KR20170066060A - Tertiary amine polyols, tertiary amine catalyst comprising same and manufacture 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 hydroxy groups to act as a reactant and also to serve as a catalyst, so that a polyurethane can be produced without a separate tertiary amine catalyst.

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 hydroxy groups to act as a reactant and also to 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,

또는

이고,L ₁ to L ₃ are each independently

or

ego,

L ₄ is C _1-6 alkylene,

And R ₁ to R ₆ are each independently hydrogen or a C _{1 -6} alkyl,

n is independently an integer of 1 to 6;

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

(1) reacting a compound of formula (8) with a compound of formula (9) to produce a compound of formula (10); And (2) reacting a compound of formula (10) with a compound of formula (11): < EMI ID =

[Chemical Formula 9]

R _{7 is} -NH-R ₈

[Chemical Formula 1]

In this formula,

또는

이고, L ₁ to L ₃ are each independently

or

ego,

L ₄ is alkylene of C _{1 -6,}

And R ₁ to R ₈ are each independently hydrogen or a C _{1 -6} alkyl,

 n is independently an integer of 1 to 6;

In addition, 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 showing an ESI-MS spectrum analysis result of the tertiary amine-based polyol of Example 1. 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, L ₁ to L ₄ , R ₁ to R _6, and n are as defined above.

Specifically, in the above-mentioned formula (I), wherein L ₄ is alkylene of C _{1 -4,} respectively, each said R ₁ and R _2, R ₃ and R _4, and R ₅ and R ₆ is an alkyl of C _{1 -4} And n may be independently 1 or 2, respectively.

The tertiary amine-based polyol may have a weight average molecular weight of 800 to 8,000, specifically 890 to 5,000. Further, the tertiary amine-based polyol may have a hydroxyl number of 25 to 250 mg KOH / g and an amine value of 25 to 280 mg KOH / g.

More specifically, in Formula 1, R ₁ to R ₆ may all be the same as C _{1 -4} alkyl.

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.

(1) reacting a compound of formula (8) with a compound of formula (9) to produce a compound of formula (10); And (2) reacting a compound of formula (10) with a compound of formula (11): < EMI ID =

[Chemical Formula 8]

[Chemical Formula 9]

R _{7 is} -NH-R ₈

[Chemical formula 10]

(11)

[Chemical Formula 1]

Wherein L ₁ to L ₄ , R ₁ to R ₈ and n are the same as defined above.

Hereinafter, the production method of the present invention will be described in detail for each step.

First, in step (1), the compound of formula (8) is reacted with the compound of formula (9) to give the compound of formula (10) as shown in the following reaction formula (2).

[Reaction Scheme 2]

Wherein n, R < ₇ > and R < ₈ > are as defined above.

In the above reaction, a preferable example of the compound of the formula (8) is epichlorohydrin, and a preferable example of the compound of the formula (9) is diethylamine, An example is glycidyl diethyl amine.

In this reaction, the compound of formula (9) may be used in an amount of 0.5 to 2.0 molar equivalents, or 0.8 to 1.5 molar equivalents, based on 1 molar equivalent of the compound of formula (8). At this time, the reaction can be carried out without a reaction solvent.

Further, the above reaction conditions can be carried out by stirring at 0 to 20 ° C, or 0 to 5 ° C, for 3 to 72 hours, or for 12 to 48 hours.

Next, in step (2), the compound of formula (10) is reacted with a compound of formula (11) as shown in the following reaction formula 3 to obtain the compound of formula (1).

[Reaction Scheme 3]

Wherein n, L ₁ to L ₄ and R ₁ to R ₈ are as defined above.

In the above reaction, a preferable example of the compound of formula (10) is glycidyl diethyl amine. Preferred examples of the compound of formula (11) include 2- (piperazin-1-yl) Amine (2- (piperazine-1-yl) ethane-1-amine).

In this reaction, the compound of formula (10) may be used in an amount of 2.0 to 4.0 molar equivalents, or 2.5 to 3.5 molar equivalents, based on 1 molar equivalent of the compound of formula (11). At this time, the solvent can be reacted without use, and if necessary, methanol, ethanol, dimethylformamide (DMF) or a mixture thereof can be used.

Further, the above reaction conditions can be carried out by stirring at 30 to 120 ° C, or 60 to 90 ° C, for 3 to 72 hours, or for 12 to 48 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 in the formation of a urethane bond between the hydroxy group of the polyol composition and the isocyanate group of the polyisocyanate, and thus, A catalyst commonly used in the production of polyurethane such as 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 polyisocyanates include, for example, 4,4'-, 2,4 'or 2,2'-isomers of diphenylmethane diisocyanate (MDI); Its blend; Its polymer; A mixture of monomeric 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 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 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 is, for example, trichloropropyl phosphate (TCPP). The non-halogenated compounds include, for example, triethyl phosphate ester (TEP) and

And dimethylphenylpiperazinium (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.

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%.

In addition, the semi-rigid polyurethane foam has a higher foam density and compressive strength than the flexible polyurethane foam, but has an open-cell structure similar to a flexible polyurethane foam and exhibits high air permeability and 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%.

