Preparation method of TCPP

Abstract

The invention relates to the technical field of preparation of TCPP, in particular to a preparation method of TCPP, which comprises the following steps: uniformly mixing phosphorus oxychloride and a catalyst, adding the mixture into a micro-channel reactor, adding propylene oxide into the micro-channel reactor for reaction and heat preservation, and transferring the material to an alkali washing kettle for post-treatment to obtain TCPP; the reaction temperature is controlled to be 49-66 DEG C; uniformly mixing the phosphorus oxychloride and the catalyst, and adding the mixture into the micro-channel reactor at a flow rate of 49-76kg / min; the epoxypropane is added into the microchannel reactor at the flow speed of 56-88 kg / min, the content of a first isomer in the TCPP can be increased, the content of the first isomer in the TCPP is made to be larger than 80%, and the flame retardant effect of the TCPP is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of the preparation of TCPP, and specifically relates to a preparation method of TCPP. Background Art

[0002] TCPP (tris(2-chloroisopropyl) phosphate) is a chlorinated organophosphorus flame retardant. After the gradual phasing out of brominated flame retardants (BFRs), it is widely used in the technical fields of fireproof coatings, polyvinyl chloride, polyurethane soft and hard foams, and engineering plastics. Four isomers are generated during the production of TCPP, namely the first isomer tris(2-chloroisopropyl) phosphate, the second isomer bis(2-chloroisopropyl)(2-chloropropyl) phosphate, the third isomer bis(2-chloropropyl)(2-chloroisopropyl) phosphate, and the fourth isomer tris(2-chloropropyl) phosphate. Among them, the first isomer tris(2-chloroisopropyl) phosphate, as the main component of TCPP, determines the flame retardancy of TCPP, and its content affects the flame retardant performance of materials. The increase in the proportion of other isomers will reduce the flame retardant performance of TCPP. The TCPP produced by conventional TCPP preparation methods often has problems such as high acid value, strong odor, yellow color, and high content of isomers of minor components. Moreover, the production process mainly performs batch operations through synthesis kettles, alkali washing kettles, water washing kettles, dehydration kettles, etc. Due to the instability of the phosphoric acid ester bond in batch post-treatment, the ester bond will break during post-treatment, affecting the quality and yield of TCPP, and there are also problems such as out-of-tune feed ratios, overheating, overpressure, and even explosion caused by too fast feeding.

[0003] Chinese Patent Application CN116239631A (June 9, 2023) discloses a preparation method of a TCPP flame retardant, in which phosphorus oxychloride and propylene oxide react under the catalysis of a Lewis acid to obtain TCPP. Under the catalysis of a Lewis acid, problems such as high acid value, strong odor, yellow color, and high content of isomers of minor components may occur.

[0004] Therefore, providing a preparation method of TCPP that can increase the content of the first isomer in TCPP is the main technical problem to be solved at present. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention provides a preparation method of TCPP, which includes the following steps:

[0006] Phosphorus oxychloride and a catalyst are mixed evenly and then added to a microchannel reactor, and propylene oxide is added to the microchannel reactor for reaction, heat preservation, and transfer to an alkali washing kettle for post-treatment to obtain TCPP; the temperature of the reaction is controlled to be 49-66°C; after the phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 49-76 kg / min; the propylene oxide is added to the microchannel reactor at a flow rate of 56-88 kg / min.

[0007] In one embodiment, the method for preparing TCPP includes the following steps: Phosphorus oxychloride and a catalyst are mixed evenly and then added to a microchannel reactor, and propylene oxide is added to the microchannel reactor for reaction. After all the feeds are completed, it is kept warm at the reaction temperature for 10-20 min and then transferred to an alkali washing kettle for post-treatment to obtain TCPP.

[0008] The inventors found during the experiment that by adding phosphorus oxychloride, a catalyst, and propylene oxide to a microchannel reactor for reaction, the precise control of the temperature during the reaction can be improved, the problem of poor heat transfer can be solved, and the yield of TCPP and the content of the first isomer can be increased.

[0009] In one embodiment, after all the feeds are completed, it is kept warm at the reaction temperature for 15 min and then transferred to an alkali washing kettle for post-treatment to obtain TCPP.

[0010] In one embodiment, the temperature of the reaction includes but is not limited to 49°C, 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C.

[0011] In one embodiment, the flow rate at which the phosphorus oxychloride and the catalyst are mixed evenly and added to the microchannel reactor includes but is not limited to 49 kg / min, 50 kg / min, 51 kg / min, 52 kg / min, 53 kg / min, 54 kg / min, 55 kg / min, 56 kg / min, 57 kg / min, 58 kg / min, 59 kg / min, 60 kg / min, 61 kg / min, 62 kg / min, 63 kg / min, 64 kg / min, 65 kg / min, 66 kg / min, 67 kg / min, 68 kg / min, 69 kg / min, 70 kg / min, 71 kg / min, 72 kg / min, 73 kg / min, 74 kg / min, 75 kg / min, 76 kg / min.

