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KR101938338B1 - Method for recycling alkylene oxide in the process of polyalkylene carbonate production - Google Patents

Method for recycling alkylene oxide in the process of polyalkylene carbonate production Download PDF

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KR101938338B1
KR101938338B1 KR1020120113620A KR20120113620A KR101938338B1 KR 101938338 B1 KR101938338 B1 KR 101938338B1 KR 1020120113620 A KR1020120113620 A KR 1020120113620A KR 20120113620 A KR20120113620 A KR 20120113620A KR 101938338 B1 KR101938338 B1 KR 101938338B1
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nitrogen
halogen
phosphorus
sulfur
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KR20130040744A (en
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한용규
정지수
정우성
장병무
옥명안
나성재
수데반 수지쓰
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에스케이이노베이션 주식회사
에스케이종합화학 주식회사
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Abstract

The present invention relates to a process for producing a polyalkylene carbonate by polymerizing carbon dioxide and an alkylene oxide in the presence of a catalyst, wherein the propylene aldehyde content in the crude alkylene oxide recovered in the step of producing the polyalkylene carbonate lowers the catalytic activity and the selectivity to polyalkylene carbonate And a step of subjecting the mixture to a reaction for a predetermined time and then distillation under reduced pressure to adjust the aldehyde content to less than 5 ppm to obtain a purified alkylene Oxide is recovered.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for purifying an alkylene oxide in a polyalkylene carbonate production process,

The present invention relates to a process for producing a polyalkylene carbonate which is produced by polymerizing carbon dioxide and an alkylene oxide monomer in the presence of a catalyst and which is unreacted to reuse the alkylene oxide which has been separated or recovered, ≪ / RTI >

The aliphatic polycarbonate is a biodegradable polymer which is useful as, for example, a packaging material or a coating material. The method of producing polycarbonate from an epoxide compound and carbon dioxide is environmentally-friendly in that it does not use poisonous compound phosgene and that carbon dioxide can be obtained at low cost.

The polyalkylene carbonate can be produced in a continuous process via a catalyst comprising monomers carbon dioxide and an alkylene oxide with a transition metal as a central metal.

However, when the alkylene oxide, which is a monomer, is circulated for reuse in a continuous process, production of an aldehyde, which is an isomer of an alkylene oxide, can not be avoided and this acts as a catalyst poison in the polymerization system, It is a major cause. That is, the content of aldehyde in the continuous process should be kept at 5 ppm or less with respect to the alkylene oxide, thereby preventing the catalyst activity from being lowered and inhibiting the production of by-product cyclic carbonates.

No. 3,464,897 discloses a process for the distillation of propylene oxide mixed with hydrocarbon contaminants in the presence of an open chain or ring paraffin containing from 8 to 12 carbon atoms, , 568 discloses a process for purifying monoepoxide by extractive distillation with ethylene glycol or an ether thereof. US Patent No. 3,881,996 discloses a process for removing aldehydes and other high boiling materials by a series of distillation steps Discloses a method for recovering propylene oxide with high purity.

These conventional purification methods for recovering propylene oxide satisfying stringent purity requirements are not economical because they use a column having a plurality of separation stages operated at a high reflux ratio or difficult to remove specific impurities below 5 ppm by simple distillation only .

Particularly, there is a problem that the content of propionaldehyde in propylene oxide which is unreacted after polypropylene carbonate polymerization reaction and separated and recovered is 50 ppm or more, which greatly decreases catalytic activity and selectivity to polypropylene carbonate. Therefore, a technique for controlling the content of propionaldehyde in the untreated propylene oxide is urgent.

It is an object of the present invention to provide an economical purification method capable of obtaining an alkylene oxide of high purity by lowering the content of aldehyde in an alkylene oxide which is separated or recovered in a process for producing polyalkylene carbonate.

The present invention relates to a process for the preparation of propylene aldehyde, comprising: a) preparing a mixture of crude propylene oxide and alkanolamine containing propionaldehyde; And

and b) distilling the mixture. The present invention also provides a method for recovering purified propylene oxide having a high purity.

In the process for recovering purified propylene oxide of high purity according to an embodiment of the present invention, the crude propylene oxide in step a) is recovered in the step of producing polypropylene carbonate by polymerizing carbon dioxide and propylene oxide in the presence of a catalyst It can be reused after purification.

