阅读说明：本技术 一种环氧氯丙烷精馏釜残合成环氧树脂的方法 (Method for synthesizing epoxy resin from epichlorohydrin rectifying still residues ) 是由 徐林 孙诚 丁克鸿 王根林 王怡明 李明 李幸霏 于 2020-06-02 设计创作，主要内容包括：本发明提供一种环氧氯丙烷精馏釜残合成环氧树脂的方法,所述方法通过将环氧氯丙烷精馏釜残与皂化剂混合反应得到的第一油相与双酚A反应制备环氧树脂,实现了精馏釜残的资源化回收,减少了三废的排放,而且合成方法简单,易于工业化,制得的环氧树脂粘度低,同时解决了三废处理和环氧树脂粘度高的问题,具有良好的工业化前景。(The invention provides a method for synthesizing epoxy resin from epichlorohydrin rectifying still residues, which is characterized in that epoxy resin is prepared by reacting bisphenol A with a first oil phase obtained by mixing and reacting the epichlorohydrin rectifying still residues and a saponifying agent, so that resource recovery of the rectifying still residues is realized, discharge of three wastes is reduced, the synthetic method is simple and easy to industrialize, the prepared epoxy resin is low in viscosity, the problems of three-waste treatment and high epoxy resin viscosity are solved, and the method has a good industrialization prospect.)

1. The method for synthesizing the epoxy resin from the epichlorohydrin rectifying still residue is characterized by comprising the following steps:

(1) mixing the epichlorohydrin rectifying still residue and a saponifying agent, reacting, and performing liquid-liquid separation to obtain a first oil phase;

(2) and (2) reacting the first oil phase, bisphenol A and a condensing agent to synthesize the epoxy resin.

2. The method according to claim 1, wherein the epichlorohydrin rectification still residue in the step (1) comprises alcohol organic matters;

preferably, the alcoholic organics comprise 3-chloro-1, 2-propanediol and 1, 3-dichloropropanol and optionally 3-chloro-1-methoxy-2-propanol;

preferably, the mass fraction of the 3-chloro-1, 2-propanediol in the epichlorohydrin rectification kettle residue is 20-50%;

preferably, the mass fraction of the 1, 3-dichloropropanol in the epichlorohydrin rectification kettle residue is 50-80%;

preferably, the mass fraction of the 3-chloro-1-methoxy-2-propanol in the epichlorohydrin rectification residue is 0-8%.

3. The method according to claim 1 or 2, characterized in that the molar ratio of the saponifying agent to the alcohol organic matters in the epichlorohydrin rectification kettle residue in the step (1) is 1.05-1.5: 1;

preferably, the reaction temperature is 35-45 ℃;

preferably, the vacuum degree of the reaction is 40-50 mmHg.

4. The method according to any one of claims 1 to 3, wherein the mixing in step (1) comprises: firstly, heating the residual epoxy chloropropane rectification kettle to the reaction temperature, and then adding a saponifying agent;

preferably, the saponifying agent of step (1) comprises a base;

preferably, the base comprises a liquid base and/or a solid base, preferably a liquid base;

preferably, the liquid alkali is added dropwise;

preferably, the liquid alkali is sodium hydroxide solution;

preferably, the mass fraction of the sodium hydroxide is 10-30 wt%.

5. The process according to any one of claims 1 to 4, characterized in that the first oily phase in step (1) comprises 1, 2-epoxy-3-methoxypropane and epichlorohydrin.

6. The method according to any one of claims 1 to 5, wherein the reaction temperature of the synthetic epoxy resin in the step (2) is 55 to 70 ℃;

preferably, the reaction time for synthesizing the epoxy resin is 1.5-4 h;

preferably, the mole ratio of the epoxy chloropropane to the bisphenol A in the first oil phase is 3-8: 1.

