A preparation method of allyl glycidyl ether

Abstract

The invention belongs to the field of fine chemical technology, discloses a kind of preparation method of allyl glycidyl ether.The preparation method is:Using allyl alcohol and epichlorohydrin as reaction raw materials, ring-opening reaction is carried out under the effect of strongly acidic cation exchange resin, after reaction terminates, filtrate is filtered to obtain;Then filtrate is mixed with strong base, ring-closed reaction is carried out under the effect of phase-transfer catalyst, after reaction terminates, through refinement, allyl glycidyl ether is obtained;The mol ratio of allyl alcohol and epichlorohydrin is 1:(0.95 1.2).The present invention uses open loop, closed loop two-step method to synthesize allyl glycidyl ether, using strongly acidic cation exchange resin as the catalyst of ring-opening reaction, it is possible to prepare the allyl glycidyl ether of high content, high yield without adding excessive allyl alcohol.

Description

Technical Field

[0001] The invention belongs to the technical field of fine chemicals, and particularly relates to a method for preparing allyl glycidyl ether. Background Art

[0002] Allyl glycidyl ether is an active monomer containing an unsaturated carbon-carbon double bond and an epoxy group. It is an important polymerization monomer and organic synthesis intermediate. It is widely used in the field of fine chemicals. In the production of epoxy resins, chemical fibers, plastics and rubber, it is widely used as an additive, solvent, catalyst, cross-linking agent and chain transfer agent, etc. It has important uses in the field of organic chemicals.

[0003] There are four main methods for synthesizing allyl glycidyl ether. The first is the phase transfer catalysis method, which uses allyl alcohol and epichlorohydrin as raw materials and reacts directly to form the product in the presence of sodium hydroxide and a phase transfer catalyst. The second is the two-step ring-opening and ring-closing method, which uses allyl alcohol and epichlorohydrin as raw materials and, under the action of a catalyst, undergoes a ring-opening addition reaction to obtain an allyl chlorohydrin ether intermediate. The intermediate is then ring-closed by removing HCl under the action of alkaline solution to obtain the product. The third is the oxidation method, which uses diallyl ether as raw material and, under the action of a catalyst, undergoes oxidation to obtain the product. The fourth is the sodium alkoxide method, which uses allyl alcohol as raw material and first reacts with sodium hydroxide to obtain sodium allyl alkoxide, which is then reacted with epichlorohydrin under anhydrous conditions to obtain the product.

[0004] Currently, a two-step ring-opening and ring-closing process is widely used to synthesize allyl glycidyl ether both domestically and internationally. The acidic catalysts used in the ring-opening reaction in the synthesis process mainly include strong acid catalysts such as concentrated sulfuric acid and perchloric acid, and Lewis acid catalysts such as boron trifluoride etherate, tin tetrachloride, aluminum chloride, and titanium chloride. To produce allyl glycidyl ether in high yields exceeding 99.5% using these catalysts, an excess of allyl alcohol must be used to improve the selectivity of the primary reaction, and the allyl alcohol must be recovered after the ring-opening reaction. This complicates the process and increases production costs, leading to extensive research focused on recovering the allyl alcohol.

[0005] Therefore, there is an urgent need to provide a method for preparing allyl glycidyl ether, which can prepare allyl glycidyl ether with high yield and high purity without excessive allyl alcohol. Summary of the Invention

[0006] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides a method for preparing allyl glycidyl ether, which can prepare allyl glycidyl ether with high yield and high purity without excessive allyl alcohol.

[0007] The invention provides a preparation method of allyl glycidyl ether.

[0008] Specifically, a method for preparing allyl glycidyl ether comprises the following steps:

[0009] Allyl alcohol and epichlorohydrin are used as reaction raw materials, a ring-opening reaction is carried out under the action of a strongly acidic cation exchange resin, and after the reaction is completed, a filtrate is obtained by filtration; the filtrate is then mixed with a strong base, and a ring-closing reaction is carried out under the action of a phase transfer catalyst. After the reaction is completed, the filtrate is purified to obtain allyl glycidyl ether;

[0010] The molar ratio of the allyl alcohol to the epichlorohydrin is 1:(0.95-1.2).

