KR101922549B1 - Process for preparing polyether polyols - Google Patents

Abstract

The present invention relates to a method for manufacturing polyether polyols, manufacturing polyether polyols having high molecular weight and optimally reduced degree of unsaturation with improved catalyst activity.

Description

PROCESS FOR PREPARING POLYETHER POLYOLS < RTI ID = 0.0 >

The present invention relates to a process for producing a polyether polyol.

Polyether polyols are widely used as raw materials for polyurethanes and sealants for polyurethane.

Generally, the polyether polyol is prepared by ring-opening addition polymerization of an alkylene oxide-based compound in the presence of a catalyst. For example, although an alkali catalyst such as KOH is usually used as the catalyst, an unsaturated polyol tends to occur more than a certain amount due to side reaction, and it is difficult to obtain a high molecular weight polyether polyol. Therefore, it has a disadvantage that it can not be used for the production of polyurethane requiring physical properties such as high elasticity.

Accordingly, an attempt has been made to prepare a high molecular weight polyether polyol by using a double metal cyanide catalyst (DMC catalyst), in which a side reaction hardly occurs. Because of the high catalytic activity, the above-mentioned DMC catalysts are advantageous in that the polyether polyol can be produced by using a low concentration, the amount of the DMC catalyst remaining in the obtained polyether polyol is very small, and the catalyst removal step becomes unnecessary. However, when the DMC catalyst is used in the production of the polyether polyol, since the concentration of the DMC catalyst used is low, there is a problem that the activity of the catalyst is drastically lowered due to the catalyst poison factor such as water or alkaline free acid present in the system . Also, the DMC catalyst has a disadvantage that it takes a considerable time to be activated.

Accordingly, the present inventors have recognized the above problems and found that, even when only a small amount of DMC catalyst is used, the amount of unsaturated polyol produced by the side reaction can be minimized by the high catalytic activity in ring opening polymerization of alkylene oxide, A method for producing a polyether polyol having a high molecular weight has been developed.

It is an object of the present invention to solve the problems of the above-mentioned double metal cyanide catalysts, and to provide a method for producing high molecular weight polyether polyols having low unsaturation with improved catalytic activity.

The present invention relates to a process for preparing a cyanide catalyst, which comprises mixing a double metal cyanide catalyst comprising a metal salt containing a transition metal represented by the following general formula (1), a metal cyanide salt represented by the following general formula (2) and an organic complexing agent and an H-functional initiator, A step of replacing the air in the reactor with an inert atmosphere or a vacuum atmosphere, and a step of injecting an alkylene oxide into the reactor and reacting. Here, the double metal cyanide catalyst includes 5 to 10 mol of the metal salt based on 1 mol of the metal cyanide salt.

[Chemical Formula 1]

M [X] _n

(2)

[Y] _a M '[CN] _b [A] _c

[In formulas (1) and (2)

M is a transition metal,

M is Fe (Ⅱ), Fe (Ⅲ), Co (Ⅱ), Co (Ⅲ), Cr (Ⅲ), Mn (II), Rh (III), Ru (II), V (V) and V (IV)

X and A are each independently an anion salt,

Y is selected from a hydrogen ion, an alkali metal ion and an alkaline earth metal ion,

_n is an integer of 1 to 5,

_a and _b are each independently an integer of 1 or more, and the sum of the charges of _a , _b and _c is equal to the sum of the charges of M '.

In the process for producing a polyether polyol according to an embodiment of the present invention, the double metal cyanide catalyst is inactivated and its activation induction time satisfies the following relational expression (1).

[Relation 1]

0.8? T ₁ / T ₀

[In the relational expression 1,

T ₀ is the activation induction time (min) of the untreated double metal cyanide catalyst,

T ₁ is the activation induction time (min) of the deactivated double metal cyanide catalyst]

In the process for producing a polyether polyol according to an embodiment of the present invention, by using a deactivated double metal cyanide catalyst, the total unsaturation level of the polyether polyol prepared therefrom is 0.007 meq / g or less .

In the method for producing a polyether polyol according to an embodiment of the present invention, the step of reacting may be such that polymerization is carried out while injecting the alkylene oxide at a pressure of 0.1 to 5 bar under a temperature of 100 to 150 ° C have.

In the process for preparing a polyether polyol according to an embodiment of the present invention, the alkylene oxide may be injected for 4 to 10 hours.

In the method for producing a polyether polyol according to an embodiment of the present invention, the double metal cyanide catalyst may be prepared by preparing a first mixed solution containing a metal salt including the transition metal of the formula 1 and an organic complexing agent, Adding a metal cyanide salt of Formula 2 to the first mixed solution to prepare a second mixed solution; adding the organic complexing agent and polyether compound to the second mixed solution to prepare a third mixed solution; And filtering the third mixed solution under an inert atmosphere to obtain a precipitate.

