阅读说明：本技术 一种新型阻燃剂及其制备方法 (Novel flame retardant and preparation method thereof ) 是由 盖登宇 于 2021-01-18 设计创作，主要内容包括：本发明提供一种新型阻燃剂及其制备方法,涉及阻燃剂制取技术领域。包括以下步骤：步骤一：原料准备：将乙基双环亚磷酸酯和甲基膦酸二甲酯进行密封,同步充入足量氮气,随后进行初步预热,步骤二：设备制备：将乙基双环亚磷酸酯和甲基膦酸二甲酯所使用的反应釜进行抽真空。通过对过量注入的甲基膦酸二甲酯和乙基双环亚磷酸酯进行预热和氮气保护,随后将制成的环状磷酸酯与磷酸三甲酯进行混合制备阻燃剂,可以极大的利用副产物提高阻燃剂的阻燃效率,提高产品的竞争力,随后通过对甲基膦酸二甲酯进行处理,利用生产环状磷酸酯的余热进行生产磷酸三甲酯和磷酸二甲酯,生产大量的高附加值产品,提高该制备方法的经济效益。(The invention provides a novel flame retardant and a preparation method thereof, and relates to the technical field of preparation of flame retardants. The method comprises the following steps: the method comprises the following steps: preparing raw materials: sealing the ethyl dicyclic phosphite ester and dimethyl methylphosphonate, synchronously filling enough nitrogen, and then carrying out primary preheating, wherein the second step is as follows: preparing equipment: the reaction kettle used by the ethyl dicyclic phosphite ester and the dimethyl methylphosphonate is vacuumized. The excessive methyl phosphonic acid dimethyl ester and the excessive ethyl dicyclic phosphite ester are preheated and protected by nitrogen, then the prepared cyclic phosphoric ester is mixed with trimethyl phosphate to prepare the flame retardant, the flame retardant efficiency of the flame retardant can be greatly improved by utilizing byproducts, the competitiveness of products is improved, then the dimethyl methyl phosphonate is treated, the trimethyl phosphate and the dimethyl phosphate are produced by utilizing the waste heat for producing the cyclic phosphoric ester, a large amount of products with high added values are produced, and the economic benefit of the preparation method is improved.)

1. A novel flame retardant and a preparation method thereof are characterized by comprising the following steps:

the method comprises the following steps: preparing raw materials: sealing the ethyl dicyclic phosphite ester and dimethyl methylphosphonate, synchronously filling sufficient nitrogen, and then carrying out primary preheating;

step two: preparing equipment: vacuumizing a reaction kettle used by the ethyl dicyclic phosphite ester and the dimethyl methylphosphonate, and mixing preheated liquid;

step three: treating by-products; adding excessive dimethyl methylphosphonate for full reaction, heating to 180 ℃, and separating cyclic phosphate ester by an extraction solvent;

step four: utilization of by-products: mixing dimethyl methylphosphonate with methanol, adding enough catalyst, and catalyzing to generate trimethyl phosphate and new dimethyl methylphosphonate;

step five: and (3) recycling of by-products: trimethyl phosphate and new dimethyl methylphosphonate are subjected to extractive separation, and then purified trimethyl phosphate is mixed with a catalyst to prepare a sufficient amount of dimethyl phosphate.

2. The novel flame retardant and the preparation method thereof according to claim 1, characterized by comprising the following steps: according to the operation steps in the step one, the purity of the ethyl dicyclic phosphite ester and the dimethyl methyl phosphonate needs to reach 98%, and the ethyl dicyclic phosphite ester and the dimethyl methyl phosphonate are stored in a ceramic sealed container in a dark low-temperature mode.

3. The novel flame retardant and the preparation method thereof according to claim 1, characterized by comprising the following steps: according to the operation steps in the first step, the preheating temperature is 50 ℃, the nitrogen is injected before preheating, and the interior of the ceramic sealed container is in an oxygen-free state.

4. The novel flame retardant and the preparation method thereof according to claim 1, characterized by comprising the following steps: according to the operation steps in the second step, the reaction kettle carries out synchronous vacuumizing operation when the waste heat reaches 80 ℃, the preheating time is 15-20 minutes, and the waste heat time of 1 minute is increased when the actual volume of the reaction kettle is increased by 10 liters.

