A co-production process of gma and 1,3-dichloropropanol
By using a co-production process to co-produce GMA and 1,3-dichloropropanol under the action of a catalyst, the problems of high energy consumption and saline wastewater in existing technologies have been solved, achieving high conversion rate and high selectivity production, and improving process safety and environmental protection.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- WANHUA CHEM GRP CO LTD
- Filing Date
- 2024-01-15
- Publication Date
- 2026-07-10
AI Technical Summary
The existing GMA production process has problems such as high energy consumption, generation of large amounts of saline wastewater and safety hazards, especially the glycidyl glycerol produced in the closed-loop reaction, which poses a safety hazard.
Methacrylic acid and epichlorohydrin were used as raw materials. A ring-opening esterification reaction was carried out in the presence of a catalyst to generate the intermediate CHPMA. Then, it was reacted with epichlorohydrin to co-produce GMA and 1,3-dichloropropanol. The use of a solid catalyst avoided the use of alkaline solution, and the reaction was carried out in a fixed-bed reactor.
This method achieves high conversion and high selectivity in the co-production of GMA and 1,3-dichloropropanol, reduces hydrolysis side reactions, avoids energy consumption and the generation of saline wastewater, improves process safety and environmental protection, and provides a new production route for 1,3-dichloropropanol.
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Figure BDA0004662813260000021
Abstract
Description
Technical Field
[0001] This invention relates to an organic production process, and more particularly to a co-production process of GMA and 1,3-dichloropropanol. Background Technology
[0002] Glycidyl methacrylate (GMA) is a type of acrylate functional monomer. Due to the presence of highly reactive epoxy groups and carbon-carbon double bonds conjugated with carbonyl groups in its structure, it can be homopolymerized or copolymerized through free radical polymerization and ionic polymerization. It is mainly used in powder coatings, adhesives, synthetic resins and other fields, playing a role in improving the adhesion of materials and improving their processing performance.
[0003] Currently, there are two main process routes for the industrial production of GMA:
[0004] (1) Glycidyl methacrylate is prepared in the next step using sodium methacrylate and epichlorohydrin as raw materials under the action of a catalyst, as disclosed in patents CN105218487A and CN109721567A. This process has a short reaction time, low impurity content and high yield. However, it has very strict requirements on moisture content, and the generated water needs to be removed by azeotropic dehydration during the reaction. Industrial production has high energy consumption and generates a large amount of sodium chloride wastewater, which increases the cost of waste treatment.
[0005] (2) Using methacrylic acid and epichlorohydrin as raw materials, a ring-opening esterification reaction is first carried out under the action of a catalyst to generate the intermediate 3-chloro-2-hydroxypropyl methacrylate (CHPMA). Subsequently, a ring-closing reaction is carried out under the action of sodium hydroxide to generate the final product, as disclosed in patent CN111138382A. The disadvantage of this process route is that a large amount of sodium chloride wastewater is generated in the ring-closing reaction, which increases the cost of waste treatment. In addition, due to the introduction of alkali, a certain amount of glycidol is generated. The glycidol accumulates in the distillation system, which may pose a safety hazard.
[0006] Based on the above problems, there is an urgent need to propose a GMA production method that is highly safe, produces less waste, and consumes less energy. Summary of the Invention
[0007] To address the above technical problems, this invention proposes a co-production process for GMA and 1,3-dichloropropanol.
[0008] A process for the co-production of GMA and 1,3-dichloropropanol includes the following steps:
[0009] 1) Using methacrylic acid and epichlorohydrin as raw materials, a ring-opening esterification reaction is carried out under the action of catalyst A to obtain the reaction solution of intermediate CHPMA;
[0010] 2) The above reaction solution and the added epichlorohydrin are reacted together under the action of catalyst B to produce GMA and 1,3-dichloropropanol.
[0011] The reaction process above is expressed as follows:
[0012]
[0013] This invention enables the co-production of GMA and 1,3-dichloropropanol with high conversion and selectivity. The GMA and 1,3-dichloropropanol products can be separated by conventional distillation. The separated 1,3-dichloropropanol is an important organic synthesis intermediate and a raw material for the flame retardant TDCPP, possessing extremely high economic value.
