A kind of preparation method of bisphenol A polyether

Abstract

The invention discloses a method for preparing bisphenol A polyether, characterized in that a liquid coordinated alkaline earth metal catalyst and bisphenol A are placed in a reaction kettle, nitrogen is replaced, an epoxy compound introduced at an initial feed temperature is stirred, and then the temperature is raised to a reaction temperature and the remaining epoxy compound is introduced to continue to react to generate bisphenol A polyether. The invention uses a liquid coordinated alkaline earth metal catalyst, which has good solubility for bisphenol A, reacts rapidly to a liquid state at low temperature, accelerates mass transfer, improves reaction efficiency, and the obtained product has few impurities, does not require post-processing, and saves costs.

Description

Technical Field

[0001] The invention belongs to the field of polyether synthesis, and particularly relates to a method for preparing bisphenol A polyether. Background Art

[0002] Bisphenol A polyether is a type of polymer with different addition numbers starting from bisphenol A, mainly including bisphenol A polyoxyethylene ether and bisphenol A polyoxypropylene ether.

[0003] Bisphenol A polyether is mainly prepared by reacting bisphenol A with epoxy compounds under acid catalysis, base catalysis, and amine catalysis with bisphenol A as the initiator. Bisphenol A has a high melting point (158-160°C), and the alkoxylation reaction involves a gas-solid-liquid three-phase reaction. When using conventional alkali metal compounds such as KOH / NaOH for catalysis, alcohol salt formation and alkoxylation reaction are difficult. At present, the commonly used methods for preparing bisphenol A polyether are mainly melting method and solvent method. The melting method is to completely melt bisphenol A and then carry out alkoxylation reaction. Because the contact area between the solid particles and the reactor is small, the heating process is very slow, the melting method has low reaction efficiency, and the initial reaction will take a lot of time. The solvent method mainly uses solvents to dissolve bisphenol A. Commonly used solvents are ethylene glycol dimethyl ether, dibutyl ether, toluene, xylene, cyclohexane, etc. The solubility of different solvents for bisphenol A varies greatly, and the use of the solvent method requires an additional solvent recovery step, which increases equipment investment and energy consumption, and it is difficult to completely remove the solvent. Residual solvents will cause the product to have a strong odor, affecting downstream applications.

[0004] Patent CN109265323A discloses a method for preparing bisphenol A polyoxyethylene ether with narrow molecular weight distribution. Ethylene carbonate is first added to react under alkali catalysis at 30-50°C to obtain bishydroxyethyl bisphenol A ether. The reaction solution is then heated, and ethylene oxide is added for addition reaction. After the reaction is completed, acetic acid is added for neutralization to obtain bisphenol A polyoxyethylene ether. The solubility of ethylene carbonate in bisphenol A is used to prepare bishydroxyethyl bisphenol A ether, and then the temperature is raised to perform ethoxylation reaction. This solution has a high cost due to the introduction of ethylene carbonate and the use of alkali catalysis for two-step reaction, so the reaction time is long, and desalination treatment is required for downstream applications.

[0005] Patent CN101367714A discloses a method for preparing a bisphenol A polyoxyethylene ether toughening agent, which includes adding bisphenol A and a NaCO3 / KOH mixed catalyst into a reactor, dropping EO monomer into a solid initiator material, and performing a solid-liquid phase reaction to obtain liquid bisphenol A polyoxyethylene ether; heating up and introducing EO to perform a normal gas-liquid phase reaction, and performing aging after the introduction of the material; and refining to obtain the finished product. In this scheme, ethylene oxide is introduced into the solid bisphenol A to perform a gas-solid-liquid three-phase reaction to obtain liquid bisphenol A polyoxyethylene ether. The viscosity of the bisphenol A solid that is not completely melted at less than 50°C is extremely high, which places stringent requirements on the mass transfer efficiency and heat transfer efficiency of the reactor and is not easy to achieve.