5. The novel flame retardant and the preparation method thereof according to claim 1, characterized by comprising the following steps: according to the operation steps in the second step, the mixing temperature of the liquid of the ethyl dicyclic phosphite ester and the dimethyl methylphosphonate is 100 ℃, and the liquid can be injected into the vacuumized reaction kettle after standing for 5 minutes during mixing.

6. The novel flame retardant and the preparation method thereof according to claim 1, characterized by comprising the following steps: according to the operation steps in the third step, the methyl phosphonate dimethyl ester is added in excess, and the reaction mass ratio of the ethyl dicyclic phosphite ester to the methyl phosphonate dimethyl ester is 1: 15.

7. the novel flame retardant and the preparation method thereof according to claim 1, characterized by comprising the following steps: according to the operation steps in the third step, the extraction solvent adopts a mixture of trichloromethane and dichloromethane for extraction and separation.

8. The novel flame retardant and the preparation method thereof according to claim 1, characterized by comprising the following steps: according to the operation steps in the fourth step, the liquid remained in the reaction kettle is dimethyl methyl phosphonate, and the mass ratio of the dimethyl methyl phosphonate to the added methanol is 1: 10.

9. the novel flame retardant and the preparation method thereof according to claim 1, characterized by comprising the following steps: according to the operation steps in the fourth step, the catalyst is potassium carbonate, and a proper amount of phosphorus oxychloride needs to be dropwise added in the catalysis.

10. The novel flame retardant and the preparation method thereof according to claim 1, characterized by comprising the following steps: according to the operation steps in the fifth step, the solvent adopted by the extraction separation is carbon tetrachloride, the carbon tetrachloride is recovered, the crude product is obtained by reduced pressure distillation, distilled water and activated carbon are added into the crude product, anhydrous potassium carbonate is added after filtration for dehydration, finally, reduced pressure distillation is carried out to obtain trimethyl phosphate, barium hydroxide is used as a catalyst for preparing dimethyl phosphate by the trimethyl phosphate, the trimethyl phosphate and cyclic phosphate are mixed to prepare the flame retardant, and the trimethyl phosphate is used as a byproduct for preparing downstream high-cost-performance chemical products in the next step.

Technical Field

The invention relates to the technical field of preparation of flame retardants, in particular to a novel flame retardant and a preparation method thereof.

Background

The flame retardant is a functional auxiliary agent for endowing the inflammable polymer with flame retardancy, and is mainly designed aiming at the flame retardancy of a high polymer material; the flame retardant is divided into additive flame retardant and reactive flame retardant according to the using method, the additive flame retardant is added into the polymer by a mechanical mixing method to enable the polymer to have flame retardance, the prior additive flame retardant mainly comprises organic flame retardant and inorganic flame retardant, halogen flame retardant (organic chloride and organic bromide) and non-halogen, organic flame retardant represented by bromine, phosphorus-nitrogen, red phosphorus and compounds, inorganic flame retardant mainly comprises flame retardant systems of antimony trioxide, magnesium hydroxide, aluminum hydroxide, silicon and the like, and the reactive flame retardant is used as a monomer to participate in polymerization reaction, so that the polymer contains flame retardant components.

At present, when cyclic phosphate with a good flame retardant effect is produced, referring to actual market price, high-value ethyl dicyclic phosphite and low-value dimethyl methyl phosphonate are adopted for preparation, in order to ensure reaction efficiency, excessive dimethyl methyl phosphonate is often added, incomplete reaction of the high-value ethyl dicyclic phosphite is avoided, actual production cost is increased, but after the reaction is finished, a large amount of residual dimethyl methyl phosphonate is generated in a reaction kettle, the actual flame retardant effect of the existing cyclic phosphate with a single component is limited, the residual dimethyl methyl phosphonate cannot be continuously used as a raw material for producing other flame retardants in a subsequent production process, the large amount of waste of the dimethyl methyl phosphonate is caused, and the actual economic benefit is not good.

Disclosure of Invention

The invention aims to provide a novel flame retardant and a preparation method thereof. During through the steelmaking, the produced calcium silicate of lime stone that drops into is collected and is being utilized, can further improve the reuse efficiency to the discarded object, avoids producing the waste of resource, secondly through preparing silica flour in a large number, can improve the preparation efficiency of whole reaction, adds excessive silica flour, can further improve the preparation volume, avoids the not good problem of productivity effect that the output is not enough to lead to.

