KR20080020269A - Method for polymerizing water-soluble monomer with water-insoluble monomer and device for the same - Google Patents

Abstract

A process for polymerizing a water soluble monomer with a non-water soluble monomer is provided to reduce or avoid the use of a surfactant, and to allow easy preparation of a polymer having a desired molecular weight. A process for polymerizing a water soluble monomer with a non-water soluble monomer comprises the steps of: (a) introducing an aqueous solution containing a water soluble monomer and an organic solution containing a non-water soluble monomer into a mixing tank(1) and mixing the monomers; and (b) introducing the aqueous-organic mixture present in the mixing tank into a micro-reactor(3) by using a pump(2), carrying out polymerization via micro-mixing, and reintroducing the resultant mixture into the mixing tank of step (a).

Description

METHOD FOR POLYMERIZING WATER-SOLUBLE MONOMER WITH WATER-INSOLUBLE MONOMER AND DEVICE FOR THE SAME}

1 is a schematic diagram of one embodiment of an apparatus for carrying out a polymerization process according to the invention, comprising one micro-reactor.

2 is a schematic diagram of one embodiment of an apparatus for carrying out the polymerization process according to the invention, comprising a plurality of micro-reactors.

Figure 3 is a graph showing the molecular weight change of the resulting polymer according to the total cycle of the polymerization reaction in Example 1 of the present invention.

[* Explanation of symbols for main parts of drawing]

1: mixing tank

2: pump

3: micro-reactor

11, 12, 13, 21, 22, 31: piping

The present invention relates to a polymerization method of a water-soluble monomer and a water-insoluble monomer, and an apparatus for carrying out the same. More specifically, (1) an aqueous solution containing a water-soluble monomer and an organic solution containing a water-insoluble monomer are added to a mixing tank. Mixing; And (2) introducing the water-organic layer mixture present in the mixing tank into a micro-reactor using a pump, micro-mixing and carrying out a polymerization reaction, and as a result the mixture is returned to the mixing tank of step (1). It relates to a polymerization method of a water-soluble monomer and a water-insoluble monomer, and a device for carrying out the same, comprising the step of adding. According to the present invention, the polymer can be easily synthesized by easily polymerizing the water-soluble monomer and the water-insoluble monomer without significantly reducing the amount of surfactant used or at all, and in particular, since the reaction time and the molecular weight of the polymer have a linear proportional relationship, By controlling the time, it is easy to obtain a polymer having a desired level of molecular weight.

A high molecular material such as polyarylate or polycarbonate is obtained by polymerizing water-soluble monomers and water-insoluble monomers. When these water-soluble monomers and water-insoluble monomers are dissolved in an aqueous layer and an organic layer and introduced into a reactor for polymerization, the mixture is a water layer. Because it is separated into an organic layer, simple agitation does not induce contact between the monomers to the extent that polymerization can occur. Therefore, conventionally, in order to polymerize between these water-soluble insoluble monomers, surfactants are used to lower the surface energy of the aqueous layer and the organic layer so that monomers dissolved in each layer can be more smoothly contacted at the two liquid interfaces. The method has been mainly used. For example, in the conventional polyarylate production method, surfactants have been used to polymerize bisphenolate dissolved in the aqueous layer and isophthaloyl chloride and terephthaloyl chloride dissolved in methylene chloride, an organic solvent. However, since such a conventional polymerization method uses a surfactant, which is an expensive material to account for about 30% of the raw material cost, the manufacturing cost of the polymer is increased, and even though it is expensive, it is impossible to recover the surfactant after the reaction. There are disadvantages. In addition, in the conventional polymerization method using a surfactant, since a small change in the amount of the input can have a great influence on the reaction result, it is very difficult to control the polymerization reaction, and therefore, it is difficult to adjust properties such as molecular weight of the resulting polymer to a desired level. The disadvantage is that it is very difficult.

In order to improve the problems caused by the use of such a large amount of surfactants, there have been proposed methods of making the homogeneous emulsion by mechanically mixing the mixture for polymerization of the aqueous-organic layer before the polymerization reaction and then proceeding with the polymerization. For example, US Pat. No. 5,886,112 discloses a technique for advancing anionic polymerization after mechanically mixing the mixture for polymerization before the polymerization reaction. However, this method is very fast because the reaction takes place without the application of heat, such as a radical reaction, so the reaction rate is very fast. Therefore, the reaction time can be applied to an anionic polymerization of about 0.2 seconds, which is very short. It is not applicable to condensation polymerization of related or polycarbonates. In addition, since the anion is very reactive and easily reacts with water, oxygen, etc., it is very difficult to control the reaction, and thus it is practically impossible to adjust the properties such as molecular weight of the resultant polymer to a desired level with this method.

