CN117736427A - Preparation method of hydroxyl-terminated polyepichlorohydrin - Google Patents

Abstract

The invention provides a preparation method of hydroxyl-terminated polyepichlorohydrin, which comprises the following steps: mixing a first material comprising a solvent, an initiator and a catalyst at the temperature of between 0 and 40 ℃ to obtain a second material, mixing the second material and epoxy chloropropane in a mixing module of the microchannel continuous flow reactor to obtain a third material, feeding the third material into a reaction module of the microchannel continuous flow reactor to react, and then feeding the third material into a quenching module of the microchannel continuous flow reactor to perform quenching treatment to obtain the hydroxyl-terminated poly (epoxy chloropropane); the reaction module comprises n micro-channel continuous flow reaction units. The preparation method can prepare the hydroxyl-terminated polyepichlorohydrin with controllable molecular weight, narrow distribution and higher yield, is favorable for preparing high-quality chlorohydrin rubber, and more importantly, can solve the problem of large fluctuation of product quality in the traditional kettle type preparation batch and amplification and conversion processes.

Description

Preparation method of hydroxyl-terminated polyepichlorohydrin

Technical Field

The invention relates to the field of fine chemical synthesis, in particular to a preparation method of hydroxyl-terminated polyepichlorohydrin.

Background

The hydroxyl-terminated polyepichlorohydrin (hydroxyl terminated polyepichlorohydrin, PECH) is obtained by cationic ring-opening polymerization of Epichlorohydrin (ECH), is a main raw material for synthesizing an azide adhesive-poly azide glycidyl ether (GAP), and is a precondition for preparing high-performance azide energetic adhesives.

It is believed that during cationic ring opening polymerization, two reaction mechanisms are prevalent, one being the living monomer mechanism (activated monomermechanism-AM mechanism) and the living chain end mechanism (activated chain end mechanism-ACE mechanism). Because the nucleophilic property of oxygen atoms in the epoxy chloropropane is weaker than that of oxygen atoms on polyether chains, the capability of the oxygen atoms on polymer chains to attack chain end active centers is larger than that of monomers, reverse biting (back-biting) in molecules is easy to occur, and a cyclic Oligomer (OCE) is generated, wherein the functionality of the cyclic oligomer is 0, and the cyclic oligomer is not easy to separate from a system, so that the mechanical property of a hydroxyl-terminated polyepichlorohydrin application product can be influenced; in contrast, the AM mechanism does not have an active chain end, so that the formation of a cyclic oligomer is impossible, and thus, the reaction conditions are controlled so that the formation of zero-functionality OCE can be reduced by proceeding according to the AM mechanism. However, if it is desired to prepare hydroxyl-terminated polyepichlorohydrins having a relatively high molecular weight, it generally takes longer holding time, OCE tends to increase with increasing molecular weight of the polymer, and the relative molecular mass distribution of the polymer is markedly broadened and the by-product content is markedly increased with increasing relative molecular mass of the polymer.

Disclosure of Invention

The invention provides a preparation method of hydroxyl-terminated polyepichlorohydrin, which has strong controllability and can prepare the polyethylene glycol with the number average molecular weight of 2200-3800 g.mol ^-1 In the range, the molecular weight distribution is narrower, and the yield is higher.

The invention provides a preparation method of hydroxyl-terminated polyepichlorohydrin, which comprises the following steps:

mixing a first material comprising a solvent, an initiator and a catalyst at the temperature of between 0 and 40 ℃ to obtain a second material, mixing the second material with epoxy chloropropane in a mixing module of the microchannel continuous flow reactor to obtain a third material, feeding the third material in a reaction module of the microchannel continuous flow reactor to react, and then feeding the third material in a quenching module of the microchannel continuous flow reactor to perform quenching treatment to obtain the hydroxyl-terminated poly (epoxy chloropropane);

the reaction module comprises n micro-channel continuous flow reaction units, wherein n is more than or equal to 1 and less than or equal to 20.

Further, the temperature of the reaction module is between-20 and 90 ℃, and the temperature of the quenching module is between 0 and 40 ℃.