In the method for recovering purified propylene oxide of high purity according to an embodiment of the present invention, the mixing weight ratio of propionaldehyde and alkanolamine in step a) may be 1: 1 to 100.

In the process for recovering high purity refined propylene oxide according to an embodiment of the present invention, the mixture of step a) is prepared by mixing the crude propylene oxide and alkanolamine with stirring at 10 to 60 DEG C for 15 to 120 minutes Lt; / RTI >

In the process for recovering purified propylene oxide of high purity according to an embodiment of the present invention, the alkanolamine is selected from the group consisting of propanolamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, And mixtures thereof.

In a method for recovering high purity purified propylene oxide according to an embodiment of the present invention, the alkanolamine may be ethanolamine.

In the method for recovering high purity purified propylene oxide according to an embodiment of the present invention, the propylene oxide in step a) may contain 5 to 200 ppm of propionaldehyde.

In a method for recovering high purity refined propylene oxide according to an embodiment of the present invention, propylene oxide may be replaced by an alkylene oxide wherein the alkylene oxide is selected from the group consisting of ethylene oxide, butene oxide, , Octene oxide, decene oxide, cyclohexene oxide, and alkyl glycidyl ether.

The present invention relates to a process for the production of (i) a reaction solution comprising a copolymer obtained in a polymerization process wherein carbon dioxide and propylene oxide are reacted in the presence of a catalyst,

(Ii) obtaining propylene oxide from the reaction solution,

(Iii) mixing the obtained propylene oxide with an alkanolamine to prepare a mixture,

(Iv) simple distillation of the mixture to recover propylene oxide, and

(V) introducing the recovered propylene oxide into the polymerization process of step (i).

In the method for producing a polypropylene carbonate according to an embodiment of the present invention, the propylene oxide in the step (ii) may contain 5 to 200 ppm of propionaldehyde.

In the process for producing a polypropylene carbonate according to an embodiment of the present invention, the mixture of step (iii) may be obtained by mixing propylene oxide and alkanolamine at 10 to 60 DEG C for 15 to 120 minutes with stirring.

In the process for preparing a polypropylene carbonate according to an embodiment of the present invention, the alkanolamine is selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, aminoethanolamine, propanolamine, 2-hydroxycyclohexane, and mixtures thereof.

In the process for preparing a polypropylene carbonate according to an embodiment of the present invention, the alkanolamine may be ethanolamine.

In the method for producing polypropylene carbonate according to an embodiment of the present invention, the catalyst may be represented by the following formula (1).

[Chemical Formula 1]

Figure 112012083091211-pat00001

In Formula 1, M is cobalt trivalent or chromium trivalent;

A is an oxygen or sulfur atom;

Q is a diradical linking two nitrogen atoms;

R 1 to R 10 independently from each other are hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl;

Two of R 1 to R 10 may be connected to each other to form a ring;

At least one of the hydrogen atoms contained in R 1 to R 10 and Q is a proton group selected from the group consisting of the following Chemical Formulas 2, 3 and 4;

(2)

Figure 112012083091211-pat00002

(3)

Figure 112012083091211-pat00003

[Chemical Formula 4]

Figure 112012083091211-pat00004

X - are independently of one another a halogen anion; HCO 3 - ; BF 4 - ; ClO 4 -; NO 3 - ; PF 6 - ; (C6-C20) aryloxy anion; (C6-C20) aryloxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarboxy anion; (C1-C20) alkylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylcarboxy anion; (C6-C20) arylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy anion; (C1-C20) alkoxy anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbonate anion; A (C1-C20) alkylcarbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbonate anion; (C6-C20) aryl carbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylsulfonate anions; (C1-C20) alkylsulfonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl amido anion; (C1-C20) alkyl amido anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylamido anion; (C6-C20) aryl amido anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbamate anion; (C1-C20) alkylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbamate anion; (C6-C20) arylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom;

Z is a nitrogen or phosphorus atom;

R 21 , R 22 , R 23 , R 31 , R 32 , R 33 , R 34 and R 35 independently of one another are (C 1 -C 20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R 21 , R 22 and R 23 or two of R 31 , R 32 , R 33 , R 34 and R 35 may be connected to each other to form a ring;

R 41 , R 42 and R 43 independently of one another are hydrogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R 41 , R 42 and R 43 may be connected to each other to form a ring;

X 'is an oxygen atom, a sulfur atom or N-R wherein R is (C1-C20) alkyl;

n is an integer of 1 to the total number of protons included in R 1 to R 10 and Q;

X - may coordinate to M;

The nitrogen atom of the imine can be decarboxylated to M.