The present invention has been made to solve the problems of the prior art as described above, the object of the present invention is to easily polymerize a water-soluble monomer and a water-insoluble monomer without significantly reducing the amount of surfactant used or at all to synthesize a polymer. In particular, it is an object of the present invention to provide a polymerization method and apparatus which can easily produce a polymer having a desired level of molecular weight.

According to one aspect of the invention, (1) the step of mixing and mixing an aqueous solution containing a water-soluble monomer and an organic solution containing a water-insoluble monomer in a mixing tank; And (2) introducing the water-organic layer mixture present in the mixing tank into a micro-reactor using a pump, micro-mixing and carrying out a polymerization reaction, and as a result the mixture is returned to the mixing tank of step (1). Provided is a polymerization method of a water-soluble monomer and a water-insoluble monomer, comprising the step of introducing.

Each substep of the polymerization process according to the invention is embodied by the following.

In the polymerization method according to the present invention, in the step (1), an aqueous solution containing a water-soluble monomer and an organic solution containing a water-insoluble monomer are charged and mixed into a mixing tank provided with a mixing means.

As used herein, the term "water-soluble monomer" is significantly higher solubility in water compared to solubility in hydrophobic organic solvents, so that a two-phase solvent system (volume ratio 1) consisting of water, preferably a basic aqueous solution and a hydrophobic organic solvent In the case of dissolving in (1), 90% or more, preferably 95% or more, and more preferably 99% or more of the added amount means a monomer compound for polymer polymerization in which the aqueous layer is dissolved. On the other hand, the term “water insoluble monomer” herein refers to a two-phase solvent system (volume ratio 1: 1) composed of water and a hydrophobic organic solvent because its solubility in water is significantly lower than that in hydrophobic organic solvents. When added to and dissolved in a solution, 90% or more, preferably 95% or more, and more preferably 99% or more of the added amount means a monomer compound for polymer polymerization in which the organic layer is dissolved. In the present invention, the water-soluble monomer and the water-insoluble monomer may vary depending on the type of polymer desired, for example, an aromatic diol such as bisphenolate (or bisphenol A) when polymerizing a polyarylate (PAR). Bisphenolate is a water soluble monomer, while aromatic dicarboxylic acid halides such as isophthaloyl chloride or terephthaloyl chloride are water insoluble monomers. And carbonyl halides such as carbonyl chloride (COCl ₂ , phosgene) correspond to water insoluble monomers.

In addition, the term "hydrophobic organic solvent" as used herein refers to an organic solvent that does not have a hydrophilic functional group such as a hydroxy group, such as methylene chloride, ethylene chloride, chloroform, toluene and benzene, and does not mix well with water.

In the aqueous solution added to the mixing tank in step (1) of the polymerization method of the present invention, in order to further increase the solubility of water-soluble monomers such as bisphenolate in water, for example, sodium hydroxide (NaOH), potassium hydroxide (KOH) and the like It is preferred to include a base. The type and amount of base may vary depending on the type of water-soluble monomer and polymerization conditions. According to one embodiment of the invention, preferably 0.5 to 4 moles, more preferably 1.5 to 2.5 moles, even more preferably 1.8 to 2.2 moles of base are used per mole of the water-soluble monomer. If the amount of base is less than 0.5 mole, the effect of increasing the water solubility of the water-soluble monomer is not sufficient, and if it exceeds 4 moles, there is a fear that unwanted by-products such as hydrochloric acid may occur. In addition, in the aqueous solution added to the mixing tank in step (1) of the present invention, the content of the water-soluble monomer may vary depending on the type, but preferably 10 to 60 parts by weight, more preferably per 100 parts by weight of water. 20 to 50 parts by weight, even more preferably 25 to 40 parts by weight, if the amount is less than 10 parts by weight, it is difficult to completely dissolve the water-soluble equivalents, and if it exceeds 60 parts by weight, the micro-reactor The viscosity rise of the mixture solution, which is circulated into the furnace, becomes too fast, making it difficult to control the reaction.