Further, the initiator is a dihydric alcohol or a polyhydric alcohol; preferably, the dihydric alcohol is one or more of ethylene glycol, propylene glycol and butanediol; the polyalcohol is one or more of glycerol, sorbitol, trimethylolpropane, pentaerythritol and inositol.

Further, the catalyst is one or more of boron trifluoride diethyl etherate, stannic chloride, trifluoroacetic acid, trichloroacetic acid and dichloroacetic acid.

Further, n is more than or equal to 5 and less than or equal to 10.

Further, the solvent is a haloalkane.

Still further, the haloalkane is one or more of dichloromethane, dichloroethane, and carbon tetrachloride.

Further, the mass ratio of the solvent to the epichlorohydrin is 0.1-5;

the mass ratio of the initiator to the epichlorohydrin is 0.001-0.1, and the mass ratio of the catalyst to the epichlorohydrin is 0.001-0.1.

Further, the mass ratio of the solvent to the epichlorohydrin is 0.25-1;

the mass ratio of the initiator to the epichlorohydrin is 0.01-0.05, and the mass ratio of the catalyst to the epichlorohydrin is 0.01-0.06.

Further, the second material and/or epichlorohydrin enters the mixing module of the micro-channel continuous flow reactor at the flow rate of 10-30 mL/min.

The preparation method provided by the invention can prepare the hydroxyl-terminated polyepichlorohydrin with controllable molecular weight, narrow distribution and higher yield, and the hydroxyl-terminated polyepichlorohydrin is favorable for preparing high-quality chlorohydrin rubber and has excellent batch repeatability.

Drawings

Fig. 1 is a flow chart of a process for preparing hydroxyl-terminated polyepichlorohydrin according to an embodiment of the invention.

Detailed Description

The present invention will be described in further detail below for the purpose of better understanding of the aspects of the present invention by those skilled in the art. The following detailed description is merely illustrative of the principles and features of the present invention, and examples are set forth for the purpose of illustration only and are not intended to limit the scope of the invention. All other embodiments, which can be made by those skilled in the art based on the examples of the invention without making any inventive effort, are intended to be within the scope of the invention.

The invention provides a preparation method of hydroxyl-terminated polyepichlorohydrin, which comprises the following steps:

mixing a first material comprising a solvent, an initiator and a catalyst at the temperature of between 0 and 40 ℃ to obtain a second material, mixing the second material with epoxy chloropropane in a mixing module of the microchannel continuous flow reactor to obtain a third material, feeding the third material in a reaction module of the microchannel continuous flow reactor to react, and then feeding the third material in a quenching module of the microchannel continuous flow reactor to perform quenching treatment to obtain the hydroxyl-terminated poly (epoxy chloropropane);

the reaction module comprises n micro-channel continuous flow reaction units, wherein n is more than or equal to 1 and less than or equal to 20.

The preparation method of the invention is a new method for preparing hydroxyl-terminated polyepichlorohydrin by utilizing a micro-channel continuous flow reactor, and compared with the traditional process, the preparation method of the invention has narrower molecular weight distribution and high yield of the hydroxyl-terminated polyepichlorohydrin, and the reason is that: on one hand, a large amount of heat can be released in the process of preparing hydroxyl-terminated polyepichlorohydrin, the traditional kettle type transfer production must be evaluated through reaction heat, the risk exists in process control, the reaction controllability is poor, the molecular weight distribution of the product is affected, and the microchannel continuous flow reactor used in the invention has the characteristic of thousands times heat exchange, is safer and more controllable, and the reaction speed is always kept in a controllable range; on the other hand, the cationic polymerization is characterized in that the higher the concentration of active species is, the smaller the concentration of monomers is, the more favorable for AM polymerization mechanism is, in the whole process of traditional kettle type preparation, the concentration of active species relative to monomers is dynamically changed from large to small, the micro-channel is a 'plug flow, no mixing back', the proportion of monomers, initiator and catalyst is in a 'relatively constant' state all the time, so that the quality of the product batch obtained by polymerization is more stable, the molecular weight distribution is narrower, the functionality and the yield of target products are also higher; in still another aspect, for obtaining a higher molecular weight of the polyepichlorohydrin, the period of the preparation is generally 6-24 hours, but the preparation method of the invention can shorten the period to less than 1 hour (for example, less than 10 minutes), thereby not only reducing the production cost, but also maintaining the molecular weight of the polyepichlorohydrin at a higher level, the hydroxyl end groups are mutually occluded, the overall functionality is reduced, and the appearance of the product is more colorless and transparent.