The present invention relates to a process for producing propylene aldehyde, which is an isomer in propylene oxide, by reacting an aldehyde with an amine using an alkanolamine in an irreversible reaction, thereby reducing the propionaldehyde content to 5 ppm or less It is very economical and highly productive because it can be removed. In addition, the propylene oxide recovery method of high purity according to the present invention is less expensive than the conventional purification method using a column having a plurality of separation stages, compared to a purification method of removing impurities by repeating simple distillation several times It is possible to minimize the time required for purification and the propylene oxide lost together with the impurities in the distillation step, and it is very effective since only propionaldehyde, which is an impurity to be selectively removed, can be removed through the reaction.

Figure 1 compares the polymerization activity according to the propionaldehyde content in propylene oxide.
Figure 2 shows a reactor system for propylene oxide purification.
Figure 3 shows the propionaldehyde removal efficiency of propylene oxide of ethanolamine over time.

The present invention relates to a process for preparing a mixture of crude propylene oxide (PO, Propylene Oxide) and Alkanolamine containing propionaldehyde (PA, Propionaldehyde) and simple distillation of the mixture, And recovering the propylene oxide.

In the process for recovering purified propylene oxide of high purity according to an embodiment of the present invention, the crude propylene oxide in step a) is recovered in the step of producing polypropylene carbonate by polymerizing carbon dioxide and propylene oxide in the presence of a catalyst It can be reused after purification. At this time, the crude propylene oxide can be separated from a polymerization mixture composed of polypropylene carbonate, unreacted carbon dioxide and unreacted propylene oxide through a phase separator composed of a plurality of polypropylene carbonate polymerization. The crude propylene oxide may be not only recovered in the polypropylene carbonate production process but also the crude propylene oxide obtained in another mode, that is, it may contain propylene oxide in addition to propylene oxide recovered in the polypropylene carbonate production process A purified propylene oxide of high purity can be obtained.

In the method for recovering high purity purified propylene oxide according to an embodiment of the present invention, the propylene oxide in step a) may contain 5 to 200 ppm of propionaldehyde. The plurality of phase separators include an intermediate pressure separator (IPS), a low pressure separator (LPS), a vacuum pressure separator (VS), and an upper effluent separated from the phase separator is supplied to a separation tower, And propylene oxide. In the intermediate pressure separator, about 30-80% of the propylene oxide and carbon dioxide are separated into the upper effluent in the polymerization mixture, and the polymerization mixture discharged to the lower part of the intermediate pressure separator is sent to the low pressure separator so that more than 90% And is transferred to a solvent surge drum constituting the separation tower. The propylene oxide transferred to the solvent surge drum was purified by the purification method according to the present invention to efficiently reduce the propionaldehyde content in the propylene oxide to less than 5 ppm to thereby obtain the catalyst activity and selectivity for the polypropylene carbonate Can be improved.

The alkanolamine is very effective in removing propionaldehyde in propylene oxide. Generally, the reaction between aldehyde and amine is well known as an imine formation reaction. However, if the water generated by the reversible reaction is not removed, the reaction proceeds again to slow down the reaction and reduce the efficiency. However, as shown in Reaction Scheme 1 below, the reaction between propionaldehyde and alkanolamine proceeds as an irreversible reaction that forms oxazolidine through rearrangement immediately after the formation of imine, No reaction and the reaction is fast. In addition, the boiling point of the alkanolamine used in this reaction and the final compound produced are different from the boiling point of propylene oxide of 34 ° C, which is above 85 ° C. Therefore, unreacted alkanolamine and propionaldehyde It is possible to effectively remove the reaction products.