In addition, in the organic solution added to the mixing tank in step (1) of the polymerization method of the present invention, at least one water-insoluble monomer is added to a hydrophobic organic solvent selected from the group consisting of methylene chloride, ethylene chloride, chloroform, toluene and benzene. Dissolves. In the organic solution added to the mixing tank in the step (1) of the present invention, the total content of the water-insoluble monomer may vary depending on the type, but preferably 2.5 to 25 parts by weight, more preferably per 100 parts by weight of the organic solvent. Preferably, the amount is less than 5 to 15 parts by weight. If the amount is less than 2.5 parts by weight, the polymerization efficiency is lowered. If the amount is more than 25 parts by weight, the viscosity of the mixture solution circulated into the micro-reactor as the polymerization proceeds is too high. The faster it becomes, the harder it is to control the reaction.

Meanwhile, according to the present invention, polymerization of the water-soluble monomer and the water-insoluble monomer is possible without using any surfactant, but in some cases, a small amount of the surfactant may be used. In this case, the surfactant may be included in the aqueous layer or the organic layer depending on the type thereof, or may be introduced into the mixing tank through a separate pipe.

The mixing tank used in step (1) of the polymerization method of the present invention is provided with a mixing means capable of mixing the aqueous layer and the organic layer, and preferably a speed-variable mechanical stirrer with an impeller is used.

In step (1) of the polymerization method of the present invention, an aqueous solution containing a water-soluble monomer and an organic solution containing a water-insoluble monomer may be simultaneously introduced into the mixing tank, and some of them may be first introduced into the reactor. In addition, the mixing of the aqueous solution and the organic solution may be started at the same time as the addition of each solution, may be started after the addition of all of the solution is completed, it is preferable to continue until the final completion of the polymerization. In addition, in the step (1), the temperature in the mixing tank is preferably lower than the temperature at which the polymerization reaction can be carried out, for example, 5 to 15 ° C, and more preferably 9 to 11 ° C, which is mixed This is because if the temperature of the tank is kept below the polymerization temperature, the polymerization can proceed substantially only in the micro-reactor to facilitate the control of the reaction. In a preferred embodiment of the present invention, the temperature of the micro-reactor in which the polymerization of the polyarylate is carried out is maintained at about 20 ° C., while the temperature of the mixing tank is maintained at about 10 ° C. so that the polymerization in the mixing tank is carried out. Suppress what happens.

In the polymerization method according to the present invention, in the step (2), the water-organic layer mixture present in the mixing tank is introduced into the micro-reactor by using a pump, micro-mixed and the polymerization reaction is carried out, and as a result, the mixture To the mixing tank of step (1). In the polymerization process according to the invention, step (2) is repeated one or more times, preferably 2 to 600 times, more preferably 40 to 480 times.

In the polymerization method of the present invention, the water-soluble monomer and the water-insoluble monomer are polymerized while undergoing one or more cycles of the 'mixing tank → pump → micro-reactor → mixing tank'. Therefore, as the circulation process is repeated, the polymer content in the circulating fluid and the degree of polymerization thereof increase, and as a result, the viscosity of the circulating fluid increases. Therefore, the pump used in step (2) of the polymerization method of the present invention is preferably a high pressure-high viscosity pump capable of conveying a fluid having a viscosity of, for example, 20,000 cP (centi-poise). Further, in view of the efficiency of the overall process, step (2) is preferably repeated at a rate of at least once per minute, more preferably at a rate of 2 to 4 times per minute, so that such a circulation rate can be met. For example, it is preferable to use a pump having a performance of producing a flow rate of 1 to 4 liters per minute.

In step (2) of the polymerization method of the present invention, the micro-reactor micro-mixes the aqueous layer-organic layer mixture introduced from the mixing tank to contact the water-soluble monomers and the water-insoluble monomers present in the aqueous layer and the organic layer, respectively, so that the monomers are polymerized. It acts to make it possible. As used herein, the term “micro-mixing” refers to the droplets of the aqueous and organic layers of 100 μm or less, preferably 50 μm or less, more preferably 10 μm or less, even more preferably through mechanical or other means. It refers to a process of grinding and mixing to a diameter of 4㎛ or less. Therefore, as the micro-reactor in the step (2) of the polymerization method of the present invention, the droplet of the fluid is 100 µm or less, preferably 50 µm or less, more preferably 10 µm or less, even more preferably 4 µm. Any device that grinds and mixes to the following diameters can be used without particular limitation. Preferably, a commercial static mixer or a micro mixer can be used. In addition, in the step (2), the temperature in the micro-reactor is maintained at a temperature at which the polymerization reaction can be performed, preferably at 18 to 25 ° C, more preferably at 19 to 21 ° C. If the temperature in the micro-reactor is less than 18 ° C., the polymerization efficiency is lowered. If it exceeds 25 ° C., the reaction is difficult to control, making it difficult to control the molecular weight and the like of the resulting polymer.

