KR20170061904A - A preparation method of polyalkylene carbonate - Google Patents
A preparation method of polyalkylene carbonate Download PDFInfo
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- KR20170061904A KR20170061904A KR1020150167066A KR20150167066A KR20170061904A KR 20170061904 A KR20170061904 A KR 20170061904A KR 1020150167066 A KR1020150167066 A KR 1020150167066A KR 20150167066 A KR20150167066 A KR 20150167066A KR 20170061904 A KR20170061904 A KR 20170061904A
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- polyalkylene carbonate
- carbonate
- methylene chloride
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- polyalkylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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Abstract
The present invention relates to a method for producing a polyalkylene carbonate. The present invention has an advantage that a polyalkylene carbonate which is suitable for transportation in a molding machine and has a constant particle diameter can be obtained economically and environmentally friendly.
Description
The present invention relates to a process for producing a polyalkylene carbonate.
Generally, the polyalkylene carbonate is prepared by a solvent polymerization method in which methylene chloride (MC) is used as a solvent. After the polyalkylene carbonate is polymerized, methylene chloride is added to dilute the remaining alkylene oxide to remove the alkylene oxide, and then the alkylene oxide / methylene chloride is evaporated.
However, since the amount of methylene chloride to be added is large at this time, it takes a long time to evaporate. Therefore, a method of obtaining a polyalkylene carbonate granule by using anti-solvent crystallization was also used.
The polyalkylene carbonate granules obtained by the anti-solvent crystallization method of the prior art are not uniform in particle size and have many large particles and are difficult to pelletize because they are not uniformly melted when they are transferred to an extruder for molding .
Thus, there has been a demand for a method for producing polyalkylene carbonate, which is suitable for transferring the particle diameter of the polyalkylene carbonate granules to the molding machine while maintaining the advantages of the anti-solvent crystallization method.
It is an object of the present invention to solve the problems of the prior art as described above and provide a method of obtaining a polyalkylene carbonate granule having a uniform particle diameter while being suitable for transfer to a molding machine while using an anti- .
In order to solve the above-mentioned problems, the present invention provides a method for producing a polyalkylene carbonate solution, which comprises recrystallizing a polyalkylene carbonate solution prepared by reacting an alkylene oxide and carbon dioxide in methylene chloride as a solvent by an anti-solvent crystallization method A method for producing a polyalkylene carbonate,
Wherein the step of recrystallization is carried out by mixing using a spinning disc.
According to the present invention, there is an advantage that a polyalkylene carbonate which is suitable for transportation to a molding machine and has a constant particle diameter can be obtained economically and environmentally friendly.
1 is a schematic view briefly showing the manufacturing method of the first to second embodiments.
Fig. 2 is a schematic view briefly showing a manufacturing method of Comparative Examples 1 to 2. Fig.
3 is a graph showing the results of Test Example 1. Fig.
The present invention relates to a process for producing a polyalkylene carbonate which comprises recrystallizing a polyalkylene carbonate solution prepared by reacting an alkylene oxide and carbon dioxide in methylene chloride as a solvent by an anti-solvent crystallization method ,
Wherein the step of recrystallization is carried out by mixing with a spinning disc.
Hereinafter, the present invention will be described in detail.
In one embodiment of the present invention,
The step of recrystallization by the above-mentioned anti-solvent crystallization method includes a step of introducing an anti-solvent having an opposite polarity to the solvent of methylene chloride into the polymerized alkylene carbonate solution to lower the solubility of the alkylene carbonate polymer to the solvent Which is a step of recrystallization.
In another embodiment of the present invention,
The polyalkylene carbonate solution means that the polyalkylene carbonate is a solution in methylene chloride.
