WO2022121245A1 - 一种高纯双酚a-双(二苯基磷酸酯)的连续工业化生产方法 - Google Patents

一种高纯双酚a-双(二苯基磷酸酯)的连续工业化生产方法 Download PDF

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WO2022121245A1
WO2022121245A1 PCT/CN2021/096202 CN2021096202W WO2022121245A1 WO 2022121245 A1 WO2022121245 A1 WO 2022121245A1 CN 2021096202 W CN2021096202 W CN 2021096202W WO 2022121245 A1 WO2022121245 A1 WO 2022121245A1
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bisphenol
reaction
continuous
bis
diphenyl phosphate
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PCT/CN2021/096202
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English (en)
French (fr)
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李旭锋
吕云兴
王秋伟
吴宪水
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浙江万盛股份有限公司
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Priority to EP21870484.9A priority Critical patent/EP4039689A4/en
Priority to US17/521,808 priority patent/US20220177497A1/en
Publication of WO2022121245A1 publication Critical patent/WO2022121245A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds

Definitions

  • the invention belongs to the technical field of chemical synthesis, and in particular relates to a continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate).
  • Bisphenol A-bis(diphenyl phosphate) is an oligomeric non-halogen flame retardant and a good plasticizer, mainly used in thermoplastic engineering plastics such as PC, ABS, PC/ABS, PPO /HIPS epoxy resin and its polymer for rigid circuit board, its flame retardant performance is much better than traditional flame retardants such as alkyl phenyl phosphate.
  • thermoplastic engineering plastics such as PC, ABS, PC/ABS, PPO /HIPS epoxy resin and its polymer for rigid circuit board
  • traditional flame retardants such as alkyl phenyl phosphate.
  • the demand for bisphenol A-bis(diphenyl phosphate) has increased significantly, and the market is in a state of short supply.
  • the preparation method of bisphenol A-bis (diphenyl phosphate) flame retardant is mainly Chinese patent CN101456879A (application number 200710179279.4, the invention name is the preparation method of flame retardant bisphenol A bis (diphenyl phosphate)) , which adopts phosphorus oxychloride to react with bisphenol A, after the reaction, phosphorus oxychloride is distilled off under reduced pressure, and then phenol is used for end-capping treatment to obtain bisphenol A-bis(diphenyl phosphate).
  • Chinese patent CN101348500A, Chinese patent CN1414968A, Chinese patent CN1367788A, etc. all disclose the production method of bisphenol A-bis(diphenyl phosphate), and the production process is: first, bisphenol A and excess phosphorus oxychloride are placed in Lewis The reaction is carried out under the participation of the catalyst, and then the excess phosphorus oxychloride is removed by distillation under high vacuum and reduced pressure, and then reacted with phenol to make the BDP crude product, and the BDP crude product is further subjected to acid washing, alkali washing, and water washing in the presence of a solvent, and then distilled off. Solvent and water, filtered to obtain BDP product.
  • this method of industrial production of BDP usually also contains about 1-3% of triphenyl phosphate TPP, about 1% of isopropenyl phenyl diphenyl ester, both of which are harmful substances, and the isopropyl group is unstable.
  • TPP triphenyl phosphate
  • isopropenyl phenyl diphenyl ester both of which are harmful substances
  • the isopropyl group is unstable.
  • Phenomenon the existence of isopropyl group makes the product appear darker in color when exposed to light, while the existence of TPP will cause defects, pollution and corrosion of the moulded product, and it is prone to volatilization, exudation and other problems after entering the material, which affects the resistance of the product. flammability and other physical properties.
  • the prepared bisphenol A phenyl polycondensate phosphate BDP product contains a lot of triphenylphosphine (TPP) , and TPP has certain toxicity to aquatic organisms, and the TPP content of this product is strictly controlled in the international market.
  • TPP triphenylphosphine
  • the object of the present invention is to provide a continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate), and the production technique of the present invention can achieve the purpose of safe and environmentally friendly production , the mass production of products is stable, the production environment of workers is greatly improved, and the discharge of waste water is minimized, realizing the production of circular economy.
  • the continuous industrialized production method of described a kind of high-purity bisphenol A-bis (diphenyl phosphate) is characterized in that comprising the following process:
  • reaction solution is fed into continuous multistage in the mode of continuous feeding
  • the reaction temperature is controlled at 80-120 ° C, and the reaction pressure is -0.015 to -0.02 MPa to carry out the reaction
  • the excess phosphorus oxychloride is removed by vacuum distillation through a thin-film evaporator, and the residual liquid is distilled organic base acid binding agent and remaining bisphenol A are added to the medium, and the reaction is carried out at a temperature of 115-120 ° C for 1.5-3 hours to obtain an intermediate product reaction solution;
  • step 2) The intermediate product reaction solution obtained in step 1) is premixed with the phenol initial raw material, and is then fed into the multistage esterification reactor in the mode of continuous feeding, and the reaction temperature is controlled at 90-150 ° C, and the reaction pressure is- Carry out the esterification reaction at 0.015 ⁇ 0.02MPa; continuously replenish the consumed phenol in the process of the multistage esterification reaction, so that the reaction accelerates the process of the reaction, and after the reaction is finished, the crude product of bisphenol A-bis(diphenyl phosphate) is obtained, and the The crude product is dissolved in an organic solvent to form a crude product solution;
  • step 2) The crude product solution obtained in step 2) is successively subjected to continuous acid washing, continuous alkali washing, continuous water washing, continuous solvent recovery and filtration to obtain bisphenol A-bis(diphenyl phosphate) finished product.