[0011] Preferably, the molar ratio (amount ratio) of the allyl alcohol to the epichlorohydrin is 1:(1-1.2); further preferably, the molar ratio of the allyl alcohol to the epichlorohydrin is 1:(1-1.1).

[0012] Preferably, the strongly acidic cation exchange resin is NKC-9 macroporous strongly acidic cation exchange resin.

[0013] Preferably, the added amount of the strong acidic cation exchange resin is 3%-10% of the mass of the allyl alcohol; further preferably, the added amount of the strong acidic cation exchange resin is 4%-8% of the mass of the allyl alcohol; more preferably, the added amount of the strong acidic cation exchange resin is 4.5%-7.5% of the mass of the allyl alcohol.

[0014] Preferably, the temperature of the ring-opening reaction is 65-90°C; further preferably, the temperature of the ring-opening reaction is 70-85°C.

[0015] Preferably, the ring-opening reaction is carried out in a stirred reactor; further preferably, the stirred reactor is a turbine stirred reactor with a baffle, which can ensure that the catalyst (strongly acidic cation exchange resin) can be suspended in the reaction mixture, thereby improving the reaction efficiency.

[0016] Preferably, the filtration process further comprises separating and recovering the strongly acidic cation exchange resin, and the recovered strongly acidic cation exchange resin can be reused as a catalyst for the ring-opening reaction.

[0017] Preferably, the strong base is sodium hydroxide and / or potassium hydroxide.

[0018] Preferably, the molar ratio of the strong base to the epichlorohydrin is (1-1.5):1; further preferably, the molar ratio of the strong base to the epichlorohydrin is (1-1.2):1.

[0019] Preferably, the mass concentration of the strong base is 18%-22%; further preferably, the mass concentration of the strong base is 20%-22%.

[0020] Preferably, the phase transfer catalyst includes at least one of benzyltriethylammonium chloride, tetrabutylammonium bromide, and tetrabutylammonium chloride.

[0021] Preferably, the added amount of the phase transfer catalyst is 0.3%-1.0% of the total mass of the allyl alcohol and the epichlorohydrin; further preferably, the added amount of the phase transfer catalyst is 0.6%-0.9% of the total mass of the allyl alcohol and the epichlorohydrin.

[0022] Preferably, the temperature of the ring-closing reaction is 30-60°C; further preferably, the temperature of the ring-closing reaction is 30-50°C.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] The invention adopts a two-step ring-opening and ring-closing method to synthesize allyl glycidyl ether. In the ring-opening reaction, a strongly acidic cation exchange resin is used as a catalyst. The oxygen atom on epichlorohydrin is first protonated, and then allyl alcohol is catalyzed to selectively ring-open the epichlorohydrin to obtain 1-allyloxy-3-chloro-2-propanol, a main product of the ring-opening reaction. In addition, since the nucleophilicity of allyl alcohol is greater than that of the main product of the ring-opening reaction, epichlorohydrin will preferentially react with allyl alcohol under the action of the catalyst to continue to generate the main product of the ring-opening reaction. Therefore, no excessive allyl alcohol is required, that is, the main reaction of the ring-opening reaction can be catalyzed with high selectivity, the product yield is greatly improved, the problem of needing to recover allyl alcohol after the ring-opening reaction is completed is solved, the process flow is shortened, and energy consumption and cost are reduced. In addition, the catalyst has low corrosion to equipment, can be separated from the reaction product by filtration after the ring-opening reaction is completed, and can be recycled and reused at least 10 times, thereby effectively saving costs.

