KR101803063B1 - Tertiary amine polyols, tertiary amine catalyst comprising same and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a tertiary amine-based polyol, a tertiary amine catalyst containing the same, and a process for preparing the tertiary amine catalyst. More particularly, the present invention relates to a tertiary amine- Based polyol may contain three or more hydroxyl groups to act as a reactant and also serve as a catalyst and thus polyurethane can be produced without a separate tertiary amine catalyst. The generation of volatile organic compounds is less.

Description

TECHNICAL FIELD [0001] The present invention relates to a tertiary amine-based polyol, a tertiary amine catalyst containing the tertiary amine-based polyol, and a method for producing the tertiary amine catalyst.

The present invention relates to a tertiary amine-based polyol, a tertiary amine catalyst containing the same, and a process for preparing the tertiary amine catalyst. More particularly, the present invention relates to a tertiary amine- Based polyol may contain three or more hydroxyl groups to act as a reactant and also serve as a catalyst, so that a polyurethane can be produced without a separate tertiary amine catalyst.

Polyurethane (PU) has excellent mechanical properties, heat insulation, shock absorbing properties, sound absorbing properties and excellent processability, whereby polyurethane is used in an amount of 15 to 20% of the total plastic usage. In addition, its applications are widely used for interior and exterior parts of automobiles, such as chair cushions, instrument panels, soundproofing materials, awnings, doors and ceiling cushions. Furthermore, as the international economy recovers, the recovery and growth of the household furniture industry, which has been stagnated with real estate, is anticipated and the usage and usage of PU materials are expected to increase.

On the other hand, a typical synthesis method of a polyurethane is shown in the following Reaction Scheme 1.

[Reaction Scheme 1]

As shown in Reaction Scheme 1, an isocyanate group (-N = C = O) easily bonds with a hydroxyl group (-OH) to form a urethane bond. More specifically, when a diisocyanate compound is reacted with a compound having two hydroxyl groups, it becomes a linear polymer, and the linear polymer is polyurethane. Generally, toluene diisocyanate is used as the diisocyanate and polyether or polyester is used as the compound having two hydroxyl groups (polyol). When a polyether is used, a softer polyurethane can be produced, and when a polyester is used, a stiffer plastic can be produced. When a compound having three or more hydroxyl groups is used as the polyol, the produced polyurethane has a three-dimensionally bonded form.

In the polyurethane synthesis, the reaction of the polyol and the polyisocyanate is carried out in the presence of a catalyst, a foaming agent, a surfactant, a flame retardant, a crosslinking agent and the like, if necessary. A variety of metal compounds and tertiary amine compounds are used either singly or in combination as a catalyst for the production of polyurethane (Korean Patent Publication No. 2001-0041368, Korean Patent Publication No. 2008-0112352, Korean Patent No. 10-1126960 And Korean Patent No. 10-0729826).

Among the catalysts, tertiary amine catalysts are widely used. Examples of the tertiary amine catalysts include triethylene diamine (TEDA), N, N, N ', N'-tetramethyl- N, N ', N' ', N' '-pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, , N, N-dimethylethanolamine, and the like. Organometallic compounds such as organic tin compounds are frequently used as the metal compounds, but the productivity, formability, and physical properties of the polyurethane are deteriorated, and the heavy metals contained in the metal compounds remain to cause toxicity, The catalyst is used in many cases, and the case of being used alone is small.

However, the tertiary amine catalysts are slowly released from the product into volatile amines after preparation of the polyurethane or polyurethane foam. As a result, a phenomenon such as headache, nausea, vomiting, temporary visual field fogging, and backlight phenomenon may occur due to the odor of volatile amine, or discoloration of other materials (for example, epidermal vinyl chloride) may occur.

As a method for solving the problem of the volatile tertiary amine catalyst, an amine catalyst (generally referred to as a reaction catalyst) having a hydroxyl group capable of reacting with a polyisocyanate in the molecule and primary and secondary amino groups Or using a bifunctional crosslinking agent having a tertiary amino group in the molecule has been proposed.

The use of the reactive catalyst as described above is effective in reducing the odor of the final resin product since the reactive catalyst is immobilized in the polyurethane resin framework in the form of reacting with the polyisocyanate. However, these reactive catalysts have a problem in that the activity of the resinization reaction (reaction of polyol and isocyanate) is reduced, and the curability of the obtained polyurethane resin is lowered.

