KR100809667B1 - Water blowned polyurethane composition having very low density and method for preparing the same - Google Patents

Abstract

A water-foamed polyurethane composition having an ultra-low density, and a method for preparing a water-foamed polyurethane foam by using the composition are provided to remove smell, to prevent the generation toxic gas in case of a fire and to lower cost by using water as a foaming agent. A water-foamed polyurethane composition comprises a resin premix; and methylene diphenyl diisocyanate in a ratio of NCO/OH of 1.0-1.4. The resin premix comprises 80-90 parts by weight of a polyol mixture which comprises 10-40 wt% of a sucrose-based polyether polyol having an average functionality of 2-6 and an average hydroxyl number of 300-600 mg KOH/g, 5-30 wt% of a glycol ether polymer having an average molecular weight of 200-800, 5-30 wt% of a polyether polyol having an average functionality of 2-5 and an average hydroxyl number of 50-200 mg KOH/g, and 10-40 wt% of a polyester polyol prepared by the addition polymerization of phthalic anhydride, ethylene oxide and propylene oxide; 3-15 parts by weight of water as a foaming agent; 0.0001-10 parts by weight of an amine-based catalyst; and 0.0001-5 parts by weight of an antifoaming agent.

Description

Water Blowned Polyurethane Composition Having Very Low density and Method for Preparing the Same

1 is an electron micrograph of the water-foamed polyurethane foam specimen prepared in Example 1. FIG.

2 is an electron micrograph of a flexible polyurethane foam specimen.

3 is an electron micrograph of a rigid polyurethane foam specimen.

Field of invention

The present invention relates to an ultra low density water-foaming polyurethane composition and a method for producing the same. More specifically, the present invention provides an ultra low density foamed polyurethane formed by mixing a catalyst and foam stabilizer with a specific polyol mixture and reacting a resin premix using water as a blowing agent with a methylene diphenyl diisocyanate (hereinafter referred to as MDI) -based isocyanate. It relates to a composition.

Background of the Invention

Polyurethane has been used as a material for insulation construction of various buildings, including refrigerated warehouses, insulated houses, ships.

In general, the polyurethane foam is prepared by mixing the isocyanate solution and the polyol solution in a fixed ratio and foaming. Freon chloro fluorocarbons (CFCs), which are commonly used as blowing agents, have been used. However, when CFC is used as a blowing agent, it causes problems such as ozone layer destruction and global warming, and has recently regulated their usage, and there is a problem of toxic gas emission in case of fire.

Accordingly, a method of applying a hydrocarbon such as pentane as a blowing agent has also been proposed, but there is a risk of explosion, and another problem of enormous facility investment cost for preventing explosion.

In order to solve this problem, the manufacture of water-foaming urethane foam using water has been steadily studied in recent years. However, when water is used as a blowing agent, the physical properties such as thermal conductivity, strength, adhesive strength, etc. are generally lowered than when using freon, so that it is difficult to apply.

In Korean Patent No. 391550, a rigid polyurethane foam is prepared by mixing a polyester polyol having a concentration of 300 to 500 mgKOH / g and a polyether polyol, and applying a mixed polyol having a functional group of 2 to 5 and a hydroxyl value of 200 to 500 mgKOH / g after mixing. It is starting.

In Korea Patent No. 316326, a polyester polyol having a functional group of 2 to 4 and a molecular weight of 300 to 800 and a mixed polyol, a crosslinking agent, a silicone oil, etc., which is a polyether polyol having a functional group of 3 to 6 and a molecular weight of 300 to 800 A low density polyurethane foam composition for spraying is disclosed.

In Korean Patent No. 561806, a polyether polyol having 10 to 50 wt% of polyoxyethylene glycol capped in a polyether polyol and a polyoxypropylene glycol having an average functional group of 2 to 6 and an average hydroxyl group of 30 to 200 mgKOH / g A low-density polyurethane foam composition for spraying is applied to an aromatic polyester polyol obtained by condensation reaction of one selected from carboxyl groups and low molecular weight esters with glycols.