The present invention is not particularly limited to the catalytic microchannel continuous flow reactor used in the reaction, and the channel diameter of the general microchannel continuous flow reactor is in the order of micrometers and millimeters, which can be selected by the technicians conventionally, but in order to further improve the mass transfer and heat transfer efficiency of the microchannel continuous flow reactor and more precisely control the raw material ratio and the reaction time, the microchannel continuous flow reactor with the microchannel diameter of 1-10 mm is preferable.

It can be understood that nitrogen purging should be used before the above-mentioned mixing reaction, and then the reaction is carried out after oxygen in the reaction vessel is removed; the micro-channel continuous flow reactor used in the invention comprises a mixing module, a reaction module and a quenching module which are sequentially connected in series; wherein, the mixing module is used for mixing the raw materials, the module does not need to be heated, and the temperature of the module is kept at room temperature (for example, in the range of 20-30 ℃); the reaction module is used for reacting the mixed raw materials, and the temperature of the module at least ensures that the polymerization reaction can be carried out; a quenching module is used to terminate the polymerization of the material, and therefore, the module requires the addition of a suitable quenching agent, illustratively, the quenching module includes a quenching agent inlet.

In addition, although the mixing module is mainly used for mixing, a certain polymerization reaction occurs in the process and heat is generated, but the reaction degree of the mixing module is lower than that of the reaction module.

In a preferred embodiment, the preheating treatment is performed in a preheating unit for preheating the first material to react the initiator and the catalyst to obtain active species C ⁺ Then mixing the mixture with the monomer, and then entering a reaction module to carry out ring-opening polymerization on the monomer one by one.

Illustratively, a metering pump may also be connected prior to the pre-heating unit to accurately meter the amount of feedstock into the microchannel continuous flow reactor.

In a preferred embodiment, the temperature of the reaction module is-20 to 90 ℃ and the temperature of the quenching module is 0 to 40 ℃.

The lower the temperature of the reaction module, the slower the reaction, especially below-20-0 ℃, the larger the molecular weight of the prepared hydroxyl-terminated polyepichlorohydrin, the lighter the color, the more colorless the reaction module, the faster the reaction, when the temperature of the reaction module exceeds 40 ℃, the molecular weight starts to gradually decrease, the color of the product deepens, and the temperature of the reaction module is more preferably in the range of 20-30 ℃ in combination with factors of production cycle, cost and process control.

In a preferred embodiment, the initiator is a diol or polyol.

In a more preferred embodiment, the glycol is one or more of ethylene glycol, propylene glycol, and butylene glycol; the polyalcohol is one or more of glycerol, sorbitol, trimethylolpropane, pentaerythritol and inositol.

The catalyst used in the reaction is not particularly limited in principle, and a conventional catalyst capable of normally catalyzing the ring-opening polymerization of epichlorohydrin may be selected by the skilled person, but in order to make the reaction more controllable, the probability of side reaction is lower, and preferably, the catalyst is one or more of boron trifluoride diethyl ether, stannic chloride, trifluoroacetic acid, trichloroacetic acid and dichloroacetic acid, more preferably boron trifluoride diethyl ether.

In a preferred embodiment, 5.ltoreq.n.ltoreq.10. The number of the micro-channel continuous flow reaction units is in the range, so that the reaction is thorough and the cost is considered.

In a preferred embodiment, the solvent is a haloalkane.