The method using the bifunctional cross-linking agent is effective in reducing the odor of the final polyurethane product and improving the working environment in the production of the polyurethane resin. However, there is a problem in that the physical properties such as the hardness of the polyurethane produced through this are insufficient.

Accordingly, the present inventors have developed a novel tertiary amine compound capable of reducing the generation of volatile organic compounds and applied it as a catalyst for the production of polyurethane.

Korean Patent Publication No. 2001-0041368 Korea Patent Publication No. 2008-0112352 Korean Patent No. 10-1126960 Korean Patent No. 10-0729826

Accordingly, an object of the present invention is to provide a tertiary amine-based polyol which is less likely to generate volatile organic compounds (VOC), a tertiary amine catalyst containing the same, and a method for producing the same, which can solve the problems of conventional amine catalysts for polyurethane production .

In order to achieve the above object, the present invention provides a tertiary amine-based polyol represented by the following general formula (1)

In Formula 1,

X is hydrogen or hydroxy;

R ¹ and R ³ are each independently hydroxy or hydroxy C _1-3 alkyl;

R ² and R ⁴ are each independently selected from 1-piperazinyl or 1-piperazinyl, C _{1 ~ 3} alkyl, wherein R ² and R ⁴ is hydroxy, C _{1 ~ 6} alkyl or hydroxy C _{1 ~ 6} alkyl ≪ / RTI >

Provided that when X is hydrogen, R ² and R ⁴ are each independently 1-piperazinyl or 1-piperazinyl C _1-3 alkyl substituted by hydroxy or hydroxy C _1-6 alkyl;

m and n are each independently an integer of 1 to 4;

The present invention also provides a tertiary amine catalyst for polyurethane production comprising the tertiary amine-based polyol as described above.

In addition, the present invention provides a process for preparing a tertiary amine-based polyol of the following general formula (1-1), comprising reacting a compound of the formula (8)

[Formula 1-1]

In the above formulas,

X is hydrogen or hydroxy;

R ⁵ is hydrogen, hydroxy, C _1-6 alkyl or hydroxy, and C _1-6 alkyl;

R ^{1 '} and R ^{3 '} are each independently hydroxy or hydroxymethyl;

또는

이고;R ^{2 '} and R ^{4 '} are each independently

or

ego;

Only when X is a hydrogen, R ⁵ is hydroxy-C _{1 ~ 6} alkyl;

m and n are each independently an integer of 1 to 4;

Further, the present invention relates to a polyol composition comprising a tertiary amine-based polyol as described above; And reacting the polyisocyanate having two or more isocyanate groups with the polyisocyanate.

The present invention also relates to a polyol composition comprising a tertiary amine-based polyol as described above; And a polyisocyanate having two or more isocyanate groups.

The tertiary amine-based polyol of the present invention is an autocatalytic polyol having a tertiary amine group and a polyol structure, so that it can act as a reactant in the production of polyurethane and can also act as a catalyst, thereby producing a polyurethane without a separate amine catalyst . In addition, the polyurethane thus produced has less volatile organic compounds than conventional polyurethane, and can minimize odor, visual field flow, discoloration of other materials, and the like.

1 is a graph of a ¹ H-NMR spectrum of a tertiary amine-based polyol of Example 1. Fig.
2 is a graph of the ¹ H-NMR spectrum of the tertiary amine-based polyol of Example 2. Fig.
3 is a graph showing an ESI-MS spectrum analysis result of the tertiary amine-based polyol of Example 2. Fig.

Hereinafter, the present invention will be described in detail.

The present invention provides a tertiary amine-based polyol represented by the following Formula 1:

[Chemical Formula 1]

In Formula 1,

X, R ¹ to R ⁴ , m and n are as defined above.

Specifically, R ¹ and R ³ are each independently hydroxy or hydroxymethyl; R ² and R ⁴ are each independently 1-piperazinyl or 1-piperazinylmethyl, wherein R ² and R ⁴ may be substituted with methyl, hydroxymethyl or hydroxyethyl; Provided that when X is hydrogen, R ² and R ⁴ are each independently 1-piperazinyl or 1-piperazinylmethyl substituted by hydroxymethyl or hydroxyethyl; m and n may each independently be 1 or 2.

The tertiary amine-based polyol may have a weight average molecular weight of 100 to 3,000. Specifically, the tertiary amine-based polyol may have a weight average molecular weight of 300 to 1,000.

