KR101633307B1 - preparation method of poly epicholorohydrin -diol and poly epicholorohydrin-diol made thereby - Google Patents

Abstract

According to the present invention, the polyepichlorohydrin-diol can be obtained in a high yield by inhibiting the formation of the cyclic oligomer as an impurity. The polyepichlorohydrin-diol thus obtained has a polydispersity index of 1.31 to 1.34 And have almost the same molecular weight. The polyepichlorohydrin-diol of the present invention can be utilized in many fields such as a solid propellant binder, a liquid crystal alignment layer, a biocompatible polymer, and the like.

Description

The preparation method of polyepichlorohydrin-diol and the preparation method of polyepichlorohydrin-diol and polyepichlorohydrin-diol made thereby]

The present invention relates to a process for producing a polyepichlorohydrin-diol (PECH-diol) used for solid propellant binders and the like.

BACKGROUND ART Polyepichlorohydrin-diol (PECH-diol) and an energized thermoplastic elastomer (ETPE) prepared therefrom are materials that can be used in many fields such as a solid propellant binder, a liquid crystal orientation layer and a biocompatible polymer. .

PECH-diol is generally synthesized through cationic ring opening polymerization (CROP). When the induction period is prolonged in CROP, it tends to form cyclic oligomer, and the chain polymer PECH- diol. < / RTI >

For this purpose, there is a method in which a chlorinating agent containing hydrogen chloride gas or an aqueous hydrochloric acid solution is reacted with a monomer to prepare a by-product. However, as the by-product, water is formed and the produced water inhibits the polymerization reaction, There is a problem.

KR Patent Publication No. 10-2012-0002338

Therefore, a problem to be solved by the present invention is to provide a method for producing a polyepichlorohydrin-diol having a high yield and a narrow molecular weight distribution by reducing induction period to inhibit the production of cyclic oligomers.

A second problem to be solved by the present invention is to provide a polyepichlorohydrin-diol prepared by the above method, and an energized thermoplastic elastomer (ETPE) and a propellant containing the same.

In order to solve the above problems, the present invention provides a process for producing a polyepichlorohydrin-diol (PECH-diol) represented by the following formula (1).

[Chemical Formula 1]

In the above formula (1)

R is a substituted or unsubstituted alkyl group having 2 to 6 carbon atoms, and n and m are integers from 4 to 28, which are the same or different.

A process for preparing a polyepichlorohydrin-diol (PECH-diol) according to the present invention is characterized by comprising the following steps.

(a) reacting a diol, which is an initiator, with boron trichloride (BF ₃ ), which is a Lewis acid, in a solvent to form a diol-BF ₃ complex,

(b) supplying the epichlorohydrin monomer to the diol-BF ₃ complex to polymerize.

In the step (a), the concentration ratio of the diol standard BF ₃ is 0.5 to 1,

In the step (b), the feeding rate of the epichlorohydrin monomer is 9.2 × 10 ^-3 to 13.8 × 10 ^-3 mol / min.

The present invention also provides a polyepichlorohydrin-diol produced by the process, and provides a propellant comprising the polyepichlorohydrin-diol.

According to the present invention, it is possible to obtain a polyepichlorohydrin-diol which has a low solubility in a solvent of a diol-BF ₃ complex and a short induction period, and thus has a low impurity content and almost the same molecular weight.

1 is a structural diagram showing an example of a reactor for producing a polyepichlorohydrin-diol according to the present invention.
Figure 2 is a diol -BF ₃ And the solubility of the complex in methylene chloride (MC).
3 is a three-dimensional graph showing the feed time vs. concentration ratio vs. reaction temperature of the polyepichlorohydrin-diol prepared in accordance with one embodiment of the present invention.
Figure 4 is a graph of the time-to-torque value of the polyepichlorohydrin-diol prepared in accordance with one embodiment of the present invention.
5 is a graph of gel permeation chromatography (GPC) of a polyepichlorohydrin-diol prepared in accordance with an embodiment of the present invention.
FIG. 6 is a graph showing changes in reaction temperature with time for supplying a monomer according to an embodiment of the present invention.
Figure 7 is a ¹ H NMR spectrum of each polyepichlorohydrin-diol prepared in accordance with one embodiment of the present invention.
8 is a graph showing reaction temperature changes according to a setting temperature according to an embodiment of the present invention.
9 is a graph of gel permeation chromatography (GPC) of the polyepichlorohydrin-diol prepared according to one embodiment of the present invention.
FIG. 10 is a graph showing a change in reaction temperature with time for supplying a monomer according to an embodiment of the present invention. FIG.
11 is a graph of gel permeation chromatography (GPC) of a polyepichlorohydrin-diol prepared according to one embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

Unless otherwise noted below, the 'concentration ratio' refers to the concentration ratio of the diol standard BF ₃ , the 'feed time' refers to the time of feeding the epichlorohydrin solution to the reactor, and the 'setting temperature' And the 'measurement temperature' is the reaction temperature measured as the polymerization reaction time elapses.