It will be appreciated that the above haloalkanes may be conveniently selected from any haloalkane which is capable of dissolving epichlorohydrin monomers, such as dichloromethane, dichloroethane, carbon tetrachloride, etc., but in order to obtain the more narrowly molecular weight distribution of the hydroxyl terminated polyepichlorohydrin, the haloalkane is preferably dichloroethane.

The amount of the catalyst used in the present invention is not particularly limited in principle, but in order to allow the catalytic reaction to proceed smoothly, the polymerization rate is more suitable, and the mass ratio of the catalyst to epichlorohydrin is preferably 0.001 to 0.1; more preferably 0.01 to 0.06.

The amount of the solvent used in the present invention is not particularly limited in principle, but in order to make the reaction rate more suitable, the mass ratio of the solvent to epichlorohydrin is preferably 0.1 to 5; more preferably 0.25 to 1.

The amount of the solvent used in the present invention is not particularly limited in principle, but in order to make the reaction rate more narrow in the molecular weight distribution, the mass ratio of the initiator to epichlorohydrin is preferably 0.001 to 0.1, more preferably 0.01 to 0.05.

In a preferred embodiment, the second material and/or epichlorohydrin enters the mixing module of the microchannel continuous flow reactor at a flow rate of 10 to 30 mL/min. It can be understood that the invention mainly controls the ratio of the second material and the epichlorohydrin by the velocity relation of the second material and the epichlorohydrin, and when the flow velocity of the second material and the epichlorohydrin is in the range of 10-30 mL/min, the reaction velocity is more suitable, and the molecular weight distribution of the hydroxyl-terminated polyepichlorohydrin is narrower.

Illustratively, a metering pump may also be connected prior to the mixing module to precisely meter the amount of feedstock into the microchannel continuous flow reactor.

Furthermore, since the quenching module requires the addition of a suitable quenching agent for ending the polymerization reaction, the kind of the quenching agent is not particularly limited in principle, for example, deionized water or the like, nor is the rate of introduction of the quenching agent, and generally the ratio by volume of the reactant stream and the quenching agent is about 1:1.

fig. 1 is a flow chart of a process for preparing hydroxyl-terminated polyepichlorohydrin according to an embodiment of the invention, as shown in fig. 1, the apparatus for preparing hydroxyl-terminated polyepichlorohydrin in the embodiment comprises a preheating unit 001, a micro-channel continuous flow reactor and a epichlorohydrin (monomer) storage unit 002, wherein the preheating unit 001 comprises a three-neck flask, a serpentine return pipe and a magnetic stirrer; the micro-channel continuous flow reactor consists of three sub-modules which are sequentially connected in series, namely a mixing module 0031, a reaction module 0032 and a quenching module 0033, wherein the reaction module 002 consists of 5 micro-channel continuous flow reaction units which are connected in series, and an inlet of the mixing module 0021 is respectively communicated with a preheating unit 001 and an epichlorohydrin storage unit 002 through a first metering pump 004 and a second metering pump 005. When the preparation device is used for preparing hydroxyl-terminated polyepichlorohydrin, firstly, a solvent, an initiator and a catalyst are mixed and reacted in a preheating unit 001 to obtain a second material, then the second material is pumped into a mixing module 0031 through a first metering pump 004, meanwhile, epichlorohydrin is pumped into the mixing module 0031 through a second metering pump 005 from a storage unit 002, the mixed material sequentially passes through 5 micro-channel continuous flow reaction units of a reaction module 0032 and finally enters a quenching module 0033, meanwhile, a quenching agent is pumped into the quenching module 0033 through a third metering pump 006, the reaction is stopped, and the product is subjected to post-purification treatment to obtain the hydroxyl-terminated polyepichlorohydrin.

The invention is further illustrated below with reference to specific examples, wherein the starting materials used may be prepared by commercially available or conventional methods, and experimental methods without specifying the specific conditions are well known in the art and conventional conditions, unless otherwise specified.