In order to solve the problems of poor environment-friendly performance and low structural strength, the invention provides the following technical scheme: a novel flame retardant and a preparation method thereof comprise the following steps:

the method comprises the following steps: preparing raw materials: the ethyl dicyclic phosphite ester and methyl dimethyl phosphonate are sealed, sufficient nitrogen is synchronously filled, and then preliminary preheating is carried out.

Step two: preparing equipment: and vacuumizing a reaction kettle used by the ethyl dicyclic phosphite ester and the dimethyl methylphosphonate, and mixing the preheated liquid.

Step three: and (4) treating by-products. Adding excessive methyl dimethyl phosphonate for full reaction, heating to 180 ℃, and separating the cyclic phosphate ester by an extraction solvent.

Step four: utilization of by-products: dimethyl methylphosphonate is mixed with methanol and sufficient catalyst is added to catalyze the production of trimethyl phosphate and new dimethyl methylphosphonate.

Step five: and (3) recycling of by-products: trimethyl phosphate and new dimethyl methylphosphonate are subjected to extractive separation, and then purified trimethyl phosphate is mixed with a catalyst to prepare a sufficient amount of dimethyl phosphate.

Further, according to the operation steps in the step one, the purity of the ethyl dicyclic phosphite ester and the dimethyl methyl phosphonate needs to reach 98%, and the ethyl dicyclic phosphite ester and the dimethyl methyl phosphonate are stored in a ceramic sealed container in a dark low temperature mode.

Further, according to the operation steps in the first step, the preheating temperature is 50 ℃, the nitrogen is injected before preheating, and the interior of the ceramic sealed container is in an oxygen-free state.

Further, according to the operation steps in the second step, the reaction kettle carries out synchronous vacuumizing operation when the waste heat reaches 80 ℃, the preheating time is 15-20 minutes, and the waste heat time of 1 minute is increased when the actual volume of the reaction kettle is increased by 10 liters.

Further, according to the operation steps in the second step, the mixing temperature of the liquid of the ethyl dicyclic phosphite ester and the dimethyl methylphosphonate is 100 ℃, and the liquid can be injected into the vacuumized reaction kettle after standing for 5 minutes during mixing.

Further, according to the operation steps in the third step, the methyl phosphonate dimethyl ester is added in excess, and the reaction mass ratio of the ethyl dicyclic phosphite ester to the methyl phosphonate dimethyl ester is 1: 15.

further, according to the operation steps in the third step, the extraction solvent is extracted and separated by adopting a mixture of trichloromethane and dichloromethane.

Further, according to the operation steps in the fourth step, the liquid remained in the reaction kettle is dimethyl methyl phosphonate, and the mass ratio of the dimethyl methyl phosphonate to the added methanol is 1: 10.

further, according to the operation steps in the fourth step, the catalyst is potassium carbonate, and a proper amount of phosphorus oxychloride needs to be added dropwise in the catalysis.

Further, according to the operation steps in the fifth step, the solvent adopted for extraction and separation is carbon tetrachloride, the carbon tetrachloride is recovered, the crude product is obtained through reduced pressure distillation, distilled water and activated carbon are added to the crude product, anhydrous potassium carbonate is added for dehydration after filtration, finally, trimethyl phosphate is obtained through reduced pressure distillation, the barium hydroxide is used as a catalyst for preparing dimethyl phosphate from trimethyl phosphate, the trimethyl phosphate and cyclic phosphate are mixed to prepare the flame retardant, and the trimethyl phosphate is used as a byproduct to prepare downstream high-cost-performance chemical products in the next step.

The invention provides a novel flame retardant and a preparation method thereof, and the novel flame retardant has the following beneficial effects: the excessive methyl phosphonic acid dimethyl ester and the excessive ethyl dicyclic phosphite ester are preheated and protected by nitrogen, then the prepared cyclic phosphoric ester is mixed with trimethyl phosphate to prepare the flame retardant, the flame retardant efficiency of the flame retardant can be greatly improved by utilizing byproducts, the competitiveness of products is improved, then the dimethyl methyl phosphonate is treated, the trimethyl phosphate and the dimethyl phosphate are produced by utilizing the waste heat for producing the cyclic phosphoric ester, a large amount of products with high added values are produced, and the economic benefit of the preparation method is improved.

Drawings

FIG. 1 is a flow chart of a novel flame retardant and a preparation method thereof.