7. The method according to any one of claims 1 to 6, wherein a surfactant is further added in the step (2);

preferably, the surfactant comprises a cationic surfactant, preferably cetyltrimethylammonium chloride and/or octadecyltrimethylammonium chloride;

preferably, the addition amount of the surfactant is 0.5-1.5% of the mass of the bisphenol A;

preferably, in the step (2), bisphenol A and a surfactant are added into the first oil phase, and after the bisphenol A is dissolved, a condensing agent is added to synthesize epoxy resin;

preferably, the dissolution is carried out in a non-oxidizing atmosphere;

preferably, the non-oxidizing atmosphere comprises nitrogen.

8. The method according to any one of claims 1 to 7, wherein the molar ratio of the condensing agent to the bisphenol A in the step (2) is 1.5 to 3: 1;

preferably, the condensing agent in step (2) comprises a base;

preferably, the base comprises a solid base, preferably solid sodium hydroxide.

9. The method according to any one of claims 1 to 8, further comprising, after step (2):

(3) carrying out solid-liquid separation and liquid-liquid separation on the reaction liquid obtained after the epoxy resin is synthesized in the step (2) to obtain a second oil phase, and distilling the second oil phase to obtain the epoxy resin;

preferably, the distillation comprises distillation under reduced pressure.

10. A method according to any one of claims 1 to 9, characterized in that the method comprises the steps of:

(1) heating the epoxy chloropropane rectifying still residue to 35-45 ℃ under stirring, wherein the vacuum degree is 40-50 mmHg, dropwise adding liquid alkali, reacting, and carrying out liquid-liquid separation to obtain a first oil phase containing 1, 2-epoxy-3-methoxypropane and epoxy chloropropane;

the epichlorohydrin rectification kettle residue comprises an alcohol organic matter, the mass fraction of 3-chloro-1, 2-propanediol in the epichlorohydrin rectification kettle residue is 20-50%, the mass fraction of 1, 3-dichloropropanol is 50-80%, and the mass fraction of 3-chloro-1-methoxy-2-propanol is 0-8%; the molar ratio of the alkali in the liquid alkali to the alcohol organic matters in the residual epoxy chloropropane rectification kettle is 1.05-1.5: 1;

(2) adding bisphenol A and a surfactant into the first oil phase in the step (1), dissolving the bisphenol A in a non-oxidizing atmosphere, adding solid alkali, and reacting at 55-70 ℃ for 1.5-4 h to synthesize epoxy resin;

wherein the molar ratio of the epichlorohydrin to the bisphenol A in the first oil phase is 3-8: 1, the addition amount of the surfactant is 0.5-1.5% of the mass of the bisphenol A, and the molar ratio of the solid alkali to the bisphenol A is 1.5-3: 1;

(3) and (3) carrying out solid-liquid separation and liquid-liquid separation on the reaction liquid obtained after the epoxy resin is synthesized in the step (2) to obtain a second oil phase, and carrying out reduced pressure distillation on the second oil phase to obtain the epoxy resin.

Technical Field

The invention relates to the technical field of organic chemical industry, in particular to a method for synthesizing epoxy resin from epichlorohydrin rectifying still residues.

Background

Epichlorohydrin is an important basic chemical raw material and is mainly applied to the production of products such as epoxy resin, epichlorohydrin rubber and the like. At present, the industrial production methods of epichlorohydrin mainly comprise two methods: the chlorohydrin process and the glycerol process. The chlorohydrin method has serious environmental pollution, and about 40 tons of salt-containing wastewater is generated every 1 ton of epichlorohydrin is produced. The glycerol method has fewer byproducts and mild operating conditions, but the productivity is limited by the raw material glycerol, so that the productivity is difficult to further expand.

The development of a clean production process of epoxy chloropropane has become an inevitable requirement of times development, and the use of hydrogen peroxide as a green oxygen source is a hot research point of olefin catalytic epoxidation in recent years. The process for synthesizing epichlorohydrin by using the titanium silicalite molecular sieve as the catalyst becomes a research hotspot due to the advantages of high selectivity, less ineffective decomposition of hydrogen peroxide and the like.

