KR101781910B1 - Method for preparing poly(epichlorohydrin)-polyol and polyglycidylazide-polyol - Google Patents

Abstract

상기 화학식 1에서, n 및 m은 1 내지 50인 자연수이고, n과 m의 합은 50 이하이며, R1은 알킬렌기이다.
본 발명에 따르면, 폴리글리시딜아자이드 합성 시 메틸렌클로라이드를 사용하지 않음으로써, 합성 및 정제시 폭발의 위험성을 해결할 수 있다. The present invention relates to a process for the preparation of polyepichlorohydrin-polyols and polyglycidyl azide-polyols. The present invention relates to a process for preparing a triflate-diol complex by mixing a diol and a trifluoride-ether salt (BF3-Etherate) and heating to form a trifluoride-diol complex, and supplying the complex with epichlorohydrin, Wherein the step of synthesizing the compound proceeds to a melt polymerization reaction. The process for producing a polyepichlorohydrin-polyol according to claim 1,
[Chemical Formula 1]

In Formula 1, n and m are natural numbers of 1 to 50, the sum of n and m is 50 or less, and R 1 is an alkylene group.
According to the present invention, the use of methylene chloride in the synthesis of polyglycidyl azide can solve the risk of explosion during synthesis and purification.

Description

METHOD FOR PREPARING POLY (EPICHLOROHYDRIN) -POLYOL AND POLYGLYCIDYLAZIDE-POLYOL] [0001] This invention relates to a process for preparing polyepichlorohydrin-polyol and polyglycidyl azide-

The present invention relates to a process for the preparation of polyepichlorohydrin-polyols and polyglycidyl azide-polyols.

Poly (epichlorohydrin) -polyol (PECH-polyol) with a hydroxyl-terminated functional group produces glycidyl azide polymer (GAP) through an azide group substitution reaction. GAP is a urethane reaction and is the main raw material for inorganic systems such as ETPE propellant or FOAM propallant. Molecular weight, molecular weight distribution, etc. The quality of GAP as a urethane raw material is determined at the PECH synthesis stage, and the polyol as a urethane raw material requires a narrow molecular weight distribution and a high quality with a minimum of impurities.

PECH-polyol, which is a precursor of GAP, is produced by cationic ring-opening polymerization. In 1996, initiation reaction and polymerization reaction by the active monomer mechanism (AM mechanism) were known in the presence of alcohol, PECH reaction is proceeding under the condition of AM mechnism to minimize side reactions such as cyclization.

The formation of side reactions such as cyclization makes it difficult to control the number of hydroxyl end group functional groups and causes the degradation of physical properties due to the plasticizing effect of the byproducts, and it is impossible to produce the polymer having the designed molecular weight, May be difficult to synthesize.

On the other hand, the synthesis reaction of PECH-polyol proceeds mainly in methylene chloride, which is a polar halogen solvent. Due to this, during the azidation reaction with PECH-polyol, methylene chloride may remain. Methylene chloride reacts with sodium azide, the raw material of the azidation reaction, to form diazid methane, which is a potentially explosive hazard. For this reason, stability problems for GAP synthesis are being raised.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a PECH-polyol having a high yield, in order to solve the above-mentioned problems.

It is another object of the present invention to provide a method for producing a polyglycidyl azide-polyol capable of eliminating the formation of diazid methane, which is a danger of explosion.

In order to accomplish the above object, the present invention provides a method for producing a polyhydroxyalkanoate comprising the steps of mixing diol and trifluoro-ether salt (BF3-Etherate) and then heating to form a trifluoride-diol complex and supplying the complex with epichlorohydrin To synthesize a compound represented by the following formula (1), and the step of synthesizing the compound proceeds to a melt polymerization reaction.

[Chemical Formula 1]

In Formula 1, n and m are natural numbers of 1 to 50, the sum of n and m is 50 or less, and R 1 is an alkylene group.

In one embodiment, the diol may be any of neopentyl glycol and 2-methyl-1,3 propanediol.

The present invention also relates to a process for preparing a polyglycidyl azide-polyglycidyl azide compound, which comprises synthesizing a compound represented by the following general formula (2) by mixing polyepichlorohydrin-polyol and sodium azide, A process for producing a polyol is provided.

 (2)

In Formula 2, n and m are natural numbers of 1 to 50, the sum of n and m is 50 or less, and R 1 is an alkylene group.

The present invention also relates to a process for preparing a triflate-triol complex by mixing triol and trifluoride-etherate (BF3-Etherate) and heating to form a trifluoride-triol complex, supplying epichlorohydrin to the complex, Wherein the step of synthesizing the compound proceeds to a melt polymerization reaction. The polyepichlorohydrin-polyol may be synthesized by a method comprising the steps of:

(3)

In Formula 3, n, m and 1 are natural numbers of 1 to 50, the sum of n, m and l is 50 or less, and R 2 is an alkylene group having one or more hydrocarbon side chains.