In addition, the rigid polyurethane foam has a highly crosslinked, 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 ]

Example  One: New Of polyol  synthesis

1-1. Glycidyl  Synthesis of diethylamine

39 g (0.42 mol, 32.96 ml) of epichlorohydrin and 29 g (0.4 mol, 41.018 ml) of diethyl amine were mixed, and the resulting mixture was added dropwise at 50 占 폚 to 50 wt. 28 g (1.75 mol) of aqueous NaOH solution was added thereto to obtain a mixture. The mixture was stirred at 10 DEG C for 24 hours and then filtered to obtain a filtrate. Ethyl acetate was then added to the filtrate and the upper liquid layer was separated using a separatory funnel. Dry the upper liquid to the Na ₂ SO _4, filtered and then vacuum distilled to give the glycidyl diethylamine (glycidyl diethyl amine).

1-2. New catalyst synthesis

The glycidyldiethylamine (0.1548 mol, 20 g) obtained in the above 1-1 was reacted with 2- (piperazine-1-yl) ethane-1- amine, 0.0503 mol, 6.5 g) at 80 DEG C and stirred for 24 hours to obtain a tertiary amine-based polyol.

Experimental Example  One.

The weight average molecular weight and the molecular formula of the amine-based polyol of Example 1 were determined using an LC / MS spectrometer (manufacturer: Thermo finnigan LCQ decaplus) and a nuclear magnetic resonance spectrum (NMR) (400 MHz FT-NMR Spectrometer MR)), ¹ H NMR spectrum of the amine-based polyol of Example 1 was obtained. Specifically, a ¹ H NMR spectrum graph 1, the ESI-MS result graph is shown in Fig.

1) Weight average molecular weight: 895 g / mol

2) ¹ H NMR data (see FIG. 1)

3) ESI-MS data at m / z 517.48 [M + H] ⁺ (calcd. For C ₂₇ H ₆₀ N ₆ O ₃ : 516.47)

As a result, it was confirmed that the tertiary amine-based catalyst (tertiary amine-based polyol) prepared in Example 1 was a compound represented by the following Chemical Formulas 2 to 7.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

Experimental Example  2: Measurement of physical and chemical properties

2-1. Hydroxyl (hydroxyl number)

The hydroxyl value of the tertiary amine-based polyol of Example 1 was measured.

Specifically, 5 ml of a mixture of tertiary amine-type polyol and acetic anhydride-pyridine (8: 2 by volume) of Example 1 was placed in a 200 ml Erlenmeyer flask according to the acetic anhydride-pyridine method (JISK 8004-1961) The shaking for 30 minutes was carried out for one cycle with shaking 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 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 198 mg KOH / g.

2-2. Measurement of amine value

The amine value of the tertiary amine-based polyol of Example 1 was measured.

Specifically, the tertiary amine-based polyol of Example 1 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 units of Eg / g in terms of 1 g equivalent .

As a result of the measurement, the amine value of the tertiary amine-based polyol of Example 1 was found to be 213 mg KOH / g.

Claims (14)

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

In Formula 1,
L ₁ to L ₃ are each independently

or

ego,
L ₄ is alkylene of C _{1 -6,}
And R ₁ to R ₆ are each independently hydrogen or a C _{1 -6} alkyl,
n is independently an integer of 1 to 6;
The method according to claim 1,
Wherein L ₄ is a C _{1 -4-alkylene,}
Wherein R ₁ and R _2, R ₃ and R _4, and R ₅ and R ₆ are equal to each other and each an alkyl of C _{1 -4,}
And n is, independently, 1 or 2, or a tertiary amine-based polyol.
3. The method of claim 2,
The R ₁ To R ₆ are the same, the tertiary amine based polyol both an alkyl of C _{1 -4.}
The method according to claim 1,
Wherein the tertiary amine-based polyol is any one of compounds represented by the following general 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 800 to 8,000.
The method according to claim 1,
Wherein the tertiary amine-based polyol has a hydroxyl number of 25 to 250 mg KOH / g.
The method according to claim 1,
The tertiary amine-based polyol has an amine value of 25 to 280 mg KOH / g.
A tertiary amine catalyst for the preparation of polyurethanes, comprising a tertiary amine-based polyol according to any one of claims 1 to 7.
(1) reacting a compound of formula (8) with a compound of formula (9) to prepare a compound of formula (10); And
(2) A process for producing a tertiary amine-based polyol represented by the following formula (1), comprising reacting a compound represented by the formula (10) with a compound represented by the following formula
[Chemical Formula 8]

[Chemical Formula 9]
R _{7 is} -NH-R ₈
[Chemical formula 10]

(11)

[Chemical Formula 1]

In this formula,
L ₁ to L ₃ are each independently

or

ego,
L ₄ is alkylene of C _{1 -6,}
And R ₁ to R ₈ are each independently hydrogen or a C _{1 -6} alkyl,
n is independently an integer of 1 to 6;
A polyol composition comprising a tertiary amine-based polyol according to any one of claims 1 to 7; And
Comprising reacting a polyisocyanate having two or more isocyanate groups.
≪ / RTI >
11. The method of claim 10,
Wherein the tertiary amine-based polyol serves 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.
11. The method of claim 10,
The production method is not limited to the above-mentioned tertiary amine-based polyol but may be a method of producing a polyurethane,
A polyol composition comprising a tertiary amine-based polyol according to any one of claims 1 to 7; And a polyisocyanate having at least two isocyanate groups.
14. The method of claim 13,
The polyurethane is in the form of a foam, polyurethane.

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