KR20160081634A - Novel tertiary amine-based polyol and use thereof for polyurethane preparation - Google Patents

Abstract

The present invention relates to a tertiary amine-based polyol represented by chemical formula 1, a method for preparing the same, and use thereof as a tertiary amine catalyst for preparing polyurethane. The tertiary amine-based polyol can provide polyurethane that causes less VOC generation. In chemical formula 1, L_1 is a linear or branched C1-C6 alkylene; each of L_2 to L_5 independently represents a linear C3-C10 alkylene having -OH bound to the second carbon atom from the bonded central atom N; and each of R_1 to R_8 independently represents a linear or branched C3-C10 alkyl group.

Description

[0001] The present invention relates to novel tertiary amine-based polyols and their polyurethane production applications,

The present invention relates to a novel tertiary amine-based polyol, a process for producing the same, a polyurethane production method for the same, and a polyurethane produced using the same.

According to the 2012 FUJI Industry Analysis Report, the world polyurethane market is estimated at 14.6 million tons in terms of raw materials, while the foam and non-foaming market in terms of products is steadily increasing to 11.55 million tons.

In the case of a small passenger car, 150kg of plastic is usually used. Polyurethane (PU) is used in 15 ~ 20% of total plastic usage due to excellent mechanical properties, insulation, shock absorption, sound absorbing characteristic and excellent processability. Seat cushions, instrument panels, soundproofing materials, sunshades, doors, ceiling cushions, and the like.

In addition, recovery / growth of the furniture industry such as mattresses, which stagnated with real estate due to the international economic recovery, is expected, and usage and usage of PU materials will continue to expand.

The synthesis scheme of the polyurethane is schematically shown in the following reaction formula.

[Reaction Scheme]

As in the above reaction formula, an isocyanate group (-N = C = O) easily bonds with a hydroxyl group (-OH) to form a urethane bond. When a molecule having two hydroxyl groups is reacted with a diisocyanate using this reaction, a linear polymer is obtained. This polymer is polyurethane. Generally, toluene diisocyanate is used as a diisocyanate, and polyether or polyester is used as a molecule (polyol) having a hydroxyl group. Using a polyether makes it smoother, and using polyester makes it harder. The polyurethane made by using a molecule having three or more hydroxyl groups as a polyol is three-dimensionally bonded.

Polyurethanes have the qualities and resistance to chemicals. In addition, it has excellent tensile strength and abrasion resistance, and can change softness without a plasticizer.

Polyurethanes can be used in various ways, and typical applications include synthetic fibers or paints. Synthetic fibers are often called spandex and are covered with fibers such as nylon and are used in underwear, socks, and swimwear. Polyurethane has a bubble structure, so it has elasticity, firmness and lightness. Therefore, it can be used on mattresses, fabrics, etc., as well as on the wings of airplane wings. Also, paints made of polyurethane (polyurethane resin (paint)) have strong adhesion, water resistance and corrosion resistance. Furthermore, polyurethane is used as an electrical insulator, structural material, foam insulation, bubble cushion, elastic fiber, etc. It is also used as a substitute for rubber because of its excellent elasticity.

In the case of polyurethane foam, the shape of the flexible foam and the rigid foam semi rigid foam can be determined depending on the ratio of gel reaction and blowing reaction.

In polyurethane synthesis, the reaction of a polyol and a polyisocyanate is usually carried out by reacting with a catalyst and if necessary, in the presence of a blowing agent, a surfactant, a flame retardant, a crosslinking agent and the like. For the production of polyurethanes, numerous metal compounds or tertiary amine compounds are used as catalysts. They are widely used industrially by being used alone or in combination.

In the production of water, a low-boiling organic compound, or a polyurethane foam using both of them as a foaming agent, since productivity and formability are excellent, a tertiary amine catalyst is in particular widely used among catalysts. Examples of such tertiary amine catalysts include N, N, N ', N'-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N , N ', N' ', N' '- pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine and the like. The metal-based compound is often used, for example, an organometal compound such as an organotin compound, but is often used in combination with a tertiary amine catalyst in many cases due to the problem of deteriorating the productivity and moldability, .