(Scheme 1)

Figure 112012083091211-pat00005

In the method for recovering purified propylene oxide of high purity according to an embodiment of the present invention, the mixing weight ratio of propionaldehyde and alkanolamine may be 1: 1 to 1: 100, preferably 1: 1 to 1: : 15, more preferably from 1: 5 to 1:10. If the mixing weight ratio is exceeded, the alkanolamine and the carbon dioxide dissolved in the propylene oxide may react with each other to generate a white impurity. This is related to the carbon dioxide absorption reaction of the first- and second-class alkanolamines. When the above-mentioned weight ratio is exceeded, the alkanolamine reacts with the carbon dioxide dissolved in the propylene oxide to generate a carbamate ion. So that various types of salts can be produced.

In the process for recovering purified propylene oxide of high purity according to an embodiment of the present invention, the mixture of step a) is prepared by reacting crude propylene oxide and alkanolamine at 10 to 60 DEG C, Min, and the propanol aldehyde is reacted with a small amount of propanolic aldehyde. When the content of propionaldehyde is less than 15 minutes, the removal efficiency of propionaldehyde is lowered. When the content of propionaldehyde is more than 120 minutes, Can fall. At this time, the stirring reaction is preferably carried out in a separate stirring reactor.

In a method for recovering high purity purified propylene oxide according to an embodiment of the present invention, the alkanolamine is NH 2 JOH; J is - [CR 2 ] n - (n is an integer from 0 to 10; R may be the same or different and is hydrogen, methyl, ethyl, propyl, butyl, cycloalkane), preferably ethanolamine, It is possible to use alkanolamines comprising diethanolamine, triethanolamine, N-methylethanolamine, aminoethanolamine, propanolamine, butanolamine and 1-amino-2-hydroxycyclohexane, more preferably ethanolamine .

In a method for recovering high purity refined propylene oxide according to an embodiment of the present invention, propylene oxide may be replaced by an alkylene oxide wherein the alkylene oxide is selected from the group consisting of ethylene oxide, butene oxide, , Octene oxide, decene oxide, cyclohexene oxide, and alkyl glycidyl ether.

The present invention relates to a process for the production of (i) a reaction solution comprising a copolymer obtained in a polymerization process wherein carbon dioxide and propylene oxide are reacted in the presence of a catalyst,

(Ii) obtaining propylene oxide from the reaction solution,

(Iii) mixing the obtained propylene oxide with an alkanolamine to prepare a mixture,

(Iv) simple distillation of the mixture to recover propylene oxide, and

(V) introducing the recovered propylene oxide into the polymerization process of step (i).

In the method for producing a polypropylene carbonate according to an embodiment of the present invention, the propylene oxide in the step (ii) may contain 5 to 200 ppm of propionaldehyde. This can efficiently purify the propylene oxide transferred for recycling, and further lowering the propionaldehyde content can increase the catalytic activity and the selectivity to the polypropylene carbonate.

At this time, the propylene oxide fed contains propionaldehyde. In the mixture of propionaldehyde and alkanolamine, the mixing weight ratio is preferably 1: 1 to 1: 100, more preferably 1: 1 to 1:15, Is in the range of 1: 1 to 1: 5, it is possible to prevent impurities from being generated when reacting with carbon dioxide dissolved in propylene oxide.

In the process for producing polypropylene carbonate according to an embodiment of the present invention, the mixture of step (iii) is obtained by mixing propylene oxide and alkanolamine at 10 to 60 DEG C for 15 to 120 minutes with stirring to effectively mix alkanolamine And propionaldehyde can be reacted.

In the process for preparing a polypropylene carbonate according to an embodiment of the present invention, the alkanolamine is selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, aminoethanolamine, propanolamine, 2-hydroxycyclohexane, and mixtures thereof.

In the process for preparing a polypropylene carbonate according to an embodiment of the present invention, the alkanolamine may be ethanolamine.

In the method for producing polypropylene carbonate according to an embodiment of the present invention, the catalyst may be represented by the following formula (1).