  • step 1) Described a kind of continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate), it is characterized in that in step 1), the bisphenol A that the first part participates in the reaction first accounts for 70-80% of the total amount of bisphenol A. %, and the remaining part of bisphenol A that finally participates in the reaction accounts for 30-20% of the total amount of bisphenol A.
  • Lewis acid catalyst is anhydrous magnesium chloride, anhydrous aluminum chloride, zinc chloride, tetramine At least one of the titanium chlorides is preferably anhydrous magnesium chloride; the weight of the Lewis acid catalyst into the feed is 0.1%-2% of the total weight of the two parts of bisphenol A.
  • step 1) the ratio of the weight of phosphorus oxychloride to the total weight of the two parts of bisphenol A is: 2.5-3.5:1.
  • the continuous industrial production method of the high-purity bisphenol A-bis(diphenyl phosphate) is characterized in that in step 1), the continuous multi-stage crosslinking reactor comprises a four-stage reactor, and the The reaction temperature is 80-85°C, the reaction temperature of the second-stage reactor is 90-100°C, the reaction temperature of the third-stage reactor is 100-110°C, and the reaction temperature of the fourth-stage reactor is 110-120°C.
  • the residence time in the vessel is 2-2.5 hours.
  • the continuous industrial production method of the high-purity bisphenol A-bis(diphenyl phosphate) is characterized in that in step 2), the multi-stage esterification reactor comprises a series-connected four-stage reactor, and the first-stage reactor
  • the temperature of the second-stage reactor is 90-105 °C
  • the reaction temperature of the second-stage reactor is 110-115 °C
  • the reaction temperature of the third-stage reactor is 130-135 °C
  • the reaction temperature of the fourth-stage reactor is 140-145 °C.
  • the material residence time is 1.5-2 hours.
  • the continuous industrial production method of the high-purity bisphenol A-bis(diphenyl phosphate) is characterized in that in step 2), the multi-stage esterification reactor comprises a series-connected four-stage reactor, the second and third The consumed phenol is additionally replenished in the reactor of the fourth stage and the fourth stage, and the replenishment amount of phenol in each stage is 1-5% of the weight of the initial raw material of phenol.
  • the continuous industrial production method of described a kind of high-purity bisphenol A-bis(diphenyl phosphate) is characterized in that the ratio of the two parts of the total weight of bisphenol A in step 1) to the weight of the phenol initial raw material in step 2) is 2. ⁇ 2.5:1.
  • the present invention reacts part of bisphenol A by adopting first, the state of bisphenol A in the reaction process is solid, if a large amount of bisphenol A is charged at one time in the reaction process, there will be a large amount of bisphenol A.
  • the solid exists in phosphorus oxychloride, which causes the reaction of bisphenol A to be very slow. Therefore, under the condition of high temperature and long stay, it is easy to cause bisphenol A to decompose side reactions and decompose allyl phenol and phenol. .
  • bisphenol A is charged in two parts, and excess phosphorus oxychloride is removed after the first-stage reaction is finished, and the produced intermediate contains a plurality of acyl chloride groups.
  • the hydroxyl group is further cross-linked, and the cross-linking reaction is carried out by adding an organic base to neutralize the hydrogen chloride gas released during the reaction, so that the reaction proceeds in the positive direction, accelerates the process of the reaction, and achieves the purpose of shortening the reaction time and reducing impurities.
  • the production process of the present invention reduces production costs, greatly reduces the labor intensity of operators, improves labor efficiency, and greatly improves product output, makes batch production quality stable, achieves safe and environmentally friendly production, and its product yield is increased to 97%
  • the product color number is increased to below 50
  • the TPP is controlled to 0.1%
  • the isopropenyl phenyl diphenyl phosphate is less than 50 ppm
  • the fluctuation of each product quality index is small.
  • Phosphorus oxychloride 4500Kg/h, magnesium chloride 20Kg/h, bisphenol A 1200kg/h are continuously fed into the premixing kettle in proportion, and after premixing by heating in the premixing kettle, the reaction liquid in the premixing kettle is continuously
  • the way of feeding flows from the first-stage reactor to the fourth-stage reactor, the reaction temperature of the first-stage reactor is 80-85 °C, the reaction temperature of the second-stage reactor is 90-100 °C, and the reaction temperature of the third-stage reactor
  • the reaction temperature is 100-110°C
  • the reaction temperature of the fourth-stage reactor is 110-120°C
  • the residence time of materials in each reactor is 2 hours
  • the reaction pressure is controlled at -0.015mpa ⁇ -0.02mpa.
  • the reaction liquid flowing out from the fourth-stage reactor is subjected to vacuum distillation of excess phosphorus oxychloride through a thin-film evaporator, the vacuum degree is 50pa, the distillation temperature is 120-130 ° C, and the distillation residual liquid is continuously sent at a flow rate of 2500kg/h.