[0014] As a preferred embodiment of the present invention, the reaction in step 1) is carried out in the presence of a polymerization inhibitor;
[0015] Preferably, the polymerization inhibitor is selected from phenolic polymerization inhibitors, amine polymerization inhibitors, and hindered free radical polymerization inhibitors, and more preferably one or more of ZJ-701, ZJ-705, HQ, phenothiazine, and MEHQ;
[0016] Preferably, the amount of the polymerization inhibitor is 100-500 ppm, more preferably 200-300 ppm, relative to the mass of methacrylic acid.
[0017] As a preferred embodiment of the present invention, in step 1), the molar ratio of methacrylic acid and epichlorohydrin is 1:(1-6), preferably 1:(2-4);
[0018] Preferably, in step 1), the feed space velocity of methacrylic acid is 0.1-0.6 h⁻¹. -1 Preferably 0.3-0.5h -1 .
[0019] As a preferred embodiment of the present invention, the catalyst A is a weakly basic anion exchange resin, preferably one or more of macroporous resins D301, D309, and D354.
[0020] As a preferred embodiment of the present invention, in step 1), the reaction temperature is 30-100℃, preferably 50-70℃.
[0021] As a preferred embodiment of the present invention, in step 2), the amount of epichlorohydrin added is 4-10 times the molar amount of methacrylic acid, preferably 6-8 times;
[0022] Preferably, in step 2), the feed space velocity of the reaction solution obtained in step 1) is 0.1-0.4 h⁻¹, calculated based on the methacrylic acid introduced in step 1. -1 The preferred time is 0.15-0.25h. -1 .
[0023] As a preferred embodiment of the present invention, the catalyst B is a mixture of a strong base anion exchange resin and a weak base anion exchange resin in a mass ratio of 5-9, preferably 6-8.
[0024] Preferably, the strongly basic anion exchange resin is one or more of the following macroporous resins: D201, D202, AmberliteIRA-900, LewatitMP-500, Diaion PA, AmberliteIRA-910, LewatitMP-600, and DiaionPa408.
[0025] Preferably, the weakly basic anion exchange resin is one or more of the macroporous resins D301, D309, D354, AmberliteIRA-93, LewatitMP-60, and DiaionWA-30.
[0026] As a preferred embodiment of the present invention, in step 2), the reaction temperature is 60-100℃, preferably 70-90℃.
[0027] Preferably, the above two reaction steps can be carried out in a fixed-bed reactor.
[0028] Compared with the prior art, the present invention has the following advantages:
[0029] 1. No water is generated during the process, reducing the hydrolysis side reaction of GMA, resulting in high reaction yield and fewer unstable by-products, significantly improving process safety; and avoiding the energy consumption caused by dehydration.
[0030] 2. The entire process avoids the use of alkaline solutions and does not produce saline wastewater or waste residue, making the production route greener and safer;
[0031] 3. The application of solid catalysts solves the problems of difficult recovery and separation from products of traditional homogeneous catalysts, and has better industrial applicability;
[0032] 4. It can simultaneously produce GMA and the high-value-added product 1,3-dichloropropanol, and also provides a new synthetic route for the production of 1,3-dichloropropanol, solving the equipment corrosion problem caused by the use of hydrochloric acid in traditional processes. Detailed Implementation
[0033] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.
[0034] Unless otherwise specified, all raw materials and reagents used in this invention can be purchased commercially.
[0035]
Example 1
[0036] (1) 1 kg of macroporous resin D301 was loaded into the first fixed-bed reactor. 250 ppm of ZJ-701 polymerization inhibitor was added to methacrylic acid and continuously added to the fixed-bed reactor at a rate of 0.4 kg / h. At the same time, epichlorohydrin was added at a rate of 1.29 kg / h. The reaction temperature was controlled at 60°C. The reaction liquid at the reactor outlet was tested. The conversion rate of MAA was 99.9% and the selectivity of CHPMA was 99.3%.
[0037] (2) 2 kg of catalyst (including 0.25 kg of macroporous resin D301 and 1.75 kg of macroporous resin D201) was loaded into the second fixed-bed reactor. All the reaction liquid obtained in step (1) was fed into the second fixed-bed reactor. 3 kg / h of epichlorohydrin was added. The reaction temperature was controlled at 80 °C. The composition of the reactor outlet was analyzed. It was calculated that the CHPMA conversion rate was 87.1%, the GMA selectivity was 98.2%, and the 1,3-dichloropropanol selectivity was 98%.
