KR20180116783A - Composition for forming eco-friendly polyurethane foam and method for preparing the polyurethane foam - Google Patents

Abstract

The present invention relates to a composition for forming an environmentally friendly polyurethane foam and a process for producing the polyurethane foam. More specifically, the present invention relates to a polyol premix composition capable of producing the environmentally friendly polyurethane foam while using an anhydrosugar alcohol derived from a natural product, especially isosorbide, and maintaining excellent foaming properties without using an organometallic compound as a catalyst, a composition for forming a two-component polyurethane foam comprising the polyol premix composition as a single component, a method for producing the polyurethane foam by using the same, and the environmentally friendly polyurethane foam produced thereby.

Description

TECHNICAL FIELD The present invention relates to a composition for forming an environmentally friendly polyurethane foam and a method for preparing the polyurethane foam,

The present invention relates to a composition for forming an environmentally friendly polyurethane foam and a process for producing a polyurethane foam, and more particularly, to a process for producing an environmentally friendly polyurethane foam by using an anhydrosugar alcohol derived from a natural product, especially isosorbide, A polyol premix composition capable of producing an environmentally friendly polyurethane foam while maintaining a good foaming property, a composition for forming a two-component polyurethane foam containing the same as a single component, a method for producing a polyurethane foam using the same, and Friendly polyurethane foam.

Flexible polyurethane foam having an open cell structure and excellent mechanical strength is used for a variety of purposes in automobiles, electric / electronic parts, and sofas and bed mattresses requiring cushioning.

Flexible polyurethane foam is classified into slabstock foam and mold foam depending on the production method. The slabstock foam refers to a foam that is used by free foaming continuously without injecting the raw solution into a mold, and cutting the hardened foam to a desired size.

Since the slabstock polyurethane foam is produced continuously, the selection of the type and amount of catalyst is important. Catalysts have been used to balance reactions by controlling reactions in continuous production processes.

In general, the catalysts used to control the reaction include amine catalysts and organometallic catalysts. The amine catalyst controls the resinization reaction and the foaming reaction, and the organometallic catalyst promotes the resin reaction. As the amine catalyst, a tertiary amine is mainly used, and as an organic metal catalyst, an organic tin compound, tin bis [2-ethylhexanoate] is mainly used.

In the past, the two catalysts were indispensable for foaming. For example, if the amine catalyst is not used, the reaction does not take place, and if the organometallic catalyst is not used, the problem of sagging during the formation of the foam occurs. However, organometallic catalysts are environmentally harmful substances and contain volatile organic compounds that are the main cause of odor in the foam that has been reacted.

Accordingly, there has been a demand for development of a slabstock polyurethane foam composition that reduces volatile organic compounds, which are the main cause of odor, as environment pests which have recently been regulated for use, and which uses environmentally friendly materials.

Korean Patent Publication No. 10-2016-0062559 Korean Patent Publication No. 10-2010-0097110

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a composition for forming a slabstock polyurethane foam capable of producing an environmentally friendly polyurethane foam while maintaining excellent foaming properties without using an organometallic compound And a method for producing a polyurethane foam by using the same.

According to a first aspect of the present invention, there is provided a polyol premix composition comprising a polyol, anhydrosugar alcohol, an amine catalyst, a foam stabilizer and a foaming agent.

According to a second aspect of the present invention, there is also provided a polyol composition comprising the polyol premix composition as a first component; And a polyisocyanate as a second component. The composition for forming a two-component type polyurethane foam is provided.

According to a third aspect of the present invention, there is also provided a process for producing a polyurethane foam, which comprises mixing and reacting the polyol premix composition and a polyisocyanate.

According to a fourth aspect of the present invention, there is provided a polyurethane foam produced by reacting the polyol premix composition with a polyisocyanate.

The use of the polyol premix composition or the composition for forming polyurethane foam of the present invention makes it possible to produce an environmentally friendly polyurethane foam while maintaining excellent foaming properties without using an organometallic compound as a catalyst.

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

The polyol premix composition of the present invention includes a polyol, anhydrosugar alcohol, an amine catalyst, a foam stabilizer and a foaming agent.

The polyol used in the present invention means a polyol other than anhydrosugar alcohol. In the present invention, a polyurethane foam having an average number of active hydrogens of 2 or more (preferably 2 to 4) and an active hydrogen equivalent of 600 to 7000 Can be used.

More specifically, a polyether polyol, a polyester polyol, a polymer polyol obtained by polymerizing the above polyether polyol or polyester polyol with a vinyl compound, and a combination thereof can be used. According to one embodiment, a polyether polyol or polyether polymer polyol obtained by polymerizing a polyether polyol and a vinyl compound can be preferably used.

The polyol may be used alone or in combination, and preferably the polymer polyol may be used for controlling the physical properties of the flexible polyurethane foam. For example, polyether polymer polyol in the form of a stable suspension can be obtained by grafting a polyvinyl filler to a polyether polyol. Examples of the vinyl compound that can be used in the production of the polymer polyol include acrylonitrile, styrene monomer, methylmethacrylonitrile, and the like. Preferably, acrylonitrile may be used alone or in combination with a styrene monomer. The vinyl compound content in the polymer polyol may be 20 to 50 wt%.

