CN108148029A

CN108148029A - A kind of preparation method of two ether dianhydride of bisphenol-A

Info

Publication number: CN108148029A
Application number: CN201711442043.5A
Authority: CN
Inventors: 刘少华
Original assignee: GUCHUANG CHEMICAL NEW MATERIALS CO Ltd SHANGHAI
Current assignee: GUCHUANG CHEMICAL NEW MATERIALS CO Ltd SHANGHAI
Priority date: 2017-12-27
Filing date: 2017-12-27
Publication date: 2018-06-12
Anticipated expiration: 2037-12-27
Also published as: CN108148029B

Abstract

The present invention relates to a kind of preparation methods of two ether dianhydride of bisphenol-A, and this method comprises the following steps；The molar ratio of sodium hydroxide and bisphenol-A is 2.1~2.3:The molar ratio of Isosorbide-5-Nitrae chloro-benzoic anhydride and bisphenol-A is 2~2.1:1, the weight of catalyst benzyltriethylammoinium chloride is 15 weight % of bisphenol-A weight, and the amount of solvent trimethylbenzene is 8 times of bisphenol-A weight；Preparation process is：Sodium hydrate aqueous solution and bisphenol-A add in reactor, heat up stirring and dissolving, it is warming up to 85 DEG C~90 DEG C, it adds in trimethylbenzene and accounts for the benzyltriethylammoinium chloride of 46 weight % of total amount, temperature rising reflux, dehydration, it is stirred to react at 172 DEG C 15~18 hours, it is cooled to 130 DEG C, it adds in 4 chloro-benzoic anhydrides and accounts for the benzyltriethylammoinium chloride of 54 weight % of total amount, 140 DEG C~145 DEG C of heating, back flow reaction 5~6 hours, it filters while hot, filtrate is cooled to room temperature, filtering, precipitation is washed respectively with deionized water and ethyl alcohol, filtering, obtain wet feed, drying, obtain two ether dianhydride product of bisphenol-A, yield 80~85%.

Description

A kind of preparation method of two ether dianhydride of bisphenol-A

One, technical fields

The present invention relates to a kind of preparation methods of two ether dianhydride of bisphenol-A, and polyetherimide is prepared more particularly to a kind of The preparation method of two ether dianhydride of bisphenol-A of amine.

Two, background technologies

Polyetherimide is by two ether dianhydride of bisphenol-A and 4.4'- diaminodiphenyl ethers or 4.4'- diaminodiphenyl-methanes Or m-phenylene diamine (MPD) reaction preparation.Polyetherimide is theRMOPLASTIC RESINS, widely used, and it is sub- that its dosage accounts for whole polyamides More than 50% amine dosage.Polyetherimide has following characteristic properties：High intensity and high rigidity under room temperature and high temperature, for a long time Temperature tolerance, size and electrical property are highly stable, and chemical-resistant resistance range is wide, are carried out using hot plastic processing method and former Melt-processed, mass production, intrinsic anti-flammability, smog is low during burning.It is widely used in space flight and aviation, automobile, computer, electrical electricity The high-temperature technologies field such as sub- medical treatment and packaging market.Two ether dianhydride of bisphenol-A is the indispensable important original of synthesizing polyether acid imide Material.So the preparation of two ether dianhydride of bisphenol-A just seems particularly significant.Prepare the requirement of two ether dianhydride method of bisphenol-A：Method letter It is single, reliably, easily implement, it is efficient.

Industrial process at present uses N- dimethylamino methyl phenyls acid imide as initial feed, through Nitritation, then with it is double Phenol A disodium salts carry out nucleophilic substitution, followed by swap and react with phthalic anhydride, are converted to two ether dianhydride of bisphenol-A.The method synthesizes Route is long, and total recovery is low, and a large amount of spent acid are generated in production process, and salkali waste, environmental pollution is serious, needs to improve producer really Method.

Three, invention contents

The present invention provides a kind of environmentally friendly, pollution less, it is simple for process, it is safe and reliable, easily implement, efficient system The method of two ether dianhydride of standby bisphenol-A.The present inventors have carried out research with great concentration, it is proposed that prepared by a kind of two ether dianhydride of bisphenol-A The complete technical solution of method.