Specifically, in the present specification, the term "polyalkylene carbonate solution" means a solvent polymerization method, that is, a method in which a polyalkylene carbonate as a polymerization product is dissolved in methylene chloride by reacting alkylene oxide and carbon dioxide in methylene chloride as a solvent , Which is used throughout this specification in the same sense as a polyalkylene carbonate / methylene chloride solution. The alkylene oxide is not limited as long as it is capable of producing a polyalkylene carbonate by polymerization.
In one embodiment of the present invention,
In the anti-solvent crystallization method, polyalkylene carbonate particles are not sufficiently produced when only water is used alone. When only the n-alkane compound is used alone, the anti-solvent crystallization effect is too strong. It is preferable to carry out the reaction using water and a mixture containing C5 to C10 normal alkene compounds because there is a problem in that it is impossible to adjust the amount relative to methylene chloride because the amount of the alkene compound to be used is small and the amount of the alkene compound to be used is small. Do.
Further, it is preferable that the above-mentioned C5 to C10 normal alkene compound is at least one member selected from the group consisting of n-hexane and n-heptane, because the solubility of methylene chloride in the polyalkylene carbonate can be significantly lowered, Heptane is more preferable because it has a boiling point higher than that of n-hexane and is easier to separate later from methylene chloride, but it is not limited thereto.
As described above, polyalkylene carbonate / methylene chloride solution was added to a mixture containing water and a C5 to C10 normal alkene compound, and the mixture was stirred to produce polyalkylene carbonate granules. However, polyalkylene carbonate / methylene chloride There is a problem that a large lump is formed as soon as the solution comes in contact with the mixture containing water as the anti-solvent and the alkaline alkene compounds of C5 to C10, making it difficult to obtain particles of a certain size and large particles are generated.
Although the charging rate of the polyalkylene carbonate / methylene chloride solution is constant, the amount of the mixture including the water in the chamber and the alkaline alkene compounds of C5 to C10 is relatively large, so that the polyalkylene carbonate precipitates rapidly, It becomes a big chunk.
The inventors of the present invention have conducted intensive studies and, as a result, have found that a polyalkylene carbonate / methylene chloride solution can be added at a constant speed by mixing with a spinning disk to obtain a polyalkylene carbonate granule having a constant particle diameter Thereby inventing a novel method for producing polyalkylene carbonate.
In the process for producing a novel polyalkylene carbonate of the present invention, a spinning disk is prepared by mixing a mixture containing water and C5 to C10 normal alkene compounds supplied from two inlet ports and a polyalkylene carbonate / methylene chloride solution at a high speed Spinning out the disk. Therefore, the amount and the ratio of the polyalkylene carbonate / methylene chloride solution and the mixture containing the water and the alkaline alkene compounds of C5 to C10 are always constant, so that the amount of the polyalkylene carbonate to be precipitated is always constant, And the size of the particles is almost constant since they are sent outward.
In one embodiment of the present invention,
The rotation speed of the spinning disc is preferably 200 rpm to 500 rpm because the desired particle size can be obtained,
If the rotation speed is 500 rpm or more, the speed is too fast and the particle diameter of the polyalkylene carbonate obtained as granules becomes too small. If the rotation speed is 200 rpm or less, the speed is too slow to increase the particle diameter and press on the spinning disk. .
In another embodiment of the present invention,
If the amount of the C5 to C10 normal alkene compound is too large, there is a problem that the particles aggregate and become too large in particle size. If the amount of the C5 to C10 normal alkene compound is too small, The mixing ratio of water and the C5 to C10 normal alkene compound is 3: 1 to 10: 1 by weight, so that it is possible to produce a polyalkylene carbonate having a particle size of a desired size, but is not limited thereto.
In another embodiment of the present invention,
If the amount of the C5 to C10 normal alkene compound is too large, there is a problem that the particles aggregate and become too large in particle size. If the amount of the C5 to C10 normal alkene compound is too small, The C5 to C10 normal alkene compound (a) is added in a weight ratio of a: b = 1: 5 to 1:20 based on the polyalkylene carbonate solution (b) to the polyalkylene carbonate But the present invention is not limited thereto.