In general, polyurethane is classified into soft, hard, and the like, and the flexible polyurethane foam has an open cell structure, as shown in FIG. 2, to allow air to move quickly and to penetrate water vapor. Therefore, it has good air permeability, can control a wide range of specific gravity and various physical properties according to the formulation, and has an advantage of having good cushioning property and mechanical strength (elongation, tensile strength, and wear resistance). On the other hand, the rigid polyurethane foam, as shown in Figure 3 all one cell is closed, the movement of air between the cells or the movement of water vapor is completely blocked structure can be applied as a heat insulating material is very low.

In the present invention, the urethane foam having a special cell structure was developed based on the features expressed according to the cell structure. In other words, if there are continuous cells connected to closed cells and some open cells exist to allow the movement of water vapor between each cell, the water vapor slowly penetrates into the continuous bubble and the water vapor gradually diffuses into the bubble having low water vapor pressure. Will be Because of their unique structure of diffusion and dispersion, continuous bubbles can balance mechanically stable water vapor pressures, and tens of thousands of cells with very dense structures make it difficult for convection of air in the insulation. It will be possible.

Therefore, the present inventors, for this purpose, by mixing the catalyst and foam stabilizer in a specific polyol mixture, and foaming it with water, environmentally friendly foaming ability significantly improved while maintaining the properties such as excellent heat insulation performance and adhesiveness of the advantages of the existing urethane foam Phosphorus ultra-low density water-foamed polyurethane composition and a method for producing the same have been developed.

An object of the present invention is to provide an ultra-low density water-foaming polyurethane composition which is a continuous bubble connected to a closed cell and there are some open cells to allow the movement of water vapor between each cell.

Another object of the present invention is to provide an environmentally friendly ultra low density foamable polyurethane composition which is foamed with water rather than a chemical blowing agent, thereby having little odor and releasing toxic gases in the event of a fire.

Still another object of the present invention is to provide an ultra low density water-foaming polyurethane composition having excellent heat insulating performance and adhesion.

Still another object of the present invention is to provide an ultra low density foamed polyurethane composition having greatly improved foaming force.

Still another object of the present invention is to provide an ultra-low density foamed polyurethane composition having excellent economic efficiency due to energy saving effect due to excellent heat insulation and anti-condensation effect.

Still another object of the present invention is to provide an ultra low density foamable polyurethane composition having excellent workability.

Another object of the present invention is to provide an ultra low density water-foaming polyurethane composition which can lower the unit cost of raw materials by foaming with water.

Another object of the present invention is to provide an ultra low density water-foaming polyurethane composition excellent in sound insulation.

The above and other objects of the present invention can be achieved by the present invention described below. Hereinafter, the content of the present invention will be described in detail.

Summary of the Invention

Ultra low density water-foaming polyurethane composition of the present invention (A) (a) 10 to 40% by weight of sucrose-based polyether polyol having an average functional group of 2 to 6, having an average hydroxyl group of 300 to 600 mgKOH / g, (b 5-30 wt% of a glycol ether polymer having an average molecular weight of 200-800, (c) 5-30 wt% of a polyether polyol having an average number of functional groups of 2-5, and an average hydroxyl group of 50-200 mgKOH / g, and (d 80 to 90 parts by weight of a polyol mixture consisting of 10 to 40% by weight of a polyester polyol prepared by adding and polymerizing ethylene oxide and propylene oxide to phthalic anhydride; (B) 3 to 15 parts by weight of the blowing agent consisting of water; (C) 0.0001 to 10 parts by weight of the amine catalyst; And (D) MDI isocyanate is mixed in a resin premix consisting of 0.0001 to 5 parts by weight of the foam stabilizer in an NCO / OH ratio of 1.0 to 1.4.