The tertiary amine-based polyol of the present invention is an autocatalytic polyol having a tertiary amine group and a polyol structure, and can act as a reactant and a catalyst in the production of polyurethane.

More specifically, the tertiary amine-based polyol may be any one of compounds represented by the following general formulas (2) to (7).

The present invention also provides a tertiary amine catalyst for polyurethane production comprising the tertiary amine-based polyol as described above.

The amine catalyst is classified into a gel reaction catalyst, a surface cure catalyst, a blowing catalyst or an isocyanate reactive catalyst depending on its structure. In the case of an autocatalyst, it has a functional group that acts as an initiator of propylene oxide and ethylene oxide, and has a structure in which an amine catalyst is bonded to a polyol. Due to the structural features described above, the autocatalyst can reduce the generation of volatile organic compounds during the production of polyurethane. Particularly, the tertiary amine catalyst for polyurethane production containing the tertiary amine-based polyol of the present invention is superior in performance as an initiator and a catalyst because the content of N and OH is high when the molecular weight is similar to that of the conventional catalyst.

In addition, the present invention provides a process for preparing a tertiary amine-based polyol of the following general formula (1-1), comprising reacting a compound of the formula (8)

[Chemical Formula 8]

[Chemical Formula 9]

[Formula 1-1]

In the above formulas, R ^{1 '} , R ^{2 '} , R ^{3 '} , R ^{4 '} , R ⁵ , X, m and n are as defined above.

Hereinafter, the production method of the present invention will be described in more detail.

The tertiary amine-based polyol of the following formula (1-1) is obtained by reacting the compound of the formula (8) with the compound of the formula (9) as shown in the following reaction formula (2).

[Reaction Scheme 2]

Wherein R ^{1 '} , R ^{2 '} , R ^{3 '} , R ^{4 '} , R ⁵ , X, m and n are as defined above.

In this reaction, the compound of formula (8) can be, for example, 1-methylpiperazine or 1- (2-hydroxyethyl) piperazine, The compound of formula (9) may be, for example, glycerol diglycidyl ether or 1,4-butanediol diglycidyl ether.

In this reaction, the compound of formula (8) can be used in an amount of 1.0 to 4.0 molar equivalents, or 1.5 to 3.5 molar equivalents, based on 1 molar equivalent of the compound of formula (9). At this time, methanol, ethanol, or a mixture thereof may be used as a reaction solvent, but the reaction may be performed without using a reaction solvent.

Further, the above reaction conditions can be carried out by stirring at 10 to 100 DEG C, or 30 to 80 DEG C, for 0.5 to 48 hours, or for 1 to 30 hours.

Further, the present invention relates to a polyol composition comprising a tertiary amine-based polyol as described above; And reacting the polyisocyanate having two or more isocyanate groups to produce a polyurethane.

The tertiary amine-based polyol can act as a catalyst when a urethane bond is formed between the hydroxyl group of the polyol composition and the isocyanate group of the polyisocyanate. Thus, in the above-mentioned preparation method, a tertiary amine catalyst A catalyst used in the production of polyurethane, for example, a primary, secondary, tertiary, quaternary amine or organometallic catalyst may be further added.

The organometallic catalyst may be selected from, for example, stannous diacetate, stannas dioctoate, stannas diolate, stannas dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate , Dibutyltin dichloride, dioctyltin dilaurate, lead octanoate, lead naphthenate, nickel naphthenate, cobalt naphthenate, and the like.

The polyol composition may further include a polyol containing at least one hydroxyl group in addition to the tertiary amine-based polyol of the present invention. The polyol containing at least one of the hydroxyl groups may be specifically a polyether polyol, a polyester polyol, or the like.

The polyisocyanate reacts with the hydroxyl group (-OH) of the polyol to generate a urethane bond, thereby forming a polyurethane.

The polyisocyanate may specifically be an aliphatic, cycloaliphatic, arylaliphatic or aromatic polyisocyanate, and more specifically, an aromatic polyisocyanate.