[0025] The beneficial effects of the present invention are:

[0026] The present invention adopts a two-step ring-opening and ring-closing method to synthesize allyl glycidyl ether. A strongly acidic cation exchange resin is used as a catalyst for the ring-opening reaction. High-content (greater than 99.5%) and high-yield allyl glycidyl ether can be prepared without adding excess allyl alcohol. Specifically, the ring-opening reaction is carried out using the strongly acidic cation exchange resin as a catalyst, eliminating the need for excess allyl alcohol to improve the selectivity of the main reaction. After the ring-opening reaction, there is no need to recover the allyl alcohol. This simplifies the process, provides a stable reaction that is easier to control, allows for recycling of the catalyst, and reduces product cost. DETAILED DESCRIPTION

[0027] In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the following examples are given for illustration. It should be noted that the following examples do not limit the scope of protection claimed by the present invention.

[0028] Unless otherwise specified, the raw materials, reagents, or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0029] Example 1

[0030] A method for preparing allyl glycidyl ether comprises the following steps:

[0031] 116 g of allyl alcohol and 4.6 g of NKC-9 macroporous strongly acidic cation exchange resin are added to a turbine stirred reactor with a baffle. Heating and stirring are initiated, and the temperature is set to 75° C. After insulation, 185 g of epichlorohydrin is uniformly added dropwise, maintaining the reaction temperature at 75-80° C. for 2 hours, and then insulation is performed for 2 hours. After the reaction is completed, the temperature is lowered to below 35° C., the NKC-9 macroporous strongly acidic cation exchange resin is filtered out, and a filtrate is obtained. 1.5 g of benzyltriethylammonium chloride is added to the filtrate, and then 440 g of a 20% by mass sodium hydroxide solution is added dropwise, the reaction temperature is controlled at 35-40° C., and the reaction is continued for 4 hours. Finally, the lower layer of brine is separated, and the upper layer of crude product is subjected to rectification to obtain 207.6 g of allyl glycidyl ether with a content of 99.76%, and the finished product yield is 91.05%.

[0032] Example 2

[0033] A method for preparing allyl glycidyl ether comprises the following steps:

[0034] 116 g of allyl alcohol and 9.3 g of NKC-9 macroporous strongly acidic cation exchange resin are added to a turbine stirred reactor with a baffle. Heating and stirring are initiated, and the temperature is set to 75° C. After insulation, 203.5 g of epichlorohydrin is added dropwise at a uniform rate, maintaining the reaction temperature at 75-80° C. for 2 hours, and then insulation is performed for 2 hours. After the reaction is completed, the temperature is lowered to below 35° C., the NKC-9 macroporous strongly acidic cation exchange resin is filtered out, and a filtrate is obtained. 3.2 g of benzyltriethylammonium chloride is added to the filtrate, and then 502.9 g of a 21% by mass sodium hydroxide solution is added dropwise. The reaction temperature is controlled at 35-40° C. for 1 hour, and the reaction is insulated for 4 hours. Finally, the lower brine layer is separated, and the upper crude product is subjected to rectification to obtain 206.3 g of allyl glycidyl ether with a content of 99.72%, and the finished product yield is 90.57%.

[0035] Example 3

[0036] A method for preparing allyl glycidyl ether comprises the following steps:

[0037] 116 g of allyl alcohol and 7.0 g of NKC-9 macroporous strongly acidic cation exchange resin are added to a turbine stirred reactor with a baffle. Heating and stirring are initiated, and the temperature is set to 75° C. After insulation, 194.3 g of epichlorohydrin is uniformly added dropwise, maintaining the reaction temperature at 75-80° C. for 2 hours, and then insulation is performed for 2 hours. After the reaction is completed, the temperature is lowered to below 35° C., the NKC-9 macroporous strongly acidic cation exchange resin is filtered out, and a filtrate is obtained. 2.5 g of benzyltriethylammonium chloride is added to the filtrate, and then 400 g of a 22% by mass sodium hydroxide solution is added dropwise, the reaction temperature is controlled at 35-40° C., and the mixture is insulated for 4 hours. Finally, the lower brine layer is separated, and the upper crude product is subjected to rectification to obtain 220.0 g of allyl glycidyl ether with a content of 99.81%, and the finished product yield is 96.49%.