In the process for producing a polyether polyol according to an embodiment of the present invention, the double metal cyanide catalyst may be one in which an organic complexing agent having an acetate group or a tartrate group is coordinated.

In the process for producing a polyether polyol according to an embodiment of the present invention, the double metal cyanide catalyst may be one in which a tertiary alcohol is coordinated, and in particular, a double metal cyanide coordinated with a tertiary alcohol not containing an unsaturated group And it is preferred in the present invention that the desired effect of the present invention is exhibited in the catalyst.

In the method for producing a polyether polyol according to an embodiment of the present invention, it may further comprise an aging reaction step after the reaction.

According to the present invention, the use of the deactivated double metal cyanide catalyst can dramatically shorten the induction time for catalyst activation in the production of the polyether polyol, and the total unsaturation level of the polyether polyol prepared therefrom Can be remarkably lowered.

Further, according to the present invention, by using a double metal cyanide catalyst satisfying a predetermined content range, a high molecular weight polyether polyol having a low degree of unsaturation despite a small amount of use can be provided in a very economical manner.

FIG. 1 shows the molecular weight analysis results of the polyether polyols prepared by the production methods of Examples and Comparative Examples according to the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and the manner of achieving them, will be apparent from and elucidated with reference to the embodiments described hereinafter in conjunction with the accompanying drawings. It should be understood, however, that the invention is not limited to the disclosed embodiments, but is capable of many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Hereinafter, the method for producing the polyether polyol according to the present invention will be described in detail.

The term "total reaction time" in the present invention means the time from the start of the injection of the alkylene oxide to the cooling of the reactor to room temperature (25 캜) and sampling of the polyether polyol.

The term "induction time" in the present invention means the time taken for activation of the double metal cyanide catalyst according to the present invention. For example, the derivation time can be obtained through the inflection point of the graph of consumption of alkylene oxide over time. If the induction time is prolonged, the productivity is decreased, and excessive heat emission is caused to cause defects due to overexcitation of the product due to an uncontrolled increase in temperature during the course of the catalyst activation, as well as a decrease in catalytic activity .

The term "H-functional initiator" in the present invention also means a compound containing at least one zerewitinoff-active hydrogen atom. The compound containing the Zeritivinov-active hydrogen atom is a compound containing a carboxy, hydroxy, thiol group or the like, and the functional value means the number of Zeritivinov-active hydrogen atoms.

The present invention provides a process for producing a polyether polyol comprising ring-opening polymerization of an alkylene oxide under a double metal cyanide catalyst. Here, the double metal cyanide catalyst includes a metal salt including a transition metal, a metal cyanide salt, and an organic complexing agent, and the metal salt is contained in an amount of 5 to 10 mol based on 1 mol of the metal cyanide salt .

As a result of deepening studies on a method for producing a polyether polyol using a double metal cyanide catalyst, the present inventors have found that a double metal cyanide catalyst satisfying a predetermined composition as described above can be used to produce a polyether polyol having a molecular weight of at least 130% It was confirmed that a polyether polyol having a molecular weight can be produced.

A process for preparing a polyether polyol according to an embodiment of the present invention comprises mixing a double metal cyanide catalyst comprising a metal salt comprising a transition metal, a metal cyanide salt and an organic complexing agent and an H-functional initiator, A step of replacing the air in the reactor with an inert atmosphere or a vacuum atmosphere, and injecting alkylene oxide into the reactor to react. As described above, the double metal cyanide catalyst comprises 5 to 10 mol of the metal salt based on 1 mol of the metal cyanide salt.

According to the process for producing a polyether polyol according to an embodiment of the present invention, it is possible to produce a polyether polyol having a high molecular weight as compared with a double metal cyanide catalyst supported on an alkali catalyst or metal oxide such as KOH, And significantly low.

Particularly, the above-mentioned double metal cyanide catalyst is preferentially deactivated. The deactivation-treated double metal cyanide catalyst according to the present invention means that the double metal cyanide catalyst is prepared and then filtered and dried in an inert atmosphere.

According to the method for producing a polyether polyol according to an embodiment of the present invention, the activation induction time of the catalyst can be remarkably shortened by using the deactivation-treated double metal cyanide catalyst. This is because the conventional double metal cyanide catalyst, which has been subjected to the filtration and drying treatment in the air after the production by the conventional method, takes more than 150 minutes to induce the activation of the untreated double metal cyanide catalyst, This will suggest the remarkable effect.

In one embodiment, the inertially treated double metal cyanide catalyst according to the present invention may have an activation induction time of less than 100 minutes in the production of the polyol.

In one embodiment, the deactivation-treated double metal cyanide catalyst according to the present invention may have an activation induction time in the range of 10 to 80 minutes in the production of the polyol.

In one embodiment, the deactivation-treated double metal cyanide catalyst according to the present invention may have an activation induction time in the range of 10 to 60 minutes in the production of the polyol.