  • the reaction temperature of the fifth-stage reactor is 115-120 °C, and the material stays After 2 hours, the intermediate product reaction solution was obtained after the reaction was completed.
  • the intermediate product reaction solution obtained in step 1 is sent into the static mixer at a flow rate of 3000kg/h, while phenol is sent into the static mixer at a flow rate of 2100kg/h for mixing, and the obtained mixed solution is continuously fed from the first-stage reaction.
  • the reactor flows to the fourth-stage reactor, the reaction temperature of the first-stage reactor is 100-105 °C, and the reaction temperature of the second-stage reactor is 120-130 °C.
  • the reaction temperature of the third-stage reactor is 130-135 ° C, and the flow rate of 100kg/h phenol is fed during the third-stage reaction, and the reaction temperature of the fourth-stage reactor is 140-145 ° C.
  • the fourth stage During the reaction, a flow rate of 100kg/h of phenol was introduced for replenishment, the material residence time of each reactor was 2 hours, and the reaction pressure was controlled at -0.015mpa ⁇ -0.02mpa, and the crude product was finally obtained.
  • the obtained crude product was dissolved in toluene at a mass ratio of 1:1 to form a crude product solution.
  • the organic layer 12800kg/h of the stratified pickling and 2000kg/h of 5% lye are passed into the caustic washing tower for caustic washing, and the mixed liquid enters the stratification in the caustic washing stratification tower, and the caustic washing process
  • the medium temperature is controlled at 60-70°C;
  • the organic layer 12800kg/h and the process water 1500kg/h of the alkali washing layered are passed into the water washing tower for water washing, the mixed liquid enters the water washing layering tower for layering, and the temperature is controlled at 60 °C during the water washing process. -70°C;
  • the crude product after washing is removed the residual solvent by thin film distillation, the thin film distillation temperature is 120-130 °C, vacuum 40-70pa, obtains bisphenol A-bis (diphenyl phosphate) finished product 4319kg, product yield 98%.
  • Example 1 A continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate), the experimental steps are the same as those of Example 1, the difference is only in that "Comparative Example 1 is in the step 1 multistage cross-linking reaction process, the two Phenol A was added at one time without adding triethylamine, and the remaining steps were the same as in Example 1.
  • Phosphorus oxychloride 4500Kg/h, magnesium chloride 20Kg/h, bisphenol A 1500kg/h are continuously fed into the premixing kettle in proportion, and after premixing by heating in the premixing kettle, the reaction liquid in the premixing kettle is continuously
  • the way of feeding flows from the first-stage reactor to the fourth-stage reactor, the reaction temperature of the first-stage reactor is 80-85 °C, the reaction temperature of the second-stage reactor is 90-100 °C, and the reaction temperature of the third-stage reactor
  • the reaction temperature is 100-110°C
  • the reaction temperature of the fourth-stage reactor is 110-120°C
  • the residence time of materials in each reactor is 2 hours
  • the reaction pressure is controlled at -0.015mpa ⁇ -0.02mpa.
  • the reaction liquid flowing out from the fourth-stage reactor is subjected to vacuum distillation of excess phosphorus oxychloride through a thin-film evaporator, the vacuum degree is 50pa, and the distillation temperature is 120-130 ° C. After the reaction is completed, the intermediate product reaction liquid is obtained for the next step. the multistage esterification reaction.
  • Example 2 A continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate), its experimental steps are the same as those of Example 1, the difference is only in that "Comparative Example 2 is in the step 1 multistage crosslinking reaction process, and the two Phenol A was added in two steps without adding triethylamine, and the remaining steps were the same as in Example 1.
  • the multi-stage crosslinking reaction process of the reference document 2 is as follows:
  • Phosphorus oxychloride 4500Kg/h, magnesium chloride 20Kg/h, bisphenol A 1200kg/h are continuously fed into the premixing kettle in proportion, and after premixing by heating in the premixing kettle, the reaction liquid in the premixing kettle is continuously
  • the way of feeding flows from the first-stage reactor to the fourth-stage reactor, the reaction temperature of the first-stage reactor is 80-85 °C, the reaction temperature of the second-stage reactor is 90-100 °C, and the reaction temperature of the third-stage reactor
  • the reaction temperature is 100-110°C
  • the reaction temperature of the fourth-stage reactor is 110-120°C
  • the residence time of materials in each reactor is 2 hours
  • the reaction pressure is controlled at -0.015mpa ⁇ -0.02mpa.
  • the reaction liquid flowing out from the fourth-stage reactor is subjected to vacuum distillation of excess phosphorus oxychloride through a thin-film evaporator, the vacuum degree is 50pa, the distillation temperature is 120-130°C, and the flow rate of the distillation residual liquid is continuously fed at a flow rate of 2500kg/h.
  • 500kg/h of bisphenol A was input into the fifth-stage reactor to carry out the esterification reaction.
  • the reaction temperature of the fifth-stage reactor was 115-120 ° C, the material stayed for 2 hours, and the intermediate product was obtained after the reaction was completed.
  • the reaction solution is subjected to the next step of the multi-stage esterification reaction.