[0038] Example 4

[0039] A method for preparing allyl glycidyl ether comprises the following steps:

[0040] To a turbine stirred reactor with a baffle, 116 g of allyl alcohol and the NKC-9 macroporous strongly acidic cation exchange resin isolated in Example 3 (with a slight loss to make up to 7.0 g) were added, and heating and stirring were started. The temperature was set to 75° C. After insulation, 194.3 g of epichlorohydrin was uniformly added dropwise, maintaining the reaction temperature at 75-80° C. for 2 h, and then incubated for 2 h. After completion of the reaction, the temperature was lowered to below 35° C., the NKC-9 macroporous strongly acidic cation exchange resin was filtered out, and a filtrate was obtained. 2.5 g of benzyltriethylammonium chloride was added to the filtrate, and then 400 g of a 22% by mass sodium hydroxide solution was added dropwise. The reaction temperature was controlled to 35-40° C. for 1 h, and the reaction was incubated for 4 h. The lower brine was separated, and the upper crude product was distilled to obtain 219.8 g of 99.79% allyl glycidyl ether, with a finished product yield of 96.40%.

[0041] Example 5

[0042] A method for preparing allyl glycidyl ether comprises the following steps:

[0043] To a turbine stirred reactor with a baffle, 116 g of allyl alcohol and the NKC-9 macroporous strongly acidic cation exchange resin separated in Example 4 (with a slight loss, making up to 7.0 g) were added, and heating and stirring were started. The temperature was set to 75° C. After insulation, 194.3 g of epichlorohydrin was uniformly added dropwise, maintaining the reaction temperature at 75-80° C. for 2 h, and then incubated for 2 h. After completion of the reaction, the temperature was lowered to below 35° C., the NKC-9 macroporous strongly acidic cation exchange resin was filtered out, and a filtrate was obtained. 2.5 g of benzyltriethylammonium chloride was added to the filtrate, and then 400 g of a 22% by mass sodium hydroxide solution was added dropwise. The reaction temperature was controlled to 35-40° C. for 1 h, and the reaction was incubated for 4 h. The lower brine was separated, and the upper crude product was distilled to obtain 219.6 g of 99.75% allyl glycidyl ether, with a finished product yield of 96.32%.

[0044] Example 6

[0045] A method for preparing allyl glycidyl ether comprises the following steps:

[0046] 116 g of allyl alcohol and 7.0 g of NKC-9 macroporous strongly acidic cation exchange resin were added to a turbine stirred reactor with a baffle. Heating and stirring were started, and the temperature was set to 70° C. After insulation, 194.3 g of epichlorohydrin was uniformly added dropwise, maintaining the reaction temperature at 70-75° C. for 2 hours, and insulation was performed for 2 hours. After the reaction was completed, the temperature was lowered to below 30° C., the NKC-9 macroporous strongly acidic cation exchange resin was filtered out, and a filtrate was obtained. 2.5 g of tetrabutylammonium chloride was added to the filtrate, and 400 g of a 22% by mass sodium hydroxide solution was dropwise added. The reaction temperature was controlled at 30-35° C. for 1 hour, and insulation was performed for 4 hours. The lower brine layer was separated, and the upper crude product was subjected to rectification to obtain 216.3 g of allyl glycidyl ether with a content of 99.78%, and the finished product yield was 94.87%.