In one embodiment, the triol can be either glycerol or trimethylol propane.

The present invention also relates to a process for producing polyglycidyl azide-polyglycidyl azide-polyglycidyl azide-polyglycidyl azide-polyglycidyl azide compounds, which comprises synthesizing a compound represented by the following formula (4) A process for producing a polyol is provided.

 [Chemical Formula 4]

In Formula 4, n, m and 1 are natural numbers of 1 to 50, the sum of n, m and l is 50 or less, and R 2 is an alkylene group having at least one hydrocarbon side chain.

According to the present invention, the use of methylene chloride in the synthesis of polyglycidyl azide can solve the risk of explosion during synthesis and purification.

In addition, since the present invention is a process that does not use a solvent, the concentration of the initiator at the initial stage of the reaction is high, and the polymer growth reaction by the chain terminal activation mechanism is suppressed. As a result, the polyglycidyl azide-polyol having the properties of suppressing the production of the low-molecular weight reactant and having the small impurity content and almost the same molecular weight can be obtained.

Hereinafter, an embodiment of the present invention will be described in detail. In the present specification, different embodiments are given the same or similar reference numerals, and the description thereof is replaced with the first explanation. As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.

Unless otherwise noted below, the 'concentration ratio' refers to the concentration ratio of initiator base BF ₃ , the 'feed time' refers to the time of supplying the epichlorohydrin solution to the reactor, and the 'setting temperature' Is the initial set temperature, and 'measurement temperature' is the reaction temperature measured over the polymerization reaction time.

The present invention provides a process for producing a polyepichlorohydrin-polyol, and a process for producing a polyglycidyl azide-polyol from a polyepichlorohydrin-polyol produced by the process.

First, a method for producing a polyepichlorohydrin-polyol according to an embodiment of the present invention will be described.

In the process for producing a polyepichlorohydrin-polyol of the present invention, an initiator and a trifluoride-ether salt (BF ₃ -Etherate) are mixed and then heated to form a trifluoride-initiator complex.

Here, the initiator may be a diol or a triol. The number of hydroxyl groups of the polyepichlorohydrin-polyol varies depending on the number of hydroxyl groups contained in the initiator. Specifically, when a diol is used as the initiator, the product is a diol, and when a triol is used, the product is a triol.

Specifically, the diol may be any one of neopentyl glycol (NPG) and 2-methyl-1,3 propanediol (MPD), and the triol may be glycerol (Gly.) And trimethylol propane (TMP) . ≪ / RTI >

Here, the concentration ratio of the initiator base BF ₃ may be 0.02 to 1.

Next, a step of synthesizing a polyepichlorohydrin-polyol by supplying epichlorohydrin to the complex is carried out.

Here, the polyepichlorohydrin-polyol may be represented by any one of the following formulas (1) and (3). As described above, when the diol is used as the initiator, a polyepichlorohydrin-polyol represented by the following general formula (1) is synthesized, and when triol is used, a polyepichlorohydrin-polyol .

[Chemical Formula 1]

In Formula 1, n and m are natural numbers of 1 to 50, the sum of n and m is 50 or less, and R 1 is an alkylene group.

(3)

Here, the reaction in which the polyepichlorohydrin-polyol is synthesized is a cationic ring opening polymerization (CROP) reaction. PEG-polyol prepared by cationic ring-opening polymerization reaction tends to react with aprotic monomer easily to form cyclic oligomer because the reactivity becomes larger as the terminal is cationized.

Thus, the step of synthesizing the polyepichlorohydrin-polyol proceeds in the absence of a solvent. That is, the step of synthesizing the polyepichlorohydrin-polyol proceeds to a melt polymerization reaction. Under the solventless conditions, the formation of cyclic oligomer is suppressed by the effect of high hydroxyl group concentration and the yield of the chain type polymer is high.

Here, the molecular weight of the polyepichlorohydrin-polyol prepared according to the production method of the present invention is 1000 to 5000 and the dispersity is 1.2 or less.

In addition, the step of synthesizing the polyepichlorohydrin-polyol can be carried out at 20 캜 to 40 캜. If the reaction temperature is high, it is difficult to control the exothermic reaction and vapor of the reactant may be generated, which can be dangerous.

In addition, the step of synthesizing the polyepichlorohydrin-polyol can be carried out for 3 to 10 hours.

On the other hand, a polyglycidyl azide-polyol can be prepared from the polyepichlorohydrin-polyol produced by the above-described production method.