[0012] In one embodiment, the flow rate of propylene oxide added to the microchannel reactor includes, but is not limited to, 56 kg / min, 57 kg / min, 58 kg / min, 59 kg / min, 60 kg / min, 61 kg / min, 62 kg / min, 63 kg / min, 64 kg / min, 65 kg / min, 66 kg / min, 67 kg / min, 68 kg / min, 68.4 kg / min, 69 kg / min, 70 kg / min, 71 kg / min, 72 kg / min, 73 kg / min, 74 kg / min, 75 kg / min, 76 kg / min, 77 kg / min, 77.5 kg / min, 78 kg / min, 79 kg / min, 80 kg / min, 81 kg / min, 82 kg / min, 83 kg / min, 84 kg / min, 85 kg / min, 86 kg / min, 87 kg / min, 88 kg / min.

[0013] In order to increase the content of the first isomer in TCPP and improve the flame retardancy effect of TCPP, the inventors found during the experiments that by limiting the flow rate of phosphorus oxychloride and the catalyst after being uniformly mixed to be 49 - 76 kg / min when added to the microchannel reactor, limiting the flow rate of propylene oxide to be 56 - 88 kg / min when added to the microchannel reactor, and limiting the reaction temperature of phosphorus oxychloride and propylene oxide to be 49 - 66 °C, the content of the first isomer in TCPP can be increased, such that the content of the first isomer in TCPP is greater than 80%. The possible reason is that by using a microchannel reactor and controlling the addition rates of phosphorus oxychloride and propylene oxide, the problem of local overheating caused by too fast addition rate or uneven mixing can be solved, thereby reducing the content of the first isomer in TCPP.

[0014] In one embodiment, the reaction temperature is 53 - 58 °C.

[0015] In one embodiment, the reaction temperature is 55 °C.

[0016] In order to make the content of the first isomer in TCPP greater than 84% and improve the flame retardancy effect of TCPP, the inventors found during the experiments that by limiting the flow rate of phosphorus oxychloride and the catalyst after being uniformly mixed to be 49 - 76 kg / min when added to the microchannel reactor, limiting the flow rate of propylene oxide to be 56 - 88 kg / min when added to the microchannel reactor, limiting the reaction temperature of phosphorus oxychloride and propylene oxide to be 53 - 58 °C, and especially limiting the reaction temperature of phosphorus oxychloride and propylene oxide to be 55 °C, the content of the first isomer in TCPP can be made greater than 84%, further increasing the content of the first isomer in TCPP and improving the flame retardancy effect of TCPP.

[0017] In one embodiment, the temperature of the reaction is 50 - 52 °C.

[0018] In one embodiment, the temperature of the reaction is 50 °C.

[0019] In order to make the content of the first isomer in TCPP greater than 85% and improve the flame retardant effect of TCPP, the inventors found during the experiment that after phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 49 - 76 kg / min, propylene oxide is added to the microchannel reactor at a flow rate of 56 - 88 kg / min, and the temperature of the reaction between phosphorus oxychloride and propylene oxide is 50 - 52 °C. In particular, when the temperature of the reaction between phosphorus oxychloride and propylene oxide is 50 °C, the content of the first isomer in TCPP can be greater than 85%, further increasing the content of the first isomer in TCPP and improving the flame retardant effect of TCPP.

[0020] In one embodiment, the temperature of the reaction is 58.5 - 63 °C.

[0021] In one embodiment, the temperature of the reaction is 60 °C.

[0022] In order to make the content of the first isomer in TCPP greater than 85% and improve the flame retardant effect of TCPP, the inventors found during the experiment that after phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 49 - 76 kg / min, propylene oxide is added to the microchannel reactor at a flow rate of 56 - 88 kg / min, and the temperature of the reaction between phosphorus oxychloride and propylene oxide is 58.5 - 63 °C. In particular, when the temperature of the reaction between phosphorus oxychloride and propylene oxide is 60 °C, the content of the first isomer in TCPP can be greater than 85%, further increasing the content of the first isomer in TCPP and improving the flame retardant effect of TCPP; the possible reason is that when the temperature of the reaction between phosphorus oxychloride and propylene oxide is lower than 65 °C, propylene oxide is more likely to break the carbon - oxygen bond with smaller steric hindrance at low temperature to form a branched chain, and the branched chain is more likely to evenly disperse TCPP molecules, improving the flame retardant effect; the carbon - oxygen bond with larger steric hindrance in propylene oxide breaks to form a straight chain at higher temperature, which will lead to the generation of the second isomer component, but the inventors found that when the temperature of the reaction between phosphorus oxychloride and propylene oxide is too low, the yield of TCPP will decrease.