Example 1

The present example provides a hydroxyl-terminated polyepichlorohydrin and a preparation method thereof, and the preparation is carried out by adopting a preparation device consistent with fig. 1, specifically comprising the following steps:

adding 10g of ethylene glycol and 200g of dichloroethane into a reaction flask, introducing nitrogen for 15min, adding a catalyst boron trifluoride diethyl ether for 15.7g, stirring at 25 ℃ for 30min, then entering a mixing module at a flow rate of 10mL/min through a first metering pump, simultaneously, entering a mixing module at a flow rate of 9.5mL/min through a second metering pump, setting the temperature of the reaction module to be 30 ℃, mixing materials for reaction when passing through each micro-channel continuous flow reaction unit, entering a quenching module after 3min, entering a quenching agent water into the quenching module at a flow rate of 19.5mL/min through a third metering pump, quenching at 20 ℃, and carrying out aftertreatment on the reactants after quenching to obtain a colorless transparent liquid product of hydroxyl-terminated poly (epichlorohydrin).

Example 2

The present example provides a hydroxyl-terminated polyepichlorohydrin and a preparation method thereof, and the preparation is carried out by adopting a preparation device consistent with fig. 1, specifically comprising the following steps:

adding 10g of ethylene glycol and 200g of methylene dichloride into a reaction flask, introducing nitrogen for 15min, adding a catalyst boron trifluoride diethyl ether for 15.7g, stirring at 25 ℃ for 30min, then entering a mixing module at a flow rate of 10mL/min through a first metering pump, simultaneously entering a mixing module at a flow rate of 9.5mL/min through a second metering pump, setting the temperature of the reaction module to be-20 ℃, mixing materials for reaction when passing through each micro-channel continuous flow reaction unit, entering a quenching module after 3min, entering quenching agent water into the quenching module at a flow rate of 19.5mL/min through a third metering pump, quenching at 10 ℃, and carrying out aftertreatment on the reactants after quenching to obtain a pale yellow transparent liquid product hydroxyl-terminated poly (epoxy chloropropane).

Example 3

The present example provides a hydroxyl-terminated polyepichlorohydrin and a preparation method thereof, and the preparation is carried out by adopting a preparation device consistent with fig. 1, specifically comprising the following steps:

adding 10g of ethylene glycol and 200g of methylene dichloride into a reaction flask, introducing nitrogen for 15min, adding a catalyst boron trifluoride diethyl ether for 15.7g, stirring at 25 ℃ for 30min, then entering a mixing module at a flow rate of 10mL/min through a first metering pump, simultaneously, entering a mixing module at a flow rate of 9.5mL/min through a second metering pump, setting the temperature of the reaction module to be 0 ℃, mixing materials for reaction when passing through each micro-channel continuous flow reaction unit, entering a quenching module after 3min, entering quenching agent water into the quenching module at a flow rate of 19.5mL/min through a third metering pump, quenching at 0 ℃, and carrying out aftertreatment on the reactants after quenching to obtain a yellow transparent liquid product of hydroxyl-terminated poly (epichlorohydrin).

Example 4

The present example provides a hydroxyl-terminated polyepichlorohydrin and a preparation method thereof, and the preparation is carried out by adopting a preparation device consistent with fig. 1, specifically comprising the following steps:

adding 6.87g of ethylene glycol and 200g of dichloroethane into a reaction flask, introducing nitrogen for 15min, adding 15.7g of boron trifluoride diethyl ether serving as a catalyst, stirring at 25 ℃ for 30min, allowing the mixture to enter a mixing module at a flow rate of 10mL/min by a first metering pump, allowing monomer epichlorohydrin to enter the mixing module at a flow rate of 9.5mL/min by a second metering pump, allowing the reaction module to set the temperature to be 60 ℃, allowing materials to undergo mixed reaction when passing through each microchannel continuous flow reaction unit, allowing the materials to enter a quenching module after 3min, allowing the water serving as a quenching agent to enter the quenching module at a flow rate of 19.5mL/min by a third metering pump, quenching at 30 ℃, and performing aftertreatment on the reactants after quenching to obtain a pale yellow transparent liquid hydroxyl-terminated polyepichlorohydrin product.