The polyepichlorohydrin-diol (PECH-diol) generally comprises a first stage in which the initiator diol and the Lewis acid, BF ₃ , form a diol-BF ₃ complex, and a second stage in which the complex (ECH) by a cationic ring opening polymerization reaction.

[Reaction Scheme 1]

However, the PECH-diol prepared by the cationic ring opening polymerization reaction tends to react with aprotic monomers easily to form a cyclic oligomer by increasing the reactivity as the terminal is cationized, and thus the yield of PECH-diol, a chain polymer, There was a problem that it fell.

The inventors of the present invention have found that there is a " induction period " which is a period from the initiation of the reaction in the cationic ring opening polymerization (CROP) stage to the completion of the reaction and a tendency to form a cyclic oligomer And found that the yield of the chain type polymer was high by controlling the induction period.

The present invention is a process for producing a polyepichlorohydrin-diol represented by the following formula (1), which comprises the following steps.

(a) reacting a diol, which is an initiator, with boron trichloride (BF ₃ ), which is a Lewis acid, to form a diol-BF ₃ complex,

(b) supplying the epichlorohydrin monomer to the diol-BF3 complex to polymerize.

[Chemical Formula 1]

In the above formula (1)

R is a substituted or unsubstituted alkyl group having 2 to 6 carbon atoms, and n and m are integers from 4 to 28, which may be the same or different from each other.

According to a preferred embodiment of the present invention, the concentration ratio of BF _{3 to} the dial standard may be 0.5 to 1. It was confirmed that the induction period was absent or shortened at the concentration ratio and the formation of the cyclic oligomer could be reduced.

The feeding rate of epichlorohydrin is preferably in the range of 9.2 × 10 ^-3 to 13.8 × 10 ^-3 mol / min. If the lower limit is above the lower limit, the reaction rate is too slow. If the upper limit is exceeded, the polymerization reaction rate is slower than the monomer feed rate The molecular weight distribution of the polyepichlorohydrin-diol (PECH-diol) formed is large and cyclic oligomers can be formed.

The initiator diol may be diethylene glycol (DEG) or 1,4-butadiol (1,4-BD). DEG is more soluble in methylene chloride (MC) than 1,4-BD. If the solubility is high, the concentration ratio is relatively high and the induction period can be reduced. Therefore, DEG is preferably used as an initiator.

The step (b) corresponding to the polymerization reaction may be carried out at -10 to 30 占 폚. At higher reaction temperatures, the induction period can be reduced or eliminated, but reaction selectivity is lowered and the formation of impurities is increased. Therefore, it is preferable to carry out the polymerization reaction at 0 to 10 캜.

Also, the step (b) may be performed for 5 to 35 hours.

The present invention also provides a polyepichlorohydrin-diol, which is produced by the above method and is characterized in that the molecular weight of each polymer is substantially the same.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments and the like. It will be apparent to those skilled in the art, however, that these examples are provided for further illustrating the present invention and that the scope of the present invention is not limited thereto.

Example .

One. Diol - BF ₃ Manufacture of Composites

The boron trichloride complex (BF ₃ -etherate) and initiator diol (0.51 mol) were placed in a round bottom flask and the mixture was stirred at room temperature for about 1 hour. The solution is 1 × 10 ^-3 torr pressure, 40 ℃ 6 hours then vacuum distilled to a clear light brown to remove diethyl yisseo diol for _three -BF Complex.

2. Polyepichlorohydrin - Of PECH-diol  Produce

The polymerization reaction was carried out in a 5 L triple glass jacketed reactor (FIG. 1) equipped with a stirrer, a monomer feeder, a thermometer, a condenser, a nitrogen feed hose and a cooler. Before the reaction, the reactor was dried at 90 DEG C for 24 hours under a nitrogen atmosphere.

A monomer solution tank in which a solenoid valve was connected via Teflon tubing was charged with epichlorohydrin (ECH) (1531 g, 16.56 mol) and methylene chloride (MC) (1000 g) To prepare an epichlorohydrin solution.

A diol -BF ₃ complex and MC (1000 g) prepared in Example 1 was added to the reactor. The epichlorohydrin solution was fed to the reactor and after 30 minutes the temperature and torque were recorded. After the epichlorohydrin solution supply was completed, the reaction solution was further stirred for 1 hour. Washed with sodium bicarbonate 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. Hereinafter, the polyepichlorohydrin-diol prepared according to each reaction condition is specified by the type of diol, the concentration ratio, the reaction temperature and the feeding time, and is specified by the diol / concentration / reaction temperature / feeding time.