According to the method for producing a polyether polyol according to an embodiment of the present invention, the activation induction time of the double metal cyanide catalyst may satisfy the following relational expression (1).

[Relation 1]

0.8? T ₁ / T ₀

[In the relational expression 1,

T ₀ is the activation induction time (min) of the untreated double metal cyanide catalyst,

T ₁ is the activation induction time (min) of the deactivated double metal cyanide catalyst]

As described above, in the process for producing a polyether polyol according to an embodiment of the present invention, the use of the above-mentioned deactivation-treated double metal cyanide catalyst leads to a significantly improved activation induction time, The ether polyol can be produced, which is very economical. In particular, according to the present invention it is possible to provide a polyether polyol having a significantly lower total unsaturation level.

In one embodiment, the polyether polyol according to the present invention may have a total unsaturation level of 0.007 meq / g or less.

In one embodiment, the polyether polyol according to the present invention may have a total unsaturation level of preferably 0.001 to 0.005 meq / g, more preferably 0.001 to 0.0045 meq / g.

Herein, the double metal cyanide catalyst is not limited as long as it is a conventional one that satisfies the molar ratio of the metal salt and the metal cyanide salt. However, for the purpose of achieving the desired molecular weight, a metal salt containing a transition metal represented by the following formula Lt; / RTI > and an organic complexing agent.

[Chemical Formula 1]

M [X] _n

(2)

[Y] _a M '[CN] _b [A] _c

[In formulas (1) and (2)

M is a transition metal,

M is Fe (Ⅱ), Fe (Ⅲ), Co (Ⅱ), Co (Ⅲ), Cr (Ⅲ), Mn (II), Rh (III), Ru (II), V (V) and V (IV)

X and A are each independently an anion salt,

Y is selected from a hydrogen ion, an alkali metal ion and an alkaline earth metal ion,

_n is an integer of 1 to 5,

_a and _b are each independently an integer of 1 or more, and the sum of the charges of _a , _b and _c is equal to the sum of the charges of M '.

In the process for producing a polyether polyol according to an embodiment of the present invention, the air inside the reactor may be replaced with an inert gas by using an inert gas, or the air inside the reactor may be replaced with a vacuum atmosphere by depressurization, And the inside of the reactor is replaced with a vacuum atmosphere by a reduced pressure.

In the process for producing a polyether polyol according to an embodiment of the present invention, the amount of the double metal cyanide catalyst to be used is not limited, but may be in the range of 10 to 500 ppm, preferably 10 to 100 ppm , And more preferably in the range of 10 to 50 ppm, but is not limited thereto.

Using the above-mentioned deactivation-treated double metal cyanide catalyst, the induction time of the double metal cyanide catalyst could be remarkably shortened while preparing a polyether polyol having a low unsaturation.

In the method for producing a polyether polyol according to an embodiment of the present invention, the reactor may be configured such that the inside air is replaced with an inert atmosphere before injecting the alkylene oxide, and the temperature of the reactor is raised to 100 to 200 ° C, It is preferable to remove the inert gas present in the reactor. At this time, the vacuum atmosphere may be one in which an inert gas is removed by decompression.

In one embodiment, the vacuum atmosphere may be a pressure of 1 to 500 mbar, preferably 1 to 300 mbar, more preferably 50 to 200 mbar.

In one embodiment, the activation time of the double metal cyanide catalyst according to the present invention can be remarkably shortened by replacing the inside of the reactor with an inert atmosphere and then replacing the atmosphere with a vacuum atmosphere.

According to one embodiment of the present invention, the H-functional initiator is an alcohol compound having 1 to 20 carbon atoms; Phenol compounds such as phenol and phenol substituted with alkyl having 1 to 20 carbon atoms; Glycol compounds such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol; Diol-based compounds such as butanediol, hexanediol, and pentanediol; And a high-functionality initiator selected from pentaerythritol, sorbitol, sucrose, hydroquinone, pyrocatechol, resorcinol, bisphenol F, bisphenol A, etc. may be an embodiment of the present invention.

In one embodiment, the H-functional initiator may be a glycol-based compound such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, which is an alkylene oxide adduct, and preferably the glycol- A hydroxyl value of 40 mg KOH / g or a molecular weight of 100 to 1,000, but the present invention is not limited thereto.

In one embodiment, the H-functional initiator may be used in an amount of 0.1 to 1,000 parts by weight, preferably 100 to 1,000 parts by weight, more preferably 300 to 700 parts by weight, based on 1 part by weight of the double metal cyanide catalyst Can be mixed.

According to the method for producing a polyether polyol according to an embodiment of the present invention, it is possible to produce a polyether polyol having a low unsaturation as well as a polyether polyol having a high molecular weight.