[0023] In one embodiment, the temperature of the reaction is 58.5 - 63 °C, and after phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 65 - 70 kg / min; propylene oxide is added to the microchannel reactor at a flow rate of 75 - 79 kg / min.

[0024] In one embodiment, the temperature of the reaction is 60 °C. After the phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 68 kg / min; the propylene oxide is added to the microchannel reactor at a flow rate of 77.5 kg / min.

[0025] In order to improve the yield of TCPP and increase the content of the first isomer in TCPP, the inventors found during the experiment that when it is specified that after the phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 65 - 70 kg / min, and it is specified that the propylene oxide is added to the microchannel reactor at a flow rate of 75 - 79 kg / min, and it is specified that the temperature of the reaction between the phosphorus oxychloride and the propylene oxide is 58.5 - 63 °C, the yield of TCPP can be improved and the content of the first isomer in TCPP can be increased. Especially when the phosphorus oxychloride and the catalyst are mixed evenly and added to the microchannel reactor at a flow rate of 68 kg / min, and it is specified that the propylene oxide is added to the microchannel reactor at a flow rate of 77.5 kg / min, and it is specified that the temperature of the reaction between the phosphorus oxychloride and the propylene oxide is 60 °C, the yield of TCPP obtained is greater than 95%, and the content of the first isomer in TCPP is greater than 85%. The possible reason is that when the temperature of the reaction between the phosphorus oxychloride and the propylene oxide is 58.5 - 63 °C, the propylene oxide is more likely to break the carbon-oxygen bond with less steric hindrance at a low temperature, generating more of the first isomer and increasing the yield of TCPP.

[0026] In one embodiment, after the phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 56 - 60 kg / min; the propylene oxide is added to the microchannel reactor at a flow rate of 65 - 70 kg / min.

[0027] In order to make the content of the first isomer in TCPP greater than 84% and improve the flame retardancy of TCPP, the inventors found during the experiment that when it is specified that after the phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 56 - 60 kg / min, and it is specified that the propylene oxide is added to the microchannel reactor at a flow rate of 65 - 70 kg / min, and it is specified that the temperature of the reaction between the phosphorus oxychloride and the propylene oxide is 53 - 58 °C, especially when the temperature of the reaction between the phosphorus oxychloride and the propylene oxide is 55 °C, the content of the first isomer in TCPP can be made greater than 84%, further increasing the content of the first isomer in TCPP and improving the flame retardancy of TCPP.

[0028] In one embodiment, after the phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 50 - 55 kg / min; the propylene oxide is added to the microchannel reactor at a flow rate of 56 - 60 kg / min.

[0029] In one embodiment, the temperature of the reaction is 60 - 65 °C. After the phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 70 - 75 kg / min; the propylene oxide is added to the microchannel reactor at a flow rate of 80 - 87 kg / min.

[0030] In order to increase the content of the first isomer in TCPP and improve the flame retardant effect of TCPP, the inventors found during the experiment that by limiting the flow rate of the phosphorus oxychloride and the catalyst to 70 - 75 kg / min when they are added to the microchannel reactor after being mixed evenly, limiting the flow rate of the propylene oxide to 80 - 87 kg / min when it is added to the microchannel reactor, and limiting the reaction temperature of the phosphorus oxychloride and the propylene oxide to 60 - 65 °C, the content of the first isomer in TCPP can be increased, and the content of the first isomer in TCPP is greater than 80%. The possible reason is that by using a microchannel reactor and controlling the addition rates of the phosphorus oxychloride and the propylene oxide, the problem of local overheating caused by too fast addition rate or uneven mixing can be solved, thereby reducing the content of the first isomer in TCPP.

[0031] In one embodiment, after the phosphorus oxychloride and the catalyst are mixed evenly, they are kept warm at 35 - 45 °C for 10 - 20 min.

[0032] In one embodiment, after the phosphorus oxychloride and the catalyst are mixed evenly, they are kept warm at 35 - 45 °C for 15 min.

[0033] In one embodiment, the temperature for keeping the phosphorus oxychloride and the catalyst warm after being mixed evenly includes but is not limited to 35 °C, 36 °C, 37 °C, 38 °C, 39 °C, 40 °C, 41 °C, 42 °C, 43 °C, 44 °C, 45 °C.

[0034] In one embodiment, the catalyst is AlCl3.

[0035] In one embodiment, the temperature for keeping the phosphorus oxychloride and the catalyst warm after being mixed evenly is 40 °C.