In one embodiment of the present invention, the amine catalyst is dimethylethanol amine (DMEA), dimethylcyclohexylamine (DMCHA), triethylenediamine (TEDA), pentamethyldiethylenetriamine (PMDETA), triethanolamine (TEA) , Tris (3-dimethylamino) propylhexahydrotriamine tetra methylene hexyldiamine (TMHDA), tripropylamine, monoethanolamine, tributylamine. Trioctylamine, hexadecyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, triisopropanol amine, bisdimethylaminoethylether and mixtures thereof.

In another embodiment of the invention the foam stabilizer is a polysiloxane ether.

The resin premix may further include 3 to 30 parts by weight of a flame retardant selected from the group consisting of tris (2-chloropropyl) phosphate (TCPP), tris (2-chloroethyl) phosphate (TCEP) and tricresyl phosphate.

The MDI isocyanate has an average functional group of 2.5 or more, and is characterized in that the polymer type 4,4'-diphenylmethane diisocyanate.

The present invention provides a method for producing an ultra low density foamed polyurethane foam. The method comprises (a) 10 to 40% by weight of sucrose-based polyether polyols having an average hydroxyl group of 2 to 6, an average hydroxyl group of 300 to 600 mgKOH / g, and (b) a glycol ether polymer having an average molecular weight of 200 to 800. 5 to 30% by weight (c) 5 to 30% by weight of polyether polyol having an average number of functional groups of 2 to 5 and an average hydroxyl group of 50 to 200 mgKOH / g, and (d) adding ethylene oxide and propylene oxide to phthalic anhydride It is characterized in that it is reacted with MDI isocyanate in a resin premix in which water is mixed as a blowing agent to a polyol mixture, an amine catalyst and a foam stabilizer made of 10 to 40% by weight of polyester polyol.

In one embodiment of the present invention, the polyol mixture and the isocyanate are reacted such that the NCO / OH ratio is 1.0 to 1.4.

Hereinafter, specific contents of the present invention will be described in detail below.

Detailed Description of the Invention

The ultra low density water-foaming polyurethane composition of the present invention comprises (A) 80 to 90 parts by weight of a polyol mixture, (B) 3 to 15 parts by weight of a blowing agent consisting of water, (C) 0.0001 to 10 parts by weight of an amine catalyst, and (D) MDI isocyanate is mixed at a NCO / OH ratio of 1.0 to 1.4 as a reactant in a resin premix consisting of 0.0001 to 5 parts by weight of a foam stabilizer.

The polyol mixture has (a) 10 to 40% by weight sucrose-based polyether polyol having an average functional group of 2 to 6, an average hydroxyl group of 300 to 600 mgKOH / g, and (b) a glycol ether having an average molecular weight of 200 to 800. 5-30% by weight of polymer (c) 5-30% by weight of polyether polyol having an average number of functional groups of 2-5, an average hydroxyl group of 50-200 mgKOH / g, and (d) ethylene oxide and propylene oxide added to phthalic anhydride It consists of 10 to 40% by weight of polyester polyol prepared by polymerization.

The said sucrose type polyether polyol (a) has an average functional group of 2-6, and the thing which has an average hydroxyl group of 300-600 mgKOH / g is used. If the average hydroxyl value is less than 300, the low-temperature dimensional stability of the product is sharply lowered, the mechanical strength is lowered. If the average hydroxyl value is 600 or more, the strength is hardened and cracking occurs, the thermal conductivity increases, the heat insulating performance is lowered as a heat insulating material.

 In the present invention, the sucrose-based polyether polyol (a) is used in an amount of 10 to 40% by weight in the total polyol mixture.

The polyether polyol (b) is used in 5 to 30% by weight of a glycol ether polymer having an average molecular weight of 200 to 800. If less than 5% by weight, less than 5% by weight of the polyol self reactivity is lowered, mechanical properties are lowered, when used in excess of 30% by weight is higher thermal conductivity is lowered thermal insulation performance.

When the polyether polyol (c) having an average number of functional groups of 2 to 5 and an average hydroxyl group of 50 to 200 mgKOH / g is used at less than 5% by weight, the strength is likely to increase and the foam may be broken or broken. If it exceeds 30% by weight, the strength is weakened, resulting in a decrease in productivity.