However, methanol is generally used as a solvent in the process, epichlorohydrin and methanol can further react to generate etherification products such as 1, 2-epoxy-3-methoxy propane, 3-chloro-1-methoxy-2-propanol and the like, wherein the boiling point of the 3-chloro-1-methoxy-2-propanol is 171 ℃, the 3-chloro-1, 2-propylene glycol, 1, 3-dichloropropanol and the like coexist in the residue of the rectifying still, and if the three wastes are treated as dangerous wastes, the three-waste treatment cost can be obviously increased.

At present, no relevant literature report about the rectification still residue treatment is found.

Although CN110156726A discloses a method for comprehensively utilizing epichlorohydrin rectification kettle residues, the rectification kettle residues contain a catalyst, and the main content of the kettle residues is still epichlorohydrin, the method also mainly focuses on the recovery and regeneration of the catalyst, and cannot be used as a reference for recovering and treating etherification products such as 1, 2-epoxy-3-methoxypropane and 3-chloro-1-methoxy-2-propanol in the rectification kettle residues.

Therefore, a process capable of recycling epichlorohydrin rectification kettle residues needs to be developed.

Disclosure of Invention

In order to solve the technical problems, the invention provides a method for synthesizing epoxy resin from epichlorohydrin rectifying still residues, the method obtains the epoxy resin by recycling the epichlorohydrin rectifying still residues, reduces the treatment cost of waste liquid, has low viscosity of the prepared epoxy resin, solves the problems of three-waste treatment and high viscosity of the epoxy resin, and has good industrial prospect.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a method for synthesizing epoxy resin from epichlorohydrin rectifying still residues, which comprises the following steps:

(1) mixing the epichlorohydrin rectifying still residue and a saponifier, and performing liquid-liquid separation after reaction to obtain a first oil phase;

(2) and (2) reacting the first oil phase, bisphenol A and a condensing agent to synthesize the epoxy resin.

The method for synthesizing the epoxy resin by using the epoxy chloropropane rectification kettle residue as a raw material comprises the steps of performing a first-step saponification reaction and simultaneously performing liquid-liquid separation, wherein the saponification reaction is performed, the rectification kettle residue is subjected to the saponification reaction to respectively obtain 1, 2-epoxy-3-methoxy propane, the epoxy propanol and the epoxy chloropropane, wherein the 1, 2-epoxy-3-methoxy propane and the epoxy chloropropane are subjected to azeotropic extraction with water, the epoxy propanol is left in a saponification kettle material and is further hydrolyzed into glycerol, the glycerol content in the kettle material is low, and the glycerol can be discharged or recycled by simple treatment. The epoxy chloropropane and the bisphenol A in the obtained mixed oil phase containing the epoxy chloropropane and the 1, 2-epoxy-3-methoxy propane react under the action of alkali to prepare the epoxy resin, and the 1, 2-epoxy-3-methoxy propane has no negative effect in the process of preparing the epoxy resin and can play a role of an active diluent, so that the viscosity of the epoxy resin is reduced, and the market value of the epoxy resin is improved. The method for synthesizing the epoxy resin by rectifying the kettle residue with the epichlorohydrin simultaneously solves the problems of three-waste treatment of the kettle residue and high viscosity of the epoxy resin, and has double benefits of environmental protection and economy.

Preferably, the epichlorohydrin rectification residue in the step (1) includes an alcohol organic matter.

Preferably, the alcoholic organics include 3-chloro-1, 2-propanediol and 1, 3-dichloropropanol and optionally 3-chloro-1-methoxy-2-propanol.

Preferably, the mass fraction of the 3-chloro-1, 2-propanediol in the epichlorohydrin rectification residue is 20-50%, for example, 20%, 22%, 25%, 30%, 35%, 40%, 45%, or 50%.

Preferably, the mass fraction of the 1, 3-dichloropropanol in the epichlorohydrin rectification residue is 50-80%, and may be, for example, 50%, 52%, 55%, 58%, 59%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, or 80%.

Preferably, the mass fraction of the 3-chloro-1-methoxy-2-propanol in the epichlorohydrin rectification residue is 0 to 8%, and may be, for example, 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, or 8%.