As described above, in the polymerization method of the present invention, as the cycle of 'mixing tank → pump → micro-reactor → mixing tank' is repeated, the polymer content in the fluid and its degree of polymerization are increased, and as a result, the viscosity of the circulating fluid is increased. Will rise. Therefore, in the present invention, by determining the end point of the step (2) by the viscosity of the fluid circulated in the step (2), the molecular weight of the resulting polymer can be easily adjusted. That is, in the polymerization method of the present invention, the fluid circulated in step (2) (for example, the mixture fluid introduced into the pump from the mixing tank, the mixture fluid introduced into the micro-reactor from the pump, or the mixed fluid from the micro-reactor into the mixing tank). The molecular weight of the resulting polymer can be easily controlled by checking the viscosity of the mixed fluid) at regular intervals and terminating the reaction when the viscosity reaches the desired level. According to an embodiment of the present invention, the step (2) is repeated after the step (2) is repeated until the viscosity of the mixture fluid introduced from the mixing tank to the pump in step (2) becomes 10,000 to 12,000 cP (centi-poise) In other words, a polyarylate having a molecular weight of 65,000 to 70,000 can be obtained.

Further, more simply, in the polymerization method of the present invention, since the repetition frequency of the step (2) and the polymerization degree of the resultant polymer, that is, the molecular weight, have a proportional relationship, preferably a linear proportional relationship, a 'mixing tank → pump → If the circulation rate of the micro-reactor → mixing tank is constant, the molecular weight of the resulting polymer can be easily controlled by determining the end point of step (2) by the execution time of step (2). That is, in the polymerization method of the present invention, the molecular weight of the resultant polymer is checked in advance for each operation time step of step (2) to induce an operating time-molecular weight relationship, and then, until the operating time required to obtain a desired molecular weight by using the above (2) The molecular weight of the resulting polymer can be easily controlled by repeating the step) and terminating the reaction. For example, according to one embodiment of the present invention in which polymerization is performed using one micro-reactor, the execution time of step (2) and the molecular weight (Mw) of the resulting polymer polyarylate satisfy the following relationship: Let:

0.9 * (350 * t + 26000) ≤ Mw ≤ 1.1 * (350 * t + 26000)

More preferably,

0.95 * (350 * t + 26000) ≤ Mw ≤ 1.05 * (350 * t + 26000)

However, in said formula, the unit of t is minutes and t is preferably 10 minutes or more.

For example, in one embodiment of the present invention to which the relationship is applied, it is predicted that repeating step (2) for 100 minutes yields a polyarylate having a molecular weight of about 55000 to 68000, more preferably about 58000 to 65000 In practice, polyarylates having a molecular weight of about 61000 are obtained.

According to another aspect of the invention, an apparatus for carrying out the polymerization process according to the invention, comprising a mixing tank, a pump and one or a plurality of micro-reactors having an aqueous solution inlet, an organic solution inlet, a stirring means and a resultant outlet And a fluid inlet of the pump is in fluid communication with the mixing tank, a fluid outlet of the pump is in fluid connection with a fluid inlet of the micro-reactor, and a fluid outlet of the micro-reactor is in fluid connection with the mixing tank. Is provided.

In the polymerization apparatus of the present invention, the stirring means provided in the mixing tank is preferably a variable speed mechanical stirrer with an impeller, and also preferably provided with cooling and / or heating means to enable temperature control.

In addition, in the polymerization apparatus of the present invention, it is preferable that the pump is for high pressure-high viscosity, for example, for high pressure-high viscosity capable of transporting a fluid having a viscosity of up to 20,000 cP, and it is also possible to produce a flow rate of 1 to 4 liters per minute. desirable.