  • Phosphorus oxychloride 4500Kg/h, magnesium chloride 20Kg/h, bisphenol A 1500kg/h are continuously fed into the premixing kettle in proportion, and after premixing by heating in the premixing kettle, the reaction liquid in the premixing kettle is continuously
  • the way of feeding flows from the first-stage reactor to the fourth-stage reactor, the reaction temperature of the first-stage reactor is 80-85 °C, the reaction temperature of the second-stage reactor is 90-100 °C, and the reaction temperature of the third-stage reactor
  • the reaction temperature is 100-110°C
  • the reaction temperature of the fourth-stage reactor is 110-120°C
  • the residence time of materials in each reactor is 2 hours
  • the reaction pressure is controlled at -0.015mpa ⁇ -0.02mpa.
  • the reaction liquid flowing out from the fourth-stage reactor is subjected to vacuum distillation of excess phosphorus oxychloride through a thin-film evaporator, the vacuum degree is 50pa, the distillation temperature is 120-130 ° C, and the distillation residual liquid 2800kg/h is continuously sent to the fifth stage.
  • 220kg/h of triethylamine was input into the fifth-stage reactor to carry out esterification reaction.
  • the reaction temperature of the fifth-stage reactor was 115-120 °C, and the material stayed for 2 hours. After the reaction was completed, an intermediate product was obtained. liquid.
  • Example 2 Basically the same as Example 1, the phosphorus oxychloride amount is changed to 5500kg/h, and other reaction conditions are unchanged.
  • Example 2 Basically the same as Example 1, change the two feeding ratios of bisphenol A, change to add 70% of the total amount of bisphenol A for the first time (that is, the flow rate of the bisphenol A that the first part first participates in the reaction is 1050kg/h), The remaining 30% was added for the second time (that is, the flow rate of the bisphenol A involved in the reaction in the second part in the later stage was 450 kg/h), and the other reaction conditions were unchanged, and the experiment was carried out.
  • Sample preparation Weigh 0.2g of sample and dilute it to 10ml with mobile phase, dissolve and inject, and inject 20ul. Calculate the content of triphenyl phosphate in the sample according to the standard curve.
  • Sample preparation Weigh 0.2g of sample and dilute it to 10ml with mobile phase, dissolve and inject, and inject 20ul. The content of isopropenyl phenyl diphenyl phosphate in the sample was calculated according to the standard curve.