When the polyester polyol (d) is used in less than 10% by weight, when used in less than 10% by weight, the strength is weakened, causing a decrease in productivity, when used in excess of 40% by weight, the strength is high, but too rigid due to excessive crosslinking, etc. There is a risk of breaking or breaking.

In the present invention, the polyol mixture (A) is used in an amount of 80 to 90 parts by weight. The polyols used have unique properties depending on the OH- value and functionality, and the initiator and viscosity during the polymerization. When the polyols having high OH-value and functionality are used, the crosslinking degree is increased, thereby obtaining a product having high strength. Higher density, poor yield, too stiff, brittle and brittle, and OH-value and low functional polyols are excellent in ductility, so they do not break or break, but their strength is too low, making them unsuitable for building materials. There is this. Therefore, the above polyols must be mixed and used properly to be able to produce excellent insulation with ductility and elasticity while having excellent insulation performance and moderate strength as a building material.

In the present invention, water is used alone as a blowing agent, and 3 to 15 parts by weight is used. If it is used less than 3 parts by weight, the foam is not foamed high density, it is impossible to produce the ultra-low density polyurethane foam of the present invention. In addition, if used in excess of 15 parts by weight, scorching may occur in the product due to the heat of reaction with isocyanate. In addition, excess CO 2 gas remains inside the foam, which is a factor of increasing the thermal conductivity.

In the present invention, an amine catalyst is used as a catalyst. The amine catalyst is dimethylethanol amine (DMEA), dimethylcyclohexylamine (DMCHA), triethylenediamine (TEDA), pentamethyldiethylenetriamine (PMDETA), triethanolamine (TEA), tris (3-dimethylamino) Propylhexahydrotriamine tetra methylene hexyldiamine (TMHDA), tripropylamine, monoethanolamine, tributylamine. Trioctylamine, hexadecyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, triisopropanol amine, bisdimethylaminoethylether and mixtures thereof.

In the present invention, it is preferable to use polysiloxane ether as the foam stabilizer, and it is used in 0.0001 to 5 parts by weight, preferably 0.0001 to 3 parts by weight. In general, the silicone foam stabilizer used for polyurethane foam foaming may be used, and may be used alone or in combination of two or more thereof.

In the present invention, when water is used as a chemical blowing agent, the innumerable cells generated when inflated with the CO ₂ gas generated in the reaction of isocyanate and water show a tendency to combine with each other by the surface tension and the pressure inside the cell to form a larger cell. However, in order to improve the properties of the low density foam, it is most preferable to form a uniform and small cell, and for this purpose, a silicon-based surfactant is used as the foam stabilizer. Silicon-based surfactants supply electric charges to the surface of the cell, thereby causing an electrostatic repulsion force between the cells to prevent large agglomeration of small and uniform cells, thereby obtaining a low density foam having excellent physical properties. When the foam stabilizer is used at less than 0.0001 parts by weight, the surface of the cells are agglomerated to form a large and uneven cell. Therefore, the properties of the low density foam deteriorate, and when used at 5 parts by weight or more, the mechanical strength of the low density foam is lowered.

MDI isocyanate is used as a reactant in a resin premix consisting of 80 to 90 parts by weight of the polyol mixture, 3 to 15 parts by weight of blowing agent, 0.0001 to 10 parts by weight of amine catalyst, and 0.0001 to 5 parts by weight of foam stabilizer.

The MDI isocyanate is mixed with an NCO / OH ratio of 1.0 to 1.4. When it becomes 1.0 or less, polyurethane reaction formation is difficult and foam formation falls, When it is 1.4 or more, the dimensional stability at low temperature falls and the crumb of a foam increases.

The said MDI type isocyanate is 2.5 or more of average functional groups, and it is preferable that it is polymeric 4,4'- diphenylmethane diisocyanate.