In the polymerization apparatus of the present invention, the micro-reactor may be used to grind droplets of fluid into a diameter of 100 µm or less, preferably 50 µm or less, more preferably 10 µm or less, even more preferably 4 µm or less. Devices capable of mixing and mixing are available, and commercially available static mixers or micro mixers are preferably used. It is also preferred that cooling and / or heating means be provided to enable temperature control.

In the polymerization apparatus of the present invention, the number of the micro-reactors may be one, but in order to increase the polymerization efficiency per hour, it is preferable that there are a plurality. In addition, it is more preferable that the plurality of micro-reactors are connected in parallel in terms of improving polymerization efficiency.

In addition to the above-described mixing tank, pump and micro-reactor, the polymerization apparatus of the present invention may further be provided with necessary accessories, such as a heat exchanger, an additional pump, and the like within the scope of achieving the object of the present invention.

Hereinafter, the present invention will be described in more detail with reference to FIGS. 1 and 2.

1 and 2 are schematic diagrams of an embodiment of an apparatus for carrying out the polymerization process according to the invention, in which FIG. 1 is for an apparatus comprising one micro-reactor, and FIG. 2 is a plurality of micro-connected in parallel. To an apparatus comprising a reactor.

In Fig. 1 or one specific example of the polymerization method of the present invention for the polymerization of polyarylates using the apparatus 2, the water-soluble monomer of bisphenol rate (BPA), water (H ₂ O) sodium hydroxide (NaOH) and the solvent An aqueous solution consisting of an aqueous solution consisting of isophthaloyl chloride (IPC) and terephthaloyl chloride (TPC) and a methylene chloride (MC) solvent are mixed tanks 11 and 12, respectively. It is put in 1). At this time, the aqueous solution, preferably 10 to 60 parts by weight, more preferably 20 to 50 parts by weight, more preferably 25 to 40 parts by weight of bisphenolate (BPA) per 100 parts by weight of water, bisphenolate Also preferably 0.5 to 4 moles, more preferably 1.5 to 2.5 moles, even more preferably 1.8 to 2.2 moles of NaOH per mole (BPA) are also included. In addition, the total amount of isophthaloyl chloride (IPC) and terephthaloyl chloride (TPC) in the organic solution is preferably 2.5 to 25 parts by weight, more preferably 5 to 15 parts by weight per 100 parts by weight of methylene chloride. . There is no particular limitation on the relative amounts of isophthaloyl chloride (IPC) and terephthaloyl chloride (TPC) and may vary depending on the specific structure of the desired resultant polymer. For example, one embodiment may be used in a molar ratio of 1: 1, while in another embodiment, either one may be used relatively much.

Simultaneously with or after the addition of the solutions, the stirrer provided in the mixing tank 1 is operated at a speed of, for example, 100 to 500 rpm per minute so that the injected aqueous solution and the organic solution are mixed. The temperature in the mixing tank 1 is kept lower than the temperature at which the polymerization can be carried out, for example at 5 to 15 ° C, more preferably at 9 to 11 ° C, even more preferably at 10 ° C.

Next, the agitation in the mixing tank 1 is continued while the pump 2 is operated to feed the water-organic layer mixture in the mixing tank 1 into the micro-reactor 3 through the pipes 21 and 22. As the micro-reactor 3, one commercial micro mixer is used in the apparatus shown in FIG. 1, and four commercial micro mixers connected in parallel are used in the apparatus shown in FIG.

The aqueous layer-organic layer introduced while maintaining the temperature in the micro-reactor 3 at a temperature at which the polymerization reaction can be performed, for example, at 18 to 25 ° C, more preferably at 19 to 21 ° C, even more preferably at 20 ° C. The mixture is micro-mixed and polymerized and the resulting mixture is reintroduced into the mixing tank 1 via piping 31. By adjusting the flow rate of the pump 2, the circulation process of 'mixing tank 1 → pump 2 → micro-reactor 3 → mixing tank 1' is performed at least once per minute, preferably 2 to 4 cycles, the viscosity of the circulating fluid is measured at regular intervals, or the circulation time is measured and the circulation process is repeated. When the viscosity or circulation time of the predetermined circulation fluid is reached, the circulation is terminated. , The polymerization reaction product is discharged from the mixing tank 1 through the pipe 13, and a post-treatment step such as filtration and drying is performed as necessary. If the required aftertreatment is carried out in the mixing tank 1, after the performance of the aftertreatment the resultant is discharged from the mixing tank 1.