[0038]
Example 2
[0039] (1) 1 kg of macroporous resin D309 was loaded into the first fixed-bed reactor. 250 ppm of ZJ-701 polymerization inhibitor was added to methacrylic acid and continuously added to the fixed-bed reactor at a rate of 0.3 kg / h. At the same time, epichlorohydrin was added at a rate of 1.29 kg / h. The reaction temperature was controlled at 60°C. The reaction liquid at the reactor outlet was tested. The conversion rate of MAA was 99.5% and the selectivity of CHPMA was 99.6%.
[0040] (2) 1.2 kg of catalyst (including 0.13 kg of macroporous resin DiaionWA-30 and 1.07 kg of macroporous resin AmberliteIRA-900) was loaded into the second fixed-bed reactor. All the reaction liquid obtained in step (1) was fed into the second fixed-bed reactor. 1.94 kg / h of epichlorohydrin was added. The reaction temperature was controlled at 80 °C. The composition of the reactor outlet was analyzed. It was calculated that the CHPMA conversion rate was 81.2%, the GMA selectivity was 98.1%, and the 1,3-dichloropropanol selectivity was 97.4%.
[0041]
Example 3
[0042] (1) 1 kg of macroporous resin D354 was loaded into the first fixed-bed reactor. 250 ppm of ZJ-701 polymerization inhibitor was added to methacrylic acid and continuously added to the fixed-bed reactor at a rate of 0.5 kg / h. At the same time, epichlorohydrin was added at a rate of 1.08 kg / h. The reaction temperature was controlled at 50°C. The reaction liquid at the reactor outlet was tested. The conversion rate of MAA was 96.1% and the selectivity of CHPMA was 99.7%.
[0043] (2) 3.3 kg of catalyst (including 0.48 kg of macroporous resin Lewatit MP-60 and 2.86 kg of macroporous resin DiaionPa408) was loaded into the second fixed-bed reactor. All the reaction liquid obtained in step (1) was fed into the second fixed-bed reactor. 4.3 kg / h of epichlorohydrin was added. The reaction temperature was controlled at 90 °C. The composition of the reactor outlet was analyzed. It was calculated that the CHPMA conversion rate was 89.4%, the GMA selectivity was 97.9%, and the 1,3-dichloropropanol selectivity was 97.5%.
[0044]
Example 4
[0045] (1) 1 kg of macroporous resin D301 was loaded into the first fixed-bed reactor. 250 ppm of ZJ-701 polymerization inhibitor was added to methacrylic acid and continuously added to the fixed-bed reactor at a rate of 0.5 kg / h. At the same time, epichlorohydrin was added at a rate of 2.15 kg / h. The reaction temperature was controlled at 70°C. The reaction liquid at the reactor outlet was tested. The conversion rate of MAA was 99.1% and the selectivity of CHPMA was 99.2%.
[0046] (2) 2 kg of catalyst (including 0.22 kg of macroporous resin AmberliteIRA-93 and 1.78 kg of macroporous resin LewatitMP-500) was loaded into the second fixed-bed reactor. All the reaction liquid obtained in step (1) was fed into the second fixed-bed reactor. 3.2 kg / h of epichlorohydrin was added. The reaction temperature was controlled at 70 °C. The composition of the reactor outlet was analyzed. It was calculated that the CHPMA conversion rate was 73.4%, the GMA selectivity was 98.4%, and the 1,3-dichloropropanol selectivity was 98.1%.
[0047] Comparative Example 1
[0048] The reaction was carried out under essentially the same conditions as in Example 1, except that the catalyst in step (2) was replaced with 2 kg of macroporous resin D201. Analysis of the reactor outlet composition revealed a CHPMA conversion rate of 89%, a GMA selectivity of 92.1%, and a 1,3-dichloropropanol selectivity of 90.9%.
[0049] Comparative Example 2
[0050] The reaction was carried out under essentially the same conditions as in Example 1, except that the catalyst in step (2) was replaced with 2 kg of macroporous resin D301. Analysis of the reactor outlet composition revealed a CHPMA conversion rate of 35%, a GMA selectivity of 98.1%, and a 1,3-dichloropropanol selectivity of 97.9%.
[0051] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.