[0047] Example 7

[0048] A method for preparing allyl glycidyl ether comprises the following steps:

[0049] 116 g of allyl alcohol and 7.0 g of NKC-9 macroporous strongly acidic cation exchange resin are added to a turbine stirred reactor with a baffle. Heating and stirring are initiated, and the temperature is set to 80° C. After insulation, 194.3 g of epichlorohydrin is uniformly added dropwise, maintaining the reaction temperature at 80-85° C. for 2 hours, and then insulation is performed for 2 hours. After the reaction is completed, the temperature is lowered to below 45° C., the NKC-9 macroporous strongly acidic cation exchange resin is filtered out, and a filtrate is obtained. 2.5 g of tetrabutylammonium bromide is added to the filtrate, and then 400 g of a 22% by mass sodium hydroxide solution is added dropwise, the reaction temperature is controlled at 45-50° C., and the reaction is continued for 4 hours. The lower brine layer is separated, and the upper crude product is subjected to rectification to obtain 216.5 g of allyl glycidyl ether with a content of 99.80%, and the finished product yield is 94.96%.

[0050] Example 8

[0051] A method for preparing allyl glycidyl ether comprises the following steps:

[0052] 116 g of allyl alcohol and 7.0 g of NKC-9 macroporous strongly acidic cation exchange resin are added to a turbine stirred reactor with a baffle. Heating and stirring are initiated, and the temperature is set to 75° C. After insulation, 194.3 g of epichlorohydrin is uniformly added dropwise, maintaining the reaction temperature at 75-80° C. for 2 hours, and then insulation is performed for 2 hours. After the reaction is completed, the temperature is lowered to below 35° C., the NKC-9 macroporous strongly acidic cation exchange resin is filtered out, and a filtrate is obtained. 2.5 g of benzyltriethylammonium chloride is added to the filtrate, and then 381.8 g of a 22% by mass sodium hydroxide solution is added dropwise, the reaction temperature is controlled at 40-45° C., and the reaction is continued for 4 hours. The lower layer of brine is separated, and the upper layer of crude product is subjected to rectification to obtain 221.6 g of allyl glycidyl ether with a content of 99.55%, and the finished product yield is 97.20%.

[0053] Comparative Example 1

[0054] A method for preparing allyl glycidyl ether comprises the following steps:

[0055] To a turbine stirred reactor with a baffle, 348 g of allyl alcohol, 4.6 g of boron trifluoride etherate, and a ternary mixed catalyst of tin dichloride and tin tetrachloride (in a ratio of 1:0.5:0.5) were added, and heating and stirring were started. The temperature was set to 75° C. After insulation, 185 g of epichlorohydrin was uniformly added dropwise, maintaining the reaction temperature at 75-80° C. for 2 hours, and then insulation was performed for 2 hours. After completion of the reaction, 229.7 g of unreacted allyl alcohol was recovered by vacuum distillation (to be used as the raw material for the next batch). The temperature was lowered to 35° C., 2.5 g of benzyltriethylammonium chloride was added, and 440 g of a 22% by mass sodium hydroxide solution was added dropwise. The reaction temperature was controlled to 35-40° C. for 1 hour, and the reaction was insulated for 4 hours. The lower layer of brine was separated, and the upper layer of crude product was subjected to rectification to obtain 206.4 g of allyl glycidyl ether with a content of 99.23%, and the finished product yield was 90.53%.

[0056] Comparative Example 2

[0057] A method for preparing allyl glycidyl ether comprises the following steps:

[0058] 348 g of allyl alcohol and 4.6 g of boron trifluoride etherate were added to a turbine stirred reactor with a baffle, and heating and stirring were started. The temperature was set to 75° C. After insulation, 185 g of epichlorohydrin was uniformly added dropwise, maintaining the reaction temperature at 75-80° C. for 2 hours, and then insulation was carried out for 2 hours. After completion of the reaction, 203 g of unreacted allyl alcohol was recovered by vacuum distillation (reused as raw material for the next batch). The temperature was lowered to 35° C., 2.5 g of benzyltriethylammonium chloride was added, and 440 g of a 22% by mass sodium hydroxide solution was added dropwise. The reaction temperature was controlled to 35-40° C. for 1 hour, and the reaction was incubated for 4 hours. The lower brine was separated, and the upper crude product was subjected to rectification to obtain 188.0 g of 99.05% allyl glycidyl ether, with a finished product yield of 82.46%.