[Chemical Formula 1]

Figure 112012083091211-pat00006

In Formula 1, M is cobalt trivalent or chromium trivalent;

A is an oxygen or sulfur atom;

Q is a diradical linking two nitrogen atoms;

R 1 To R 10 is independently from each other hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl;

The R 1 To R 10 medium Two of which may be connected to each other to form a ring;

The R 1 To R 10 and Q is a proton radical selected from the group consisting of the following formulas (2), (3) and (4);

(2)

Figure 112012083091211-pat00007

(3)

Figure 112012083091211-pat00008

[Chemical Formula 4]

Figure 112012083091211-pat00009

X - are independently of one another a halogen anion; HCO 3 - ; BF 4 - ; ClO 4 -; NO 3 - ; PF 6 - ; (C6-C20) aryloxy anion; (C6-C20) aryloxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarboxy anion; (C1-C20) alkylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylcarboxy anion; (C6-C20) arylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy anion; (C1-C20) alkoxy anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbonate anion; A (C1-C20) alkylcarbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbonate anion; (C6-C20) aryl carbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylsulfonate anions; (C1-C20) alkylsulfonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl amido anion; (C1-C20) alkyl amido anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylamido anion; (C6-C20) aryl amido anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbamate anion; (C1-C20) alkylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbamate anion; (C6-C20) arylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom;

Z is a nitrogen or phosphorus atom;

R 21 , R 22 , R 23 , R 31 , R 32 , R 33 , R 34 and R 35 independently of one another are (C 1 -C 20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R 21 , R 22 and R 23 or R 31 , R 32 , R 33 , R 34 and R 35 Two of which may be connected to each other to form a ring;

R 41 , R 42 and R 43 independently of one another are hydrogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R 41 , R 42 and R 43 may be connected to each other to form a ring;

X 'is an oxygen atom, a sulfur atom or N-R wherein R is (C1-C20) alkyl;

n is < RTI ID = To R < 10 > and Q plus 1 to the total number of protons included;

X - may coordinate to M;

The nitrogen atom of the imine can be decarboxylated to M.

In this case, in the process for producing polypropylene carbonate according to an embodiment of the present invention, the propylene carbonate may be replaced with an alkylene carbonate, wherein the alkylene is ethylene, 1-butylene, cyclohexene, Alkyl glycidyl ether, n-butyl, n-octyl, and the like.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples.

The propylene oxide purity, propionaldehyde and heavy impurity content were measured by gas chromatography (FID, Flame Ionization Detector) and CP-wax 52CB (60 m × 0.32 mm × 1.2 μm, Varian CP-8073) GC, Gas Chromatography, Agilent 7890A) and calculated based on the area of the graph. 0.7 ml / min of helium was used as the mobile phase, and the injection volume and split rate were 1 μl and 30: 1. At this time, the temperature of the injector and the detector was maintained at 210 ° C, and the oven was maintained at 35 ° C for 10 minutes, then heated to 210 ° C at a rate of 4 ° C / min, and then maintained for 40 minutes.

(Example 1)

332 g of 99.57% propylene oxide containing 84 ppm of propionaldehyde (0.48 mmol) and 4114 ppm of heavy impurity recovered in the polypropylene carbonate manufacturing process were placed in a 1 L flask, and 0.147 g (2.40 mmol, ethanolamine / Propionaldehyde = 5) were mixed to start the stirring reaction. After reaction at room temperature for 15 minutes, 99.97% of purified propylene oxide containing 18 ppm of propionaldehyde and 150 ppm of heavy impurity was recovered by distillation under reduced pressure.

(Example 2)

The reaction was carried out in the same manner as in Example 1 except that the stirring reaction time at room temperature was 30 minutes. 99.97% of purified propylene oxide containing 8 ppm of propionaldehyde and 155 ppnm of heavy impurity was recovered.

(Example 3)

The reaction was carried out in the same manner as in Example 1 except that the stirring reaction time at room temperature was 60 minutes. 99.97% of purified propylene oxide containing 4 ppm of propionaldehyde and 156 ppm of heavy impurity was recovered.

(Example 4)

The reaction was carried out in the same manner as in Example 1 except that the stirring reaction time at room temperature was changed to 90 minutes to recover 99.97% of purified propylene oxide containing 3 ppm of propionaldehyde and 156 ppm of heavy impurity.