Detailed Description

Referring to fig. 1, the present invention provides a technical solution: a novel flame retardant and a preparation method thereof comprise the following steps:

the method comprises the following steps: preparing raw materials: the ethyl dicyclic phosphite ester and methyl dimethyl phosphonate are sealed, sufficient nitrogen is synchronously filled, and then preliminary preheating is carried out.

Step two: preparing equipment: and vacuumizing a reaction kettle used by the ethyl dicyclic phosphite ester and the dimethyl methylphosphonate, and mixing the preheated liquid.

Step three: and (4) treating by-products. Adding excessive methyl dimethyl phosphonate for full reaction, heating to 180 ℃, and separating the cyclic phosphate ester by an extraction solvent.

Step four: utilization of by-products: dimethyl methylphosphonate is mixed with methanol and sufficient catalyst is added to catalyze the production of trimethyl phosphate and new dimethyl methylphosphonate.

Step five: and (3) recycling of by-products: trimethyl phosphate and new dimethyl methylphosphonate are subjected to extractive separation, and then purified trimethyl phosphate is mixed with a catalyst to prepare a sufficient amount of dimethyl phosphate.

Specifically, according to the operation steps in the step one, the purity of the ethyl dicyclic phosphite ester and the dimethyl methyl phosphonate needs to reach 98%, and the ethyl dicyclic phosphite ester and the dimethyl methyl phosphonate are stored in a ceramic sealed container in a dark low temperature mode.

Specifically, according to the operation steps in the first step, the preheating temperature is 50 ℃, nitrogen is injected before preheating, and the interior of the ceramic sealed container is in an oxygen-free state.

Specifically, according to the operation steps in the second step, the reaction kettle carries out vacuum pumping operation when the residual heat reaches 80 ℃, the preheating time is 15-20 minutes, and the residual heat time is increased by 1 minute when the actual volume of the reaction kettle is increased by 10 liters.

Specifically, according to the operation steps in the second step, the mixing temperature of the liquid of the ethyl dicyclic phosphite ester and the dimethyl methylphosphonate is 100 ℃, and the liquid can be injected into the vacuumized reaction kettle after standing for 5 minutes during mixing.

Specifically, according to the operation steps in the third step, dimethyl methylphosphonate is added in excess, and the reaction mass ratio of ethyl dicyclic phosphite ester to dimethyl methylphosphonate is 1: 15.

specifically, according to the operation steps in the third step, the extraction solvent is extracted and separated by adopting a mixture of trichloromethane and dichloromethane.

Specifically, according to the operation steps in the fourth step, the liquid remaining in the reaction kettle is dimethyl methylphosphonate, and the mass ratio of the dimethyl methylphosphonate to the added methanol is 1: 10.

specifically, according to the operation steps in the fourth step, the catalyst is potassium carbonate, and a proper amount of phosphorus oxychloride needs to be added dropwise during catalysis.

Specifically, according to the operation steps in the fifth step, the solvent adopted for extraction and separation is carbon tetrachloride, the carbon tetrachloride is recovered, the crude product is obtained through reduced pressure distillation, distilled water and activated carbon are added into the crude product, anhydrous potassium carbonate is added after filtration for dehydration, finally, trimethyl phosphate is obtained through reduced pressure distillation, dimethyl phosphate prepared from trimethyl phosphate adopts barium hydroxide as a catalyst, the trimethyl phosphate and cyclic phosphate are mixed to prepare a flame retardant, and the trimethyl phosphate is used as a byproduct for the next step of preparing downstream high-cost-performance chemical products.

The method of the examples was performed for detection analysis and compared to the prior art to yield the following data:

	flame retardant efficiency	Production efficiency
			Examples	Is higher than	Is higher than
Prior Art	Is lower than	Is lower than

According to the table data, when the embodiment is used, the novel flame retardant and the preparation method thereof further improve the flame retardant efficiency of the product, improve the utilization of the product and improve the overall production benefit.

