CN88102947A - 卤代酰亚胺的制备方法 - Google Patents
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Abstract
本发明涉及卤代酰亚胺的制备,它是由联氨、卤素和二羧酸酐衍生而来,可用作塑料的防火剂。
先将二羧酸酐进行卤化,然后,使所得到的反应物不用进行任何纯化和预先分离就与联氨反应。
Description
本发明涉及多元卤代酰亚胺的合成,尤其是从像四溴代邻苯二酸那样的卤代二羧酸衍生而来的酰亚胺的合成。
多元卤代酰亚胺,尤其是四溴代邻苯二酰亚胺以及双-四溴代邻苯二酰亚胺是很著名的化合物,它们是大量易燃物质尤其塑料的阻燃剂。(例如,请参阅S.M.SPATZ等的文章,标题为“Some N-substituted tetrabromophthalimide fire-retardant additives”在Industrial and Enginee-ring Chemistry product Research and Develop-ment,Vol.8,NO.4(1969)Pages 397-398,以及专利US3873567和FR2369261及专利申请JP74-045062和75-064337)。
然而,在上述参考文献中所叙述的制备方法只给出一般的产率并且生成的产品经常带有黄色,或者在使用时显出颜色,同时使塑料(化合物或模成型的物体)产生一种可造成严重防害性的和不能接受的色彩。另一方面,这些产物经常含有一些某些聚合材料在使用温度时挥发的物质,因而引起模具的腐蚀。此外制备这些化合物,使用有机溶剂(尤其是甲苯、二甲苯、酒精、醋酸),就需要采用比较费钱的分离和回收溶剂的操作,以及合适的去除有机溶剂蒸汽的干燥方法。所用的有机溶剂,通常选用能与水形成共沸混合物的,以便能带走由酰亚胺化产生的缩合水或溶解卤代二酸酐。
上面提到的缺点尤其存在于在由联氨和卤代二羧酸酐所衍生的多卤代酰亚胺的情况中。
此外,为了随意使用上述的后一种原料,需先将二羧酸酐卤化。这一点无论在技术上还是在经济上都构成了另外一种不利条件,因为多卤代酰亚胺的合成包含以下步骤:
羧酸酐的卤化反应,
所得到的卤代酸酐的分离和纯化。
现在已经找到一种方法,不需要分离和纯化中间体卤代酸酐,也不必使用一种有机溶剂去溶解酸酐和/或者除去缩合水并且在某些条件下,不用有机溶剂也能进行操作并可获得很高产率的无色的或者颜色很浅的产品,不用预先纯化,这些产品完全适合于高分子材料的防火处理,包括在高温下进行使用,尤其是在250℃以上使用。
本发明方法包括卤化二羧酸酐,然后使联氨与卤化的粗产品反应,其特征在于:
a)进行二羧酸酐的卤化反应,
b)然后,使从a所得的反应物与联氨反应。
在可用的酸酐中间,特别可以列举的有:
芳香二羧酸酐(苯、萘、蒽),尤其是符合下列通式的酸酐:
在该式中,P是从0至2的整数。
部分卤化的芳香二羧酸酐(苯、萘、蒽),尤其是符合下列通式的酸酐:
在该式中,x是一个氯或一个溴,m从0至4变化,n从0至2变化,m+n低于4+2p,p从0至2变化。x也可以是一个氯和一个溴(m+n大于1),也就是说在同一个分子上,能够具有所有的氯和溴的组合。
按照本发明,可使用单一的酸酐或者几种酸酐的混合物。当使用酸酐的混合物时,这些酸酐中的一种或几种,但不是全部,能够被卤素饱和。最好使用邻苯二酸酐。
二羧酸酐的卤化反应,第a阶段是根据技术人员的熟练技巧来实现的。卤化反应包括一氯化反应或溴化反应,或者先氯化随后溴化,或者反之。尽管人们能够部分地或者全部地进行卤化,但最好使卤化反应进行到所获得的产品中m大于或者等于2。使用单一的卤素较好,最好使用溴。
例如,按照德国专利DE1,934,174中所描述的方法,可在氯磺酸中氯化邻苯二酸酐。根据这种方法,在氯磺酸(HSO3Cl)中制成一种邻苯二酸酐的溶液,加入碘,加热至120℃,然后用含有ICl3的氯气流来处理。也可以在含有少量碘的发烟硫酸溶液中氯化邻苯二酸,即于该溶液中通入氯。最好在发烟硫酸中间进行氯化。
例如根据英国专利GB1,084,375中所说的技术邻苯二甲酸酐的溴化是在65%(重量)的发烟硫酸介质中进行的,同时由碘和铁催化。
在卤化反应结束时,不必将卤代二羧酸酐从所得到的反应物中分出。
根据本发明进行b阶段的反应是使a阶段所得的上述反应物与联氨反应。
很显然本发明的好处之一是,在与联氨反应以前不需要分离在a阶段所获得的卤代中间产物。联氨可用水合物或其盐(例如硫酸盐、氢卤化物、醋酸盐)。联氨或它的衍生物可按其原样或以硫酸溶液的形式使用。硫酸的用量可以在很大范围内变化,唯一的条件是用量要足以保证使反应物适当地分散并可得到很好地搅拌。卤代酸酐和联氨的摩尔比低于2,最好是在1至2之间,b阶段的反应可在大气压下,温度在80至220℃,最好是在110和200℃之间进行。
反应时间可以在很大范围内变化,但一般在1至20小时之间。反应物冷却后,将所得到的固体悬浮液稀释,然后过滤并用水洗至中性,接着用常用的干燥方法将产品干燥。
根据本发明的最好形式,联氨是用其水合物或其盐的硫酸溶液,逐渐地将这种溶液慢慢加入到预先所得到的卤代酸酐的a反应物中;所计算的硫酸用量以及它的浓度要使得在加完联氨时,于反应混合物中以每摩尔参加a阶段的酸酐含有500至1500毫升,最好是600至1200毫升硫酸溶液为最有利,这种溶液的浓度是在80%的H2SO4和65%的发烟硫酸之间,最好是在90%的H2SO4和40%的发烟硫酸之间。
根据本发明方法,b阶段的反应在温度至少等于130℃时进行,所得到的产物一般是符合下面结构式的双酰亚胺:
在该结构中,A表示所使用的卤代酸酐的其余部分。
根据本发明方法,所得到的产物,在任何性质的塑料中都能特别好地作为阻燃剂。可通过所有已知的方法把这些物质掺入,它的重量同易燃物质重量的比从5至40%。
下列实例用以阐明并非限制本发明,在实例中份数和百分数均以重量表示。
实例1
在一个玻璃反应器内,装有一个搅拌器和一个回流装置,于其中相继加入:
148克邻苯二(甲)酸酐
1.5克碘
700克65%的发烟硫酸
在反应物均匀后,加热至60-70℃,用4小时慢慢加入345克溴;加完以后,保持4小时同时将温度逐渐升高至110℃。
然后将107克硫酸联氨溶于1000克96%H2SO4中的溶液在2小时内加入其中,并将温度从110逐渐升高到180℃,反应物在此温度下保持11小时左右。
冷却以后,用水稀释,过滤并将所得到的固体洗至呈中性,然后干燥,得430克白色固体(产率93%),产品的红外光谱与下式相对应:
实例2
在同实例1相同的设备里,相继加入:
148克邻苯二(甲)酸酐
1.5克碘
700克65%的发烟硫酸
邻苯二(甲)酸酐溶解以后,加热至40℃,即反应介质的沸腾温度,以90克/小时的流量注入氯;保持这种氯的通入速度5小时,同时逐渐升高温度直到130℃。
冷却以后,在二小时内将90克硫酸联氨溶于900克96%的硫酸中的溶液加入其中,同时逐渐加热至100-110℃;联氨加完后,将温度升高到170℃,保持此温度11小时。
然后,人们将反应混合物冷却,用水稀释,过滤并洗涤所得固体直至呈中性;干燥后,得一白色固体,重量百分产率为92%,红外光谱与下式相符:
Claims (7)
1、从卤素、二羧酸酐和联氨制备卤代酰亚胺的方法,其特征在于:
a)进行二羧酸酐的卤化反应
b)然后,使从a阶段获得的反应物与联氨反应。
3、根据权利要求1或2中之一的方法,其特征在于,酸酐最好是邻苯二(甲)酸酐。
4、根据权利要求1至3中之一的方法,其特征在于,卤素最好是溴。
5、根据权利要求1至4中之一的方法,其特征在于,在a阶段进行卤化反应使得m大于或等于2。
6、根据权利要求1至5中之一的方法,其特征在于,所用的联氨最好用溶于硫酸中的硫酸联氨。
7、根据权利要求1至6中之一的方法,其特征在于,b阶段的反应在80和220℃,最好是在110和200℃温度之间进行。
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Application Number | Priority Date | Filing Date | Title |
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FR8706904 | 1987-05-18 | ||
FR8706904A FR2615510B1 (fr) | 1987-05-18 | 1987-05-18 | Procede de preparation d'imides halogenes |
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CN88102947A true CN88102947A (zh) | 1988-12-21 |
CN1023008C CN1023008C (zh) | 1993-12-08 |
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CN88102947A Expired - Fee Related CN1023008C (zh) | 1987-05-18 | 1988-05-18 | 卤代酰亚胺的制备方法 |
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US (1) | US5977379A (zh) |
EP (1) | EP0292362B1 (zh) |
JP (1) | JPH0674247B2 (zh) |
KR (1) | KR960007079B1 (zh) |
CN (1) | CN1023008C (zh) |
AT (1) | ATE79867T1 (zh) |
AU (1) | AU610590B2 (zh) |
CA (1) | CA1338353C (zh) |
DE (1) | DE3873983T2 (zh) |
DK (1) | DK168435B1 (zh) |
ES (1) | ES2034300T3 (zh) |
FI (1) | FI91962C (zh) |
FR (1) | FR2615510B1 (zh) |
GR (1) | GR3006273T3 (zh) |
IE (1) | IE63144B1 (zh) |
IL (1) | IL85986A (zh) |
NO (1) | NO173734C (zh) |
NZ (1) | NZ224640A (zh) |
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US4997953A (en) * | 1989-10-23 | 1991-03-05 | Ethyl Corporation | Process for preparing N,N'-bis(tetrabromophthalimide) |
WO1994013638A1 (en) * | 1992-12-04 | 1994-06-23 | Albemarle Corporation | Process for preparing bisimide products |