In one embodiment, the polyether polyol prepared by the process of the present invention may have a total unsaturation level of 0.007 meq / g or less, preferably 0.001 to 0.005 meq / g, more preferably 0.001 to 0.0045 meq / g. < / RTI >

In one embodiment, the polyether polyol prepared by the process of the present invention may have a molecular weight of 300 or more, preferably 500 to 10,000, more preferably 700 to 8,000. At this time, according to the present invention, it is possible to prepare a polyether polyol having a desired molecular weight by controlling the amount of the double metal cyanide catalyst used.

In the process for producing a polyether polyol according to an embodiment of the present invention, the step of reacting may be performed at a temperature of 100 to 150 ° C, preferably 100 to 140 ° C, more preferably 100 to 130 ° C Lt; / RTI >

The preheating is not limited as long as the temperature is at least 10 ° C higher than the temperature of the step of reacting, preferably 40 to 80 ° C, more preferably 50 to 70 ° C, but is not limited thereto.

According to one embodiment of the present invention, the alkylene oxide may be an alkylene oxide having 2 to 20 carbon atoms, and non-limiting examples thereof include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, But are not limited to, ethylene oxide, octene oxide, nonene oxide, decene oxide, undecene oxide, dodecene oxide, cyclopentene oxide, situhexane oxide, cycloheptene oxide, cyclohexene oxide and the like.

Further, in the process for producing a polyether polyol according to an embodiment of the present invention, the step of reacting may be such that polymerization is carried out while injecting the alkylene oxide at a pressure of 0.1 to 5 bar. At this time, according to the present invention, as the induction time is shortened as well as the enhanced catalytic activity, the desired high molecular weight polyether polyol can be produced even though the alkylene oxide is injected for 4 to 10 hours.

Also, in the method for producing a polyether polyol according to an embodiment of the present invention, the reaction may further include an aging reaction step. By performing the aging reaction step, the alkylene oxide remaining in the reactor after the reaction can be removed, and the odor can be removed without performing the additional deodorization step. However, it goes without saying that it is possible to further include additional deodorization steps depending on the purpose.

As described above, according to one embodiment of the present invention, it is possible to produce a polyether polyol having a low degree of unsaturation as well as a high molecular weight polyether polyol. At this time, the present inventors searched for a method for maximizing the production efficiency of the polyether polyol, as well as the process parameters described above, in the process for producing the double metal cyanide catalyst.

The double metal cyanide catalyst according to an embodiment of the present invention is prepared by the following method to maximize catalytic activity and significantly shorten the activation induction time of the double metal cyanide catalyst, The desired high molecular weight polyether polyol in the preparation of the polyether polyol can be provided in a very economical manner. In particular, it was confirmed that the degree of unsaturation by the double metal cyanide catalyst can be drastically reduced.

Wherein the double metal cyanide catalyst comprises the steps of: preparing a first mixed solution containing a metal salt including a transition metal represented by the following formula (1) and an organic complexing agent; introducing a metal cyanide salt of the following formula Preparing a second mixed solution by adding the organic complexing agent and a polyether compound to the second mixed solution to prepare a third mixed solution, and filtering the third mixed solution under an inert atmosphere to obtain a precipitate Step. ≪ / RTI >

As described above, the double metal cyanide catalyst according to the present invention is inactivated by filtering and drying the reaction product obtained from the third mixed solution under an inert atmosphere.

Generally, the reaction product obtained from the third mixed solution is filtered in air or a precipitate is obtained by centrifugation or the like. However, in the present invention, it is possible to easily separate unreacted materials and reaction by-products, and to maximize the activity of the resultant double metal cyanide catalyst, by performing filtration in an inert atmosphere instead of the filtration process Respectively. In particular, in the case of the inactivated double metal cyanide catalyst according to the present invention, a remarkably shortened catalyst activation induction time can be realized.

In addition, according to the present invention, it was confirmed that a polyether polyol having a remarkably improved molecular weight can be produced when a predetermined composition is satisfied.

In one embodiment, the double metal cyanide catalyst according to the present invention has a molecular weight of at least 130% in the case where the metal cyanide salt and the metal salt satisfy a 1: 5 to 1: 10 molar ratio, A high molecular weight polyether polyol can be produced.

In one embodiment, the double metal cyanide catalyst according to the present invention is excellent in the above-mentioned effect when the metal cyanide salt and the metal salt satisfy the molar ratio of 1: 8 to 1:10.

The inert atmosphere may be formed using an inert gas such as nitrogen, argon, helium, or the like, and the filtration step may be repeated one or more times in terms of maximizing catalyst characteristics.

At this time, the metal cyanide salt may serve as an active ingredient and may include at least one metal and at least two cyan groups.

The M 'of the metal cyanide salt may be Fe (II), Fe (III), Co (II), Co (III), Cr (II) (A) may be a metal selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate is an anion salt selected from the group consisting of isocyanate, isocyanate, isothiocyanate, carboxylate and nitrate, and Y is an alkali metal such as hydrogen and lithium, sodium, And _a and _b are each independently an integer of 1 to 10, and the sum of charges of _a , _b, and _c may be the same as the sum of charges of M '.