The epichlorohydrin rectification kettle residue refers to the rectification kettle residue remaining after the basic reaction of the epichlorohydrin is finished, and the components of the epichlorohydrin rectification kettle residue mainly comprise 3-chloro-1, 2-propanediol, 1, 3-dichloropropanol and optionally 3-chloro-1-methoxy-2-propanol, and are difficult to treat.

Preferably, the molar ratio of the saponifying agent to the alcohol organic matter in the epichlorohydrin rectification residue in step (1) is 1.05 to 1.5:1, and may be, for example, 1.05:1, 1.1:1, 1.15:1, 1.2:1, 1.25:1, 1.3:1, 1.35:1, 1.4:1, 1.45:1, or 1.5: 1.

Preferably, the reaction temperature is 35 ~ 45 ℃, for example can be 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃ or 45 ℃ etc..

The degree of vacuum in the reaction is preferably 40 to 50mmHg, and may be, for example, 40mmHg, 41mmHg, 42mmHg, 43mmHg, 44mmHg, 45mmHg, 47mmHg, 48mmHg, 49mmHg, or 50 mmHg.

Preferably, the mixing in step (1) comprises: firstly, heating the residual epoxy chloropropane rectifying kettle to the reaction temperature, and then adding a saponifying agent.

According to the invention, the temperature of the epichlorohydrin rectifying still residue is preferably raised, and then the saponifying agent is added, so that saponification instead of hydrolysis reaction can be realized after the saponifying agent is added.

Preferably, the saponifying agent of step (1) comprises a base.

Preferably, the base comprises a liquid base and/or a solid base, preferably a liquid base.

Preferably, the liquid alkali is added dropwise.

The invention preferably adopts a gradual dripping mode to prevent hydrolysis.

Preferably, the liquid alkali is sodium hydroxide solution.

Preferably, the mass fraction of sodium hydroxide is 10 to 30 wt%, and may be, for example, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, or 30 wt%.

Preferably, the first oil phase in step (1) comprises 1, 2-epoxy-3-methoxypropane and epichlorohydrin.

The first oil phase in the invention comprises 1, 2-epoxy-3-methoxy propane, which not only can be used for preparing epoxy resin without being separated from epoxy chloropropane, but also can play a role of a reactive diluent of the epoxy resin and reduce the viscosity of the prepared epoxy resin.

Preferably, the reaction temperature of the synthetic epoxy resin in the step (2) is 55 to 70 ℃, and may be, for example, 55 ℃, 56 ℃, 58 ℃, 60 ℃, 62 ℃, 65 ℃, 68 ℃ or 70 ℃.

Preferably, the reaction time for synthesizing the epoxy resin is 1.5-4 h, for example, 1.5h, 1.8h, 2.0h, 2.2h, 2.5h, 2.8h, 3h, 3.2h, 3.5h, 3.8h or 4h, etc.

Preferably, the molar ratio of epichlorohydrin to bisphenol a in the first oil phase is 3 to 8:1, and may be, for example, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, or 8: 1.

Preferably, a surfactant is also added in step (2).

According to the invention, the bisphenol A is added and the surfactant is also added, so that the dissolution of the bisphenol A can be promoted, and the reaction effect is improved.

Preferably, the surfactant includes a cationic surfactant, and may be, for example, any one of or a combination of at least two of cetyltrimethylammonium chloride, octadecyltrimethylammonium bromide, or hexadecyltrimethylammonium bromide, and the like, wherein typical non-limiting combinations are a combination of octadecyltrimethylammonium bromide and hexadecyltrimethylammonium bromide, a combination of octadecyltrimethylammonium chloride and hexadecyltrimethylammonium bromide, a combination of octadecyltrimethylammonium bromide and octadecyltrimethylammonium chloride, and the like, and further preferably cetyltrimethylammonium chloride and/or octadecyltrimethylammonium chloride.

The amount of the surfactant added is preferably 0.5 to 1.5% by mass of bisphenol a, and may be, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, or the like.