[0006] Patent CN1507950A discloses a catalyst for alkoxylation reaction, which is obtained by reacting calcium and magnesium compounds with alcohol ether carboxylic acid in water or organic solvent environment. The alcohol ether carboxylic acid structure contains C2-C30 alkyl or alkenyl ethoxylates, and the number of EO connected is 1-16. The catalyst is used to obtain narrow distribution alkoxy compounds. The catalyst is used in the synthesis of bisphenol A polyether, which will introduce ligands with different structures, participate in the reaction and cannot be refined and removed, which will affect downstream high-precision applications. At the same time, the raw material needs to use alcohol ether carboxylic acid, which needs to be prepared by conventional anionic surfactants through oxidation or chloroacetic acid method, and the preparation process is relatively cumbersome. Summary of the invention

[0007] In view of the problems existing in the prior art, the present invention provides a method for preparing bisphenol A polyether, which comprises preparing a liquid coordinated alkaline earth metal catalyst to catalyze the reaction of bisphenol A and an epoxy compound, utilizing the good solubility of the ligand in the catalyst for bisphenol A, thereby avoiding the problem of slow reaction speed caused by the inability of conventional alkali metal catalysts to alkoxide with solid bisphenol A; lowering the reaction temperature, catalyzing the alkoxylation reaction of bisphenol A with ethylene oxide / propylene oxide at low temperature, rapidly liquefying and improving the reaction efficiency; the obtained product has a narrower molecular weight distribution than the traditional alkali metal catalyst, does not require post-treatment for desalination, and has excellent reaction performance in downstream application reactions.

[0008] A method for preparing bisphenol A polyether comprises placing a liquid coordinated alkaline earth metal catalyst and bisphenol A in a reaction kettle, replacing with nitrogen, stirring an epoxy compound introduced at an initial feed temperature, and then heating to a reaction temperature and introducing the remaining epoxy compound to continue reacting to generate bisphenol A polyether.

[0009] The obtained bisphenol A polyether can be aged, cooled and degassed to obtain a bisphenol A polyether product, which has a low impurity content and a narrow molecular weight distribution and can be directly used in downstream applications without refining.

[0010] Preferably, the preparation method of the liquid coordinated alkaline earth metal catalyst is:

[0011] (1) heating bisphenol A polyether, adding alkaline earth metal or alkaline earth metal compound to bisphenol A polyether, and stirring to make the two fully coordinated;

[0012] (2) adding an acid dropwise to the bisphenol A polyether coordinated alkaline earth metal in step (1) for neutralization;

[0013] (3) Dehydration: The reaction system is controlled at 80-140°C for dehydration to obtain a liquid coordinated alkaline earth metal catalyst.

[0014] Preferably, the heating temperature in step (1) is 60-120°C.

[0015] For better coordination, alkaline earth metal or alkaline earth metal compound is added to bisphenol A polyether in batches under stirring condition, and the system temperature is controlled at 60-120°C.

[0016] Preferably, the alkaline earth metal or alkaline earth metal compound includes but is not limited to calcium, calcium oxide, calcium hydroxide, magnesium, magnesium oxide, magnesium hydroxide and the like.

[0017] Preferably, the molar ratio of bisphenol A polyether to alkaline earth metal or alkaline earth metal compound is 1:1-2:1.

[0018] Preferably, the bisphenol A polyether used in the catalyst is of the same type as the epoxy compound used to produce the target bisphenol A polyether, and when producing bisphenol A polyoxypropylene ether, the coordination compound used in the catalyst is also bisphenol A polyoxypropylene ether, and when producing bisphenol A polyoxyethylene ether, the coordination compound used in the catalyst is also bisphenol A polyoxyethylene ether, wherein the degree of alkoxylation of the bisphenol A polyether is 1-20, preferably 4-10.

[0019] In step (2), the neutralization temperature is 60-100° C., and the acid addition time is 1-5 hours. The acid may be an inorganic acid or an organic acid, including but not limited to sulfuric acid, phosphoric acid, hydrochloric acid or nitric acid.

[0020] Preferably, in step (3), the dehydration time is 1-2 hours, and the mass content of water needs to be less than 2%.

[0021] Preferably, the epoxy compound is selected from one or more of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran and the like.

[0022] Preferably, the amount of the liquid coordinated alkaline earth metal catalyst used is 0.3-1% of the mass of bisphenol A.

[0023] Preferably, the amount of the epoxide added can be conventionally selected according to the molecular weight of the target product, such as an amount of 2-40 times the molar number of bisphenol A.