Specifically, the polyglycidyl azide-polyol is prepared by mixing the polyepichlorohydrin-polyol and sodium azide in a predetermined solvent by the above-described production method. Here, the Cl group of the polyepichlorohydrin-polyol is substituted with an azide group.

The substitution reaction product may be a compound represented by any one of the following formulas (2) and (4) according to the kind of the polyepichlorohydrin-polyol.

 (2)

In Formula 2, n and m are natural numbers of 1 to 50, the sum of n and m is 50 or less, and R 1 is an alkylene group.

 [Chemical Formula 4]

In Formula 4, n, m and 1 are natural numbers of 1 to 50, the sum of n, m and l is 50 or less, and R 2 is an alkylene group having at least one hydrocarbon side chain.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the scope and contents of the present invention are not construed to be limited or limited by the following Examples and Experimental Examples.

Example 1 - Polyepichlorohydrin - Of PECH-diol  Produce

The synthesis reaction of the polyepichlorohydrin-polyol was carried out in a 10 L glass jacketed reactor equipped with a stirrer, a monomer feeder, a thermometer, a condenser, a nitrogen feed hose and a cooler.

The boron trichloride complex (BF ₃ -etherate) and initiator diol (0.51 mol) were placed in a reactor and the mixture was stirred at 70 ° C for about 30 minutes to prepare a diol-BF ₃ complex.

Epichlorohydrin (ECH) (1531 g, 16.56 mol) was added via a teflon tubing to a monomer tank to which a solenoid valve was connected to prepare an epichlorohydrin aqueous solution The feed time was maintained at the rate of maintaining the reaction temperature in the 30 ° C reactor and the dropping was completed.

The reaction solution was stirred for 20 minutes even after completion of feeding of the epichlorohydrin solution. To facilitate purification, the polyepichlorohydrin prepared by adding 300 g of toluene was dissolved in toluene, washed with sodium hydrogencarbonate solution (1 L, 10 wt%) and washed several times with distilled water until neutral. The solvent was removed by evaporation and a polyepichlorohydrin-diol was obtained.

The reaction conditions of each polyepichlorohydrin-diol thus obtained are summarized in Table 1 below. Hereinafter, the polyepichlorohydrin-polyol prepared according to each reaction condition is specified by the diol / concentration / design molecular weight according to the type of initiator, the concentration ratio, and the design molecular weight.

Name of sample Initiator Reaction temperature (캜) Concentration ratio Design molecular weight PECH _{MPD / 0.1} 900diol MPD 30 0.1 900 PECH _{MPD / 0.2} 3000 diol MPD 30 0.2 2800 PECH _{MPD / 0.5} 3000diol MPD 30 0.5 2800 PECH _{NPG / 0.05} 3000diol NPG 40 0.05 2800

Example 2 - Polyglycidyl azide - Diol (GAP-diol)  Produce

The poly-epichlorohydrin (1300 g) prepared in Example 1, DMSO and sodium azide were placed in a 1 L-3 neck reactor. The temperature was gradually raised from room temperature to 110 ° C under agitation. The reaction was terminated after confirming that the C-Cl characteristic peak completely disappeared at 748 cm ^-1 using FT-IR. After completion of the reaction, ethyl acetate and distilled water were added to the reaction product to purify GAP.

Example 3 - Polyepichlorohydrin - Of triol (PECH-triol)  Produce

The polymerization reaction was carried out in a 10 L glass jacketed reactor equipped with a stirrer, a monomer feeder, a thermometer, a condenser, a nitrogen feed hose and a cooler.

The boron trichloride complex (BF ₃ -etherate) and initiator triol (0.51 mol) were placed in a reactor and the mixture was stirred at 40 ° C for about 30 minutes to prepare a triol-BF ₃ complex.

Epichlorohydrin (ECH) (1531 g, 16.56 mol) was added via a teflon tubing to a monomer tank to which a solenoid valve was connected to prepare an epichlorohydrin aqueous solution The feed time was maintained at the rate of maintaining the reaction temperature to complete the dropwise addition.

The reaction solution was further stirred for 20 minutes after completion of supplying the epichlorohydrin solution. To facilitate purification, 300 g of toluene was added to dissolve the prepared poly-epichlorohydrin, washed with sodium hydrogencarbonate solution (1 L, 10 wt%) and washed several times with distilled water until neutral. The solvent was removed by evaporation to give the polyepichlorohydrin-triol.