  • Example 1 shows that: by comparing Example 1-3 with Comparative Example 1-2 and Example 4, the content of isopropenyl phenyl diphenyl phosphate and triphenyl phosphate in the product prepared by the method of the present invention is greatly reduced, The content of triphenyl phosphate is reduced from more than 2% to less than 0.1% of triphenyl phosphate, the content of isopropenyl phenyl diphenyl phosphate is reduced to less than 40ppm, and the product yield is increased to more than 97%.
  • the method provided by the present invention has higher yield, higher purity, lower impurity content than the prior art method, and the method is stable.

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Abstract

本发明公开了一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，将双酚A分两部分，部分双酚A与三氯氧磷和路易斯酸催化剂混合，加料到连续多级交联反应器中反应，反应结束后蒸除过量的三氯氧磷，蒸馏剩余液中加入有机碱缚酸剂与剩余的双酚A在115-120℃温度下反应1.5-3h，获得的反应液再与苯酚混合后加料到多级酯化反应器中进行酯化反应，酯化的过程中连续补给消耗的苯酚，反应结束后得到粗品，依次经连续酸洗、连续碱洗、连续水洗，连续溶剂回收、过滤得到双酚A-双(二苯基磷酸酯)成品。本发明的方法降低生产成本，其产品收率提高到97％以上，产品色号提升至50以下、TPP控制0.1％，异丙烯基苯基二苯基磷酸酯小于50ppm，各产品质量指标波动小。

Description

一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法 技术领域
本发明属于化工合成技术领域，具体涉及一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法。
背景技术
双酚A-双(二苯基磷酸酯)(简称BDP)分子式为C 39H 34O 8P 2，分子量为692，其结构式如下：
Figure PCTCN2021096202-appb-000001
双酚A-双(二苯基磷酸酯)是一种低聚非卤型阻燃剂，同时也是一种良好的增塑剂，主要应用于热塑性工程塑料如PC，ABS，PC/ABS，PPO/HIPS硬质电路板用环氧树脂及其聚合物，其阻燃性能大大优于烷基苯基磷酸酯等传统阻燃剂。近年来新能源汽车的广泛普及，对于双酚A-双(二苯基磷酸酯)的需求明显的加大，市场供不应求的状态。
目前，关于双酚A-双(二苯基磷酸酯)阻燃剂的制备方法主要是中国专利CN101456879A(申请号200710179279.4，发明名称阻燃剂双酚A双(磷酸二苯酯)的制备方法)，其采用三氯氧磷与双酚A反应，反应后减压蒸馏出三氯氧磷，然后用苯酚进行封端处理得到双酚A-双(二苯基磷酸酯)。
如中国专利CN101348500A、中国专利CN1414968A、中国专利CN1367788A等均公开了双酚A-双(二苯基磷酸酯)的生产方法，生产过程为：先将双酚A和过量的三氯氧磷在路易斯催化剂参与下进行反应，然后高真空减压蒸馏去除过量的三氯氧磷，再与苯酚进行反应制成BDP粗品，进一步对BDP粗品在溶剂存在下通过酸洗、碱洗、水洗后，蒸馏脱溶剂与水，过滤得到BDP产品。通常这种方法工业方法生产BDP通常还含有1-3％左右的三苯基磷酸酯TPP，1％左右异丙烯基苯二苯酯，这两种物质都是有害物质，异丙基的不稳定现象，异丙烯基的存在使得产品在光照的时候出现颜色变色深，而TPP的存在会引起模制品的缺陷、污染和腐蚀模具，进入材料后易发生挥发、渗出等问题，影响制品的阻燃性及其它物理性能。
现有双酚A-双(二苯基磷酸酯)的生产方法，大多是以间歇合成反应为主，间隙式反应具有时间周期长，需要大量的工人，化工厂泡冒滴漏现象很严重，工人操作环境很差，会危害人体的健康，有时候会发生生命的危险，不仅能耗高，而且生产收率低。另外由于周围环境中空气和水汽的存在，对于间隙式工艺的反应过程和结果影响很大，所制备的双酚A苯基缩聚磷酸酯BDP产品中含有较多的三苯基氧磷(TPP)，而TPP对水生物有一定的毒性，国际市场上对该产品的TPP含量严格的控制。
因此，提供一种高纯连续化制备双酚A-双(二苯基磷酸酯)的方法，具有十分重要的意义。
发明内容
为了克服现有技术中存在的上述问题，本发明的目的在于提供一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，本发明的生产工艺能够达到安全、环保生产的目的，其批量生产产品稳定，工人生产环境大大的改善，且最大限度地降低了废水排放，实现了循环经济生产。
所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于包括以下过程：
1)将双酚A分为两部分，先将其中部分双酚A与三氯氧磷和路易斯酸催化剂预先混合，形成反应液；所述反应液以连续化进料的方式加料到连续多级交联反应器中，反应温度控制在80-120℃，反应压力为-0.015～-0.02MPa下进行反应；反应结束后，通过薄膜蒸发器减压蒸馏除去过量的三氯氧磷，蒸馏剩余液中加入有机碱缚酸剂与剩余的双酚A，在115-120℃温度下反应1.5-3h，获得中间产物反应液；
2)将步骤1)获得的中间产物反应液与苯酚初始原料预先混合，然后以连续化进料的方式加料到多级酯化反应器中，反应温度控制在90-150℃，反应压力为-0.015～0.02MPa下进行酯化反应；多级酯化反应的过程中连续补给消耗的苯酚，使得反应加速反应的进程，反应结束后得到双酚A-双(二苯基磷酸酯)粗品，将粗品溶于有机溶剂中形成粗品溶液；
3)将步骤2)所得粗品溶液依次经连续酸洗、连续碱洗、连续水洗，连续溶剂回收、过滤得到双酚A-双(二苯基磷酸酯)成品。