In this embodiment, the polymerization of the water-soluble monomer and the water-insoluble monomer is carried out without using a surfactant, but in some cases, a small amount of the surfactant may be used. In this case, the surfactant may be included in the water layer or the organic layer depending on the type thereof, or may be introduced into the mixing tank 1 through a separate pipe (not shown).

As described above, in the present invention, even if the surfactant is not used at all or the surfactant is used, the polymer can be synthesized by easily polymerizing the water-soluble monomer and the water-insoluble monomer, while significantly reducing the amount of use thereof. It is possible to easily prepare a polymer having

Hereinafter, the present invention will be described in more detail with reference to Examples, but the protection scope of the present invention is not limited to Examples.

Example 1

Polymerization of the water-soluble monomer and the water-insoluble monomer was performed using the apparatus shown in FIG.

Water-soluble monomer-containing aqueous solution was prepared by adding 42.32 g and 16.48 g of bisphenol A and sodium hydroxide, respectively, to 296.6 g of water, while 18.84 g of isophthaloyl chloride and terephthaloyl chloride were added to 471.72 g of methylene chloride, respectively, to contain water-insoluble monomer. An organic solution was made.

The produced aqueous solution was put into the mixing tank, and the temperature in the mixing tank was kept at 10 degreeC. The resulting organic solution was cooled to 10 ° C separately. The organic solution cooled to 10 ° C. was added to a mixing tank containing an aqueous solution. Simultaneously with the addition of the organic solution, the impeller stirrer provided in the mixing tank was operated to continue stirring at a speed of 200 rpm.

A high viscosity gear pump (model name: G724, manufactured by Viking pumps) was operated at a flow rate of 4.0 liters per minute while maintaining the agitation of the water-to-organic mixture in the mixing tank with a Caterpillar Split-Recombine type micro Micro-mixing and polymerization were carried out in a mixer (Model: Caterpillar ver. 2, manufacturer: IMM). The temperature in the micromixer was maintained at 20 ° C. during the polymerization, and the resulting mixture exited the micromixer and was reinserted into the mixing tank. The circulation rate of the reaction was four times per minute.

The above cycle polymerization reaction was continued for 2 hours (total cycle number: 480 cycles), and the sample in the mixing tank was taken every 10 minutes (ie, every 40 cycles) after the start of the cycle polymerization. The molecular weight of the polymer was analyzed by gel permeation chromatography (Model name: TriSEC Model302, manufacturer: Viscotek), and the results are shown in Table 1 below. As shown.

TABLE 1

According to Table 1, as the cyclic polymerization proceeds, the monomers polymerized with each other as the micro-reactor passed, and the molecular weight of the polymer gradually increased linearly.

Example 2

Example 1, except that micro-mixing and polymerization were carried out using the apparatus shown in FIG. 2, that is, four micromixers (model name: Caterpillar ver. 2, manufacturer: IMM) connected in parallel for 30 minutes. In the same manner the polymerization of the water soluble monomer and the water insoluble monomer was carried out.

After 30 minutes of cyclic polymerization, samples in the mixing tank were taken and analyzed by gel permeation chromatography (Model: TriSEC Model302, manufacturer: Viscotek). As a result of the analysis, the molecular weight of the polymer contained in the sample was 70500.

Comparative Example 1

296.6 g of water, 42.32 g of bisphenol A and 16.48 g of sodium hydroxide were added to the reactor to form an aqueous solution containing a water-soluble monomer, and the temperature was maintained at 20 ° C. Next, 1.677 g of benzyltriethylammonium chloride (BTEAC) was dissolved in 29.6 g of methylene chloride as a surfactant, and then charged into the reactor and stirred to prepare a pre-emulsion state. After about 5 minutes, 18.84 g each of isophthaloyl chloride and terephthaloyl chloride was added to 471.72 g of methylene chloride to prepare a water-insoluble monomer-containing organic solution, which was added to the reactor.

After the addition of the reactants, the impeller stirrer provided in the reactor was operated at 700 rpm to perform the polymerization while stirring the reactants. At this time, the temperature was maintained at 20 ℃, the reaction was carried out for a total of 60 minutes, 30 minutes after the start of the reaction and 60 minutes after the analysis sample was taken from the mixture in the reactor.