[0036] After the phosphorus oxychloride and AlCl3 are mixed evenly until the AlCl3 is dissolved without solids, they are kept warm at 40 °C.

[0037] In one embodiment, the mass ratio of the catalyst to the phosphorus oxychloride is 1:(350 - 535).

[0038] In one embodiment, the process of transferring the material to an alkali washing kettle for post-treatment to obtain TCPP includes: transferring the material to an alkali washing kettle, adding liquid caustic soda accounting for 30 wt% of the transferred material amount to the alkali washing kettle, heating to 70°C, stirring for 30 min, then separating the layers to remove the aqueous layer to obtain organic phase a, adding soft water accounting for 30 wt% of organic phase a to organic phase a, heating to 70°C, stirring for 30 min, then separating the layers to remove the aqueous layer to obtain organic phase b, adding soft water accounting for 30 wt% of organic phase b to organic phase b, heating to 70°C, stirring for 30 min, then removing the aqueous layer to obtain organic phase c, and dehydrating organic phase c to obtain TCPP.

[0039] In one embodiment, the liquid caustic soda is an aqueous NaOH solution with a mass concentration of 1-5%.

[0040] In one embodiment, the liquid caustic soda is an aqueous NaOH solution with a mass concentration of 2%.

[0041] Beneficial effects

[0042] 1. In this application, by limiting that after phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 49-76 kg / min, limiting that propylene oxide is added to the microchannel reactor at a flow rate of 56-88 kg / min, and limiting the reaction temperature of phosphorus oxychloride and propylene oxide to 49-66°C, the content of the first isomer in TCPP can be increased, so that the content of the first isomer in TCPP is greater than 80%, and the flame retardant effect of TCPP is improved.

[0043] 2. In this application, by limiting that after phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 49-76 kg / min, limiting that propylene oxide is added to the microchannel reactor at a flow rate of 56-88 kg / min, and limiting the reaction temperature of phosphorus oxychloride and propylene oxide to 53-58°C, the content of the first isomer in TCPP can be greater than 84%, further increasing the content of the first isomer in TCPP and improving the flame retardant effect of TCPP.

[0044] 3. In this application, by limiting that after phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 49-76 kg / min, limiting that propylene oxide is added to the microchannel reactor at a flow rate of 56-88 kg / min, and limiting the reaction temperature of phosphorus oxychloride and propylene oxide to 50-52°C, the content of the first isomer in TCPP can be greater than 85%, improving the flame retardant effect of TCPP.

[0045] 4. In this application, after phosphorus oxychloride and the catalyst are uniformly mixed, they are added to the microchannel reactor at a flow rate of 65 - 70 kg / min, and propylene oxide is added to the microchannel reactor at a flow rate of 75 - 79 kg / min. When the reaction temperature of phosphorus oxychloride and propylene oxide is 58.5 - 63 °C, the yield of TCPP can be increased to more than 95%, the content of the first isomer in TCPP can be increased to more than 85%, and the flame retardant effect of TCPP can be improved.

[0046] 5. In this application, by using a microchannel reactor and controlling the feeding rates of phosphorus oxychloride and propylene oxide, the problem of local overheating caused by too fast feeding rate or uneven mixing can be solved, thereby increasing the content of the first isomer in TCPP and the yield of TCPP.

[0047] 6. In this application, after phosphorus oxychloride and the catalyst are uniformly mixed, they are added to the microchannel reactor at a flow rate of 70 - 75 kg / min, and propylene oxide is added to the microchannel reactor at a flow rate of 80 - 87 kg / min. When the reaction temperature of phosphorus oxychloride and propylene oxide is 60 - 65 °C, the content of the first isomer in TCPP can be increased, and the content of the first isomer in TCPP is greater than 80%.

[0048] 7. In this application, after phosphorus oxychloride and the catalyst are uniformly mixed, they are added to the microchannel reactor at a flow rate of 56 - 60 kg / min, and propylene oxide is added to the microchannel reactor at a flow rate of 65 - 70 kg / min. When the reaction temperature of phosphorus oxychloride and propylene oxide is 53 - 58 °C, the content of the first isomer in TCPP can be greater than 84%, further increasing the content of the first isomer in TCPP and improving the flame retardant effect of TCPP. Detailed implementation mode

[0049] Example 1

[0050] This example provides a method for preparing TCPP, which includes the following steps:

[0051] Mix 5500 kg of phosphorus oxychloride and 15 kg of catalyst evenly and add them to a microchannel reactor. Then add 6287 kg of propylene oxide to the microchannel reactor for reaction. After all the feeds are completed, keep the temperature at 50 °C for 15 min and then transfer the material to an alkali washing kettle. Add liquid caustic soda accounting for 30 wt% of the transferred material amount to the alkali washing kettle, heat it to 70 °C, stir for 30 min, and then separate the layers to remove the aqueous layer to obtain organic phase a. Continue to add soft water accounting for 30 wt% of organic phase a to organic phase a, heat it to 70 °C, stir for 30 min, and then separate the layers to remove the aqueous layer to obtain organic phase b. Continue to add soft water accounting for 30 wt% of organic phase b to organic phase b, heat it to 70 °C, stir for 30 min, and then separate the aqueous layer to obtain organic phase c. Dehydrate organic phase c to obtain TCPP.