In one embodiment, the metal cyanide salt may be an alkali metal hexacyanocobaltate or an alkali metal hexacyanoferrate. Nonlimiting examples of the metal cyanide salt include potassium hexacyanocobaltate (III), potassium hexa Potassium hexacyanoferrate (III), calcium hexacyanocobaltate (III), lithium hexacyanoylidate (III), and the like, but the present invention is not limited thereto.

The metal salt includes all water-soluble metal salts which form a complex with the above-described metal cyanide salt, and in the present invention, a metal salt containing a transition metal is preferred.

According to one embodiment of the present invention, the M of the metal salt is Zn (II), Fe (II), Fe (III), Ni (II) Transition metal selected from Pb (II), Mo (IV), Al (III), V (V), V (II), W (IV), Cu And X is at least one selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate Is an anion selected from isothiocyanate, carboxylate and nitrate, and n is an integer of 1 to 3, which may satisfy the valence of M.

In one embodiment, the metal salt is selected from the group consisting of zinc chloride, zinc bromide, zinc acetate, zinc acetonate, zinc acetate, zinc benzoate, zinc nitrate, iron bromide (II), cobalt chloride (II), cobalt thiocyanate (II), or nickel (II) nitrate, but are not limited thereto.

According to one embodiment of the present invention, the double metal cyanide catalyst may be an organic complexing agent having an acetate group or a tartrate group or a tertiary alcohol coordinated thereto. In particular, in the implementation of the desired effect of the present invention, the double metal cyanide catalyst is preferably coordinated with a tertiary alcohol.

In one embodiment, the double metal cyanide catalyst is one in which an organic complexing agent, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, or diethylene glycol monoethyl ether acetate, But is not limited thereto.

In one embodiment, the double metal cyanide catalyst is (+) - dimethyl-L-tartrate ((+) - Dimethyl- ) -Diethyl-L-tartrate, ET), (+) - diisopropyl-L-tartrate (IPT) and (+) - dibutyl-L-tartrate +) -Dibuthyl-L-tartrate, BT), and the like, but the present invention is not limited thereto.

In one embodiment, the double metal cyanide catalyst is selected from the group consisting of tert-butyl alcohol (TBA), allyl alcohol (AAL), propargyl alcohol (PPA) Methyl-3-butyne-2-ol (MBY) and tert-amyl alcohol (TAA) may be coordinated.

In one embodiment, particularly preferred is a double metal cyanide catalyst in which an organic complexing agent selected from tertiary alcohols such as tert-butyl alcohol (TBA), tert-amyl alcohol (TAA), etc., It shows the remarkable effect of the desired effect.

According to the process for producing a polyether polyol according to an embodiment of the present invention, when the above-mentioned double metal cyanide catalyst coordinated with a tertiary alcohol not containing an unsaturated group is used, And is preferred in the present invention.

[Relation 1]

0.1? T ₁ / T ₀ ? 0.7

[In the relational expression 1,

T ₀ is the activation induction time (min) of the untreated double metal cyanide catalyst,

T ₁ is the activation induction time (min) of the deactivated double metal cyanide catalyst]

Also, the double metal cyanide catalyst may include 1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 3 to 10 parts by weight, of the organic complexing agent based on 1 part by weight of the metal salt have.

Also, the polyether compound according to an embodiment of the present invention is intended to effectively bind to the active sites of the double metal cyanide catalyst, which is a lattice structure, to achieve higher catalytic activity. The material used as the polyether compound may be, but not limited to, a polyether polyol, and non-limiting examples thereof include propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, poly ), Poly (propylene glycol), block copolymers of ethylene oxide and propylene oxide, and the like, but are not limited thereto.

As described above, in the case of using the double metal cyanide catalyst produced by the production method according to the present invention, the improved catalytic activity remarkably reduces the induction time compared to the double metal cyanide catalyst produced by the known process, .

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

(Assessment Methods)

1. Hydroxyl value (OH value, KOH mg / g)

The hydroxyl value was measured by the following method using the titration method.

(1) Each polyether polyol (1 g) prepared by the following method was mixed with phthalic anhydride (25 ml) and heated at 100 ° C for 1 hour.

(2) The heated mixed solution was cooled for 30 minutes, and then 1 drop of phenolphthalein indicator was added.

(3) The amount of KOH used in the observation and titration of the color (purple) change of the solution was measured by titrating 0.5N KOH solution into the mixed solution to which phenolphthalein was added, and the value calculated by the following formula 1 was recorded in terms of hydroxyl value.

(Equation 1)

2. Viscosity (cP)

Viscosity was measured at room temperature (25 ° C) using a Brookfield DV2T viscometer.

3. Molecular weight (g / mol)

The molecular weight of each polyether polyol prepared by the following production method was recorded as the value calculated from the following formula 2 through the result derived from the hydroxyl value.