所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方 法，其特征在于步骤1)中，第一部分首先参与反应的双酚A占双酚A总量的70-80％，剩余部分最后参与反应的双酚A占双酚A总量的30-20％。
所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于步骤1)中，路易斯酸催化剂为无水氯化镁、无水氯化铝、氯化锌、四氯化钛中的至少一种，优选为无水氯化镁；路易斯酸催化剂放入投料重量为两部分双酚A总重量的0.1％-2％。
所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于步骤1)中，三氯氧磷的投料重量与两部分双酚A总投料重量之比为2.5-3.5:1。
所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于步骤1)中，所述有机碱缚酸剂为有机胺，有机碱缚酸剂的投料重量与两部分双酚A总投料重量之比为1:7-8。
所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于所述有机胺为三乙胺、氨气或N-甲基吗啉，优选为三乙胺。
所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于步骤1)中，连续多级交联反应器包括四级反应器，第一级反应器的反应温度80-85℃，第二级反应器的反应温度90-100℃，第三级反应器的反应温度100-110℃，第四级反应器的反应温度110-120℃，物料在各反应器内的停留时间为2-2.5小时。
所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方 法，其特征在于步骤2)中，多级酯化反应器包括串联的四级反应器，第一级反应器的温度90-105℃，第二级反应器的反应温度110-115℃，第三级反应器的反应温度130-135℃，第四级反应器的反应温度140-145℃，各反应器的物料停留时间为1.5-2小时。
所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于步骤2)中，多级酯化反应器包括串联的四级反应器，第二、第三及第四级反应器内均额外补给消耗的苯酚，且每级苯酚的补给量为苯酚初始原料重量的1-5％。
所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于步骤1)的两部分双酚A总重量与步骤2)苯酚初始原料的重量之比为2～2.5:1。
通过采用上述技术，与现有技术相比，本发明的有益效果如下：
1)本发明通过采用先将部分双酚A进行反应，双酚A在反应过程中的状态是固体，如果在反应过程中将大量的双酚A一次性投料，就会有大量的双酚A固体存在三氯氧磷里面，导致双酚A反应很慢，由此在较高温度且长时间停留情况下，这时候很容易使得双酚A产生分解副反应，分解出烯丙基苯酚和苯酚。这两个物质与三氯氧磷很容易反应，烯丙基苯酚与三氯氧磷容易反应生成杂质异丙烯基苯基二苯基磷酸酯，苯酚容易与三氯氧磷反应生成杂质磷酸三苯酯，这两个物质具有有害性，产品生产过程中要求严格控制其含量。
在本发明的生产工艺中，双酚A分两部分投料，第一阶段反应结束后除去过量的三氯氧磷，生产的中间体是含有多个酰氯基团，在与剩下 的双酚中的羟基进一步进行交联反应，交联反应通过加入有机碱进行中和反应过程中放出的氯化氢气体，使得反应向正方向进行，加速反应的进程，达到缩短反应时间，降低杂质的目的。
2)本发明在多级酯化反应过程中，酯化的反应过程中放出大量的氯化氢气体，氯化氢气体通过负压的操作除去，反应除去的过程中很容易使苯酚带出去，通过在各个反应器中反应过程中连续通入苯酚补给的方法，来使得反应向正方向进行，使得酯化反应完全，避免收率低。
3)本发明的生产工艺降低了生产成本，降低了操作人员劳动强度大幅，提高了劳动效率，且产品产量大幅提高，使批生产质量稳定，达到安全环保生产，其产品收率提高到97％以上，产品色号提升至50以下、TPP控制0.1％，异丙烯基苯基二苯基磷酸酯小于50ppm，各产品质量指标波动小。
具体实施方式
下面结合具体实施例对本发明作进一步说明，但本发明的保护范围并不限于此。
实施例1：
一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，具体包括以下步骤：
1、多级交联反应：
三氯氧磷4500Kg/h，氯化镁20Kg/h，双酚A 1200kg/h按比例连续进料预混釜内，在预混釜内通过加热预混合后，预混釜内的反应液以连续化进料的方式从第一级反应器流到第四级反应器，第一级反应器的反 应温度80-85℃，第二级反应器的反应温度90-100℃，第三级反应器的反应温度100-110℃，第四级反应器的反应温度110-120℃，物料在各反应器内的停留时间为2小时，反应压力均控制在-0.015mpa～-0.02mpa下进行。
从第四级反应器内流出的反应液，通过薄膜蒸发器减压蒸馏过量的三氯氧磷，真空度为50pa，蒸馏温度为120-130℃，蒸馏剩余液以2500kg/h的流速连续送入第五级反应器中，同时在第五级反应器中输入双酚A 300kg/h、三乙胺220kg/h进行酯化反应，第五级反应器的反应温度115-120℃，物料停留2小时，反应完全后得到中间产物反应液。
2、多级酯化反应
步骤1所得中间产物反应液以3000kg/h的流速送入静态混合器，同时苯酚以2100kg/h的流速送入静态混合器进行混合，所得混合液以连续化进料的方式从第一级反应器流到第四级反应器，第一级反应器的反应温度100-105℃，第二级反应器的反应温度120-130℃，第二级反应的同时通入100kg/h的流速苯酚进行补给，通入第三级反应器的反应温度130-135℃，第三级反应的同时通入100kg/h的流速苯酚进行补给，第四级反应器的反应温度140-145℃，第四级反应的同时通入100kg/h的流速苯酚进行补给，各反应器物料停留时间2小时，反应压力均控制在-0.015mpa～-0.02mpa下进行，最终得到粗品。所得粗品以1:1的质量比溶于甲苯中，形成粗品溶液。
3、粗品精制