[0059] Comparative Example 3

[0060] A method for preparing allyl glycidyl ether comprises the following steps:

[0061] 348 g of allyl alcohol and 4.6 g of activated carbon-supported boron trifluoride catalyst were added to a turbine stirred reactor with a baffle, and heating and stirring were started. The temperature was set to 75° C. After insulation, 185 g of epichlorohydrin was uniformly added dropwise, maintaining the reaction temperature at 75-80° C. for 2 hours, and then insulation was carried out for 2 hours. After completion of the reaction, the temperature was lowered, the catalyst was filtered, and the unreacted 214.6 g of allyl alcohol was recovered by vacuum distillation (reused as the raw material for the next batch). The temperature was lowered to 35° C., 2.5 g of benzyltriethylammonium chloride was added, and then 440 g of a 22% by mass sodium hydroxide solution was added dropwise. The reaction temperature was controlled to 35-40° C. for 1 hour, and the reaction was insulated for 4 hours. The lower brine was separated, and the upper crude product was subjected to rectification to obtain 195.6 g of allyl glycidyl ether with a content of 99.12%, and the finished product yield was 85.79%.

[0062] It can be seen from the above examples and comparative examples that the allyl glycidyl ether prepared in the embodiments of the present invention does not require the addition of excessive allyl alcohol, and therefore does not require the recovery of allyl alcohol. This not only shortens the process flow, reduces energy consumption and costs, but also enables the preparation of allyl glycidyl ether with a high content and high yield. When the content is above 99.7%, the yield can reach above 90.5%, and when the content is above 99.5%, the yield can reach above 97%.

[0063] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A method for preparing allyl glycidyl ether, characterized in that: The following steps are involved: Allyl alcohol and epichlorohydrin are used as reaction raw materials, a ring-opening reaction is carried out under the action of a strongly acidic cation exchange resin, and after the reaction is completed, a filtrate is obtained by filtration; the filtrate is then mixed with a strong base, and a ring-closing reaction is carried out under the action of a phase transfer catalyst. After the reaction is completed, the filtrate is purified to obtain allyl glycidyl ether; The molar ratio of the allyl alcohol to the epichlorohydrin is 1:(0.95-1.2); The strong acid cation exchange resin is NKC-9 macroporous strong acid cation exchange resin; the phase transfer catalyst includes at least one of benzyltriethylammonium chloride, tetrabutylammonium bromide and tetrabutylammonium chloride.

2. The preparation method according to claim 1, characterized in that The molar ratio of the allyl alcohol to the epichlorohydrin is 1:(1-1.2).

3. The preparation method according to claim 1 or 2, characterized in that The added amount of the strongly acidic cation exchange resin is 3%-10% of the mass of the allyl alcohol.

4. The preparation method according to claim 1 or 2, characterized in that The temperature of the ring-opening reaction is 65-90°C.

5. The preparation method according to claim 1 or 2, characterized in that The strong base is sodium hydroxide and / or potassium hydroxide; and / or, The molar ratio of the strong base to the epichlorohydrin is (1-1.5):

1.

6. The preparation method according to claim 5, characterized in that The mass concentration of the strong base is 18%-22%.

7. The preparation method according to claim 1, characterized in that The added amount of the phase transfer catalyst is 0.3%-1.0% of the total mass of the allyl alcohol and the epichlorohydrin.

8. The preparation method according to claim 7, characterized in that The added amount of the phase transfer catalyst is 0.6%-0.9% of the total mass of the allyl alcohol and the epichlorohydrin.

9. The preparation method according to claim 1 or 2, characterized in that: The temperature of the ring-closing reaction is 30-60°C.