CN100366627C - 制备含多dopo有机化合物的方法及其用途 - Google Patents
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Abstract
制备含多DOPO的新型反应性有机化合物的方法，该化合物与先前已知的可比较的DOPO(9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物)-加成物相比，具有较高磷含量，以及其用于耐火热塑性聚合物例如聚酯和聚酰胺的用途，达到同样阻燃效果的加入量比以前常用的低，从而降低了对聚合物物理性质，特别是织物物理性质的影响。该含多DOPO的加成物是通过在催化剂存在下、DOPO与带有反应性基团的炔类进行反应而形成的。
Description
本发明涉及一种制备新型含多DOPO的反应性有机化合物的方法，该化合物与先前已知的可比较的DOPO-加成物相比，具有较高的磷含量，并涉及其用于耐火热塑性聚合物，优选聚酯和聚酰胺的用途；达到同样阻燃效果的添加量比先前常用的低，从而降低了对聚合物物理性质，特别是织物物理性质的影响。该含多DOPO的加成物是通过DOPO与带有反应性或酯基团的炔类进行反应而形成的。
现有技术
文献公开了9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(本发明说明书中称为DOPO)及其一系列衍生物的制备方法。例如，SAITO在DOS2034887中描述了DOPO以及多种DOPO衍生物的制备方法。DE2646218涉及DOPO与衣康酸和衣康酸酐的反应以及这些加成物的进一步改性。ENDO等人在这方面发现，DOPO与马来酸和马来酸酐的加成物以及由此制得的酯，由于加成物的羧基不充分的酯化度而不适合于共聚反应。DIETRICH等人在DE19522876中还限定了特别是DOPO和DOPO衍生物及其与衣康酸或衣康酸化合物的反应产物的制备方法，以及它们用于耐火聚酯纤维的用途。UTZ和SPRENGER在EP0806429中描述了DOPO衍生物，其是特别通过与表氯醇反应而得到的。这些产物意在用于结合到环氧树脂中。环氧树脂的耐火也是LIN，WU和WANG文章的主题(J.Appl.Polym.Sci.78.，2000，228-235页)。为了制备环氧树脂，他们使用与马来酸和与衣康酸反应的DOPO加成物，并使其与二环氧甘油或双酚A反应。在EP1090922中，TAKEUCHI等人公开了用邻-苯基苯酚制备DOPO的方法，以及用α，β-不饱和羧酸及其酯、二醇等制备DOPO衍生物的方法，它们总是与二价金属，优选锌的化合物一起结合到聚酯中。因此，在制备耐火聚酯时锑催化剂的氧化受到抑止。
上述所有制备DOPO衍生物的方法的共同点在于，在形成DOPO加成物时仅使用烯属不饱和化合物作为反应物。因此，可以被加到每个双键(因此通常每个烯烃分子)的DOPO分子数被限定为一个。但是，例外的是，具有较长碳链的二烯或多烯没有被保护权或文献内容公开。由此产生以下缺点，这些有机磷化合物的磷含量有一上限，这样，为了在将这些阻燃剂结合到聚合物中时达到确定的阻燃效果，必须以最低量相对较高的阻燃剂作为共聚单体。这又会对所形成的共聚物性质带来不利影响。
发明目的
因此，本发明的目的是开发一种制备含多DOPO的反应性有机化合物的方法，该化合物比先前基于DOPO衍生物可达到的磷含量具有更高的磷含量，该化合物适合作为共聚单体用于耐火热塑性聚合物，例如聚酯和聚酰胺。
该目的令人惊讶地实现了，并且根据本发明，其是在适合于在三键上加成的催化剂存在下，通过9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)加成到带有反应性基团的炔属不饱和化合物上而得到的。对于在三键上加成，常见的催化剂可以是汞盐或铜盐或胺，例如三乙胺，或者对于该反应类型非特征性的催化剂，例如三异丙醇铝。当使用合适的DOPO与炔属不饱和化合物的摩尔比例如1.5/1～3/1，优选1.9/1～2.1/1时，每摩尔炔属不饱和化合物加成两摩尔DOPO，同时牺牲C≡C-三键。
这样形成一些如下通式结构的加成物：
其中，R可以是羧基、羧基烷基、羧基芳基、羟基烷基、烷氧基烷基、芳氧基烷基、羟基芳基、烷氧基芳基、芳氧基芳基或类似基团，并且可以是相同或不同的取代基。
该加成反应优选在溶液中进行。适合的溶剂特别是那些能够溶解起始物、但不溶解反应产物的溶剂。这样的溶剂例如为1，4-二烷。