向酸洗塔内通入粗品溶液4800kg/h及10％盐酸800kg/h，开启循环 泵强制循环，等物料上升至酸洗罐体积的一半时，开启酸洗上料泵，同时通入混合溶剂8000kg/h在洗涤塔进行萃取，混合后的液体进入酸洗分层塔内分层，酸洗过程中温度控制在60-70℃；
酸洗结束后，将酸洗分层的有机层12800kg/h，5％碱液2000kg/h通入向碱洗塔碱洗，混合后的液体进入碱洗分层塔内分层，碱洗过程中温度控制在60-70℃；
碱洗结束后，将碱洗分层的有机层12800kg/h及工艺水1500kg/h，通入水洗塔进行水洗，混合后的液体进入水洗分层塔内分层，水洗过程中温度控制在60-70℃；
水洗后的粗品通过薄膜蒸馏脱除残留的溶剂，薄膜蒸馏温度在120-130℃，真空40-70pa，得到双酚A-双(二苯基磷酸酯)成品4319kg，产品收率98％。
对比例1：
一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其实验步骤与实施例1相同，不同之处仅在于“对比例1在步骤1多级交联反应工序中，双酚A是一次性加入，不加三乙胺”，其余步骤与实施例1相同。
具体地，对比文件1的多级交联反应工序过程如下：
1、多级交联反应：
三氯氧磷4500Kg/h，氯化镁20Kg/h，双酚A 1500kg/h按比例连续进料预混釜内，在预混釜内通过加热预混合后，预混釜内的反应液以连续化进料的方式从第一级反应器流到第四级反应器，第一级反应器的反 应温度80-85℃，第二级反应器的反应温度90-100℃，第三级反应器的反应温度100-110℃，第四级反应器的反应温度110-120℃，物料在各反应器内的停留时间为2小时，反应压力均控制在-0.015mpa～-0.02mpa下进行。
从第四级反应器内流出的反应液，通过薄膜蒸发器减压蒸馏过量的三氯氧磷，真空度为50pa，蒸馏温度为120-130℃，反应完全后得到中间产物反应液进行下一步的多级酯化反应。
对比例2：
一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其实验步骤与实施例1相同，不同之处仅在于“对比例2在步骤1多级交联反应工序中，双酚A分两次加入，不加三乙胺”，其余步骤与实施例1相同。
具体地，对比文件2的多级交联反应工序过程如下：
1、多级交联反应：
三氯氧磷4500Kg/h，氯化镁20Kg/h，双酚A 1200kg/h按比例连续进料预混釜内，在预混釜内通过加热预混合后，预混釜内的反应液以连续化进料的方式从第一级反应器流到第四级反应器，第一级反应器的反应温度80-85℃，第二级反应器的反应温度90-100℃，第三级反应器的反应温度100-110℃，第四级反应器的反应温度110-120℃，物料在各反应器内的停留时间为2小时，反应压力均控制在-0.015mpa～-0.02mpa下进行。
从第四级反应器内流出的反应液，通过薄膜蒸发器减压蒸馏过量的三氯氧磷，真空度为50pa，蒸馏温度为120-130℃，蒸馏剩余液2500kg/h 的流速连续送入第五级反应器中，同时在第五级反应器中输入双酚A500kg/h进行酯化反应，第五级反应器的反应温度115-120℃，物料停留2小时，反应完全后得到中间产物反应液进行下一步的多级酯化反应。
对比例3：
一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其实验步骤与实施例1相同，不同之处仅在于“对比例3在步骤1多级交联反应工序中，双酚A一次性加入，加三乙胺”，其余步骤与实施例1相同。
具体地，对比文件3的多级交联反应工序过程如下：
1、多级交联反应：
三氯氧磷4500Kg/h，氯化镁20Kg/h，双酚A 1500kg/h按比例连续进料预混釜内，在预混釜内通过加热预混合后，预混釜内的反应液以连续化进料的方式从第一级反应器流到第四级反应器，第一级反应器的反应温度80-85℃，第二级反应器的反应温度90-100℃，第三级反应器的反应温度100-110℃，第四级反应器的反应温度110-120℃，物料在各反应器内的停留时间为2小时，反应压力均控制在-0.015mpa～-0.02mpa下进行。
从第四级反应器内流出的反应液，通过薄膜蒸发器减压蒸馏过量的三氯氧磷，真空度为50pa，蒸馏温度为120-130℃，蒸馏剩余液2800kg/h连续送入第五级反应器中，同时在第五级反应器中输入三乙胺220kg/h进行酯化反应，第五级反应器的反应温度115-120℃，物料停留2小时，反应完全后得到中间产物反应液。
实施例2：
与实施例1基本相同，把三氯氧磷量改为5500kg/h，其他反应条件不变。
实施例3：
与实施例1基本相同，改变双酚A的两次投料比例，改为第一次加入双酚A总量的70％(即第一部分首先参与反应的双酚A的流量是1050kg/h)，第二次加入剩下的30％(即第二部分后期参与反应的双酚A的流量是450kg/h)，其他反应条件不变，进行试验。
实施例4：传统的方法进行试验
1、在搪玻璃反应釜中依次加入三氯氧磷4500kg，氯化镁20kg。搅拌，缓慢升温。升温至90℃～100℃开始投双酚A 1500kg，投料时间4小时。投料完毕后，升温至115-120℃保温，保温时间8小时。保温完毕，转釜脱三氯氧磷。开真空泵，蒸馏除去三氯氧磷，先低温脱走大部分三氯氧磷，再调真空至-0.98mpa继续升温至130～140℃，保温至无三氯氧磷蒸出，蒸馏时间共约为5-8小时，得到中间体。
2、将上述中间体转入反应釜中，升温至110-120℃下滴加苯酚2400kg，滴加时间大约4小时，滴加完成后，升温至140-150℃，保温4小时，取样分析，得到粗品。
3、粗品完全转入洗釜洗涤釜中，加溶剂，升温至65-70℃，再缓慢加入定量水800kg，加30％盐酸1000kg，升温至65℃～70℃，搅拌1小时，静置半小时分出水层；然后加入水1000kg，加入液碱30％400kg,升温至65℃～70℃，搅拌1小时，静置半小时分出水层。料层缓慢加入水1500kg升温至65℃～70℃下保温1小时，静置半小时分出水层，水 洗二次测试pH＝6～7。洗涤结束，送料至蒸馏釜脱溶剂，减压蒸馏温度最后升至140℃～150℃，脱完溶剂后，得到样品。
对制备的双酚A-双(二苯基磷酸酯)产品的性能测试：
1、检测方法：
1)色号测定方法：GB-3143；