(Equation 2)

4. Unsaturation (meq / g)

0.1g)을 정평하여 용해시킨 후 N/10 KOH 표준 용액으로 적정하였다. 이의 결과를 통하여, 하기 식 3으로부터 계산된 수치로 기록하였다.(1) Measurement of acidity: Into a 200 ml Erlenmeyer flask, a solvent (50 ml of methanol was taken, 1 drop of phenolphthalein indicator was titrated with N / 10 KOH standard solution to make it violet, and then used) Polyether polyol (sample, 15.0

0.1 g) was dissolved and then titrated with N / 10 KOH standard solution. From the result, the numerical value calculated from the following formula 3 was recorded.

(2) Measurement of unsaturation: 25 ml of a methanolic solution of mercuric acetate (C ₄ H ₆ H _g O ₄ ) was taken in a 200 ml Erlenmeyer flask, and a standard sample was dissolved according to the following Table 1 and left for 30 minutes. Thereafter, 4.5 g of sodium bromide was added to the Erlenmeyer flask, thoroughly shaken, mixed, and titrated with N / 10 KOH standard solution after 1 drop of the phenolphthalein indicator, and titration was carried out as the end point where reddish color appeared (after addition of sodium bromide, 15 Minute, and a blank test is performed in parallel). From the result, the numerical value calculated from the following formula 4 was recorded.

Unsaturation degree Sample weight 3.0 or higher 0.4 or less 3.0 to 1.6 0.4 to 0.5 1.6 to 0.8 0.5 to 1.0 0.8 to 0.4 1.0 to 2.0 0.4 to 0.2 2.0 to 4.0 0.2 to 0.1 4.0 to 8.0 0.1 or less 15

(Equation 3)

Acid D (meq / g) = A * f * 0.1 / S

(Equation 4)

Unsaturation (meq / g) = [(C-B) * f * 0.1 / S] - D

A: titration of N / 10 KOH standard solution used for acidity measurement

B: Titration of the N / 10 KOH standard solution used in the blank test for unsaturation measurement

C: Amount of titration of the N / 10 KOH standard solution used in this test for unsaturation measurement

f: factor of N / 10 KOH standard

S: Standard amount of sample (g: 4 decimal places)

Related ground: JIS K 1557

5. Total reaction time

The total reaction time is defined as the reaction time from the start of propylene oxide (PO) injection to the time when the reactor is cooled to room temperature and the product is sampled.

(Example 1)

Step 1. Preparation of double metal cyanide catalysts

(1) A first mixed solution containing zinc chloride (ZnCl ₂ , 0.1 mol) and t-butyl alcohol (TBA, 100 ml) was prepared (diluted with 1: 5 volume ratio of TBA and distilled water).

(2) Potassium hexacyanocobaltate (0.01 mol) and distilled water (40 ml) were mixed and then charged into the first mixed solution (0.66 ml / min) at a temperature of 50 ° C. After the dropping, the mixture was stirred for 30 minutes to prepare a second mixed solution.

(3) Dipropylene glycol ( DPG, 2 g), t-butyl alcohol (TBA, 20 ml) and distilled water (1 ml) were mixed and then introduced into the second mixed solution (2 ml / min). After the dropping, the mixture was stirred for 30 minutes.

(4) The stirred mixture was filtered at room temperature (25 캜) in a nitrogen atmosphere to extract a solid content. The solids were re-slurried and stirred (20 minutes, 50 DEG C) using an aqueous solution (TBA and distilled water diluted 10: 1 by volume) mixed with 1 g of DPG and TBA.

(5) The above method (4) was repeated twice to extract the solid content. The extracted solids were dried under vacuum drying for 12 hours and then pulverized to obtain the final double metal cyanide catalyst (Zn: Co = 10: 1).

Step 2. Preparation of polyether polyol

(1) A 5 L high-pressure reactor was charged with 750 g of H-functional initiator (DPG) and 1.2 g of the DMC catalyst obtained in step 1, wherein the amount of DMC catalyst was 30 ppm in a 5 L high- .

(2) The reactor was replaced with nitrogen atmosphere (3 to 4 times) while preheating and stirring at 50 캜.

(3) The reactor was replaced with a nitrogen atmosphere, and the reactor was heated to 100 DEG C for 1 hour, and the atmosphere was replaced with a vacuum atmosphere (pressure condition: 100 mbar).

(4) The reactor in a vacuum atmosphere was adjusted to 115 ° C, propylene oxide (PO) was injected, and the temperature was slowly raised to 2 atm.

(5) After confirming the pressure drop and exothermic reaction in the reactor, additional injection (confirming the activity of the catalyst by pressure drop) at a certain pressure (2 atmospheres).

(6) After using all of the prepared PO, aging reaction was performed for 2 hours.

(7) kept under vacuum for 30 minutes.

(8) The temperature of the reactor was lowered to room temperature, and a high molecular weight polyether polyol was recovered.