On the other hand, the tertiary amine catalyst compound is gradually released as a volatile amine from a polyurethane product. For example, in automobile interiors and the like, there is a problem of odor due to volatile amines and a problem of discoloration of other materials (for example, . Further, the tertiary amine catalyst generally has strong odor, and the working environment at the time of producing the polyurethane resin is remarkably deteriorated.

The volatile organic catalysts added during the production of the polyurethane foam come out of the product through migration and volatilization after the production of the foam, and generally have a molecular weight of 110 to 170 g / mol, a specific gravity of 0.9 to 1.1 at 20 ° C, 210 ° C and a viscosity of 5 ~ 115 cps / 25 ° C. Short-term exposure to these catalysts at the production site can cause headaches, nausea, vomiting, transient visual field blurring, haloing, Serious illnesses can also be caused when exposed.

Amine catalysts are classified as hazardous substances in the material safety and health regulations and may affect the health of workers and consumers. Polyurethanes prepared with tertiary amines as catalysts have tertiary amines themselves remaining in the polymer and high volatility, which can adversely affect the health of workers. In addition, automobile interior and exterior parts and life furniture manufactured using this product contain volatile organic compounds (VOC), which affects the quality such as staining, fogging, yellowing smell and the like.

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

Since the amine compound is immobilized in the polyurethane resin framework in the form of reacting with the polyisocyanate, the method is an effective method for reducing the odor of the final resin product. However, these amine catalysts have a problem of lowering the curability of the polyurethane resin because the activity of the resinization reaction (reaction of polyol and isocyanate) is lowered. The method of using the crosslinking agent is effective for reducing the odor of the final polyurethane product and for improving the working environment in the production of the polyurethane resin, but there is a problem that the physical properties such as the hardness of the polyurethane are insufficient.

On the other hand, the metal-based compound does not cause problems such as the above-mentioned tertiary amine catalysts or the problem of deteriorating other materials, but when the metal-based compound is used alone, the productivity, physical properties and moldability are deteriorated, Lead, tin, mercury and the like, and toxicity problems caused by heavy metals remaining in the products and environmental problems are being discussed.

Accordingly, the present inventors have developed a novel tertiary amine compound capable of reducing the generation of volatile organic compounds (VOC).

The present invention aims at solving the problems of the polyurethane production catalyst and providing a tertiary amine-based polyol having little VOC and a process for producing polyurethane using the same.

A first aspect of the present invention is a tertiary amine-based polyol represented by the following general formula (1)

[Chemical Formula 1]

In this formula,

L ₁ is linear or branched C _1-6 alkylene;

L ₂ to L ₅ are straight chain C _3-10 alkylenes each of which is bound to the second carbon atom from the independently bonded central atom N;

R ₁ to R ₈ is a C _{3 -10} alkyl group of hydrogen, linear or branched independently.

The tertiary amine-based polyol is a novel tertiary amine compound, wherein at least two of L ₂ to L ₅ may be the same alkylene group, and R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , and R ₇ and R ₈ may be the same alkyl group, respectively. Each of R ₁ to R ₄ and R ₅ to R ₈ may be the same alkyl group, and R ₁ To R < ₈ > may all be the same alkyl group.

A second aspect of the present invention is a tertiary amine catalyst for the production of polyurethane, which contains the tertiary amine-based polyol according to the first aspect.

A third aspect of the present invention is a process for preparing a compound of formula And

Reacting the product of the first step with a compound of formula (5): < EMI ID = 15.1 >

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In this formula,

n is an integer from 1 to 8;

Ra and Rb are each independently selected from R ₁ to R ₈ are each individually selected from the group consisting of, R ₁ to R ₈ are each independently hydrogen, linear or branched C _{3 -10} alkyl group;

L ₁ is linear or branched C _{1 -6} alkylene.

The product of the first step prepared by reacting the compound of formula (3) with the compound of formula (4) is as shown in the following formula (6).

[Chemical Formula 6]

In the above formula, n is an integer of 1 to 8.

A fourth aspect of the present invention is a method for producing a polyurethane by reacting a polyol according to the first aspect and a polyisocyanate having at least two isocyanate groups.