The invention provides a novel flame retardant and a preparation method thereof, and the preparation method comprises the following steps: the method comprises the following steps: preparing raw materials: the method comprises the steps of sealing the ethyl dicyclic phosphite ester and the dimethyl methylphosphonate, synchronously filling sufficient nitrogen, then carrying out primary preheating, carrying out waste heat on the ethyl dicyclic phosphite ester and the dimethyl methylphosphonate, further reducing energy loss in the subsequent reaction process, further reducing reaction time, improving preparation efficiency, wherein the purity of the ethyl dicyclic phosphite ester and the dimethyl methylphosphonate needs to reach 98 percent, carrying out light-proof low-temperature storage on the ethyl dicyclic phosphite ester and the dimethyl methylphosphonate by adopting a ceramic sealed container, carrying out low-temperature light-proof storage on the high-value ethyl dicyclic phosphite ester, avoiding reaction, causing failure of the high-value ethyl dicyclic phosphite ester, reducing reaction efficiency, preheating temperature being 50 ℃, injecting nitrogen before preheating, and reducing oxygen in a reaction kettle and the ceramic sealed container through the nitrogen, avoiding the raw materials from being oxidized, wherein the inside of the ceramic sealed container is in an anaerobic state, and the step two is as follows: preparing equipment: vacuumizing a reaction kettle used by the ethyl dicyclic phosphite and the dimethyl methylphosphonate, vacuumizing the reaction kettle to avoid the advanced oxidation of raw materials caused by oxygen, mixing preheated liquid, preheating the reaction kettle to 80 ℃, synchronously vacuumizing the reaction kettle, preheating the reaction kettle to 80 ℃, discharging the internal oxygen of the reaction kettle, quickly discharging the internal gas of the reaction kettle through thermal expansion, reducing the energy consumption of vacuumizing, wherein the preheating time is 15-20 minutes, the actual volume of the reaction kettle is increased by 10 liters every time, the waste heat time of 1 minute is increased, the mixing temperature of the ethyl dicyclic phosphite and the dimethyl methylphosphonate liquid is 100 ℃, the ethyl dicyclic phosphite and the dimethyl methylphosphonate liquid can be injected into the vacuumized reaction kettle after standing for 5 minutes during mixing, and the mixing temperature of the ethyl dicyclic phosphite and the dimethyl methylphosphonate liquid is 100 ℃, the preliminary waste heat of the reaction can be realized, the high efficiency of the reaction is ensured, and the subsequent heating energy consumption is reduced, and the third step is that: and (3) treating by-products: adding excessive dimethyl methylphosphonate for full reaction, heating to 180 ℃, separating cyclic phosphate by using an extraction solvent, adding excessive dimethyl methylphosphonate, wherein the reaction mass ratio of ethyl dicyclic phosphite to dimethyl methylphosphonate is 1: 15, excessive methyl phosphonic acid dimethyl ester is added, a large amount of residue is generated, after cyclic phosphate ester separation is carried out, continuous heat preservation is carried out, the heat preservation temperature is 80 ℃, the extraction solvent is extracted and separated by adopting a mixture of trichloromethane and dichloromethane, a catalyst is potassium carbonate, a proper amount of phosphorus oxychloride needs to be dripped in catalysis, and the fourth step is: utilization of by-products: mixing dimethyl methylphosphonate with methanol, adding sufficient catalyst to catalyze and generate trimethyl phosphate and new dimethyl methylphosphonate, wherein the residual liquid in the reaction kettle is the dimethyl methylphosphonate, and the mass ratio of the dimethyl methylphosphonate to the added methanol is 1: 10, by adding methanol, the method can realize the production of a large amount of dimethyl methylphosphonate as a reaction raw material, and comprises the following steps: and (3) recycling of by-products: trimethyl phosphate and new dimethyl methylphosphonate are extracted and separated, and then the purified trimethyl phosphate is mixed with a catalyst, the flame retardant efficiency can be improved by mixing the cyclic phosphate and the trimethyl phosphate, and does not improve the actual production cost of the product, preparing sufficient dimethyl phosphate, adopting carbon tetrachloride as a solvent for extraction and separation, recovering carbon tetrachloride, carrying out reduced pressure distillation to obtain a crude product, adding distilled water and activated carbon into the crude product, filtering, adding anhydrous potassium carbonate for dehydration, finally carrying out reduced pressure distillation to obtain trimethyl phosphate, adopting barium hydroxide as a catalyst for preparing dimethyl phosphate from trimethyl phosphate, mixing the trimethyl phosphate and cyclic phosphate to prepare a flame retardant, and adopting the trimethyl phosphate as a byproduct to prepare a downstream high-cost-performance chemical product in the next step, in the actual production process, the mass ratio of the flame retardant trimethyl phosphate to the cyclic phosphate is 3: and the redundant trimethyl phosphate can prepare high-value dimethyl phosphate, so that the additional value in the whole preparation process is improved, and the competitiveness of the product is improved.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.