The aromatic polyisocyanate may be, for example, a 4,4'-, 2,4'- or 2,2'-isomer of diphenylmethane diisocyanate (MDI); Mixtures thereof; Polymers thereof; A mixture of MDI and toluene-2,4- or 2,6-diisocyanate (TDI); m- or p-phenylenediisocyanate; Chlorophenylene-2,4-diisocyanate; Diphenylen-4,4'-diisocyanate; 4,4'-diisocyanate-3,3'-dimethyldiphenyl; 3-methyldiphenyl-methane-4,4'-diisocyanate; Diphenyl ether diisocyanate; 2,4,6-triisocyanatotoluene; And 2,4,4'-triisocyanatodiphenyl ether.

The polyisocyanate may be used in an amount of 0.5 to 2 equivalents based on 1 equivalent of the polyol.

The polyurethane manufacturing method may include the step of adding an additive depending on the intended use of the polyurethane produced. The additive may be a foaming agent, water, a crosslinking agent, a cell stabilizer, a flame retardant, a chain extender, an epoxy resin, a filler, a pigment, a surfactant, and the like.

The blowing agent may be specifically selected from the group consisting of water, methylene chloride, acetone, fluorocarbon chloride, hydrogen fluorocarbon, hydrogen fluorocarbon, hydrocarbons, and combinations thereof. Examples of the hydrogen fluoride (HFC) include HFC-245fa, HFC-134a, and HFC-365. Examples of the hydrogen fluoride carbon (HCFC) include HCFC-141b, HCFC-22, and HCFC-123. The hydrocarbons include, for example, n-pentane, iso-pentane, cyclopentane, or combinations thereof.

The amount of the foaming agent to be added may vary depending on the intended use, the use, the foam stiffness and the foam density of the polyurethane product to be produced. Specifically, it may be added in an amount of 1 to 13.5, or 3 to 4.5 parts by weight based on 100 parts by weight of the polyol composition.

The amount of water not used for the foaming agent may be added in an amount of 0 to 20 parts by weight based on 100 parts by weight of the polyol composition.

The crosslinking agent may be, for example, diethanolamine, diisopropanolamine, triethanolamine, tripropanolamine, etc. The amount of the crosslinking agent may be 0.1 to 5.4, or 0.3 to 1.8 parts by weight based on 100 parts by weight of the polyol composition .

The cell stabilizer may be, for example, a surfactant such as an organopolysiloxane. The amount of the cell stabilizer to be added may be 0.1 to 3.6, or 0.3 to 1.2 parts by weight based on 100 parts by weight of the polyol composition.

The flame retardant includes, for example, halogenated compounds and non-halogenated compounds. The halogenated compound may be, for example, trichloropropyl phosphate (TCPP). The non-halogenated compound may be selected from the group consisting of, for example, triethyl phosphate ester (TEP) and dimethyl methylphosphonate (DMMP). The amount of the flame retardant added may be 0 to 50 parts by weight, 0 to 40 parts by weight, 0 to 30 parts by weight, or 0 to 20 parts by weight based on 100 parts by weight of the polyol composition.

The chain extender may be, for example, a chain extender of diols such as ethylene glycol, butanediol, and the like.

In one embodiment, the process for preparing the polyurethane of the present invention can be carried out by dissolving the polyol composition and the polyisocyanate in a solvent and stirring the mixture, and then injecting the mixture into a suitable container or mold. The stirring may be carried out using a conventional stirrer, and a polyurethane foaming machine may be used for the foam molding. The polyurethane foamer may be, for example, a high pressure, low pressure or spray type device.

Specifically, the polyol composition and the polyisocyanate may be mixed and stirred at a high speed of 7,000 rpm or higher for 1 to 30 seconds, and the mixture may be injected into a suitable container or mold for foam molding.

Further, the present invention provides a polyurethane produced by the above-described production method. The polyurethane obtained by the production method of the present invention can be molded into, for example, an elastomer not using a blowing agent, a polyurethane foam using a blowing agent, or the like.

Furthermore, the polyurethane produced by the process of the present invention may be in the form of a foam. Examples of the polyurethane foams include flexible polyurethane foams, semi-rigid polyurethane foams, and rigid polyurethane foams. Specifically, it may be a car seat of a flexible polyurethane foam, an instrument panel or handle of a semi-rigid polyurethane foam, and a heat insulating material using a rigid polyurethane foam, which can be used as an automobile interior material.

The flexible polyurethane foam has an open cell structure, exhibits high air permeability and is capable of reversible deformation. The physical properties of the flexible polyurethane foam may be, for example, a density of 10 to 100 kg / m 2, a compressive strength (ILD 25%) of 200 to 8000 ㎪, and an elongation of 80 to 500%.