A fifth aspect of the present invention is a polyurethane produced according to the fourth aspect. In one embodiment, the polyurethane is in the form of a foam.

Hereinafter, the present invention will be described in detail.

The polyol of the present invention is a catalyst having a molecular weight similar to that of the conventional autocatalyst but high in nitrogen and hydroxyl (OH) contents, and thus has high performance and catalytic effect of the initiator.

The polyol of the present invention is an autocatalytic polyol having a hydroxyl group (-OH) which is two or more functional groups and can act as a reactant in itself and also as a catalyst.

In one embodiment, the polyol is a tertiary amine-based polyol represented by the following formula (2), and may have four hydroxyl groups:

(2)

In one embodiment, the weight average molecular weight (Mw) of the polyol of the present invention may be from 1000 to 8000. [

The amine catalysts are classified into gel reaction catalysts, surface cure catalysts, blowing catalysts and isocyanate reactive catalysts depending on their structure. In the case of the autocatalyst, there is a functional group serving as an initiator of propylene oxide (PO) and ethylene oxide (EO), and a structure in which an amine catalyst is bonded to the polyol has a structure capable of reducing the volatile organic compound (VOC) have.

In one embodiment, the average hydroxyl number of the autocatalytic polyol of the present invention ranges from 25 to 250 mg KOH / g and the amine value can be from 25 to 280 mg KOH / g.

In the production of the polyurethane according to the present invention, not only the tertiary amine-based polyol according to the present invention but also a polyol having two or more hydroxyl groups such as at least one polyether polyol, at least one polyester polyol or any combination thereof is further used .

The polyisocyanate which can be used in the production of the polyurethane of the present invention is a compound having two or more isocyanate groups and generates a urethane bond by causing a gel reaction with the hydroxyl group (-OH) of the polyol to finally form a polyurethane.

In the present invention, the compound having two or more isocyanate groups may include aliphatic, cycloaliphatic, arylaliphatic, and aromatic polyisocyanate compounds. Preferably, the compound having two or more isocyanate groups may be an aromatic polyisocyanate compound.

Examples of suitable aromatic polyisocyanate compounds include 4,4'-, 2,4 ', 2,2'-isomers of diphenylmethane diisocyanate (MDI) and blends thereof, polymers thereof, monomers MDI blends Toluene-2,4 - or 2,6-diisocyanate (TDI), m- or p-phenylenediisocyanate, chlorophenylene-2,4-diisocyanate, diphenylen- Isocyanate-3,3'-dimethyldiphenyl, 3-methyldiphenyl-methane-4,4'-diisocyanate, diphenyl ether diisocyanate, 2,4,6- triisocyanatotoluene, 4'-triisocyanatodiphenyl ether.

In the preparation of the polyurethane according to the present invention, the tertiary amine-based polyol of the present invention simultaneously acts as a catalyst, so that a separate tertiary amine catalyst may not be used. In the production of the polyurethane of the present invention, a polyurethane production catalyst such as a primary, secondary, tertiary, quaternary amine or organometallic catalyst commonly used in the art can be used.

Examples of the organometallic catalyst include conventionally known catalysts such as stannous diacetate, stannas dioctoate, stannas dioleate, stannas diallylate, dibutyltin oxide Oxides, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, lead octanoate, lead naphthenate, nickel naphthenate, and cobalt naphthenate.

Examples of the foaming agent include water, methylene chloride, acetone, carbon fluoride (CFC), hydrogen fluoride (HFC), hydrogen fluoride (HCFC), and the like. The foaming agent may be used alone or in combination. ) And hydrocarbons, but are not limited thereto. Non-limiting examples of the HFC include HFC-245fa, HFC-134a and HFC-365. Exemplary HCFCs include HCFC-141b, HCFC-22, and HCFC-123. Examples of the hydrocarbons include n-pentane, iso-pentane, cyclopentane, and the like, or any combination thereof.