[0052] The liquid caustic soda is an aqueous NaOH solution with a mass concentration of 2%.

[0053] The reaction temperature for the reaction is 50 °C.

[0054] After the phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 50 kg / min.

[0055] The propylene oxide is added to the microchannel reactor at a flow rate of 57 kg / min.

[0056] The catalyst is AlCl3.

[0057] After the phosphorus oxychloride and the AlCl3 are mixed evenly until the AlCl3 is dissolved without solids, keep the temperature at 40 °C, and the heat preservation time is 15 min.

[0058] The CAS number of the phosphorus oxychloride is 10025-87-3.

[0059] The CAS number of the propylene oxide is 75-56-9.

[0060] The CAS number of the AlCl3 is 7446-70-0.

[0061] Example 2

[0062] This example provides a preparation method of TCPP, including the following steps:

[0063] Mix 5350 kg of phosphorus oxychloride and 10 kg of catalyst evenly and add them into a microchannel reactor. Then add 6116 kg of propylene oxide into the microchannel reactor for reaction. After all the feeding is completed, keep the temperature at 55 °C for 15 min and then transfer the material to an alkali washing kettle. Add liquid caustic soda accounting for 30 wt% of the transferred material amount into the alkali washing kettle, heat it to 70 °C, and stir for 30 min. Then separate the layers to remove the aqueous layer to obtain organic phase a. Continue to add soft water accounting for 30 wt% of organic phase a into organic phase a, heat it to 70 °C, and stir for 30 min. Then separate the layers to remove the aqueous layer to obtain organic phase b. Continue to add soft water accounting for 30 wt% of organic phase b into organic phase b, heat it to 70 °C, and stir for 30 min. Then separate the aqueous layer to obtain organic phase c. Perform dehydration treatment on organic phase c to obtain TCPP.

[0064] The liquid caustic soda is an aqueous NaOH solution with a mass concentration of 2%.

[0065] The reaction temperature for the reaction is 55 °C.

[0066] After the phosphorus oxychloride and the catalyst are mixed evenly, they are added into the microchannel reactor at a flow rate of 60 kg / min.

[0067] The propylene oxide is added into the microchannel reactor at a flow rate of 68.4 kg / min.

[0068] The catalyst is AlCl3.

[0069] After the phosphorus oxychloride and the AlCl3 are mixed evenly until the AlCl3 is completely dissolved without solids, keep the temperature at 40 °C, and the heat preservation time is 15 min.

[0070] The CAS number of the phosphorus oxychloride is 10025 - 87 - 3.

[0071] The CAS number of the propylene oxide is 75 - 56 - 9.

[0072] The CAS number of the AlCl3 is 7446 - 70 - 0.

[0073] Example 3

[0074] This example provides a preparation method of TCPP, including the following steps:

[0075] Mix 6300 kg of phosphorus oxychloride and 18 kg of catalyst evenly, then add them into a microchannel reactor. Add 7202 kg of propylene oxide into the microchannel reactor for reaction. After all the feeding is completed, keep the temperature at 60 °C for 15 min, then transfer the material to an alkali washing kettle. Add liquid caustic soda accounting for 30 wt% of the transferred material amount into the alkali washing kettle, heat it to 70 °C, and stir for 30 min. Then separate the layers to remove the water layer to obtain organic phase a. Continue to add soft water accounting for 30 wt% of organic phase a into organic phase a, heat it to 70 °C, and stir for 30 min. Then separate the layers to remove the water layer to obtain organic phase b. Continue to add soft water accounting for 30 wt% of organic phase b into organic phase b, heat it to 70 °C, and stir for 30 min. Then remove the water layer to obtain organic phase c. Perform dehydration treatment on organic phase c to obtain TCPP.

[0076] The liquid caustic soda is an aqueous NaOH solution with a mass concentration of 2%.

[0077] The reaction temperature for the reaction is 60 °C.

[0078] After the phosphorus oxychloride and the catalyst are mixed evenly, they are added into the microchannel reactor at a flow rate of 68 kg / min.