The semi-rigid polyurethane foam has a higher foam density and compressive strength than the flexible polyurethane foam, but has an open-cell structure like a flexible polyurethane foam, exhibits high air permeability and is capable of reversible deformation. The physical properties of the semi-hard urethane foam may be, for example, a density of 40 to 800 kg / m 3, a compressive strength (ILD 25%) of 10 to 200 ㎪, and a growth rate of 40 to 200%.

The rigid polyurethane foam has a highly crosslinked and closed cell structure and is incapable of reversible transformation. The physical properties of the rigid urethane foam may be, for example, a density of 10 to 100 kg / m 3 and a compressive strength of 50 to 1000 ㎪.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following examples and experimental examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[ Example ]

Of polyol  synthesis

Example  One

Glycerol diglycidyl ether (represented by the following formula 9-1; 0.1 mol, 20.41 g) was added to 1-methylpiperazine (0.3 mol, 30 g) Added dropwise over 1 hour, and stirred for 24 hours. Thereafter, unreacted 1-methylpiperazine was removed at 100 ° C for 10 hours under a vacuum of 10 torr to prepare tertiary amine-type polyol (44.3 g, yield: 88%) represented by the following formulas 2 to 4.

[Formula 8-1]

[Formula 9-1]

(2)

(3)

[Chemical Formula 4]

Example  2

A solution of 1,4-butanediol (1, 2-hydroxyethyl) piperazine was added to 1- (2-hydroxyethyl) piperazine, diglycidyl ether, the following formula (9-2; 0.1 mol, 20.2 g) was added dropwise at 55 占 폚 over 1 hour, and the mixture was stirred for 24 hours. Then, unreacted 1-methylpiperazine was removed at 100 ° C for 10 hours under a vacuum of 10 torr to prepare a tertiary amine-type polyol (52.7 g, yield: 89%) represented by the following formulas 5 to 7.

[Formula 8-2]

[Formula 9-2]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

Experimental Example  One

The weight average molecular weight and the molecular formula of the tertiary amine-based polyol prepared in Examples 1 and 2 were determined using an LC / MS spectrometer (manufacturer: Thermo finnigan LCQ decaplus), and a nuclear magnetic resonance spectrum (NMR) Spectrometer (Varian, 400-MR) ) for use by the first and second examples of the amine-based polyol ¹ H-NMR and ¹³ C-NMR spectrum was obtained for a. Further, ¹ H-NMR of the amine-based polyol of Examples 1 and 2 is shown in FIGS. 1 and 2, and the graph of the ESI-MS of the amine-based polyol of Example 2 is shown in FIG.

Example  1 third Amine system Polyol

1) ¹ H-NMR (300 MHz, CDCl ₃ ):? 2.24 (s, 6H),? 2.3-2.7 (bm, 20H)

2) ¹³ C-NMR (75 MHz, CDCl ₃ ): 隆 45.9, 53.0, 55.0, 60.4, 66.1, 67.1, 71.3, 74.1

3) ESI-MS data at m / e 405.30 (M + H) + (calcd for C 19 H 40 N 4 O 5 (M +): 404.30)

Example  3 of 3 Amine system Polyol

1) ¹ H-NMR (300 MHz, CDCl ₃ ):? 1.6 (s, 4H),? 2.3-2.9 (bm, 24H),? 3.3-3.7 (bm, 12H),? 3.7-3.9 )

2) ¹³ C-NMR (75 MHz, CDCl ₃ ):? 26.4, 53.3, 58.0, 60.8, 66.2, 71.5, 73.4

3) ESI-MS data at m / z: 462.34 (M + H) + (calcd for C 22 H 46 N 4 O 6 (M +): 462.34)

Experimental Example  2: Measurement of physical and chemical properties

2-1. Hydroxyl value (hydroxyl number)

The hydroxyl values of the tertiary amine-based polyols prepared in Examples 1 and 2 were measured.