The amount of the blowing agent to be used may vary depending on, for example, the intended use purpose of the polyurethane product, the intended use, and the desired foam stiffness and density. In the preparation of the polyurethane foam of the present invention, the blowing agent may be used in an amount of about 1 to 13.5, or about 3 to about 4.5 parts by weight (pphp) per 100 parts by weight of the total polyol composition according to the present invention.

When water is present in the formulation in the manufacture of polyurethane, water may be present in the range of 0 to about 20 pphp.

Depending on the requirements for the end use of the polyurethane, various additives may be used in the polyurethane formulation to tailor certain properties. The additives include, but are not limited to, a crosslinking agent, a cell stabilizer, a flame retardant, a chain extender, an epoxy resin, an acrylic resin, a filler, a pigment and the like or any combination thereof.

Suitable crosslinking agents include, but are not limited to, diethanolamine, diisopropanolamine, triethanolamine, tripropanolamine, or the like, or any combination thereof. The crosslinking agent may be used in an amount of about 0.1 to 5.4, or about 0.3 to about 1.8 pphp, based on the total composition.

The cell stabilizer may include a surfactant such as an organopolysiloxane. Surfactants may be used in an amount of about 0.1 to 3.6, or about 0.3 to about 1.2 pphp, based on the total composition.

Non-limiting examples of flame retardants include halogenated organophosphorus compounds and non-halogenated compounds. A non-limiting example of a halogenated flame retardant is trichloropropyl phosphate (TCPP). For example, triethyl phosphate ester (TEP) and DMMP are non-halogenated flame retardants. Depending on the end use, the flame retardant may be used in an amount of from 0 to about 50 pphp, from 0 to about 40 pphp, from 0 to about 30 pphp, or from 0 to about 20 pphp, based on the total composition.

For example, a chain extension system of diols such as ethylene glycol, butanediol and the like can be used in the present invention.

For example, the polyurethane of the present invention can be produced by stirring a mixed solution obtained by mixing raw materials and then injecting the mixture into an appropriate container or mold to form a foam. The stirring can be carried out using a general stirrer or a dedicated polyurethane foaming machine. As the polyurethane foaming agent, for example, a high-pressure, low-pressure or spray-type apparatus can be used.

Examples of the molded article using the polyurethane obtained by the method of the present invention include an elastomer not using a foaming agent and a polyurethane foam using a foaming agent.

Examples of polyurethane foam products include flexible polyurethane foams, semi-rigid polyurethane foams, and rigid polyurethane foams. The method for producing a polyurethane according to the present invention is specifically applicable to the production of a heat insulating material using a car seat of a flexible polyurethane foam, an instrument panel or handle of a semi-rigid polyurethane foam and a rigid polyurethane foam, Can be suitably used.

The flexible polyurethane foam generally has an open-cell structure and is reversibly deformable, exhibiting high air permeability. The physical properties of the flexible polyurethane foam are not particularly limited, but they generally have a density of 10 to 100 kg / m 2, a compressive strength (ILD 25%) of 200 to 8000 kPa and an elongation of 80 to 500%.

In addition, the semi-rigid polyurethane foam has an open-cell structure similar to that of the flexible polyurethane foam and has reversible deformation showing high air permeability, although the foam density and compressive strength are higher than those of the flexible polyurethane foam. The physical properties of the semi-hard urethane foam are not particularly limited, but they generally have a density of 40 to 800 kg / m 3, a compressive strength (ILD 25%) of 10 to 200 kPa and a growth rate of 40 to 200%.

In addition, the rigid polyurethane foam has a highly crosslinked closed cell structure and is not reversibly deformable. The physical properties of the rigid urethane foam are not particularly limited, but they generally have a density of 10 to 100 kg / m 3 and a compressive strength of 50 to 1,000 kPa.

The novel tertiary amine-based polyol of the present invention is an autocatalytic polyol, which is a reactant in the production of a polyurethane and can act as a catalyst, and has a high catalytic activity since a tertiary amine group and a polyol structure exist together.

In addition, in the production of polyurethane, there is no need to additionally supply an amine catalyst, which makes it possible to produce a polyurethane which is economical and has a small VOC content. Furthermore, since the amount of the amine to be vaporized from the polyurethane produced is very small, the catalyst activity can be further improved while suppressing odor of the amine catalyst from the obtained foam and maintaining the moldability of the foam.