A kind of preparation method of two ether dianhydride of bisphenol-A, the preparation method include the following steps；In catalyst benzyl triethyl ammonium In the presence of ammonium chloride, in front three benzene solvent, bisphenol-A and sodium hydrate aqueous solution is first allowed to carry out salt-forming reaction, generates bisphenol-A two Sodium salt, then, bisphenol-A disodium salt carry out necleophilic reaction desalination, bis- ether dianhydrides of producing bisphenol A with 4- chloro-benzoic anhydrides；Rate of charge is The molar ratio of sodium hydroxide and bisphenol-A is 2.1~2.3:The molar ratio of Isosorbide-5-Nitrae-chloro-benzoic anhydride and bisphenol-A is 2~2.1:1, catalysis The weight of agent benzyltriethylammoinium chloride is 15 weight % of bisphenol-A weight, accounts for three second of benzyl of 46 weight % of catalyst total amount Ammonium chloride is just added in reaction system in salt-forming stage, accounts for 54 weight % benzyltriethylammoinium chlorides of catalyst total amount in parent The nuclear reaction stage adds in, and solvent trimethylbenzene addition is 8 times of bisphenol-A weight；Preparation process is：Sodium hydrate aqueous solution and double Phenol A adds in reactor by proportioning, and heat up stirring and dissolving, and when temperature is raised to 85 DEG C~90 DEG C, the transparent state of solution adds in solvent Trimethylbenzene and the benzyltriethylammoinium chloride for accounting for 46 weight % of catalyst total amount, temperature rising reflux, dehydration, then, in 172 DEG C of heat preservations It is stirred to react 15~18 hours, is cooled to 130 DEG C, 4- chloro-benzoic anhydrides are added in by proportioning and account for the benzyl of 54 weight % of catalyst total amount Triethylammonium chloride heats up 140 DEG C~145 DEG C, and back flow reaction 5~6 hours then filters while hot, and filtrate is evacuated to crystallization In kettle, filtered fluid is cooled to room temperature, and is crystallized 12 hours, and filtering, obtained crystallization is washed with deionized water, obtains wet feed, after Filter, obtained crystallization are washed 2 hours with ethyl alcohol, are filtered, are obtained two ether dianhydride wet feed of bisphenol-A, are dried, are obtained two ether dianhydride of bisphenol-A Product, yield 80~85%.

Sodium hydrate content in heretofore described sodium hydrate aqueous solution is the weight % of 30 weight %~50.

Here illustratively, catalyst is suitable for the invention, in addition to benzyltriethylammoinium chloride, also benzyl triethyl ammonium Ammonium bromide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriphenyl phosphonium phosphonium chloride are also suitable the present invention, the present invention Selection benzyltriethylammoinium chloride.

According to the two ether dianhydride wet feed of bisphenol-A for preparing of the present invention, drying obtains two ether dianhydride product of bisphenol-A, and yield 80~ 85%, 185 DEG C~186 DEG C of fusing point, apparent white powder, purity is up to more than 99.5%.

The present invention provides a kind of environmentally friendly, pollution less, it is simple for process, it is safe and reliable, easily implement, efficient system The method of two ether dianhydride of standby bisphenol-A.

Four, specific embodiments

In order to preferably implement the present invention, special illustration, but embodiment is no the limit to the scope of the present invention System.

Embodiment 1

32 weight % sodium hydrate aqueous solutions 79g (0.63mol) and 62.4g (0.3mol) bisphenol-A are added in reactor, are stirred Rising temperature for dissolving is mixed, temperature rises to 85 DEG C of transparent states of solution, is subsequently added into 510g front threes benzene solvent and 4.2g benzyl triethyl ammoniums Ammonium chloride catalyst, temperature rising reflux dehydration, temperature rise to 172 DEG C, and insulated and stirred is reacted 15 hours, is then cooled to 130 DEG C, is added Enter 108g (0.6mol) 4- chloro-benzoic anhydrides and 4.86g benzyltriethylammoinium chloride catalyst, heat up 140 DEG C~145 DEG C, reflux is anti- It answers 5 hours, then filters while hot, filtrate is evacuated in crystallization kettle, filtered fluid is cooled to room temperature, and is crystallized 12 hours, is filtered, precipitation It is washed with deionized water, filters, obtain precipitating and be washed again with 250g ethyl alcohol, is stirred at reflux 2 hours, filtered, obtain wet feed 125g, dried Two ether dianhydride product 120g (yield 85%) of bisphenol-A, product shows white powder, 185 DEG C~186 DEG C of fusing point, purity are obtained after dry 99.5%.