[0079] The propylene oxide is added into the microchannel reactor at a flow rate of 77.5 kg / min.

[0080] The catalyst is AlCl3.

[0081] After the phosphorus oxychloride and the AlCl3 are mixed evenly until the AlCl3 is completely dissolved without solids, keep the temperature at 40 °C, and the heat preservation time is 15 min.

[0082] The CAS number of the phosphorus oxychloride is 10025-87-3.

[0083] The CAS number of the propylene oxide is 75-56-9.

[0084] The CAS number of the AlCl3 is 7446-70-0.

[0085] Example 4

[0086] This example provides a preparation method of TCPP, including the following steps:

[0087] Mix 5780 kg of phosphorus oxychloride and 14 kg of catalyst evenly, then add them to a microchannel reactor. Add 6605 kg of propylene oxide to the microchannel reactor for reaction. After all the feeds are completed, keep the temperature at 65 °C for 15 min, then transfer the material to an alkali washing kettle. Add liquid caustic soda accounting for 30 wt% of the transferred material amount to the alkali washing kettle, heat it to 70 °C, and stir for 30 min. Then separate the layers to remove the aqueous layer to obtain organic phase a. Continue to add soft water accounting for 30 wt% of organic phase a to organic phase a, heat it to 70 °C, and stir for 30 min. Then separate the layers to remove the aqueous layer to obtain organic phase b. Continue to add soft water accounting for 30 wt% of organic phase b to organic phase b, heat it to 70 °C, and stir for 30 min. Then remove the aqueous layer to obtain organic phase c. Perform dehydration treatment on organic phase c to obtain TCPP.

[0088] The liquid caustic soda is an aqueous NaOH solution with a mass concentration of 2%.

[0089] The reaction temperature for the reaction is 65 °C.

[0090] After the phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 75 kg / min.

[0091] The propylene oxide is added to the microchannel reactor at a flow rate of 87 kg / min.

[0092] The catalyst is AlCl3.

[0093] After the phosphorus oxychloride and the AlCl3 are mixed evenly until the AlCl3 is completely dissolved without solids, keep the temperature at 40 °C, and the holding time is 15 min.

[0094] The CAS number of the phosphorus oxychloride is 10025-87-3.

[0095] The CAS number of the propylene oxide is 75-56-9.

[0096] The CAS number of the AlCl3 is 7446-70-0.

[0097] Example 5

[0098] This example provides a method for preparing TCPP, including the following steps:

[0099] Mix 5140 kg of phosphorus oxychloride and 12 kg of catalyst evenly, then add them into a microchannel reactor. Next, add 5873 kg of propylene oxide into the microchannel reactor for reaction. After all the feeding is completed, keep the temperature at 72 °C for 15 min, and then transfer the material to an alkali washing kettle. Add liquid caustic soda accounting for 30 wt% of the transferred material amount into the alkali washing kettle, heat it to 70 °C, stir for 30 min, and then separate the layers to remove the water layer to obtain organic phase a. Continue to add soft water accounting for 30 wt% of organic phase a into organic phase a, heat it to 70 °C, stir for 30 min, and then separate the layers to remove the water layer to obtain organic phase b. Continue to add soft water accounting for 30 wt% of organic phase b into organic phase b, heat it to 70 °C, stir for 30 min, and then remove the water layer to obtain organic phase c. Dehydrate organic phase c to obtain TCPP.

[0100] The liquid caustic soda is an aqueous NaOH solution with a mass concentration of 2%.

[0101] The reaction temperature for the reaction is 72 °C.

[0102] After the phosphorus oxychloride and the catalyst are mixed evenly, they are added into the microchannel reactor at a flow rate of 86 kg / min.

[0103] The propylene oxide is added into the microchannel reactor at a flow rate of 99.76 kg / min.

[0104] The catalyst is AlCl3.

[0105] After the phosphorus oxychloride and the AlCl3 are mixed evenly until the AlCl3 is completely dissolved without solids, keep the temperature at 40 °C, and the heat preservation time is 15 min.

[0106] The CAS number of the phosphorus oxychloride is 10025 - 87 - 3.

[0107] The CAS number of the propylene oxide is 75 - 56 - 9.

[0108] The CAS number of the AlCl3 is 7446 - 70 - 0.