Example 5

The present example provides a hydroxyl-terminated polyepichlorohydrin and a preparation method thereof, and the preparation is carried out by adopting a preparation device consistent with fig. 1, specifically comprising the following steps:

adding 6.87g of glycerol and 200g of dichloroethane into a reaction flask, introducing nitrogen for 15min, adding 15.7g of boron trifluoride diethyl ether serving as a catalyst, stirring at 25 ℃ for reaction for 30min, then entering a mixing module at a flow rate of 10mL/min through a first metering pump, simultaneously, entering a mixing module at a flow rate of 9.5mL/min through a second metering pump, setting the temperature of the reaction module to 90 ℃, mixing and reacting materials when the materials pass through each micro-channel continuous flow reaction unit, entering a quenching module after 3min, entering quenching agent water into the quenching module at a flow rate of 19.5mL/min through a third metering pump, quenching at 40 ℃, and performing aftertreatment on the quenched reactants to obtain a pale yellow transparent liquid hydroxyl-terminated polyepichlorohydrin product.

Example 6

The present example provides a hydroxyl-terminated polyepichlorohydrin and a preparation method thereof, and the preparation is carried out by adopting a preparation device consistent with fig. 1, specifically comprising the following steps:

adding 6.87g of glycerol and 200g of dichloroethane into a reaction flask, introducing nitrogen for 15min, adding 15.7g of boron trifluoride diethyl ether serving as a catalyst, stirring at 25 ℃ for reaction for 30min, then entering a mixing module at a flow rate of 15mL/min through a first metering pump, simultaneously, entering a mixing module at a flow rate of 14.25mL/min through a second metering pump, setting the temperature of the reaction module to be 30 ℃, mixing materials for reaction when passing through each microchannel continuous flow reaction unit, entering a quenching module after 2min, entering quenching agent water into the quenching module at a flow rate of 29.25mL/min through a third metering pump, quenching the reactants, and then carrying out aftertreatment to obtain a pale yellow transparent liquid hydroxyl-terminated polyepichlorohydrin product.

Example 7

The present example provides a hydroxyl-terminated polyepichlorohydrin and a preparation method thereof, and the preparation is carried out by adopting a preparation device consistent with fig. 1, specifically comprising the following steps:

adding 6.87g of glycerol and 200g of dichloroethane into a reaction flask, introducing nitrogen for 15min, adding 15.7g of boron trifluoride diethyl ether serving as a catalyst, stirring at 25 ℃ for reaction for 30min, then entering a mixing module at a flow rate of 20mL/min through a first metering pump, simultaneously entering a mixing module at a flow rate of 19mL/min through a second metering pump, setting the temperature of the reaction module to be 30 ℃, mixing materials for reaction when the materials pass through each microchannel continuous flow reaction unit, entering a quenching module after 1.5min, entering quenching agent water into the quenching module at a flow rate of 39mL/min through a third metering pump, quenching at 40 ℃, and carrying out aftertreatment on the quenched reactants to obtain the light yellow transparent liquid product hydroxyl-terminated poly (epoxy chloropropane).

Comparative example 1

The present example provides a hydroxyl-terminated polyepichlorohydrin and a preparation method thereof, and the preparation is carried out by adopting a preparation device consistent with fig. 1, specifically comprising the following steps:

adding 6.87g of glycerol and 200g of dichloroethane into a reaction flask, introducing nitrogen for 15min, adding 15.7g of boron trifluoride diethyl ether serving as a catalyst, stirring at 25 ℃ for reaction for 30min, then entering a mixing module at a flow rate of 10mL/min through a first metering pump, simultaneously, entering a mixing module at a flow rate of 9.5mL/min through a second metering pump, setting the temperature of the reaction module to be 100 ℃, mixing materials for reaction when passing through each microchannel continuous flow reaction unit, entering a quenching module after 3min, entering quenching agent water into the quenching module at a flow rate of 19.5mL/min through a third metering pump, quenching the reactants, and then carrying out aftertreatment to obtain a pale yellow transparent liquid hydroxyl-terminated polyepichlorohydrin product.