Specifically, 5 ml of a mixture of tertiary amine polyol of Example 1 or 2 and acetic anhydride-pyridine mixture (8: 2 by volume) was added to a 200 ml Erlenmeyer flask according to the acetic anhydride-pyridine method (JISK 8004-1961) The shaking for 30 minutes at < RTI ID = 0.0 > 30 C < / RTI > was shaken once for three times, followed by cooling with an oil bath for 90 minutes. Thereafter, 1 ml of distilled water was added, and the mixture was shaken 5 times as described above, and left in the oil bath for 10 minutes. Then, it was taken out from the oil bath and left at room temperature for 10 minutes. Then, the inner wall of the cooler was washed with 10 ml of acetone and then shaken 5 times as described above. Four drops of phenolphthalein indicator were then added and titrated with 0.5 N KOH standard solution. The hydroxyl value was calculated by the following equation (1).

[Equation 1]

Hydroxyl value = [(B - A) x F x 28.05 / S] + acid value

In the above formula (1), B is a 0.5N KOH content (ml) required for a blank,

A is the amount of 0.5N KOH (ml) required in the above experiment,

F is the acid value of the sample used in the experiment,

S is the amount (ml) of the tertiary amine-based polyol of Example 1 or 2 used in the above experiment.

As a result of calculation, the hydroxyl value of the tertiary amine-based polyol of Example 1 was found to be 430 mg KOH / g, and the hydroxyl value of the tertiary amine-based polyol of Example 2 was found to be 490 mg KOH / g.

2-2. Measurement of amine value

The amine values of the tertiary amine-based polyols prepared in Examples 1 and 2 were measured.

Specifically, the tertiary amine-based polyol of Examples 1 and 2 was dissolved in methanol, bromocresolide was used as an indicator, and titrated with hydrochloric acid standard solution. The molecular weight of the polyol was measured in terms of mg KOH / g in terms of 1 g equivalent. Were measured.

As a result of the measurement, the amine value of the tertiary amine-type polyol of Example 1 was 540 mg KOH / g, and the amine value of the tertiary amine-type polyol of Example 2 was 470 mg KOH / g.

Example  3

70 g of the polyol of Example 1 and 7 g of a 48% by volume aqueous KOH solution were added as a starting material to a 2 L high-pressure reactor and then heated to 110 캜. Thereafter, while stirring the mixture, the water was removed under reduced pressure with a vacuum pump, and 930 g of propylene oxide monomer (PO) was injected in a vacuum state for 5 hours. After the PO injection, the reactor was aged for 1 hour while raising the temperature of the reactor to 120 DEG C in order to aged the unreacted propylene oxide monomer. After aging, the reactor was kept in a vacuum for 30 minutes at 110 DEG C to remove the reacted PO. After that, 50 g of magnesia (magnesium silicate) and 5 g of filter were added to the reactor to remove the remaining amount of KOH as a catalyst, and the mixture was stirred for 1 hour. After filtering the catalyst, the catalyst was removed and 1 kg of polyol was obtained.

Example  4

A polyol was prepared in the same manner as in Example 3, except that the temperature for raising unreacted propylene oxide monomer was raised to 125 ° C.

Comparative Example  One

A polyol was prepared in the same manner as in Example 3, except that glycerin was used in place of the polyol of Example 1.

Comparative Example  2

A polyol was prepared in the same manner as in Example 3, except that triethanolamine was used in place of the polyol in Example 1.

Comparative Example  3

A polyol was prepared in the same manner as in Example 3, except that diethanolamine was used in place of the polyol of Example 1.

Experimental Example  3

The hydroxyl value (OHV, hydroxyl number), the weight average molecular weight (Mw), the ethylene oxide monomer content ratio (EO content ratio) and the amine value of the polyols of Examples 3 and 4 and Comparative Examples 1 to 3 were measured, Are shown in Table 1 below.

Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 OHV (mg KOH / g) 56 44 55 57 43 Mw 2,970 2,200 2,010 2,080 2,400 EO content ratio (% by weight) 8.6 8.4 8.5 8.4 8.5 Amine value (mg KOH / g) 36 39 - 16 23

Manufacture of polyurethane

Example  5

The polyol, water and polyisocyanate of Example 3 were mixed at 25 占 폚, mixed at a high speed of 7,000 rpm for 7 seconds, poured into a square of 30 cm 占 30 cm 占 10 cm (width 占 length 占 height) rise to foam polyurethane.

Example  6

A polyurethane was prepared in the same manner as in Example 5, except that the polyol of Example 4 was used instead of the polyol of Example 3.

Comparative Example  4 to 6

Polyurethane was prepared in the same manner as in Example 5, except that the polyols of Comparative Examples 1 to 3 were used in place of the polyol of Example 3.