The collected sample was analyzed by gel permeation chromatography (Model name: TriSEC Model302, manufacturer: Viscotek). As a result of analysis, after 30 minutes and 60 minutes after the start of the reaction, the molecular weights of the polymers included in the sample were 71000 and 72000, respectively.

Comparative Example 2

A polymerization reaction was performed for 120 minutes in the same manner as in Comparative Example 1, except that benzyltriethylammonium chloride, a surfactant, was used and the stirrer was operated at 800 rpm.

After 60 minutes and 120 minutes after the start of the reaction, analytical samples were taken from the mixture in the reactor, and the collected samples were analyzed by gel permeation chromatography (Model: TriSEC Model302, manufacturer: Viscotek). As a result of analysis, after 60 minutes and 120 minutes after the start of the reaction, the molecular weights of the polymers included in the sample were 21000 and 51000, respectively.

As described above, according to the present invention, polymers can be easily synthesized by easily polymerizing a water-soluble monomer and a water-insoluble monomer without significantly reducing the amount of surfactant used or at all, and in particular, when the circulation rate of the circulation reaction is constant. Since the time and the polymer molecular weight have a linear proportional relationship, and the total reaction time is fixed, the cycle number and the polymer molecular weight have a linear proportional relationship, and in the latter case, the reaction time is controlled. By controlling the flow rate, it is possible to easily obtain a polymer having a desired level of molecular weight by controlling the overall cycle number. In addition, when a plurality of micro-reactors are used in parallel, the reaction time can be significantly reduced.

While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also natural.

Claims (17)

(1) adding an aqueous solution containing a water soluble monomer and an organic solution containing a water insoluble monomer to a mixing tank and mixing; And (2) The water-organic layer mixture present in the mixing tank was introduced into the micro-reactor using a pump, micro-mixed and subjected to polymerization, and as a result, the mixture was fed back into the mixing tank of step (1). A method of polymerizing a water-soluble monomer and a water-insoluble monomer, comprising the step of. The method of claim 1 wherein the water soluble monomer is an aromatic diol. The process of claim 1 wherein the water insoluble monomer is an aromatic dicarboxylic acid halide or carbonyl halide. The polymerization method according to claim 1, wherein the aqueous solution introduced into the mixing tank in step (1) contains 0.5 to 4 moles of base per mole of water-soluble monomer in the aqueous solution. The polymerization method according to claim 1, wherein the water-soluble monomer content in the aqueous solution added to the mixing tank in the step (1) is 10 to 60 parts by weight per 100 parts by weight of water. According to claim 1, wherein the organic solution added to the mixing tank in the step (1) is characterized in that at least one water-insoluble monomer is dissolved in a hydrophobic organic solvent selected from the group consisting of methylene chloride, ethylene chloride, chloroform, toluene and benzene. Polymerization method. The method of claim 1, wherein the water-insoluble monomer content in the organic solution added to the mixing tank in the step (1) is 2.5 to 25 parts by weight per 100 parts by weight of the organic solvent. The method of claim 1, wherein the temperature in the mixing tank in the step (1) is maintained at 5 to 15 ℃. The polymerization method according to claim 1, wherein step (2) is repeated one or more times, and the repetition rate is one or more times per minute. 2. The polymerization method according to claim 1, wherein the micro-reactor of step (2) is a device for pulverizing and mixing droplets of fluid to a diameter of 100 mu m or less. The process according to claim 1, wherein the micro-reactor of step (2) is a static mixer or a micro mixer. The method of claim 1, wherein the temperature in the micro-reactor in step (2) is maintained at 18 to 25 ℃. The polymerization method according to claim 1, wherein the end point of the step (2) is determined by the viscosity of the fluid circulated in the step (2) or by the execution time of the step (2). A mixing tank, a pump and one or a plurality of micro-reactors having an aqueous solution inlet, an organic solution inlet, a stirring means and a resultant outlet, The fluid inlet of the pump is in fluid connection with the mixing tank, The fluid outlet of the pump is in fluid communication with the fluid inlet of the micro-reactor, The fluid outlet of the micro-reactor is in fluid communication with the mixing tank, A polymerization apparatus for carrying out the method of any one of claims 1 to 13. 15. The apparatus of claim 14, wherein the pump is for high pressure-high viscosity. The apparatus of claim 14, wherein the micro-reactor is a static mixer or a micro mixer. 15. The apparatus of claim 14, wherein the plurality of micro-reactors are connected in parallel.

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