[0024] The preferred initial feed temperature is 20-120°C, preferably 20-50°C, and the reaction temperature is 100-160°C.

[0025] According to the different types of bisphenol A polyether, different initial feed temperatures and reaction temperatures can be adjusted. If bisphenol A polyoxyethylene ether is produced, the initial feed temperature is 20-120°C and the reaction temperature is 120-160°C; if bisphenol A polyoxypropylene ether is produced, the initial feed temperature is 20-100°C and the reaction temperature is 100-160°C; wherein the amount of epoxy compound initially added accounts for 5-20% of the total amount of epoxy compound added, preferably 5-10%. After the system temperature rises to the reaction temperature, the remaining epoxy compound is introduced, and the reaction time is 0.5-5h;

[0026] Technical effects of the present invention:

[0027] 1. Use liquid coordinated alkaline earth metal catalyst, which has good solubility for bisphenol A and can quickly react bisphenol A to liquid at low temperature, accelerate mass transfer and improve reaction efficiency;

[0028] 2. Compared with traditional alkali metal catalysts, the liquid alkaline earth metal coordination catalyst reduces the alcohol salt process, has higher reaction efficiency, and has a narrower molecular weight distribution of the obtained product. No post-treatment desalination is required for downstream application reactions, and the reaction performance is excellent;

[0029] 3. The liquid alkaline earth metal coordination catalyst uses bisphenol A polyether as a ligand, thereby avoiding the influence of impurities in the ligands used in other types of alkaline earth metal catalysts on product quality.

[0030] The obtained product is used in electrophoretic paint coatings. An addition amount of less than 10% can reduce the flexibility to 1mm and increase the impact resistance to 70cm; it can be used in the glass fiber field to greatly improve the wettability of the material; the monomer reactivity is higher in the polyester field and the product batch stability is good; because the molecular weight distribution is narrower, it is used as a skeleton intermediate in downstream surfactant preparation, with higher reactivity and better physical and chemical properties of the product. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The gel permeation chromatogram of Example 1 is

[0032] Figure 2 The gel permeation chromatogram of Example 2

[0033] Figure 3 The gel permeation chromatogram of Example 3 is

[0034] Figure 4 The gel permeation chromatogram of Comparative Example 1 is

[0035] Figure 5 The gel permeation chromatogram of Comparative Example 2 is DETAILED DESCRIPTION

[0036] The present invention is further described below in conjunction with embodiments, but the protection scope of the present invention is not limited thereto:

[0037] Bisphenol A polyoxyethylene ether BPA-6EO, with a degree of polymerization of 6, was purchased from Zhejiang Royal Madrid Technology Co., Ltd.

[0038] Bisphenol A polyoxyethylene ether BPP-06, with a polymerization degree of 6, was purchased from Hangzhou Bailang Additive Co., Ltd.

[0039] Bisphenol A polyoxyethylene ether BPA-10EO, with a degree of polymerization of 10, was purchased from Zhejiang Royal Madrid Technology Co., Ltd.

[0040] Example 1: Preparation of Bisphenol A Polyoxyethylene Ether

[0041] 1. Preparation of liquid coordinated alkaline earth metal catalyst: Weigh 49.2g of bisphenol A polyoxyethylene ether BPA-6EO and place it in a flask, heat it to 80°C, add 7.4g of calcium hydroxide in batches, and stir for 0.5h until it becomes uniform; cool it to 70°C, slowly add 9.8g of concentrated sulfuric acid within 1.5h, and control the neutralization temperature at 70-80°C; heat it to 120°C and dehydrate it under vacuum for 2h, and the final catalyst presents a milky white uniform emulsion with a water content of 1.5%;

[0042] 2. Synthesis of bisphenol A polyether: 0.98 g of liquid coordinated alkaline earth metal catalyst and 228 g of bisphenol A were placed in a reactor, and 13 g of ethylene oxide was introduced at 20°C under stirring. When the temperature rose to 140°C, 261 g of ethylene oxide was introduced for ethoxylation reaction for 0.6 h. After the feeding was completed, the reactor was aged until the pressure no longer changed. After aging, the temperature was lowered and degassed.