Embodiment 2

50 weight % sodium hydrate aqueous solutions 55.2g (0.69mol) and 62.4g (0.3mol) bisphenol-A are added in reactor, Rising temperature for dissolving is stirred, temperature rises to 85 DEG C of transparent states of solution, is subsequently added into three second of 510g front threes benzene solvent and 4.2g benzyls Ammonium chloride catalyst, temperature rising reflux dehydration, temperature rise to 172 DEG C, and insulated and stirred is reacted 18 hours, is then cooled to 130 DEG C, 114g (0.63mol) 4- chloro-benzoic anhydrides and 4.86g benzyltriethylammoinium chloride catalyst are added in, is heated up 140 DEG C~145 DEG C, is returned Stream reaction 5 hours, then filters, filtrate is evacuated in crystallization kettle while hot, and filtered fluid is cooled to room temperature, and crystallizes 12 hours, filtering, Precipitation is washed with deionized water, and filtering is obtained precipitating and be washed again with 250g ethyl alcohol, is stirred at reflux 2 hours, is filtered, is obtained wet feed 118g, after drying two ether dianhydride product 113g (yield 80%) of bisphenol-A, product shows white powder, 185 DEG C~186 DEG C of fusing point, Purity 99.5%.

Claims

1. a kind of preparation method of two ether dianhydride of bisphenol-A, which is characterized in that the preparation method includes the following steps；In catalyst In the presence of benzyltriethylammoinium chloride, in front three benzene solvent, bisphenol-A and sodium hydrate aqueous solution is first allowed to carry out salt-forming reaction, Bisphenol-A disodium salt is generated, then, bisphenol-A disodium salt carries out necleophilic reaction desalination, producing bisphenol A diether two with 4- chloro-benzoic anhydrides Acid anhydride；Rate of charge is that the molar ratio of sodium hydroxide and bisphenol-A is 2.1~2.3:The molar ratio of Isosorbide-5-Nitrae-chloro-benzoic anhydride and bisphenol-A for 2~ 2.1:1, the weight of catalyst benzyltriethylammoinium chloride is 15 weight % of bisphenol-A weight, accounts for 46 weight % of catalyst total amount Benzyltriethylammoinium chloride be just added in reaction system in salt-forming stage, account for 54 weight % benzyl triethyl ammoniums of catalyst total amount Ammonium chloride adds in the necleophilic reaction stage, and solvent trimethylbenzene addition is 8 times of bisphenol-A weight；Preparation process is：Sodium hydroxide Aqueous solution and bisphenol-A add in reactor by proportioning, and heat up stirring and dissolving, and when temperature is raised to 85 DEG C~90 DEG C, solution is transparent State adds in solvent trimethylbenzene and accounts for the benzyltriethylammoinium chloride of 46 weight % of catalyst total amount, temperature rising reflux, dehydration, then, It is reacted 15~18 hours in 172 DEG C of insulated and stirreds, is cooled to 130 DEG C, 4- chloro-benzoic anhydrides are added in by proportioning and account for catalyst total amount The benzyltriethylammoinium chloride of 54 weight % heats up 140 DEG C~145 DEG C, and back flow reaction 5~6 hours then filters while hot, will Filtrate is evacuated in crystallization kettle, and filtered fluid is cooled to room temperature, and is crystallized 12 hours, and filtering, obtained precipitation is washed with deionized water, mistake Filter, what is precipitated is washed 2 hours with ethyl alcohol, and filtering obtains two ether dianhydride wet feed of bisphenol-A, dries, obtains two ether dianhydride of bisphenol-A Product, yield 80~85%.

A kind of 2. preparation method of two ether dianhydride of bisphenol-A according to claim 1, which is characterized in that the sodium hydroxide Sodium hydrate content in aqueous solution is the weight % of 30 weight %~50.