In the present invention, in order to impart flame retardancy, it may further comprise 3 to 30 parts by weight of a flame retardant as necessary. The flame retardant may include tris (2-chloropropyl) phosphate (TCPP), tris (2-chloroethyl) phosphate (TCEP), tricresyl phosphate and mixtures thereof, and the like, but is not limited thereto. If the flame retardant is less than 3 parts by weight, the basic flame retardant fire is removed, and the self-extinguishing property is not secured. If the flame retardant is used in excess of 30 parts by weight, the flame retardant is no longer improved. This increases the yield of low density foams, reducing the production efficiency.

The method for producing an ultra low density water-foaming polyurethane foam of the present invention comprises (a) 10 to 40% by weight of sucrose-based polyether polyol having an average functional group of 2 to 6 and an average hydroxyl group of 300 to 600 mgKOH / g, (b 5 to 30% by weight glycol ether polymer having an average molecular weight of 200 to 800 (c) 5 to 30% by weight of polyether polyol having an average number of functional groups of 2 to 5 and an average hydroxyl group of 50 to 200 mgKOH / g, and (d Reaction with MDI isocyanate in a resin premix of a polyol mixture consisting of 10 to 40% by weight of a polyester polyol prepared by addition polymerization of ethylene oxide and propylene oxide to phthalic anhydride, an amine catalyst and a foam stabilizer mixed with water as a blowing agent It is characterized by. The polyol mixture and isocyanate are reacted such that the NCO / OH ratio is 1.0 to 1.4.

In addition, fillers and antioxidants commonly used in polyurethane foams, ultraviolet absorbers, stabilizers, deodorants, viscosity reducing agents, colorants and the like can be used as necessary.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example 1

The catalyst, flame retardant, surfactant, and water were mixed in the mixed polyol in the amounts shown in Table 1 below, and then adjusted to the index 1.1 with the reactants, vigorously stirred for 3 seconds at a stock solution temperature of 13 ° C., and then the reaction proceeded. Free foaming was performed by measuring the time according to the degree. The electron micrographs of the prepared urethane foam specimens are shown in FIG. 1, and the physical properties were evaluated by the Korea Testing Institute according to the provisions of KS M 3809 of the Korea Institute of Standards and Certification, and the results are shown in Table 1.

Property evaluation method

Physical properties were measured by the test method of KS M 3809: 2006.

Polyol a: The sucrose type polyether polyol which has an average functional group of 2-6, and has an average hydroxyl group of 300-600 mgKOH / g was used.

Polyol b: glycol ether polymer having an average molecular weight of 200 to 800 was used.

Polyol c: The polyether polyol whose average number of functional groups is 2-5, and whose average hydroxyl group is 50-200 mgKOH / g was used.

Polyol d: Polyester polyol prepared by addition polymerization of ethylene oxide and propylene oxide to phthalic anhydride was used.

Catalyst A: Dimethylcyclohexylamine (DMCHA) was used.

Catalyst B: Bisdimethylaminoethyl ether was used.

Catalyst C: Tetramethylene hexyldiamine (TMHDA) was used.

Flame retardant: Trischloroisopropyl phosphate was used.

Reagent: A polymethylenediphenyl isocyanate having a viscosity of 187 cps / 25 DEG C and containing 31.2% by weight of NCO was used.

cream time: The time when the stock solution starts to mix and the color starts to swell as the color starts to swell.

gel time: It means the time when the polymer starts to form and the polyurethane foam comes to the straw when taken with a straw.

Rise time: It means the time when the polyurethane foam reaction is over and no longer rises.

As shown in Table 1, when the amount of the glycol ether polymer having an average molecular weight of 200 to 800 was increased, the self-responsiveness of the mixed polyol was improved and the mechanical properties were also improved. However, when too much was added, the thermal conductivity rapidly increased, resulting in poor thermal insulation performance. In addition, the reactivity of the low-density foam was measured while varying the addition amount of the glycol ether polymer (b) having an average molecular weight of 200 to 800. If the addition amount is too small, the mixed polyol self-reaction is slow, which is not suitable for spraying, and it is excessively added. In this case, it was found that the self-reaction of the mixed polyol was so fast that spraying was not suitable.