Further, when producing a polyurethane, a polyurethane product can be produced without using a metal-based catalyst such as lead, tin, and mercury together, and good moldability can be obtained. Without causing toxicity and environmental problems, The discoloration of PVC (polyvinyl chloride) on the automotive instrument panel due to the catalyst, and the fogging of the window glass caused by volatile components evaporated from the foam.

1 is a ¹³ C-NMR spectrum of a tertiary amine-based polyol prepared according to Example 1. Fig.
2 is a ¹ H-NMR spectrum of a tertiary amine-based polyol prepared according to Example 1. Fig.

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  One: New Of polyol  synthesis

1. Synthesis of glycidylamine

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 dropwise funnel was charged with 28 g (1.75 mol). The following mixture was stirred at room temperature overnight and filtered to use the bottom liquid. The upper liquid was separated by layer separation with ethyl acetate using a seperatory funnel. The water was absorbed by Na ₂ SO ₄ and filtered to obtain a glycidyl amine. The glycidylamine was finally separated via vacuum distillation.

2. Synthesis of 7,12-bis (3- (diethylamino) -2-hydroxypropyl) -3,16-diethyl-3,7,12,16-tetraazaoctadecane-5,14-diol

The glycidylamine (0.0387 mol, 3.41 g) produced in the above 1 was mixed with diaminobutane (0.1548 mol, 20 g) and reacted at 55 ° C for 24 hours to finally obtain the compound represented by the following formula Tertiary amine type polyol was prepared.

(2)

Claims (16)

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

In this formula,
L ₁ is linear or branched C _1-6 alkylene;
L ₂ to L ₅ are straight chain C _3-10 alkylenes each of which is bound to the second carbon atom from the independently bonded central atom N;
R ₁ to R ₈ are each independently hydrogen, a linear or branched C _3-10 alkyl group. The method according to claim 1,
Wherein at least two of said L < _{2 >} -L < ₅ > are the same alkylene group. The method according to claim 1,
The tertiary amine-based polyol in which R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , and R ₇ and R ₈ are each the same alkyl group. The method according to claim 1,
Wherein R ₁ to R ₄ , and R ₅ to R ₈ are each the same alkyl group. 5. The method of claim 4,
The tertiary amine-based polyol wherein R ₁ to R ₈ are all the same alkyl group. The method according to claim 1,
Wherein the polyol is represented by the following formula (2).
(2)

The method according to claim 1,
Wherein the polyol has a weight average molecular weight (Mw) of 1,000 to 8,000. The method according to claim 1,
Wherein the polyol has a hydroxyl number of 25 to 250 mgKOH / g. The method according to claim 1,
The polyol has an amine value of 25 to 280 mg KOH / g. A tertiary amine catalyst for the production of polyurethanes, comprising tertiary amine-based polyols according to any one of claims 1 to 9. (3) and (4); And
A process for producing a tertiary amine-based polyol according to any one of claims 1 to 9, comprising a second step of reacting the product of the first stage with a compound of the formula
(3)

[Chemical Formula 4]

[Chemical Formula 5]

In this formula,
n is an integer from 1 to 8;
Ra and Rb are each independently selected from R ₁ to R ₈ are each individually selected from the group consisting of, R ₁ to R ₈ are each independently hydrogen, straight-chain or a C _3-10 alkyl branched chain;
L ₁ is linear or branched C _1-6 alkylene. A process for producing a polyurethane by reacting a polyol composition containing a tertiary amine-based polyol according to any one of claims 1 to 9 and a polyisocyanate having at least two isocyanate groups. A tertiary amine-based polyol according to any one of claims 1 to 9, characterized in that when a urethane bond is formed between the hydroxyl group of the polyol composition and the isocyanate group of the polyisocyanate, Lt; RTI ID = 0.0 > polyurethane. ≪ / RTI > 13. The process of claim 12, wherein no tertiary amine catalyst is used. 13. A polyurethane produced according to the process of claim 12. 16. The polyurethane according to claim 15, wherein the polyurethane is in the form of a foam.

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