Comparative example 2

The example provides a hydroxyl-terminated polyepichlorohydrin and a preparation method thereof, and the example adopts a traditional batch reaction kettle method in the patent for preparation, and specifically comprises the following steps:

adding 6.87g of glycerol and 200g of dichloroethane into a reaction flask, introducing nitrogen for 15min, adding 15.7g of boron trifluoride diethyl ether serving as a catalyst, stirring at 25 ℃ for 30min, gradually dropwise adding 460g of epoxy chloropropane into the reaction flask by a metering pump, dropwise adding the epoxy chloropropane at the reaction temperature of 30 ℃ for 4 hours, preserving the heat for 12 hours after the dropwise adding is finished, adding water serving as a quenching agent, quenching at the temperature of 30 ℃, and performing aftertreatment after-treatment on the reactants to obtain the pale yellow transparent liquid product of hydroxyl-terminated poly (epoxy chloropropane).

Performance testing

The properties of the hydroxyl-terminated polyepichlorohydrin prepared in each example are shown in Table 1 below;

wherein, the calculation formula of the yield of the hydroxyl-terminated polyepichlorohydrin is as follows: yield = m (hydroxyl terminated polyepichlorohydrin)/m (sum of all products) ·100%;

the hydroxyl value is determined by acid-base titration.

Table 1:

as can be seen from the results in Table 1, the hydroxyl-terminated polyepichlorohydrin prepared by the method of the invention has better yield and molecular weight, the reaction temperature exceeds the upper limit of the temperature of the invention, the product yield is greatly reduced, and compared with the traditional batch method for synthesizing the hydroxyl-terminated polyepichlorohydrin, the method of the invention has simple process and preparation efficiency which is far higher than that of the traditional batch method, and the molecular weight distribution of the prepared hydroxyl-terminated polyepichlorohydrin product is narrower.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The preparation method of the hydroxyl-terminated polyepichlorohydrin is characterized by comprising the following steps of:

mixing a first material comprising a solvent, an initiator and a catalyst at the temperature of between 0 and 40 ℃ to obtain a second material, mixing the second material with epoxy chloropropane in a mixing module of the microchannel continuous flow reactor to obtain a third material, feeding the third material in a reaction module of the microchannel continuous flow reactor to react, and then feeding the third material in a quenching module of the microchannel continuous flow reactor to perform quenching treatment to obtain the hydroxyl-terminated poly (epoxy chloropropane);

the reaction module comprises n micro-channel continuous flow reaction units, wherein n is more than or equal to 1 and less than or equal to 20.

2. The method according to claim 1, wherein the temperature of the reaction module is-20 to 90 ℃ and the temperature of the quenching module is 0 to 40 ℃.

3. The method of claim 1, wherein the initiator is a diol or a polyol; preferably, the dihydric alcohol is one or more of ethylene glycol, propylene glycol and butanediol; the polyalcohol is one or more of glycerol, sorbitol, trimethylolpropane, pentaerythritol and inositol.

4. The preparation method according to claim 1, wherein the catalyst is one or more of boron trifluoride diethyl ether, stannic chloride, trifluoroacetic acid, trichloroacetic acid and dichloroacetic acid.

5. The method according to claim 1, wherein n is 5.ltoreq.10.

6. The method of claim 1, wherein the solvent is a haloalkane.

7. The method according to claim 6, wherein the halogenated alkane is one or more of dichloromethane, dichloroethane, and carbon tetrachloride.

8. The production method according to any one of claims 1 to 6, wherein the mass ratio of the solvent to epichlorohydrin is 0.1 to 5;

the mass ratio of the initiator to the epichlorohydrin is 0.001-0.1, and the mass ratio of the catalyst to the epichlorohydrin is 0.001-0.1.

9. The preparation method according to claim 8, wherein the mass ratio of the solvent to epichlorohydrin is 0.25 to 1;

the mass ratio of the initiator to the epichlorohydrin is 0.01-0.05, and the mass ratio of the catalyst to the epichlorohydrin is 0.01-0.06.

10. The method of claim 8 or 9, wherein the second material and/or epichlorohydrin enters the mixing module of the microchannel continuous flow reactor at a flow rate of 10-30 mL/min.