[0109] Example 6

[0110] This example provides a preparation method of TCPP, including the following steps:

[0111] Mix 5540 kg of phosphorus oxychloride and 13 kg of catalyst evenly and add them into a microchannel reactor. Then add 6330 kg of propylene oxide into the microchannel reactor for reaction. After all the feeding is completed, keep the temperature at 80 °C for 15 min and then transfer the material to an alkali washing kettle. Add liquid caustic soda accounting for 30 wt% of the transferred material amount to the alkali washing kettle, heat it to 70 °C, stir for 30 min, then separate the layers to remove the aqueous layer to obtain organic phase a. Continue to add soft water accounting for 30 wt% of organic phase a to organic phase a, heat it to 70 °C, stir for 30 min, then separate the layers to remove the aqueous layer to obtain organic phase b. Continue to add soft water accounting for 30 wt% of organic phase b to organic phase b, heat it to 70 °C, stir for 30 min, then separate the aqueous layer to obtain organic phase c. Perform dehydration treatment on organic phase c to obtain TCPP.

[0112] The liquid caustic soda is an aqueous NaOH solution with a mass concentration of 2%.

[0113] The reaction temperature for the reaction is 80 °C.

[0114] After the phosphorus oxychloride and the catalyst are mixed evenly, they are added into the microchannel reactor at a flow rate of 94 kg / min.

[0115] The propylene oxide is added into the microchannel reactor at a flow rate of 109 kg / min.

[0116] The catalyst is AlCl3.

[0117] After the phosphorus oxychloride and the AlCl3 are mixed evenly until the AlCl3 is dissolved without solids, keep the temperature at 40 °C, and the holding time is 15 min.

[0118] The CAS number of the phosphorus oxychloride is 10025 - 87 - 3.

[0119] The CAS number of the propylene oxide is 75 - 56 - 9.

[0120] The CAS number of the AlCl3 is 7446 - 70 - 0.

[0121] Performance test

[0122] 1. Yield test:

[0123] Obtain TCPP according to the preparation method of TCPP provided in Examples 1 - 6, calculate the yield of TCPP, and the results are shown in Table 1.

[0124] Yield calculation method: Yield = mass of product TCPP / (mass of phosphorus oxychloride / 153.3 * 327.6) * 100%.

[0125] 2. Content test of isomers in TCPP:

[0126] The contents of the first isomer, the second isomer, the third isomer, and the fourth isomer in the TCPP provided in Test Examples 1-6 were tested, and the test results are shown in Table 1.

[0127] Test method: Use a gas chromatograph to analyze different isomer components in TCPP, and the gas chromatograph is equipped with a flame ionization detector.

[0128] The chromatographic column model used in the gas chromatograph is Agilent HP-5 or a comparable chromatographic column, with a length of 30 m, an inner diameter of 0.32 mm, and a film thickness of 0.25 μm.

[0129] The injection volume of the micro-syringe used in the gas chromatograph is 10 μL.

[0130] The operating conditions of the gas chromatography include: the column oven temperature is 40 °C; the column injector temperature is 220 °C; the detector temperature is 280 °C; the temperature programming conditions for sample testing include: the initial temperature is set at 40 °C, held at 40 °C for 3 minutes, then heated at a rate of 20 °C per minute to 280 °C, and held at 280 °C for 8 minutes.

[0131] The contents of the isomers in the TCPP provided in Examples 1-6 were tested using the above test method. The process of testing the contents of the isomers in the TCPP provided in Examples 1-2 using a gas chromatograph is shown in Table 2; the process of testing the contents of the isomers in the TCPP provided in Examples 3-4 using a gas chromatograph is shown in Table 3; the process of testing the contents of the isomers in the TCPP provided in Examples 5-4 using a gas chromatograph is shown in Table 3.

[0132] Table 1

[0133]

[0134] As can be seen from the test results in Table 1, in the TCPP preparation methods provided in Examples 1-4, it is specified that after phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 49-76 kg / min, propylene oxide is added to the microchannel reactor at a flow rate of 56-88 kg / min, and the reaction temperature of phosphorus oxychloride and propylene oxide is 49-66 °C, which can increase the content of the first isomer in TCPP, making the content of the first isomer in TCPP greater than 80%, and improving the flame retardancy effect of TCPP. At the same time, by specifying that after phosphorus oxychloride and the catalyst are mixed evenly, they are added to the microchannel reactor at a flow rate of 65-70 kg / min, propylene oxide is added to the microchannel reactor at a flow rate of 75-79 kg / min, and the reaction temperature of phosphorus oxychloride and propylene oxide is 58.5-63 °C, the yield of TCPP can be increased to more than 95%, and the content of the first isomer in TCPP can be increased to more than 85%, improving the flame retardancy effect of TCPP.