[0043] The process of heating to the reaction temperature is about 0.5h, the reaction time is about 0.6h, the whole production process is about 1.5h, and the product molecular weight distribution PDI=1.011.

[0044] Example 2: Preparation of Bisphenol A Polyoxypropylene Ether

[0045] 1. Preparation of liquid coordinated alkaline earth metal catalyst: Weigh 46g of bisphenol A polyoxypropylene ether BPP-06 and place it in a flask, heat it to 90°C, add 5.6g of calcium oxide in batches, and stir for 1h until it becomes uniform; slowly add 11.5g of phosphoric acid (85%) dropwise within 2h, and control the neutralization temperature at 70-80°C; heat it to 100°C and dehydrate it in vacuum for 2h, and the final catalyst presents a milky white uniform emulsion with a water content of 1.8%;

[0046] 2. Synthesis of bisphenol A polyether: 1.38 g of liquid coordinated alkaline earth metal catalyst and 228 g of bisphenol A were placed in a reactor, and 23 g of propylene oxide was introduced at 40°C under stirring. When the temperature rose to 130°C, 220 g of propylene oxide was introduced for propoxylation reaction for 1 hour. After the feeding was completed, the reactor was aged until the pressure no longer changed. After aging, the temperature was lowered and degassed.

[0047] The process of heating to the reaction temperature is about 0.5h, the reaction time is about 3h, the overall production process is about 4h, and the product molecular weight distribution PDI=1.012.

[0048] Example 3: Preparation of Bisphenol A Polyoxyethylene (10) Ether (BPA10)

[0049] 1. Preparation of liquid coordinated alkaline earth metal catalyst: weigh 58g of bisphenol A polyoxyethylene ether BPA-10EO and place it in a flask, heat it to 70°C, add 8.7g of magnesium oxide in batches, and stir for 1h until it becomes uniform; slowly add 10.5g of concentrated sulfuric acid dropwise within 3h, and control the neutralization temperature at 70-80°C; heat it to 110°C and dehydrate it in vacuum for 2h, and the final catalyst presents a milky white uniform emulsion with a water content of 2%;

[0050] 2. Synthesis of bisphenol A polyether: 2 g of liquid coordinated alkaline earth metal catalyst and 228 g of bisphenol A were placed in a reactor, and 26 g of ethylene oxide was introduced at 50°C under stirring. When the temperature rose to 150°C, 418 g of ethylene oxide was introduced for ethoxylation reaction for 0.6 h. After the feeding was completed, the reactor was aged until the pressure in the reactor no longer changed. After aging, the temperature was lowered and degassed.

[0051] The process of heating to the reaction temperature is about 0.8h, the reaction time is about 0.6h, the overall production process is about 2h, and the product molecular weight distribution PDI=1.021.

[0052] Comparative Example 1: Preparation of Bisphenol A Polyoxyethylene Ether

[0053] 1. Add 228g of bisphenol A solid and 2g of KOH catalyst into a pressure-resistant stirring reactor, start stirring and heat to 160°C, and stir for 3h until bisphenol A is completely melted;

[0054] 2. Add 26.4 g of ethylene oxide at 50 °C for ethoxylation. When the temperature rises to 160 °C, add 237.6 g of ethylene oxide within 1.5 h. During the reaction, the reaction heat is continuously removed. After aging, the temperature is lowered to 80 °C for degassing.

[0055] 3. Add 3.8 g of phosphoric acid to the product, neutralize at 80°C for 0.5 h, then add 7.38 g of adsorbent and adsorb at 100°C for 1 h, slowly dehydrate for 2 h, and filter with 200 mesh filter paper to obtain the product.

[0056] The overall reaction time was about 8 h, the product molecular weight distribution PDI = 1.18, and a large amount of small molecule impurities appeared.

[0057] Comparative Example 2: Preparation of Bisphenol A Polyoxypropylene Ether

[0058] 1. Add 228g of bisphenol A solid, 1.84g of KOH catalyst, and 228g of ethylene glycol dimethyl ether into a pressure-resistant stirred reactor, start stirring and heat to 130°C, and stir for 2h until the bisphenol A alcohol salt is completely formed;

[0059] 2. Add 23.2 g of propylene oxide at 40 °C. After the temperature rises to 130 °C, add 208.8 g of propylene oxide within 2 hours. During the reaction, the reaction heat is continuously removed. After aging for 3 hours, the temperature is lowered to 80 °C.