(Example 5)

332 g of 99.57% propylene oxide containing 84 ppm of propionaldehyde (0.48 mmol) recovered in the polypropylene carbonate manufacturing process and 4114 ppm of heavy impurity were placed in a 1 L flask, and 0.293 g (4.80 mmol, ethanolamine / Propionaldehyde = 10) was added and stirring was started. After stirring at room temperature for 15 minutes, 99.97% of purified propylene oxide containing 4 ppm of propionaldehyde and 143 ppm of heavy impurity was recovered by vacuum distillation.

(Example 6)

The reaction was carried out in the same manner as in Example 5 except that the stirring reaction time at room temperature was 30 minutes to recover 99.97% of purified propylene oxide containing 2 ppm of propionaldehyde and 157 ppm of heavy impurity.

(Example 7)

332 g of 99.98% propylene oxide containing 45 ppm of propionaldehyde (0.26 mmol) and 23 ppm of heavy impurity recovered in the polypropylene carbonate manufacturing process were placed in a 1 L flask, and 0.079 g (1.29 mmol, ethanolamine / Propionaldehyde = 5) was added and stirring was started. After stirring at room temperature for 15 minutes, 99.98% of purified propylene oxide containing 11 ppm of propionaldehyde and 4 ppm of heavy impurity was recovered by vacuum distillation.

(Example 8)

The reaction was carried out in the same manner as in Example 7 except that the stirring reaction time at room temperature was 30 minutes. 99.98% of purified propylene oxide containing 6 ppm of propionaldehyde and 2 ppm of heavy impurity was recovered.

(Example 9)

The reaction was carried out in the same manner as in Example 7 except that the stirring reaction time at room temperature was 60 minutes. 99.98% of purified propylene oxide containing 3 ppm of propionaldehyde and 2 ppm of heavy impurity was recovered.

(Example 10)

The reaction was carried out in the same manner as in Example 7 except that the stirring reaction time at room temperature was 90 minutes. 99.98% of purified propylene oxide containing 3 ppm of propionaldehyde and 2 ppm of heavy impurity was recovered.

(Example 11)

332 g of 99.98% propylene oxide containing 45 ppm of propionaldehyde (0.26 mmol) and 23 ppm of heavy impurity recovered in the polypropylene carbonate manufacturing process was placed in a 1 L flask, and 0.157 g (2.57 mmol, ethanolamine / Propionaldehyde = 10) was added and stirring was started. After stirring at room temperature for 15 minutes, 99.99% of purified propylene oxide containing 5 ppm of propionaldehyde and 2 ppm of heavy impurity was recovered by distillation under reduced pressure.

(Example 12)

The reaction was carried out in the same manner as in Example 11 except that the stirring reaction time at room temperature was 30 minutes. 99.98% of purified propylene oxide containing 3 ppm of propionaldehyde and 3 ppm of heavy impurity was recovered.

(Example 13)

FIG. 2 shows an example of a reactor system for purifying propylene oxide. Propylene oxide recovered for recycling propylene oxide, which is applied as a monomer and a polymerization solvent in the production process of polypropylene carbonate, is distilled to R- (CSTR, Continuous Stirred-Tank Reactor). Ethanolamine was added dropwise to the propylene oxide in the R-301 reactor to remove the propionaldehyde generated during the polymerization, and the propionaldehyde was reacted with 2- Ethyl-oxazolidine and then removed by simple distillation to purify the propylene oxide.

At this time, the propylene oxide having high concentration of propionaldehyde stored in D-203 is removed from the V-301 stripper and then transferred to the R-301 reactor to convert ethanolamine and propionaldehyde into high boiling point compounds . In the final column of V-302, the low boiling propylene oxide was separated into the upper part of the column and the higher boiling matter was separated into the lower part, thereby maximizing the purity of the propylene oxide.

Experimental Results As shown in FIG. 3, propylene oxide containing propionaldehyde at 20 to 30 ppm level (case 1: when EA was not added) was stirred together with ethanolamine to prepare propionaldehyde at a concentration of 5 ppm or less (case 2: EA Hour).

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be clear to the person.