CN101444228B (zh) * | 2008-12-25 | 2011-06-08 | 中国科学院南海海洋研究所 | 一种海洋放线菌发酵提取物及其组合物和在抗生物污损的应用 |
CN112079803B (zh) * | 2020-09-11 | 2023-01-31 | 山东润科化工股份有限公司 | 一种4-卤代苯酐及其衍生物的合成方法 |
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US2420702A (en) * | 1944-06-28 | 1947-05-20 | British Celanese | Amino-aliphatic hydrazines and process for making same |
CH410898A (de) * | 1961-12-01 | 1966-04-15 | Kalk Chemische Fabrik Gmbh | Verfahren zur Herstellung von Tetrabromphthalsäureanhydrid |
DE1518647A1 (de) * | 1965-05-06 | 1969-02-13 | Kalk Chemische Fabrik Gmbh | Verfahren zur Herstellung von Tetrabromphthalsaeureanhydrid |
US3873567A (en) | 1968-09-05 | 1975-03-25 | Universal Oil Prod Co | N-substituted polybromoaromatic ortho-dicarboximides |
US3705127A (en) * | 1970-12-21 | 1972-12-05 | Universal Oil Prod Co | Polymeric flame retardant compositions |
US3734925A (en) * | 1971-02-08 | 1973-05-22 | Tenneco Chem | N-amino-3,4-dimethyl-6-isobutyl-phthalimides |
US3798327A (en) * | 1971-02-08 | 1974-03-19 | Tenneco Chem | Fungicidal compositions and their use |
JPS4945062A (zh) * | 1972-09-08 | 1974-04-27 | ||
JPS5625955B2 (zh) * | 1973-12-27 | 1981-06-16 | ||
US4003862A (en) * | 1975-10-23 | 1977-01-18 | Michigan Chemical Corporation | N-substituted tetrahalophthalimides as flame retardants |
US4087441A (en) * | 1976-07-19 | 1978-05-02 | Cities Service Company | Process for preparing aromatic bisimides |
FR2369261A1 (fr) * | 1976-10-28 | 1978-05-26 | Dynamit Nobel Ag | Derives de tetrabromophtalimide et leur application a titre d'agents d'ignifugation |
DE2648970A1 (de) * | 1976-10-28 | 1978-05-11 | Dynamit Nobel Ag | Azomethinimide |
GB1584203A (en) * | 1976-12-16 | 1981-02-11 | Dynamit Nobel Ag | Tetrabromophthalimide derivatives and their use as flameprroofing agents |
JPS555958A (en) * | 1978-06-30 | 1980-01-17 | Dainippon Ink & Chem Inc | Flame-retardant resin composition |
US4254011A (en) * | 1979-11-19 | 1981-03-03 | Bayer Aktiengesellschaft | Flame retarded polyethylene terephthalate compositions with improved drip suppression |
US4464240A (en) * | 1982-11-08 | 1984-08-07 | Canusa Coating Systems Limited | Thiodipropionoyl bis (halo benzhydrazide) additives for polymers |
US4465571A (en) * | 1982-11-08 | 1984-08-14 | Canusa Coating Systems Limited | Thiodipropionoyl bis(halo 5-norbornene 2,3-dicarboxylic acid hydrazide) additives for polymers |