按照文献(Organikum，第4版，VEB Deutscher Verlagder WissenschaftenBerlin 1964，223页)，H-酸化合物与炔类的亲电加成只在特定催化剂如汞盐和铜盐存在下进行，因为炔键对亲电试剂反应能力较小。按照Houben-Weyl(Methoden der Organischen Chemie，第4版，Georg Thieme Verlag Stuttgart，1977，5/2a卷，725页)，对于膦与C≡C-三键的亲核加成，必须存在作为催化剂的胺。现在根据本发明发现，DOPO与某些炔类的加成反应还可以被诸如三异丙醇铝的化合物催化。用于有机磷化合物DOPO与炔属不饱和化合物反应的催化剂为汞盐或铜盐或胺，或优选三异丙醇铝。DOPO与不饱和化合物反应的这些方案迄今还没有公开。
使用的炔属不饱和化合物为例如以下物质：如2-丁炔-1，4-二醇二乙酸酯、2-丁炔-1，4二醇、3-己炔-2，5-二醇、2，4-己二炔-1，6-二醇及其酯，以及优选为乙炔二羧酸和乙炔二羧酸二酯。
在聚酯缩合中，所得到的磷含量高达12.7％的DOPO加成物作为共聚单体的用量为1～15％。具有羟基端基的DOPO加成物并不一定需要进一步衍生化。乙炔二羧酸和乙炔二羧酸二酯的DOPO加成物在作为共聚单体使用前，有利地将其转化为二甘醇酯。DOPO/乙炔二羧酸加成物，少数情况下是其衍生物，在约200℃和更高温度下表现出脱羧化。已经证实，将DOPO加成物计量加入已经预缩合的缩聚混合物中是有利的。用于聚酯缩聚的催化剂为现有技术已知的产品，例如三氧化锑、乙酸锑或原钛酸四正丁酯。
为了将该加成化合物转化成适合作为共聚单体，特别是共聚酰胺的共聚单体形式，进行进一步衍生化，例如形成羧酸氨基酰胺或羧酸/铵盐。为此，DOPO/二羧酸加成物与相应的等摩尔量二胺反应，类似形成AH-盐，并作为共聚单体用于制备聚酰胺。添加量取决于共聚酰胺中所需的磷含量。该量在3～20％之间变化，优选在5～15％之间。除了DOPO/乙炔二羧酸加成物，同样的原理，DOPO/马来酸加成物也是适合的。
实施例
实施例1：
将108g DOPO和1g三异丙醇铝在约30℃下溶于700ml二烷中。在搅拌下向该澄清溶液中滴加22.8g乙炔二羧酸在80ml二烷和40ml二乙醚中的溶液，该溶液在稍微加热下制得。加入结束时，将温度升高到50-60℃。继续处理约20小时以上。通过过滤，将逐渐形成的沉淀物与上清液分开。除去残留溶剂后，得到白色粉末状产物，以所用乙炔二羧酸计，产率为94.5％。该产物(总分子式：C28H20O8P2)的磷含量为10.9％(理论值：11.3％)。羧基基团含量为2777μequ/g。该产物的熔点为199℃，在熔化过程后直接发生脱羧化。
实施例2：
将162g DOPO和1.2g硫酸汞(II)在约30℃下溶于600ml二烷中。在搅拌下向轻微乳化的溶液中滴加21.5g 2-丁炔-1，4-二醇在100ml二烷中的溶液。加入结束时，将温度升高到50-60℃。继续处理约20小时以上。蒸馏除去溶剂和未反应的丁炔二醇后，得到带黄色的产物。用二异丙醚萃取后，该产物(总分子式：C28H24O6P2)的磷含量为11.5％(理论值：11.95％)。该产物的熔点为105℃。
实施例3：
将86.4g DOPO和1.0g三乙胺在约30℃下溶于700ml二烷中。在搅拌下向该澄清溶液中滴加21.3g乙炔二羧酸二甲醚在100ml二烷中的溶液。加入结束时，逐渐将温度升高到96-98℃。反应继续进行约10小时以上。所形成的沉淀物在放置过夜后通过过滤与上清液分开。除去残留溶剂后，得到白色产物，以所用的乙炔二羧酸二甲醚计，产率为87.9％。该产物(总分子式：C30H24O8P2)的磷含量为10.7％(理论值：10.79％)。该产物的熔点为281.6℃(DSC)。没有出现如在实施例1的DOPO/乙炔二羧酸加成物所发现的脱羧化作用。
实施例4：
将实施例1制备的54.6g DOPO/乙炔二羧酸加成物与1g对-甲苯磺酸和60g乙二醇悬浮于100ml二烷中。在100℃处理该混合物16小时。通过过滤将沉积的白色沉淀物与上清液分开。通过真空蒸馏除去残留溶剂和乙二醇。得到白色粉末状产物，以所用的DOPO/乙炔二羧酸加成物计，产率为68.5％。认为该产物(总分子式：C32H28O10P2)是DOPO/乙炔二羧酸二甘醇酯加成物，其磷含量为10.1％(理论值：9.8％)。
实施例5：
将实施例1制备的54.6g DOPO/乙炔二羧酸加成物在加热下溶于260ml新蒸馏的二甲基乙酰胺中。向该溶液中滴加23.2g 1，6-二氨基己烷在二甲基乙酰胺中的50％溶液。加入结束后，约30分钟撤去热源。将反应混合物冷却到室温时形成白色沉淀物。通过过滤将其分离，用二甲基乙酰胺并且随后用乙醇洗涤。之后在80℃在真空干燥箱中干燥该产物。