[0060] 3. Evacuate to 20 mbar, remove the solvent, and use cooling water to cool and recover. Continue to remove the solvent for 3 hours until the solvent is completely removed;

[0061] 3. Add 3.5 g of phosphoric acid to the product, neutralize at 80°C for 0.5 h, then add 6.9 g of adsorbent and adsorb at 100°C for 1 h, slowly dehydrate for 2 h, and filter with 200 mesh filter paper to obtain the product.

[0062] The overall reaction time was about 11 h, the product molecular weight distribution PDI = 1.35, and a large amount of small molecule impurities appeared.

Claims

1. A method for preparing bisphenol A polyether, characterized in that: A liquid coordinated alkaline earth metal catalyst and bisphenol A are placed in a reaction kettle, replaced with nitrogen, and the epoxy compound introduced at the initial feed temperature is stirred, and then the temperature is raised to the reaction temperature and the remaining epoxy compound is introduced to continue the reaction to generate bisphenol A polyether; The preparation method of the liquid coordinated alkaline earth metal catalyst is as follows: (1) heating bisphenol A polyether, adding alkaline earth metal or alkaline earth metal compound to bisphenol A polyether, and stirring to make the two fully coordinated; (2) adding an acid dropwise to the bisphenol A polyether coordinated alkaline earth metal in step (1) for neutralization; (3) Dehydration: The reaction system is controlled at 80-140° C. to dehydrate to obtain a liquid coordinated alkaline earth metal catalyst; In the catalyst, the molar ratio of bisphenol A polyether to alkaline earth metal or alkaline earth metal compound is 1:1-2:1; The bisphenol A polyether used in the catalyst has an alkoxylation degree of 1-20.

2. The preparation method according to claim 1, characterized in that: The dissolving temperature in the step (1) is 60-120°C.

3. The preparation method according to claim 1, characterized in that: The alkaline earth metal or alkaline earth metal compound is added into the bisphenol A polyether in batches under stirring conditions.

4. The preparation method according to claim 1, characterized in that: The alkaline earth metal or alkaline earth metal compound is selected from one or more of calcium, calcium oxide, calcium hydroxide, magnesium, magnesium oxide and magnesium hydroxide.

5. The preparation method according to claim 1, characterized in that: The bisphenol A polyether used in the catalyst is of the same type as the epoxy compound used in the target bisphenol A polyether produced, wherein the alkoxylation degree of the bisphenol A polyether is 1-20.

6. The preparation method according to claim 5, characterized in that: The bisphenol A polyether used in the catalyst is of the same type as the epoxy compound used in the target bisphenol A polyether produced, wherein the alkoxylation degree of the bisphenol A polyether is 4-10.

7. The preparation method according to any one of claims 1 to 6, characterized in that: In step (2), the neutralization temperature is 60-100° C., the acid addition time is 1-5 hours, and the acid is an inorganic acid or an organic acid selected from sulfuric acid, phosphoric acid, hydrochloric acid or nitric acid.

8. The preparation method according to any one of claims 1 to 6, characterized in that: In step (3), the dehydration time is 1-2 hours, and the mass content of water must be less than 2%.

9. The preparation method according to any one of claims 1 to 6, characterized in that: The epoxy compound is selected from one or more of ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran.

10. The preparation method according to any one of claims 1 to 6, characterized in that: The amount of the liquid coordinated alkaline earth metal catalyst used is 0.3-1% of the mass of bisphenol A.

11. The preparation method according to any one of claims 1 to 6, characterized in that: The initial feed temperature is 20-120°C and the reaction temperature is 100-160°C.

12. The preparation method according to claim 11, characterized in that: The initial feed temperature was 20-50°C.

13. The preparation method according to any one of claims 1 to 6, characterized in that: The amount of epoxy compound initially added accounts for 5-20% of the total amount of epoxy compound added. After the system temperature rises to the reaction temperature, the remaining epoxy compound is introduced. The reaction time is 0.5-5h.

14. The preparation method according to claim 13, characterized in that: The amount of epoxy compound initially added accounts for 5-10% of the total amount of epoxy compound added.

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