 The present invention is environmentally friendly by foaming with water, not a chemical blowing agent, odorless and does not emit toxic gases in the event of a fire, lowers the cost of raw materials, and has a unique cell structure, excellent heat insulating performance and adhesion The foaming ability is greatly improved, and the energy saving effect can be obtained due to the excellent heat insulation and condensation prevention effect, thereby providing an excellent economic efficiency, excellent workability, and excellent sound absorption and sound absorption, and providing a super low density foamable polyurethane composition and a method of manufacturing the same. Has the effect of the invention.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (7)

(A) 10 to 40% by weight of sucrose-based polyether polyol having an average functional group of 2 to 6 and an average hydroxyl group of 300 to 600 mgKOH / g, (b) a glycol ether polymer having an average molecular weight of 200 to 800 5 to 30% by weight (c) 5 to 30% by weight of polyether polyol having an average number of functional groups of 2 to 5 and an average hydroxyl group of 50 to 200 mgKOH / g, and (d) adding ethylene oxide and propylene oxide to phthalic anhydride 80 to 90 parts by weight of a polyol mixture consisting of 10 to 40% by weight of polyester polyol prepared by combining; (B) 3 to 15 parts by weight of the blowing agent consisting of water; (C) 0.0001 to 10 parts by weight of the amine catalyst; And (D) 0.0001 to 5 parts by weight of foam stabilizer; Methylene diphenyl diisocyanate (MDI) isocyanate as a reactant in a resin premix consisting of ultra-low density water-foaming polyurethane composition in which the NCO / OH ratio is 1.0 to 1.4. The method of claim 1, wherein the amine catalyst is dimethylethanol amine (DMEA), dimethylcyclohexylamine (DMCHA), triethylenediamine (TEDA), pentamethyldiethylenetriamine (PMDETA), triethanolamine (TEA), tris (3-dimethylamino) propylhexahydrotriamine tetra methylene hexyldiamine (TMHDA), tripropylamine, monoethanolamine, tributylamine. Ultra low density, characterized in that it is selected from trioctylamine, hexadecyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, triisopropanol amine, bisdimethylaminoethyl ether and mixtures thereof Water-foaming polyurethane composition. The ultra-low density water-foaming polyurethane composition according to claim 1, wherein the foam stabilizer is a polysiloxane ether. According to claim 1, wherein the resin premix is 3 to 30 parts by weight of a flame retardant selected from the group consisting of tris (2-chloropropyl) phosphate (TCPP), tris (2-chloroethyl) phosphate (TCEP) and tricresyl phosphate Ultra-low density water-foaming polyurethane composition, characterized in that it further comprises. The ultra-low density foamable polyurethane composition according to claim 1, wherein the methylene diphenyl diisocyanate (MDI) isocyanate is an average functional group of 2.5 or more and is a polymer type 4,4'-diphenylmethane diisocyanate. (a) 10 to 40% by weight of sucrose polyether polyol having an average functional group of 2 to 6 and an average hydroxyl group of 300 to 600 mgKOH / g, (b) a glycol ether polymer having an average molecular weight of 200 to 800 5 to 30 % By weight (c) 5 to 30% by weight of polyether polyols having an average number of functional groups of 2 to 5 and an average hydroxyl group of 50 to 200 mgKOH / g, and (d) ethylene oxide and propylene oxide added to phthalic anhydride. Ultra-low density water-foamed polyurethane prepared by reacting a methylene diphenyl diisocyanate (MDI) isocyanate in a resin premix of a polyol mixture, an amine catalyst and a foam stabilizer made of 10 to 40% by weight of a polyester polyol, as a blowing agent Method of making foams. The method of claim 6, wherein the polyol mixture and the isocyanate are reacted such that the NCO / OH ratio is 1.0 to 1.4.

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