CA1192559A (en) * | 1982-04-09 | 1985-08-27 | Ralph H. Hansen | Polymer parts and compound useful therein |
US4477523A (en) * | 1982-04-26 | 1984-10-16 | National Distillers And Chemical Corporation | Flame retardant crosslinked polyolefin insulation material |
JPS60161974A (ja) * | 1984-01-31 | 1985-08-23 | Nippon Shokubai Kagaku Kogyo Co Ltd | テトラクロロ無水フタル酸の製造方法 |
JPS61118378A (ja) * | 1984-11-14 | 1986-06-05 | Kanto Denka Kogyo Kk | テトラクロロフタル酸無水物の製造法 |
FR2618430B1 (fr) * | 1987-07-24 | 1991-02-15 | Atochem | Procede de preparation d'imides halogenes et leur application comme agents d'ignifugation |
US5137948A (en) * | 1986-02-12 | 1992-08-11 | Atochem | Preparation of flame-resistant halogenated imides |
-
1987
- 1987-05-18 FR FR8706904A patent/FR2615510B1/fr not_active Expired - Lifetime
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1988
- 1988-04-05 IL IL85986A patent/IL85986A/xx not_active IP Right Cessation
- 1988-04-19 ZA ZA882731A patent/ZA882731B/xx unknown
- 1988-05-04 NO NO881944A patent/NO173734C/no not_active IP Right Cessation
- 1988-05-10 AT AT88401140T patent/ATE79867T1/de not_active IP Right Cessation
- 1988-05-10 EP EP88401140A patent/EP0292362B1/fr not_active Expired - Lifetime
- 1988-05-10 DE DE8888401140T patent/DE3873983T2/de not_active Expired - Fee Related
- 1988-05-10 ES ES198888401140T patent/ES2034300T3/es not_active Expired - Lifetime
- 1988-05-16 NZ NZ224640A patent/NZ224640A/xx unknown
- 1988-05-16 PT PT87494A patent/PT87494B/pt not_active IP Right Cessation
- 1988-05-17 CA CA000567006A patent/CA1338353C/fr not_active Expired - Fee Related
- 1988-05-17 FI FI882314A patent/FI91962C/fi not_active IP Right Cessation
- 1988-05-17 IE IE147988A patent/IE63144B1/en not_active IP Right Cessation
- 1988-05-17 AU AU16341/88A patent/AU610590B2/en not_active Ceased
- 1988-05-17 DK DK268188A patent/DK168435B1/da not_active IP Right Cessation
- 1988-05-18 CN CN88102947A patent/CN1023008C/zh not_active Expired - Fee Related
- 1988-05-18 KR KR1019880005781A patent/KR960007079B1/ko not_active IP Right Cessation
- 1988-05-18 JP JP63121691A patent/JPH0674247B2/ja not_active Expired - Lifetime
-
1992
- 1992-03-19 US US07/854,744 patent/US5977379A/en not_active Expired - Fee Related
- 1992-11-18 GR GR920402631T patent/GR3006273T3/el unknown
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