[0135] As can be seen from the test results in Table 1, in Example 5, phosphorus oxychloride and the catalyst were mixed evenly and added to the microchannel reactor at a flow rate of 86 kg / min, propylene oxide was added to the microchannel reactor at a flow rate of 99.76 kg / min, and the reaction temperature of phosphorus oxychloride and propylene oxide was 72 °C; although the yield of TCPP prepared in Example 5 was 95.5%, the content of the first isomer decreased to 79.617%, reducing the flame retardancy effect of TCPP; in Example 6, phosphorus oxychloride and the catalyst were mixed evenly and added to the microchannel reactor at a flow rate of 94 kg / min, propylene oxide was added to the microchannel reactor at a flow rate of 109 kg / min, and the reaction temperature of phosphorus oxychloride and propylene oxide was 80 °C; although the yield of TCPP prepared in Example 6 was 96.1%, the content of the first isomer decreased to 70.048%, reducing the flame retardancy effect of TCPP.

[0136] Table 2

[0137]

[0138]

[0139] The elution order of the first isomer, the second isomer, the third isomer, and the fourth isomer in TCPP is sequential elution. The first isomer and the second isomer will elute sequentially within the range of 25 - 26 min; the third isomer and the fourth isomer will elute sequentially within the range of 26 - 27 min. As can be seen from Table 2, the content of the first isomer in TCPP provided in Example 1 is 85.015%, the content of the second isomer is 13.528%, the content of the third isomer is 1.266%, and the content of the fourth isomer is 0.038%. The content of the first isomer in TCPP provided in Example 2 is 84.75%, the content of the second isomer is 13.748%, the content of the third isomer is 1.302%, and the content of the fourth isomer is 0.039%.

[0140] Table 3

[0141]

[0142] As can be seen from Table 2, the content of the first isomer in TCPP provided in Example 3 is 85.857%, the content of the second isomer is 12.668%, the content of the third isomer is 1.278%, and the content of the fourth isomer is 0.038%. The content of the first isomer in TCPP provided in Example 4 is 81.857%, the content of the second isomer is 16.668%, the content of the third isomer is 1.278%, and the content of the fourth isomer is 0.038%.

[0143] Table 4

[0144]

[0145] As can be seen from Table 2, the content of the first isomer in TCPP provided in Example 5 is 79.617%, the content of the second isomer is 18.491%, the content of the third isomer is 1.713%, and the content of the fourth isomer is 0.062%. The content of the first isomer in TCPP provided in Example 6 is 70.048%, the content of the second isomer is 25.891%, the content of the third isomer is 3.606%, and the content of the fourth isomer is 0.175%.

Claims

1. A preparation method of TCPP, characterized in that, It includes the following steps: Phosphorus oxychloride and a catalyst are mixed evenly and then added into a microchannel reactor, and propylene oxide is added into the microchannel reactor for reaction, heat preservation, and transferred to an alkali washing kettle for post-treatment to obtain TCPP; the temperature of the reaction is controlled at 49-66°C; After the phosphorus oxychloride and the catalyst are mixed evenly, they are added into the microchannel reactor at a flow rate of 49-76 kg / min; The propylene oxide is added into the microchannel reactor at a flow rate of 56-88 kg / min.

2. The preparation method of TCPP according to claim 1, wherein, The temperature of the reaction is 53-58°C.

3. The preparation method of TCPP according to claim 1, wherein, The temperature of the reaction is 50-52°C.

4. The preparation method of TCPP according to claim 1, wherein The temperature of the reaction is 58.5-63°C.

5. The preparation method of TCPP according to claim 1, characterized in that, The temperature of the reaction is 58.5-63°C. After the phosphorus oxychloride and the catalyst are mixed evenly, they are added into the microchannel reactor at a flow rate of 65-70 kg / min; the propylene oxide is added into the microchannel reactor at a flow rate of 75-79 kg / min.

6. The preparation method of TCPP according to claim 2, wherein, After the phosphorus oxychloride and the catalyst are mixed evenly, they are added into the microchannel reactor at a flow rate of 56-60 kg / min; the propylene oxide is added into the microchannel reactor at a flow rate of 65-70 kg / min.

7. The preparation method of TCPP according to claim 3, wherein, After the phosphorus oxychloride and the catalyst are mixed evenly, they are added into the microchannel reactor at a flow rate of 50-55 kg / min; the propylene oxide is added into the microchannel reactor at a flow rate of 56-60 kg / min.

8. The preparation method of TCPP according to claim 1, wherein The temperature of the reaction is 60-65°C. After the phosphorus oxychloride and the catalyst are mixed evenly, they are added into the microchannel reactor at a flow rate of 70-75 kg / min; the propylene oxide is added into the microchannel reactor at a flow rate of 80-87 kg / min.

9. The preparation method of TCPP according to claim 1, characterized in that, After the phosphorus oxychloride and the catalyst are mixed evenly, they are kept warm at 35-45°C.

10. The preparation method of TCPP according to claim 1, wherein, The mass ratio of the catalyst to the phosphorus oxychloride is 1:(350-535).

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