实施例6：
将96.6g对苯二甲酸二甘醇酯与0.1g原钛酸四正丁酯混合，在稍微加入氮气下放入200℃浴中。在60分钟内将浴温升高到270℃。在连续搅拌下开始蒸馏乙二醇，这是开始缩合的可靠信号。在少许的真空下进行蒸馏。之后，蒸馏掉约40％理论上希望的乙二醇，在剧烈搅拌下加入12.7g DOPO/乙炔二羧酸二甘醇酯加成物。继续在真空下蒸馏乙二醇，以及进而继续在真空下缩聚。约120分钟后，在＜1mbar的真空下将温度升高到280℃。在该条件下继续进行缩聚约30分钟。然后倒出很粘的熔融物。所形成的改性聚酯在229-231℃熔化。测定该溶液的相对粘度为1.26。该产物的羧基含量为63μequ/g，磷含量为1.58％。
实施例7：
将84g ε-己内酰胺与16g实施例5制备的产物以及1ml水混合，并用氮气彻底冲洗。将装有反应混合物的容器放入温度为200℃的浴中。在混合物熔化后，剧烈搅拌该混合物。将温度逐渐升高到260℃，在稳定地加入少量氮气情况下，继续进行聚合约14小时以上。形成溶液相对粘度为1.45的共聚酰胺。在回流下进行水萃取后，得到溶液粘度稍微升高到1.47的共聚酰胺。羧基含量为64.5μequ/g，氨基含量为50.2μequ/g。与萃取前的1.38％相比，该产物的磷含量为1.5％。其在214℃熔化。
实施例8：
将96.6g对苯二甲酸二甘醇酯与10.4g实施例2制备的DOPO/丁炔二醇加成物和0.1g原钛酸四正丁酯混合，在稍微加入氮气下放入200℃浴中。在60分钟内将浴温度升高到270℃。在连续搅拌下蒸馏掉乙二醇。在少许真空下进行蒸馏。在逐渐升高到约1mbar的真空下，继续进行缩聚。约120分钟后，在＜1mbar的真空下将温度升高到280℃。在该条件下再继续缩聚约30分钟。然后倒出很粘的熔融物。所形成的改性聚酯在232-234℃熔化。测定溶液相对粘度为1.22。该产物的磷含量为1.47％。
Claims (6)
1.一种制备含多DOPO的反应性有机化合物的方法，其是在适合于在三键上加成的催化剂存在下，通过9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)加成到带有反应性基团的炔属不饱和化合物上而得到所述化合物。
2.根据权利要求1的方法，其中所述有机磷化合物DOPO与所述炔属不饱和化合物以1.5～3摩尔DOPO/三键的比例彼此进行反应。
3.根据权利要求1或2的方法，其中所使用的炔属不饱和化合物为炔烃、炔醇、炔羧酸、炔羧酸酯或相应的链二炔化合物。
4.根据权利要求1或2的方法，其中用于所述有机磷化合物DOPO与所述炔属不饱和化合物反应的催化剂为汞盐或铜盐或胺，或三异丙醇铝。
5.根据权利要求1或2的方法，其中所述加成反应在溶液中进行，其中所使用的溶剂为1，4-二烷。
6.根据权利要求1到5中任一项所述方法制得的含多DOPO的反应性有机化合物作为热塑性聚合物的阻燃剂的用途。
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| PCT/DE2003/002030 WO2004113355A1 (de) | 2003-06-18 | 2003-06-18 | Verfahren zur herstellung mehrfach dopo-haltiger organischer verbindungen und ihre verwendung |
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| DE102008012806A1 (de) * | 2008-03-06 | 2009-09-10 | Schill + Seilacher Ag | Halogenfreie Flammschutzmittel |
| DE102009005967A1 (de) * | 2009-01-23 | 2010-07-29 | Domo Caproleuna Gmbh | Licht- und wärmestabilisierte Polyamide und Verfahren zu ihrer Herstellung |
| TWI598357B (zh) | 2009-05-19 | 2017-09-11 | 亞比馬利股份有限公司 | Ｄｏｐｏ衍生物阻燃劑 |
| TWI503339B (zh) | 2009-05-19 | 2015-10-11 | Albemarle Corp | Ｄｏｐｏ衍生的阻燃劑及環氧樹脂組合物 |