Preferably, in the step (2), bisphenol a and a surfactant are added into the first oil phase, and after dissolving the bisphenol a, a condensing agent is added to synthesize the epoxy resin.

Preferably, the dissolution is carried out in a non-oxidizing atmosphere.

Preferably, the non-oxidizing atmosphere comprises nitrogen.

Preferably, the molar ratio of the condensing agent to bisphenol a in step (2) is 1.5 to 3:1, and may be, for example, 1.5:1, 1.6:1, 1.8:1, 2.0:1, 2.2:1, 2.5:1, 2.8:1, or 3.0: 1.

Preferably, the condensing agent in step (2) comprises a base.

Preferably, the base comprises a solid base, preferably solid sodium hydroxide.

Preferably, after the step (2), the method further comprises the following steps:

(3) and (3) carrying out solid-liquid separation and liquid-liquid separation on the reaction liquid obtained after the epoxy resin is synthesized in the step (2) to obtain a second oil phase, and distilling the second oil phase to obtain the epoxy resin.

Preferably, the distillation comprises distillation under reduced pressure.

The method of distillation under reduced pressure in the present invention is not particularly limited, and any method known to those skilled in the art can be used to separate the liquid phase.

As a preferred technical scheme of the invention, the method comprises the following steps:

(1) heating the epoxy chloropropane rectifying still residue to 35-45 ℃ under stirring, keeping the vacuum degree at 40-50 mmHg, dropwise adding liquid alkali, and after reaction, carrying out liquid-liquid separation to obtain a first oil phase containing 1, 2-epoxy-3-methoxypropane and epoxy chloropropane;

the epichlorohydrin rectification kettle residue comprises an alcohol organic matter, the mass fraction of 3-chloro-1, 2-propanediol in the epichlorohydrin rectification kettle residue is 20-50%, the mass fraction of 1, 3-dichloropropanol is 50-80%, and the mass fraction of 3-chloro-1-methoxy-2-propanol is 0-8%; the molar ratio of the alkali in the liquid alkali to the alcohol organic matters in the residual epoxy chloropropane rectification kettle is 1.05-1.5: 1;

(2) adding bisphenol A and a surfactant into the first oil phase in the step (1), dissolving the bisphenol A in a non-oxidizing atmosphere, adding solid alkali, and reacting at 55-70 ℃ for 1.5-4 h to synthesize epoxy resin;

wherein the molar ratio of the epichlorohydrin to the bisphenol A in the first oil phase is 3-8: 1, the addition amount of the surfactant is 0.5-1.5% of the mass of the bisphenol A, and the molar ratio of the solid alkali to the bisphenol A is 1.5-3: 1;

(3) and (3) carrying out solid-liquid separation and liquid-liquid separation on the reaction liquid obtained after the epoxy resin is synthesized in the step (2) to obtain a second oil phase, and carrying out reduced pressure distillation on the second oil phase to obtain the epoxy resin.

The liquid-liquid separation method of the present invention is not particularly limited, and any method known to those skilled in the art can be used for liquid-liquid separation, for example, a method of standing oil-water for layer separation, etc.

The solid-liquid separation method of the present invention is not particularly limited, and any method for solid-liquid separation known to those skilled in the art may be used, and examples of the method include solid-liquid separation methods such as filtration, centrifugation, and/or standing sedimentation.

Compared with the prior art, the invention has at least the following beneficial effects:

(1) the method for synthesizing the epoxy resin from the epichlorohydrin rectification kettle residue can realize resource treatment of the rectification kettle residue, reduce discharge of three wastes and have good environmental protection benefit;

(2) according to the method for synthesizing the epoxy resin by rectifying the kettle residue with the epichlorohydrin, the kettle residue is saponified to obtain the mixed oil phase containing the 1, 2-epoxy-3-methoxypropane and the epichlorohydrin, and the finally prepared epoxy resin has low viscosity which is less than or equal to 13000cps and has better market application value;

(3) the method for synthesizing the epoxy resin by using the epichlorohydrin rectification residue is simple and easy for industrial production.

Detailed Description

For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.