Name of sample Initiator Reaction temperature (캜) Concentration ratio Design molecular weight PECH _{Gly / 0.1} 800 triol Glycerol 30 0.1 800 PECH _{TMP / 0.05} 3000triol TMP 30 0.5 2800 PECH _{TMP / 0.05} 3000triol TMP 30 0.5 2800

Example 4 - Polyglycidyl azide - Of triol (GAP-triol)  Produce

1 L-3neck-reactor was charged with the polyepichlorohydrin (1300 g) prepared in Example 3, DMSO and sodium azide. The temperature was gradually raised from room temperature to 110 ° C under agitation. The reaction was terminated after confirming that the C-Cl characteristic peak completely disappeared at 748 cm ^-1 using FT-IR. After completion of the reaction, ethyl acetate and distilled water were added to the reaction product, and GAP was purified.

Experimental Example 1 - GPC  analysis

The relative average molecular weight and polydispersity index (PDI = M _w / M _n ) of the polyepichlorohydrin-polyol prepared in Example 1 were measured using a Shodex ^TM column (KF-801, KF-802, KF-804, KF-805 ) And a 2410 detector (differential refractive index detector). The operating temperature was 40 ° C, the mobile phase was tetrahydrofuran (THF), the feed rate was 1.0 ml / min, and the raw data were calibrated by standard calibrations with standard polystyrene (M _w = 162-2,400,000).

Table 3 shows the results of analysis of polyepichlorohydrin-polyol and polyglycidyl azide-polyol prepared according to the above Examples.

Name of sample M _n
(g /
mol) M _w
(g /
mol) PDI Yield
(%) Name of sample M _n
(g /
mol) M _w
(g /
mol) PDI PECH _{MPD / 0.1} 900diol 870 957 1.1 96 GAP _{MPD / 0.1} 900 diol 1070 1057 1.1 PECH _{MPD / 0.2} 3000 diol 2750 3162 1.15 92 GAP _{MPD / 0.2} 3000 diol 2960 3372 1.15 PECH _{MPD / 0.5} 3000diol 2760 3174 1.15 94 GAP _{MPD / 0.5} 3000 diol 2960 3364 1.15 PECH _{NPG / 0.05} 3000diol 2870 3197 1.14 95 GAP _{NPG / 0.05} 3000diol 3070 3400 1.14 PECH _{Gly / 0.1} 800 triol 780 897 1.1 92 GAP _{Gly / 0.1} 800 diol 970 1097 1.1 PECH _{TMP / 0.05} 3000triol 2740 3151 1.14 93 GAP _{TMP / 0.05} 3000 diol 2930 3351 1.14 PECH _{TMP / 0.05} 3000triol 2750 3162 1.14 92 GAP _{TMP / 0.05} 3000 diol 2950 3372 1.14

In Table 3, Mn is the number average molecular weight, Mw is the weight average molecular weight, and PDI is the polydispersity.

It will be apparent to those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof.

In addition, the above detailed description should not be construed in all aspects as limiting and should be considered illustrative. The scope of the present invention should be determined by rational interpretation of the appended claims, and all changes within the scope of equivalents of the present invention are included in the scope of the present invention.

Claims (6)

Mixing diol and trifluoride-ether salt (BF3-Etherate) and heating to form a trifluoride-diol complex;
Synthesizing a polyepichlorohydrin-polyol represented by the following formula (1) by supplying epichlorohydrin to the complex; And
[Chemical Formula 1]

Mixing the compound of Formula 1 with a solvent to synthesize a compound represented by Formula 2,
(2)

Wherein the step of synthesizing the compound of Formula 1 proceeds to a solvent-less solvent-free melt polymerization reaction and has a polydispersity index (PDI) of 1.1 to 1.15. The polyglycidyl azide- ≪ / RTI >
In the general formulas (1) and (2), n and m are natural numbers of 1 to 50, the sum of n and m is 50 or less, and R 1 is an alkylene group.
The method according to claim 1,
Wherein the diol is any one of neopentyl glycol and 2-methyl-1,3-propanediol. delete Mixing triol and trifluoride-ether salt (BF3-Etherate) and heating to form a trifluoride-triol complex;
Synthesizing a polyepichlorohydrin polyol represented by the following formula (3) by supplying epichlorohydrin to the complex; and
(3)

Mixing the compound of Formula 3 with a solvent to synthesize a compound represented by Formula 4,
[Chemical Formula 4]

Wherein the step of synthesizing the compound of Formula 3 proceeds to a solvent-less solvent-free melt polymerization reaction and has a polydispersity index (PDI) of 1.1 to 1.15. The polyglycidyl azide- ≪ / RTI >
In the general formulas (3) and (4), n, m and 1 are natural numbers of 1 to 50, the sum of n, m and l is 50 or less, and R 2 is an alkylene group having one or more hydrocarbon side chains. 5. The method of claim 4,
Wherein the triol is any one of glycerol and trimethylol propane. delete