In one embodiment of the present invention,
In the polyalkylene carbonate solution, the total solid content (TSC) is preferably 5% to 15%. If the content is less than 5%, the particles are formed too small. If the content is 15% or more, the viscosity is too strong, Therefore, the above range is preferable, but not limited thereto.
In another embodiment of the present invention,
The polyalkylene carbonate is preferably polyethylene carbonate, but is not limited thereto.
Hereinafter, the present invention will be described in more detail by way of non-limiting examples. The embodiments of the present invention described below are by way of example only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are on a mass basis unless otherwise specified.
Example
Manufacturing example 1. Polyethylene Carbonate Preparation of solution
In a high-pressure reactor equipped with an agitator, 1.78 kg of the prepared methylene chloride (MC) was added. 18.5 g of Zn-glutarate catalyst and 330 g of ethylene oxide were charged, and CO 2 (carbon dioxide) was charged at a pressure of 10 atm, followed by stirring for 10 minutes. CO 2 was then added until the total charge reached 410 g, the temperature was raised to 70 ° C and reaction was carried out at a rate of 50 rpm for 5 hours. As the polymerization proceeded, CO 2 was consumed, and thus a continuous addition was carried out at a flow rate of 105 g / hr. After completion of the polymerization reaction, unreacted CO 2 and ethylene oxide (EO) were blown off in the gas phase to lower the viscosity of the polyethylene carbonate / methylene chloride (PEC / MC) solution while lowering the concentration of residual ethylene oxide 3.22 kg of methylene chloride was further added to prepare a polyethylene carbonate solution having a total solids content (TSC) of about 10% of polyethylene carbonate (PEC).
Example 1. Polyethylene Of carbonate Produce
The polyethylene carbonate solution obtained in Production Example 1 was passed through a polymer type filter to remove the catalyst. Water was added to the chamber so that the spinning disc was slightly submerged. Thereafter, heat was applied to the chamber and maintained at about 60 ° C. A 15 cm diameter spinning disc was rotated at a speed of 400 rpm. 2 kg of water and 0.5 kg of n-heptane were fed at a flow rate of 10 kg / hr and 5 kg of a polyethylene carbonate / methylene chloride (PEC / MC) solution at a flow rate of 20 kg / hr to one of the two inlets at the top of the chamber Respectively. The weight ratio of water (n-heptane: polyethylene carbonate / methylene chloride) was 4: 1: 10.
Since the methylene chloride evaporated from the time when the polyethylene carbonate solution was introduced, the vent line at the upper part of the chamber connected to the condenser was opened. The process was terminated when no more flow was visible in the vent line. Water in the polyethylene carbonate granules was removed by a dehydrator, 500 g of water was added to the washing chamber, and the mixture was stirred at 100 rpm for about 30 minutes.
Thereafter, the moisture of the polyethylene carbonate granules was again removed by a dehydrator.
Example 2. Polyethylene Of carbonate Produce
A polyethylene carbonate was prepared in the same manner as in Example 1, except that a spinning disc having a diameter of 15 cm was rotated at a speed of 300 rpm.
Comparative Example 1. Polyethylene Of carbonate Produce
The polyethylene carbonate solution obtained in Production Example 1 was passed through a polymer type filter to remove the catalyst. 2 kg of water and 0.5 kg of n-heptane were added to the chamber, and the mixture was stirred at a speed of 400 rpm while keeping the temperature at about 60 ° C (without using a spinning disc). 5 kg of a polyethylene carbonate / methylene chloride solution was introduced into the chamber at a flow rate of 20 kg / hr. The weight ratio of water (n-heptane: polyethylene carbonate / methylene chloride) was 4: 1: 10. Since the evaporation of MC occurred from the time when the PEC / MC solution was introduced, the vent line at the upper part of the chamber connected to the condenser was opened. The process was terminated when no more flow was visible in the vent line. Water in the polyethylene carbonate granules was removed by a dehydrator, 500 g of water was added to the washing chamber, and the mixture was stirred at 100 rpm for about 30 minutes.