As an example, the sample name of the polyepichlorohydrin-diol prepared with diol (DEG), a concentration ratio of 0.2, a setting temperature of -5 ° C and a feeding time of 30 hours was DEG 0.2 -5 30h. The reaction conditions of each of the obtained samples are summarized in Table 1 below.

Name of sample Initiator
Diol Setting temperature
(° C) Concentration ratio Feed rate
(x10 ^-3)
(mol min ^-1 ) Supply time
(h) BD 1.0 -5T 30h 1,4-BD -5 1.0 9.2 30 BD 0.5 -5T 30h 1,4-BD -5 0.5 9.2 30 BD 0.2 -5T 30h 1,4-BD -5 0.2 9.2 30 DEG 1.0 -5T 30h DEG -5 1.0 9.2 30 DEG 0.5 -5T 30h DEG -5 0.5 9.2 30 DEG 0.2 -5T 30h DEG -5 0.2 9.2 30 DEG 1.0 -5T 20h DEG -5 One 13.8 20 DEG 0.5 -5T 20h DEG -5 0.5 13.8 20 DEG 1.0 -5T 10h DEG -5 One 27.6 10 DEG 0.5 -5T 10h DEG -5 0.5 27.6 10 DEG 0.5 + 5T 30h DEG +5 0.5 9.2 30 DEG 0.5 + 30T 30h DEG +30 0.5 9.2 30 DEG 1.0 -5T 30h DEG -5 1.0 9.2 30

Experimental Example

One. GPC  analysis

The relative average molecular weight and polydispersity index (PDI = M _w / M _n ) of the polyepichlorohydrin-diol prepared in the above example were measured using a Shodex ^TM column (KF-801, KF-802, 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).

2. Nuclear magnetic resonance spectroscopy ( ^One H NMR ) analysis

The polyepichlorohydrin-diol prepared in the above example Nuclear Magnetic Resonance Spectroscopy ( ¹ H NMR) The analytical spectrum was determined using a Digital Avance III-400 NMR spectrometer (Bruker Co.) in chloroform substituted with deuterium at 400 MHz.

Figure 8 is a ¹ H NMR spectrum of each polyepichlorohydrin-diol prepared in accordance with one embodiment of the present invention.

8B is BD 0.5-5T 30h, FIG. 8C is BD 0.2-5T 30h, FIG. 8D is DEG 1.0 -5T 30h, FIG. 8E is DEG 0.5 -5T 30h, FIG. 8G is DEG 0.2 ≪ ¹ > H NMR spectrum of -5T30h.

1.6 ppm (-CH ₂ O of 1,4-butanol), 3.6 ppm (-CH ₂ -Cl group) and 3.7 ppm (-O-CH ₂ -, -O- ) Was observed to confirm that a polyepichlorohydrin-diol was produced.

Further, in the case of 3.6 ppm (-CH ₂ -Cl) and 3.7 ppm (-O-CH ₂ , -O-CH _{2 -} , -O-CH ₂ - in diethylene glycol) in d, Peak was observed and it was confirmed that the polyepichlorohydrin-diol was produced.

8 of a to f of the -O-CH ₂ at 2.70, epichlorohydrin monomer remaining without reaction, which was a peak is observed at 2.89, 3.24 and 3.5 ppm -, -O-CH-, -CH 2 -Cl .

Since the peaks of a, b and c in Fig. 8 are the same, the structure of the polyepichlorohydrin-diol produced irrespective of the ratio of diol to BF ³ when 1,4-butadiol is used as the initiator diol And the peaks of d, e and f in FIG. 8 are the same, the structure of the polyepichlorohydrin-diol produced regardless of the concentration ratio of diol and BF ³ when diethylene glycol is used as the initiator diol Is also the same.

3. Analysis results of each sample

The results of analysis of each polyepichlorohydrin-diol prepared according to the above examples are summarized in the following [Table 2].

