自三(2，6-二甲基苯基)膦、间苯二酚双[二(2,6-二甲基 苯基)磷酸酯]、间苯二酚四苯基二磷酸酯等。
目前用于间苯二酚四苯基二磷酸酯酯交换反应的催化剂主要包括液体酸或碱催化剂，固体酸或碱催化剂以及脂肪酶等。相对于酶催化剂和液体催化剂，固体催化剂，特别是固体碱催化剂，具有工艺简单，环境污染小，易于回收利用等优势， 但固体碱催化剂活性还是偏低，达到较高甘油转化率所需反应时间过长；同时，该催化剂抗失活性能也不够好。
发明内容
针对现有技术的不足，本发明提供了一种间苯二酚四苯基二磷酸酯的制备方法，通过以下步骤实现：
（1)固体催化剂的制备
选用业内共知的大孔苯乙烯系离子交换树脂聚合生产标准工艺配方,升温方法及反应时间，区别之处在于：按单体总重量100份，加入0.5-2份 6-(2,2-二氰基乙烯基)-N-(2-羟基乙基)-1,2,3,4-四氢喹啉、加入0.01-0.1份2-[[4-(2,2-二氰乙烯基)-3-甲基苯基]乙基氨基]乙基-1,4-苯二甲酸甲酯作为共聚单体, 加入0.01-0.05份2,4-二苯基-4-甲基-1-戊烯为链转移剂,经聚合反应生成聚合白球，烘干后，将致孔剂抽提干净，烘干待用。按公知的大孔阳离子交换树脂的磺化工艺进行磺化反应，可得固体催化剂。
（2）酯交换反应
按重量份，在反应器中加入三苯基磷酸酯100份，间苯二酚20-60份；固体催化剂的用量为5～15份；反应温度为110～250℃；反应时间5-15小时，再经蒸馏，洗涤，得到间苯二酚四苯基二磷酸酯产品。
所述大孔苯乙烯系离子交换树脂包括D001大孔苯乙烯系离子交换树脂,D201大孔苯乙烯系离子交换树脂。
所述公知的大孔阳离子交换树脂的磺化工艺为D001大孔苯乙烯系离子交换树脂标准磺化工艺。
所述的6-(2,2-二氰基乙烯基)-N-(2-羟基乙基)-1,2,3,4-四氢喹啉；2,4-二苯基-4-甲基-1-戊烯；2-[[4-(2,2-二氰乙烯基)-3-甲基苯基]乙基氨基]乙基-1,4-苯二甲酸甲酯；三苯基磷酸酯；间苯二酚均为市售产品。
本发明的有益效果：
间苯二酚四苯基二磷酸酯使用骨架中含二氰基以及喹啉等杂环基团的固体催化剂，催化剂抗失活性能增强，可重复使用，提高了酯交换反应的收率，所得产品的收大于95％。
具体实施方式
以下实施例仅仅是进一步说明本发明，并不是限制本发明保护的范围。
实施例1
（1)固体催化剂的制备
选用业内共知的D001大孔苯乙烯系离子交换树脂生产标准工艺配方,升温方法及反应时间，区别之处在于：按单体总重量100份，加入2份 6-(2,2-二氰基乙烯基)-N-(2-羟基乙基)-1,2,3,4-四氢喹啉、加入0.06份2-[[4-(2,2-二氰乙烯基)-3-甲基苯基]乙基氨基]乙基-1,4-苯二甲酸甲酯作为共聚单体, 加入0.03份2,4-二苯基-4-甲基-1-戊烯为链转移剂,经聚合反应生成聚合白球，烘干后，将致孔剂抽提干净，烘干待用。按公知的D001大孔阳离子交换树脂的磺化工艺进行磺化反应，可得固体催化剂。
（2）酯交换反应
按重量份，在反应器中加入三苯基磷酸酯100份，间苯二酚40份；固体催化剂的用量为7份；反应温度为180℃；反应时间8小时，再经蒸馏，洗涤，得到间苯二酚四苯基二磷酸酯产品。编号为M-1。
实施例2
（1）固体催化剂的制备
选用业内共知的D201大孔苯乙烯系离子交换树脂聚合生产标准工艺配方,升温方法及反应时间，区别之处在于：按单体总重量100份，加入0.5份 6-(2,2-二氰基乙烯基)-N-(2-羟基乙基)-1,2,3,4-四氢喹啉、加入0.01份2-[[4-(2,2-二氰乙烯基)-3-甲基苯基]乙基氨基]乙基-1,4-苯二甲酸甲酯作为共聚单体, 加入0.01份2,4-二苯基-4-甲基-1-戊烯为链转移剂,经聚合反应生成聚合白球，烘干后，将致孔剂抽提干净，烘干待用。按公知的D001大孔阳离子交换树脂的磺化工艺进行磺化反应，可得固体催化剂。