The physical properties of the polyether polyol obtained by the above production method were measured by the above evaluation method. The results are shown in Table 2 and FIG. 1, and the total reaction time was 290 minutes.

(Example 2)

The final double metal cyanide catalyst (Zn: Co = 8: 1) was obtained in the same manner as in step 1 of Example 1 except that 0.08 mol of zinc chloride was used instead of 0.1 mol of zinc chloride .

The polyether polyol was obtained in the same manner as in the step 2 of Example 1 using the obtained double metal cyanide catalyst (Zn: Co = 8: 1), and the properties were measured by the above evaluation method, The results are shown in Table 2 and FIG. 1, and the total reaction time was 320 minutes.

(Example 3)

(Zn: Co = 6: 1) was obtained in the same manner as in step 1 of Example 1 except that 0.06 mol of zinc chloride was used instead of 0.1 mol of zinc chloride to obtain the final double metal cyanide catalyst .

Using the obtained double metal cyanide catalyst (Zn: Co = 6: 1), a polyether polyol was obtained in the same manner as in the step 2 of Example 1, and the properties were measured by the above evaluation method, The results are shown in Table 2 and FIG. 1, and the total reaction time was 240 minutes.

(Example 4)

(Zn: Co = 7: 1) was obtained in the same manner as in step 1 of Example 1, except that 0.07 mol of zinc chloride was used instead of 0.1 mol of zinc chloride to obtain the final double metal cyanide catalyst .

The polyether polyol was obtained in the same manner as in the step 2 of Example 1 using the obtained double metal cyanide catalyst (Zn: Co = 7: 1), and the properties were measured by the above evaluation method, The results are shown in Table 2 below, and the total reaction time was 2490 minutes.

(Example 5)

The procedure of Example 1 was repeated except that 1.6 g of the DMC catalyst was used instead of 1.2 g of the DMC catalyst to obtain a polyether polyol. Table 2 shows the total reaction time was 560 minutes.

 (Example 6)

Except that 2.0 g of the DMC catalyst was used instead of 1.2 g of the DMC catalyst in the step 2 of Example 1 to obtain a polyether polyol and the physical properties were measured by the above evaluation method, Table 2 shows the total reaction time was 470 minutes.

 (Example 7)

The procedure of Example 1 was repeated except that 2.4 g of the DMC catalyst was used instead of 1.2 g of the DMC catalyst to obtain a polyether polyol. Table 2 shows the total reaction time was 380 minutes.

 (Example 8)

In step 1 of Example 1 above, the same procedure was followed except that allyl alcohol (1.05 mol) was used in place of TBA to obtain the final double metal cyanide catalyst.

The obtained double metal cyanide catalyst was used in the same manner as in Step 2 of Example 1 to obtain a polyether polyol. The properties of the polyether polyol were measured by the above evaluation method. The results are shown in Table 2 below, The total reaction time was 240 minutes.

 (Example 9)

In step 1 of Example 1 above, the same procedure was followed except that propargyl alcohol (1.05 mol) was used in place of TBA to obtain the final double metal cyanide catalyst.

The obtained double metal cyanide catalyst was used in the same manner as in Step 2 of Example 1 to obtain a polyether polyol. The properties of the polyether polyol were measured by the above evaluation method, and the results are shown in Table 2 below. The total reaction time was 240 minutes.

 (Comparative Example 1)

The final double metal cyanide catalyst (Zn: Co = 4: 1) was obtained in the same manner as in step 1 of Example 1 except that 0.04 mol of zinc chloride was used instead of 0.1 mol of zinc chloride .

The polyether polyol was obtained in the same manner as in the step 2 of Example 1 using the obtained double metal cyanide catalyst (Zn: Co = 4: 1), and the properties were measured by the above evaluation method, The results are shown in Table 2 and FIG. 1, and the total reaction time was 290 minutes.

(Comparative Example 2)

(Zn: Co = 2: 1) was obtained in the same manner as in step 1 of Example 1 except that 0.02 mol of zinc chloride was used instead of 0.1 mol of zinc chloride to obtain the final double metal cyanide catalyst .

The polyether polyol was obtained in the same manner as in the step 2 of Example 1 using the obtained double metal cyanide catalyst (Zn: Co = 2: 1) to obtain a polyether polyol, The results are shown in Table 2 and FIG. 1, and the total reaction time was 290 minutes.

(Comparative Example 3)

In the step 1 of Example 1 above, the final double metal cyanide catalyst was obtained in the same manner except that the filtration was carried out by centrifugation in air instead of filtration at room temperature (25 캜) in a nitrogen atmosphere.

The obtained double metal cyanide catalyst was used in the same manner as in Step 2 of Example 1 to obtain a polyether polyol. The properties of the polyether polyol were measured by the above evaluation method. The results are shown in Table 2 below, The total reaction time was 460 minutes.