Experimental Example  4

The density, tear strength, tensile strength, elongation, compressive strength (ILD 25%) and amine emission of the polyurethanes of Examples 5 and 6 and Comparative Examples 4 to 6 were measured and the results are shown in Table 2 below.

Example 5 Example 6 Comparative Example 4 Comparative Example 5 Comparative Example 6 Density (kg / m3) 27 27 27 15 23 Compressive strength (kg / 314 cm3) 21 22 21 16 19 Tear strength (kg / cm) 0.75 0.76 0.73 0.5 0.65 Tensile strength (kg / cm 2) 0.95 0.96 0.94 0.6 0.75 Elongation (%) 110 113 110 80 94 Amine Emission (㎍ / ㎥) 2,000 1,800 3,300 2,800 2,000

As can be seen from Table 2, the polyurethanes of Examples 5 and 6 exhibited higher values in terms of density, compressive strength, tear strength, tensile strength and elongation than the polyurethanes of Comparative Examples 4 to 6, All exhibited excellent physical properties. Furthermore, the polyurethanes of Examples 5 and 6 exhibited significantly lower amine emissions than Comparative Examples 4 and 5, indicating that they are more environmentally friendly than the polyurethanes prepared using conventional amine catalysts.

Claims (10)

A tertiary amine-based polyol represented by the following general formula (1)
[Chemical Formula 1]

In Formula 1,
X is hydrogen or hydroxy;
R ¹ and R ³ are each independently hydroxy or hydroxy C _1-3 alkyl;
R ² and R ⁴ are each independently selected from 1-piperazinyl or 1-piperazinyl, C _{1 ~ 3} alkyl, wherein R ² and R ⁴ is hydroxy, C _{1 ~ 6} alkyl or hydroxy C _{1 ~ 6} alkyl ≪ / RTI >
Provided that when X is hydrogen, R ² and R ⁴ are each independently 1-piperazinyl or 1-piperazinyl C _1-3 alkyl substituted by hydroxy or hydroxy C _1-6 alkyl;
m and n are each independently an integer of 1 to 4;
The method according to claim 1,
R ¹ and R ³ are each independently hydroxy or hydroxymethyl;
R ² and R ⁴ are each independently 1-piperazinyl or 1-piperazinylmethyl, wherein R ² and R ⁴ may be substituted with methyl, hydroxymethyl or hydroxyethyl;
Provided that when X is hydrogen, R ² and R ⁴ are each independently 1-piperazinyl or 1-piperazinylmethyl substituted by hydroxymethyl or hydroxyethyl;
m and n are each independently 1 or 2;
The method according to claim 1,
Wherein the tertiary amine-based polyol is any one of compounds represented by Chemical Formulas 2 to 7:
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

The method according to claim 1,
The tertiary amine-based polyol has a weight average molecular weight of 100 to 3,000.
A tertiary amine catalyst for the production of polyurethanes, comprising a tertiary amine based polyol according to any one of claims 1 to 4.
A process for producing a tertiary amine-based polyol represented by the following formula (1-1), comprising reacting a compound represented by the following formula (8) with a compound represented by the following formula
[Chemical Formula 8]

[Chemical Formula 9]

[Formula 1-1]

In the above formulas,
X is hydrogen or hydroxy;
R ⁵ is hydrogen, hydroxy, C _1-6 alkyl or hydroxy, and C _1-6 alkyl;
R ^{1 '} and R ^{3 '} are each independently hydroxy or hydroxymethyl;
R ^{2 '} and R ^{4 '} are each independently

or

ego;
Only when X is a hydrogen, R ⁵ is hydroxy-C _{1 ~ 6} alkyl;
m and n are each independently an integer of 1 to 4;
A polyol composition comprising a tertiary amine-based polyol according to any one of claims 1 to 4; And
Reacting a polyisocyanate having two or more isocyanate groups.
8. The method of claim 7,
Wherein said tertiary amine-based polyol acts as a catalyst in the production of a urethane bond between the hydroxy group of the polyol composition and the isocyanate group of the polyisocyanate.
8. The method of claim 7,
Wherein the production method does not use a tertiary amine catalyst in addition to the tertiary amine-based polyol.
A polyol composition comprising a tertiary amine-based polyol according to any one of claims 1 to 4; And a polyisocyanate having at least two isocyanate groups.

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