（2）酯交换反应
按重量份，在反应器中加入三苯基磷酸酯100份，间苯二酚20份；固体催化剂的用量为5份；反应温度为110℃；反应时间15小时，再经蒸馏，洗涤，得到间苯二酚四苯基二磷酸酯产品。编号为M-2。
实施例3
（1)固体催化剂的制备
选用业内共知的D001大孔苯乙烯系离子交换树脂生产标准工艺配方,升温方法及反应时间，区别之处在于：按单体总重量100份，加入2份 6-(2,2-二氰基乙烯基)-N-(2-羟基乙基)-1,2,3,4-四氢喹啉、加入0.1份2-[[4-(2,2-二氰乙烯基)-3-甲基苯基]乙基氨基]乙基-1,4-苯二甲酸甲酯作为共聚单体, 加入0.05份2,4-二苯基-4-甲基-1-戊烯为链转移剂,经聚合反应生成聚合白球，烘干后，将致孔剂抽提干净，烘干待用。按公知的D001大孔阳离子交换树脂的磺化工艺进行磺化反应，可得固体催化剂。
（2）酯交换反应
按重量份，在反应器中加入三苯基磷酸酯100份，间苯二酚60份；固体催化剂的用量为15份；反应温度为250℃；反应时间5小时，再经蒸馏，洗涤，得到间苯二酚四苯基二磷酸酯产品。编号为M-3。
比较例1
不加入6-(2,2-二氰基乙烯基)-N-(2-羟基乙基)-1,2,3,4-四氢喹啉，其它同实施例1。所得产品编号为M-4。
比较例2
不加入2-[[4-(2,2-二氰乙烯基)-3-甲基苯基]乙基氨基]乙基-1,4-苯二甲酸甲酯，其它同实施例1。所得产品编号为M-5。
比较例3
不加入2,4-二苯基-4-甲基-1-戊烯，其它同实施例1。所得产品编号为M-6。
实施例4
催化剂重复使用第5次的实施例1-3和比较例1-3的酯交换反应收率见表1。
表1.检测酯交换反应收率：
| 产品编号 | 收率% |
| M-1 | 95 |
| M-2 | 94 |
| M-3 | 96 |
| M-4 | 91 |
| M-5 | 88 |
| M-6 | 84 |
Claims (3)
1.一种间苯二酚四苯基二磷酸酯的制备方法，其特征在于，通过以下步骤实现：
按重量份，在反应器中加入三苯基磷酸酯100份，间苯二酚20-60份；固体催化剂的用量为5～15份；反应温度为110～250℃；反应时间5-15小时，再经蒸馏，洗涤，得到间苯二酚四苯基二磷酸酯产品，
所述固体催化剂的制备方法为：
选用业内共知的大孔苯乙烯系离子交换树脂聚合生产标准工艺配方,升温方法及反应时间，区别之处在于：按单体总重量100份，加入0.5-2份 6-(2,2-二氰基乙烯基)-N-(2-羟基乙基)-1,2,3,4-四氢喹啉、加入0.01-0.1份2-[[4-(2,2-二氰乙烯基)-3-甲基苯基]乙基氨基]乙基-1,4-苯二甲酸甲酯作为共聚单体, 加入0.01-0.05份2,4-二苯基-4-甲基-1-戊烯为链转移剂,经聚合反应生成聚合白球，烘干后，将致孔剂抽提干净，烘干待用；按公知的D001大孔阳离子交换树脂的磺化工艺进行磺化反应，可得酯交换反应催化剂。
2.权利要求1所述的一种间苯二酚四苯基二磷酸酯的制备方法，其特征在于，所述大孔苯乙烯系离子交换树脂包括D001大孔苯乙烯系离子交换树脂,D201大孔苯乙烯系离子交换树脂。
3.权利要求1所述的一种间苯二酚四苯基二磷酸酯的制备方法，其特征在于，所述公知的大孔阳离子交换树脂的磺化工艺为D001大孔苯乙烯系离子交换树脂标准磺化工艺。
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