Thereafter, the moisture of the polyethylene carbonate granules was again removed by a dehydrator.
Comparative Example 2. Polyethylene Of carbonate Produce
The preparation of polyethylene carbonate was carried out in the same manner as in Comparative Example 1, except that 2 kg of water and 0.5 kg of n-heptane were added to the chamber, and the mixture was stirred at a speed of 300 rpm while keeping the temperature at about 60 캜 by heating.
Test Example 1. Measurement of particle size distribution
The particle size distributions of the polyethylene carbonate (PEC) granules obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were measured by using various meshes. The results are shown in Table 1 below.
Measurement results According to Comparative Examples 1 and 2, the polyethylene carbonate granules obtained without using a spinning disk were torn into small particles due to the agitation effect, but the particles were not uniform in size and were suitable for transport to an extruder Large particles that did not exist were also generated.
On the contrary, it was confirmed that the particle size of the polyethylene carbonate granules prepared by using the spinning disk was constant as in Examples 1 and 2.
It was also confirmed that the particle size of the polyethylene carbonate granules was reduced by increasing the rotation speed (rpm) of the spinning disk or the agitator.
Claims (9)
Characterized in that the step of recrystallization is carried out by mixing with a spinning disc.
Wherein the anti-solvent crystallization is carried out using a mixture comprising water and C5 to C10 normal alkene compounds.
Wherein the C5 to C10 normal alkene compound is at least one selected from the group consisting of n-hexane and n-heptane.
Wherein the anti-solvent crystallization method is carried out using water and n-heptane.
Wherein the mixing ratio of water and the C5 to C10 normal alkene compound is 3: 1 to 10: 1 by weight.
Wherein the C5 to C10 normal alkene compound (a) is added in a weight ratio of a: b = 1: 5 to 1: 20 to the polyalkylene carbonate solution (b).
Wherein the polyalkylene carbonate solution is a solution in which the polyalkylene carbonate produced by the reaction is dissolved in methylene chloride.
Wherein the rotating speed of the spinning disc is from 200 rpm to 500 rpm.
Wherein the polyalkylene carbonate is polyethylene carbonate. ≪ RTI ID = 0.0 > 11. < / RTI >
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007126547A (en) | 2005-11-02 | 2007-05-24 | Mitsui Chemicals Inc | Polyalkylene carbonate production method |
| JP2011195637A (en) * | 2010-03-17 | 2011-10-06 | Univ Of Tokyo | Polycarbonate composition |
| KR20120139660A (en) * | 2010-02-03 | 2012-12-27 | 엠. 테크닉 가부시키가이샤 | Method for producing nanoparticles |
| KR20150060274A (en) * | 2013-11-26 | 2015-06-03 | 주식회사 엘지화학 | Apparatus for producing polycarbonate particles and method for producing producing polycarbonate particles using the same |
| KR101562079B1 (en) * | 2008-03-17 | 2015-10-20 | 주식회사 다이셀 | Process for production of polymer |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007126547A (en) | 2005-11-02 | 2007-05-24 | Mitsui Chemicals Inc | Polyalkylene carbonate production method |
| KR101562079B1 (en) * | 2008-03-17 | 2015-10-20 | 주식회사 다이셀 | Process for production of polymer |
| KR20120139660A (en) * | 2010-02-03 | 2012-12-27 | 엠. 테크닉 가부시키가이샤 | Method for producing nanoparticles |
| JP2011195637A (en) * | 2010-03-17 | 2011-10-06 | Univ Of Tokyo | Polycarbonate composition |
| KR20150060274A (en) * | 2013-11-26 | 2015-06-03 | 주식회사 엘지화학 | Apparatus for producing polycarbonate particles and method for producing producing polycarbonate particles using the same |
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