Claims (13)

a) in the step of producing polypropylene carbonate by polymerizing carbon dioxide and propylene oxide in the presence of a catalyst,
The recovered propylene aldehyde-containing crude propylene oxide is mixed with an alkanolamine,
Propionic aldehyde and alkanolamine in a weight ratio of 1: 5 to 1:10; And
b) distilling the mixture. < Desc / Clms Page number 13 >
delete delete The method according to claim 1,
Wherein the mixture of step a) is prepared by mixing the propylene oxide and the alkanolamine at 10 to 60 DEG C for 15 to 120 minutes with stirring to obtain purified propylene oxide.
The method according to claim 1,
The alkanolamine may be any one selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, aminoethanolamine, propanolamine, butanolamine, 1-amino-2-hydroxycyclohexane, And recovering the purified propylene oxide.
The method according to claim 1,
Wherein the alkanolamine is an ethanolamine, and recovering the purified propylene oxide of high purity.
The method according to claim 1,
Wherein the propylene oxide in step a) contains 5 to 200 ppm of propionaldehyde.
(I) obtaining a reaction solution comprising a copolymer obtained in a polymerization process in which carbon dioxide and propylene oxide are reacted in the presence of a catalyst,
(Ii) obtaining propylene oxide containing propionaldehyde from the reaction solution,
(Iii) mixing the obtained crude propylene oxide with an alkanolamine to prepare a mixture of propionaldehyde and alkanolamine in a weight ratio of 1: 5 to 1:10,
(Iv) distilling the mixture to recover purified propylene oxide, and
(V) introducing the recovered purified propylene oxide into the polymerization process of step (i).
9. The method of claim 8,
Wherein the propylene oxide of the step (ii) contains 5 to 200 ppm of propionaldehyde.
9. The method of claim 8,
Wherein the mixture of step (iii) is obtained by mixing propylene oxide and alkanolamine with stirring at 10 to 60 DEG C for 15 to 120 minutes.
9. The method of claim 8,
The alkanolamine may be any one selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, aminoethanolamine, propanolamine, butanolamine, 1-amino-2-hydroxycyclohexane, By weight based on the total weight of the polypropylene carbonate.
9. The method of claim 8,
Wherein the alkanolamine is ethanolamine.
9. The method of claim 8,
Wherein the catalyst is a polypropylene carbonate represented by the following formula (1).
[Chemical Formula 1]
Figure 112019500938515-pat00010

[In the above formula (1)
M is a cobalt trivalent or chromium trivalent,
A is an oxygen or sulfur atom,
Q is a di-radical linking two nitrogen atoms,
R 1 - R 10 is independently from each other hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl,
The R < 1 & R 10 Two rings may be connected to each other to form a ring,
The R < 1 & At least one of the hydrogen atoms contained in R 10 and Q is a proton group selected from the group consisting of the following formulas (2), (3) and (4)
(2)
Figure 112019500938515-pat00011

(3)
Figure 112019500938515-pat00012

[Chemical Formula 4]
Figure 112019500938515-pat00013

X - are independently of one another a halogen anion; HCO 3 - ; BF 4 - ; ClO 4 -; NO 3 - ; PF 6 - ; (C6-C20) aryloxy anion; (C6-C20) aryloxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarboxy anion; (C1-C20) alkylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylcarboxy anion; (C6-C20) arylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy anion; (C1-C20) alkoxy anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbonate anion; A (C1-C20) alkylcarbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbonate anion; (C6-C20) aryl carbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylsulfonate anions; (C1-C20) alkylsulfonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl amido anion; (C1-C20) alkyl amido anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylamido anion; (C6-C20) aryl amido anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbamate anion; (C1-C20) alkylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbamate anion; (C6-C20) arylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; , ≪ / RTI >
Z is a nitrogen or phosphorus atom,
R 21 , R 22 , R 23 , R 31 , R 32 , R 33 , R 34 and R 35 independently of one another are (C 1 -C 20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R 21 , R 22 and R 23 or two of R 31 , R 32 , R 33 , R 34 and R 35 may be connected to each other to form a ring,
R 41 , R 42 and R 43 independently of one another are hydrogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R 41 , R 42 and R 43 may be connected to each other to form a ring,
X 'is an oxygen atom, a sulfur atom or NR (where R is (C1-C20) alkyl)
n is from R < R < 10 > and Q,
X < - > may coordinate to M,
The nitrogen atom of the imine can be decarboxylated to M.]
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