Claims
1. A process for the co-production of GMA and 1,3-dichloropropanol, characterized in that, Includes the following steps: 1) Using methacrylic acid and epichlorohydrin as raw materials, a ring-opening esterification reaction is carried out under the action of catalyst A to obtain a reaction solution; wherein catalyst A is one or more of macroporous resins D301, D309, and D354; 2) The above reaction solution and the added epichlorohydrin are reacted together under the action of catalyst B to produce GMA and 1,3-dichloropropanol; the catalyst B is a mixture of a strong base anion exchange resin and a weak base anion exchange resin in a mass ratio of 5-9; the strong base anion exchange resin is one or more of the following macroporous resins: D201, D202, AmberliteIRA-900, LewatitMP-500, AmberliteIRA-910, LewatitMP-600, and DiaionPa408; the weak base anion exchange resin is one or more of the following macroporous resins: D301, D309, D354, AmberliteIRA-93, LewatitMP-60, and DiaionWA-30. The reaction in step 1) is carried out in the presence of a polymerization inhibitor; the polymerization inhibitor is selected from phenolic polymerization inhibitors, amine polymerization inhibitors, and hindered free radical polymerization inhibitors.
2. The co-production process of GMA and 1,3-dichloropropanol according to claim 1, characterized in that, The polymerization inhibitor is selected from one or more of ZJ-701, ZJ-705, HQ, phenothiazine, and MEHQ.
3. The co-production process of GMA and 1,3-dichloropropanol according to claim 1, characterized in that, The amount of the polymerization inhibitor is 100-500 ppm, relative to the mass of methacrylic acid.
4. The co-production process of GMA and 1,3-dichloropropanol according to claim 3, characterized in that, The amount of the polymerization inhibitor is 200-300 ppm, relative to the mass of methacrylic acid.
5. The co-production process of GMA and 1,3-dichloropropanol according to any one of claims 1-4, characterized in that, In step 1), the molar ratio of methacrylic acid and epichlorohydrin is 1:(1-6).
6. The co-production process of GMA and 1,3-dichloropropanol according to claim 5, characterized in that, In step 1), the molar ratio of methacrylic acid and epichlorohydrin is 1:(2-4).
7. The co-production process of GMA and 1,3-dichloropropanol according to claim 5, characterized in that, In step 1), the feed space velocity of methacrylic acid is 0.1-0.6 h⁻¹.
8. The co-production process of GMA and 1,3-dichloropropanol according to claim 7, characterized in that, In step 1), the feed space velocity of methacrylic acid is 0.3-0.5 h⁻¹.
9. The co-production process of GMA and 1,3-dichloropropanol according to any one of claims 1-4, characterized in that, In step 1), the reaction temperature is 30-100℃.
10. The co-production process of GMA and 1,3-dichloropropanol according to claim 9, characterized in that, In step 1), the reaction temperature is 50-70℃.
11. The co-production process of GMA and 1,3-dichloropropanol according to any one of claims 1-4, characterized in that, In step 2), the amount of epichlorohydrin added is 4-10 times the molar amount of methacrylic acid.
12. The co-production process of GMA and 1,3-dichloropropanol according to claim 11, characterized in that, In step 2), the amount of epichlorohydrin added is 6-8 times the molar amount of methacrylic acid.
13. The co-production process of GMA and 1,3-dichloropropanol according to claim 11, characterized in that, In step 2), the feed space velocity of the reaction liquid obtained in step 1) is 0.1-0.4 h⁻¹, based on the methacrylic acid introduced in step 1).
14. The co-production process of GMA and 1,3-dichloropropanol according to claim 13, characterized in that, In step 2), the feed space velocity of the reaction liquid obtained in step 1) is 0.15-0.25 h⁻¹, based on the methacrylic acid introduced in step 1).
15. The co-production process of GMA and 1,3-dichloropropanol according to any one of claims 1-4, characterized in that, The catalyst B is a mixture of a strong base anion exchange resin and a weak base anion exchange resin in a mass ratio of 6-8.
16. The co-production process of GMA and 1,3-dichloropropanol according to any one of claims 1-4, characterized in that, In step 2), the reaction temperature is 60-100℃.
17. The co-production process of GMA and 1,3-dichloropropanol according to claim 16, characterized in that, In step 2), the reaction temperature is 70-90℃.