| CN101613374B (zh) * | 2009-07-22 | 2012-03-14 | 中国科学技术大学 | 一种侧基为dopo的聚合型含磷阻燃剂及其制备方法 |
| DE102009037631A1 (de) * | 2009-08-14 | 2011-02-17 | Schill + Seilacher "Struktol" Gmbh | Phosphorhaltiges Flammschutzmittel |
| CN101792530A (zh) * | 2010-03-19 | 2010-08-04 | 苏州兰特纳米材料科技有限公司 | 聚合物型无卤阻燃剂(pdptp)及其制备方法 |
| MX341388B (es) | 2010-03-31 | 2016-08-18 | Albemarle Corp | Proceso para preparacion de compuestos derivados de 9, 10-dihidro-9-oxa-10-fosfafenantreno-10-oxido (dopo) y composiciones de estos. |
| DE102011116178A1 (de) | 2011-10-14 | 2013-04-18 | Schill + Seilacher "Struktol" Gmbh | Halogenfreies, phosphorhaltiges Flammschutzmittel |
| CN103772434A (zh) * | 2012-10-26 | 2014-05-07 | 常州市华润复合材料有限公司 | 反应型无卤阻燃剂的制备方法 |
| US20160060281A1 (en) * | 2013-05-31 | 2016-03-03 | Scott Edward Angell | Butadien2,3-diyl linked di-dopo derivatives as flame retardants |
| CN104086593B (zh) * | 2014-07-14 | 2017-04-12 | 中国科学院宁波材料技术与工程研究所 | 一类dopo衍生物、其制备方法及应用 |
| CN104119673B (zh) * | 2014-07-14 | 2018-04-27 | 中国科学院宁波材料技术与工程研究所 | 无卤阻燃高温尼龙 |
| EP3476853A1 (en) * | 2017-10-26 | 2019-05-01 | Rhodia Operations | Flame-retardant polymer; method for preparing it and thermoplastic polymer composition comprising it |
| CN112442072A (zh) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | 一种带有羧酸或酸酐基团的反应型阻燃剂及其制备方法和应用 |
| CN112442176A (zh) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | 一种含磷的反应型阻燃剂、硅橡胶组合物、制备方法及应用 |
| CN114409842B (zh) * | 2022-02-25 | 2023-03-31 | 陕西科技大学 | 一种丙烯酸酯类煤炭阻燃抑尘剂及其制备方法 |
| CN115216129B (zh) * | 2022-09-19 | 2023-01-10 | 河北百展科技发展有限公司 | 一种耐热性生物基降解复合材料及其制备方法 |
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| DE19522876C1 (de) | 1995-06-23 | 1996-11-14 | Schill & Seilacher | Verfahren zur Herstellung eines DOP-haltigen Gemisches und dessen Verwendung |
| DE19619095A1 (de) | 1996-05-06 | 1997-11-13 | Schill & Seilacher | Flammfeste Epoxidharze und Flammschutzmittel für Epoxidharze |
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