Name of sample Maximum temperature
(T _max ,) Induction period (h) M _n
(g / mol) M _w
(g / mol) PDI Cyclic oligomer (%) Yield
(%) BD 1.0 -5T 30h - - 3352 4987 1.48 3.32 96 BD 0.5 -5T 30h +4.9 5 3355 4642 1.38 3.43 92 BD 0.2 -5T 30h +54.2 17 2570 3544 1.31 9.86 85 DEG 1.0 -5T 30h - - 2599 3430 1.31 3.44 95 DEG 0.5 + 30T 30h - - 2308 3253 1.40 6.85 95 DEG 0.5 + 5T 30h +1.06 6min 2401 3164 1.31 4.01 96 DEG 0.5 -5T 30h +1.4 3 2649 3566 1.34 4.29 96 DEG 0.2 -5T 30h +1.8 11.2 1450 1954 1.34 16.43 67

In Table 2, the maximum temperature (? T _max ) is the highest temperature measured during the reaction, the induction period is the time until the maximum temperature is reached, Mn is the number average molecular weight, Mw is the weight average molecular weight, PDI is the polydispersity index.

(One) Initiator Diol  Influence of

As shown in the above Table 2, when the initiator diol diethylene glycol (DEG) was used, the induction period was shorter than that of 1,4-butadiol (1,4-BD) PDI) was small and showed little cyclic oligomer formation. This seems to be due to the fact that DEG is dissolved well in the solvent MC and induction period is shortened.

Figure 3 is a diol -BF ₃ And the solubility of the complex in methylene chloride (MC).

3 (a) to 3 (d) are photographs showing solubility in MC with increasing concentration ratio using 1,4-butadiol (1,4-BD) as an initiator diol, and a 'to d' (DEG) of initiator diol and the solubility to MC with increasing concentration ratio.

As shown in Fig. 3, it can be seen that the solubility is higher when DEG is used as the initiator diol.

4) and torque (FIG. 5) are almost constant when the initiator diol is diethylene glycol (DEG), and the 1,4-buta It is confirmed that fewer cyclic oligomers than the diol (1,4-BD) are formed (Fig. 6).

(2) Influence of setting temperature

Referring to Table 2, FIG. 9, and FIG. 10, it can be seen that the temperature at a setting temperature of 5 ° C is substantially constant over time (FIG. 9) and less cyclic oligomer is generated (FIG. 10). This is because the induction period tends to decrease or disappear as the temperature increases. However, if the temperature is as high as 30 ° C, the polymerization rate is high but the selectivity is decreased and the generation of the cyclic oligomer and the unknown impurity is increased.

(3) Influence of supply time

FIG. 11 is a graph showing the reaction temperature changes according to the supply times (10h, 20h and 30h). As shown in [Table 2] and FIG. 11, it can be seen that the temperature variation is small as the supply time increases. This is because the polymerization reaction, which is an exothermic reaction, proceeds faster as the monomer feed time is shorter.

11 is a graph of gel permeation chromatography (GPC) of a polyepichlorohydrin-diol prepared according to one embodiment of the present invention.

a, DEG 1.0 -5T 30h, DEG 1.0 -5T 30h and DEG 1.0 -5T 30h, and b is shown in the GPC of DEG 0.5 -5T 30h, DEG 0.5 -5T 30h and DEG 0.5 -5T 30h. Respectively. As shown in Table 2 and FIG. 11, it can be seen that the shorter the feeding time, the greater the formation of the cyclic oligomer.

Claims (11)

A process for producing a polyepichlorohydrin-diol represented by the following formula (1), comprising the steps of:
(a) reacting a diol, which is an initiator, with boron trichloride (BF ₃ ), which is a Lewis acid, to form a diol-BF ₃ complex; And
(b) supplying the epichlorohydrin monomer to the diol-BF ₃ complex at a rate of 9.2 × 10 ^-3 to 13.8 × 10 ^-3 mol / min and polymerizing at 0 to 10 ° C;
[Chemical Formula 1]

In the above formula (1)
R is an unsubstituted alkylene group having 2 to 6 carbon atoms, and n and m are integers from 4 to 28, which are the same or different.
The method according to claim 1,
Wherein the concentration ratio of the diol to BF _{3 in} the step (a) is 1: 0.5 to 1: 1.
delete The method according to claim 1,
Wherein the diol is diethylene glycol (DEG) or 1,4-butanediol. ≪ RTI ID = 0.0 > 11. < / RTI >
delete The method according to claim 1,
Wherein the step (b) is carried out for 5 to 35 hours.
delete A polyepichlorohydrin-diol prepared according to the process of any one of claims 1, 2, 4 and 6, wherein the polydispersity index (PDI) is from 1.31 to 1.34 and the total content Wherein the content of the cyclic oligomer is reduced. ≪ RTI ID = 0.0 > 11. < / RTI >
A glycidyl azide polymer (GAP) prepared from the polyepichlorohydrin-diol according to claim 8.
An energized thermoplastic elastomer (ETPE) comprising a glycidylazide polymer (GAP) according to claim 9.
A propellant comprising a glycidylazide polymer (GAP) according to claim 9.

Images