(Comparative Example 4)

The polyether polyol was obtained in the same manner as in the step 2 of Example 1 using a commercially available double metal cyanide catalyst (catalyst of HongKong Huaran international Industrial Co., Ltd.) to obtain a polyether polyol. Respectively.

As a result, the molecular weight of the polyether polyol prepared by the above method was 2762 (g / mol, OH value (40.6)) and the degree of unsaturation was 0.0068 meg / g.

division Molecular Weight
(OH value) Viscosity
(cP) Unsaturation degree
(meq / g) Activation induction time
(min) Example 1 2770
(40.48) 610 0.0033 20 Example 2 2540
(44.17) 600 0.0041 30 Example 3 730
(153.69) 130 0.0044 60 Example 4 840
(133.57) 140 0.0044 45 Example 5 5830
(19.23) 1280 0.0045 20 Example 6 4840
(23.17) 1020 0.0048 20 Example 7 3867
(29.01) 840 0.0049 20 Example 8 750
(149.6) 120 0.0043 80 Example 9 760
(147.63) 130 0.0042 70 Comparative Example 1 530
(211.70) 100 0.0134 100 Comparative Example 2 543
(206.63) 100 0.1580 100 Comparative Example 3 2500
(44.8) 550 0.0056 169

As shown in Table 2 above, according to the present invention, it was confirmed that a polyether polyol having a molecular weight of at least 130% can be produced when the double metal cyanide catalyst satisfies a predetermined composition ratio (Example 3 vs Comparative Example 1). In particular, in the case of the embodiment in which the double metal cyanide catalyst contains 8 to 10 mol of the metal salt based on 1 mol of the metal cyanide salt, it is confirmed that a polyether polyol having a molecular weight of 520% (Example 1 vs. Comparative Example 1).

In addition, according to the present invention, the activation induction time is significantly shortened compared to Comparative Example 3 which is filtered and dried by a conventional method, and the degree of unsaturation of the polyether polyol thus prepared, that is, the total unsaturation level, is excellent.

In short, according to the present invention, the activation induction time of the double metal cyanide catalyst can be remarkably shortened, and by maximizing the activity of the double metal cyanide catalyst, a high molecular weight poly It can be confirmed that the ether polyol can be produced in a very economical manner.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments or constructions. Various changes, substitutions and alterations can be made hereto without departing from the spirit and scope of the invention. It will be clear to those who have knowledge.

Claims (10)

Mixing a double metal cyanide catalyst with an H-functional initiator, preheating the temperature of the reactor and then replacing the air in the reactor with an inert or vacuum atmosphere; and
Injecting an alkylene oxide into the reactor and reacting the alkylene oxide,
The double metal cyanide catalyst may be prepared by,
Preparing a first mixed solution comprising a metal salt including a transition metal represented by the following formula (1) and an organic complexing agent;
Adding a metal cyanide salt represented by the following formula (2) to the first mixed solution to prepare a second mixed solution;
Adding the organic complexing agent and polyether compound to the second mixed solution to prepare a third mixed solution; and
And filtering the third mixed solution under an inert atmosphere to obtain a precipitate, wherein the double metal cyanide catalyst is prepared by reacting the metal salt in an amount of 5 to 10 mol A method for producing a polyether polyol;
[Chemical Formula 1]
M [X] _n
(2)
[Y] _a M '[CN] _b [A] _c
[In formulas (1) and (2)
M is a transition metal,
M is Fe (Ⅱ), Fe (Ⅲ), Co (Ⅱ), Co (Ⅲ), Cr (Ⅲ), Mn (II), Rh (III), Ru (II), V (V) and V (IV)
X and A are each independently an anion salt,
Y is selected from a hydrogen ion, an alkali metal ion and an alkaline earth metal ion,
_n is an integer of 1 to 5,
_a and _b are each independently an integer of 1 or more, and the sum of the charges of _a , _b and _c is equal to the sum of the charges of M '. delete The method according to claim 1,
Wherein the activation induction time of the double metal cyanide catalyst satisfies the following relational expression (1).
[Relation 1]
0.8? T ₁ / T ₀
[In the relational expression 1,
T ₀ is the activation induction time (min) of the untreated double metal cyanide catalyst,
T ₁ is the activation induction time (min) of the deactivated double metal cyanide catalyst] The method according to claim 1,
Wherein the total unsaturation level is 0.007 meq / g or less. The method according to claim 1,
Wherein the step of reacting is carried out under a temperature condition of 100 to 150 ° C, and the polymerization is carried out while the alkylene oxide is fed under a pressure of 0.1 to 5 bar. 6. The method of claim 5,
Wherein the alkylene oxide is injected for 4 to 10 hours. delete The method according to claim 1,
Wherein the double metal cyanide catalyst is coordinated with an organic complexing agent having an acetate group or a tartrate group. The method according to claim 1,
Wherein the double metal cyanide catalyst is coordinated with a tertiary alcohol. The method according to claim 1,
Wherein the polyether polyol further comprises an aging reaction step after the reaction step.

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