2)酸值测定方法：GB-264-1983；
3)磷酸三苯酯含量检测，采用液相色谱方法，具体为：
色谱条件：流动相：甲醇：水＝90:10，色谱柱:Diamonsil(150mm×4.6mm,5um)检测波长：254nm。柱温：25℃，进样体积：20ul；
称取磷酸三苯酯标准品(含量99.8％)，配置0.1％，0.2％，0.4％，0.6％，1.0％，1.5％，2.0％的溶液，用甲醇稀释，做标准曲线。
样品制备：称取样品0.2g样品用流动相稀释至10ml，溶解进样，进样20ul。依据标准曲线计算样品中磷酸三苯酯的含量。
4)异丙烯基苯基二苯基磷酸酯含量检测，采用液相色谱方法，具体为：
色谱条件：流动相：甲醇：水＝90:10，色谱柱:Diamonsil(150mm×4.6mm,5um)检测波长：254nm。柱温：25℃，进样体积：20ul；
称取异丙烯基苯基二苯基磷酸酯标准品(含量99.8％)，配置10ppm，20ppm，40ppm，60ppm，80ppm，100ppm的溶液，用甲醇稀释，做标准曲线。
样品制备：称取样品0.2g样品用流动相稀释至10ml,溶解进样,进样20ul。依据标准曲线计算样品中异丙烯基苯基二苯基磷酸酯的含量。
2、样品：实施例1～4和对比例1、3制备得到的产物。
3、实验结果：见表1。
表1：实验结果
Figure PCTCN2021096202-appb-000002
表1结果显示：实施例1-3与对比例1-2、实施例4进行比较，本发明方法制备的产品中异丙烯基苯基二苯基磷酸酯、磷酸三苯酯含量大大的降低，磷酸三苯酯的含量由2％以上降低到磷酸三苯酯的含量0.1％以下，异丙烯基苯基二苯基磷酸酯的含量降低到40ppm以下，产品收率提高到97％以上。
智能化生产过程中能够节约消耗，工人操作环境大大的改善，降低人工成本，批生产过程中产品的质量，收率稳定，能够稳定的生成高端的产品。总之，本发明提供的方法较现有技术方法收率增加、纯度增加、 杂质含量减少，方法稳定。
本说明书所述的内容仅仅是对发明构思实现形式的列举，本发明的保护范围不应当被视为仅限于实施例所陈述的具体形式。

Claims (10)

  1. 一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于包括以下过程：
    1)将双酚A分为两部分，先将其中部分双酚A与三氯氧磷和路易斯酸催化剂预先混合，形成反应液；所述反应液以连续化进料的方式加料到连续多级交联反应器中，反应温度控制在80-120℃，反应压力为-0.015～-0.02MPa下进行反应；反应结束后，通过薄膜蒸发器减压蒸馏除去过量的三氯氧磷，蒸馏剩余液中加入有机碱缚酸剂与剩余的双酚A，在115-120℃温度下反应1.5-3h，获得中间产物反应液；
    2)将步骤1)获得的中间产物反应液与苯酚初始原料预先混合，然后以连续化进料的方式加料到多级酯化反应器中，反应温度控制在90-150℃，反应压力为-0.015～0.02MPa下进行酯化反应；多级酯化反应的过程中连续补给消耗的苯酚，使得反应加速反应的进程，反应结束后得到双酚A-双(二苯基磷酸酯)粗品，将粗品溶于有机溶剂中形成粗品溶液；
    3)将步骤2)所得粗品溶液依次经连续酸洗、连续碱洗、连续水洗，连续溶剂回收、过滤得到双酚A-双(二苯基磷酸酯)成品。
  2. 如权利要求1所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于步骤1)中，第一部分首先参与反应的双酚A占双酚A总量的70-80％，剩余部分最后参与反应的双酚A占双酚A总量的30-20％。
  3. 如权利要求1所述的一种高纯双酚A-双(二苯基磷酸酯)的连续 工业化生产方法，其特征在于步骤1)中，路易斯酸催化剂为无水氯化镁、无水氯化铝、氯化锌、四氯化钛中的至少一种，优选为无水氯化镁；路易斯酸催化剂放入投料重量为两部分双酚A总重量的0.1％-2％。
  4. 如权利要求1所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于步骤1)中，三氯氧磷的投料重量与两部分双酚A总投料重量之比为2.5-3.5:1。
  5. 如权利要求1所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于步骤1)中，所述有机碱缚酸剂为有机胺，有机碱缚酸剂的投料重量与两部分双酚A总投料重量之比为1:7-8。
  6. 如权利要求5所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于所述有机胺为三乙胺、氨气或N-甲基吗啉，优选为三乙胺。
  7. 如权利要求1所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于步骤1)中，连续多级交联反应器包括四级反应器，第一级反应器的反应温度80-85℃，第二级反应器的反应温度90-100℃，第三级反应器的反应温度100-110℃，第四级反应器的反应温度110-120℃，物料在各反应器内的停留时间为2-2.5小时。
  8. 如权利要求1所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于步骤2)中，多级酯化反应器包括串联的四级反应器，第一级反应器的温度90-105℃，第二级反应器的反应温度110-115℃，第三级反应器的反应温度130-135℃，第四级反应器的反应温度140-145℃，各反应器的物料停留时间为1.5-2小时。
  9. 如权利要求1所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于步骤2)中，多级酯化反应器包括串联的四级反应器，第二、第三及第四级反应器内均额外补给消耗的苯酚，且每级苯酚的补给量为苯酚初始原料重量的1-5％。
  10. 如权利要求1所述的一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法，其特征在于步骤1)的两部分双酚A总重量与步骤2)苯酚初始原料的重量之比为2～2.5:1。
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