The anhydrosugar alcohol used in the present invention is prepared from hydrogenated sugars derived from natural products.

Hydrogenated sugar (also referred to as " sugar alcohol ") refers to a compound obtained by adding hydrogen to the reducing end group of a saccharide, generally HOCH ₂ (CHOH) _n CH ₂ OH (wherein n is an integer of 2 to 5 ), And classified into tetritol, pentitol, hexitol and heptitol (C 4, 5, 6 and 7, respectively), depending on the number of carbon atoms.

Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol and the like, and sorbitol and mannitol are particularly useful substances.

Anhydrous alcohol has a diol form with two hydroxyl groups in the molecule and can be prepared using hexitol derived from starch. Since alcohol-free alcohol is an eco-friendly substance derived from renewable natural resources, there has been much interest for a long time and studies on the manufacturing method have been carried out. Among these alcohol-free alcohols, isosorbide prepared from sorbitol has the widest industrial application currently.

The use of anhydrous alcohol is widely used in the treatment of cardiovascular diseases, patches, adhesives, oral cleansers and the like, solvents for compositions in the cosmetics industry, and emulsifiers in the food industry. In addition, it is possible to increase the glass transition temperature of a polymer substance such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, to improve the strength of these materials, and to be an environmentally friendly material derived from natural materials. useful. It is also known to be used as an environmentally friendly solvent for adhesives, environmentally friendly plasticizers, biodegradable polymers, and water-soluble lacquers. As such, alcohol-free alcohol has attracted a great deal of attention due to its versatility and its use in real industry is increasing.

In the present invention, as the alcohol without sugar, dianhydrohexitol, which is a dehydrate of hexitol, may be used, more preferably isosorbide (1,4-3,6-dianhydroisorbitol), isomannide Dianhydroidanitol), and mixtures thereof, and most preferably, isosorbide (1,4-diol hydroperoxide) Is used.

In the present invention, since the alcohol without anhydride plays a role of promoting the resin reaction, the polyol premix composition of the present invention does not contain an organometallic compound as a catalyst and does not contain an organometallic compound as a catalyst, Can be improved.

The polyol premix composition of the present invention may contain 1 to 10 parts by weight of anhydrosugar alcohol based on 100 parts by weight of the polyol, more preferably 1 to 5 parts by weight, still more preferably 2 to 4 parts by weight ≪ / RTI > If the content of anhydrosugar alcohol in the polyol premix composition is too small, the polyol premix composition may fail to function as a catalyst for the resin reaction and may not be foamed. On the contrary, if the amount is too large, There may still be a problem that an excessive amount of anhydrous alcohol remains in the form of powder.

The amine catalyst used in the present invention promotes the reaction between the polyol and the isocyanate compound.

In the present invention, the kind of the amine catalyst is not particularly limited, but preferably one or a mixture of two or more selected from tertiary amine catalysts can be used. More specifically, triethylene diamine, triethylamine, Triethylamine, N-methyl morpholine, N-ethyl morpholine, and combinations thereof may be used.

The polyol premix composition of the present invention may contain the amine catalyst in an amount of 0.01 to 5 parts by weight, more preferably 0.1 to 2.5 parts by weight based on 100 parts by weight of the polyol. If the amount of the amine catalyst used is too small, the reaction may be delayed, resulting in poor curing or a problem of sagging during the formation of the foam. On the other hand, if the amount is too large, the reaction may become too rapid or shrinkage may occur.

The foam stabilizer used in the present invention functions to prevent the cells generated when the cells are formed in the polyurethane foam foam from being united or broken and to adjust the cells to have uniform shapes and sizes .

In the present invention, the foam stabilizer can be used without any particular limitations as long as it is conventionally used in the production of polyurethane foam foam, and for example, silicone foam stabilizer can be preferably used. The silicon-based foaming agent may be at least one kind selected from silicone oil and derivatives thereof, and specifically may be a polyalkylene oxide methyl siloxane copolymer.

In the polyol premix composition of the present invention, the foaming agent may be contained in an amount of 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polyol. If the amount of the foam stabilizer used is too small, the foam may be unevenly formed. On the contrary, if the foam stabilizer is used in an excessively large amount, the foam may be shrunk.

As the foaming agent to be used in the present invention, a known foaming agent component conventionally used for the production of flexible polyurethane foam can be appropriately selected and used in consideration of various physical properties of the foamed foam required.

In the present invention, water is typically used as the foaming agent. In addition, water may be used as the foaming agent from the group consisting of methylene chloride, n-butane, isobutane, n-pentane, isopentane, dimethyl ether, acetone, carbon dioxide, You can use the selected one. These foaming agents can be suitably used according to known methods of use and depending on the density and other properties of the foam foam desired.

There is no particular limitation on the amount of the foaming agent used in the polyol premix composition of the present invention. For example, the foaming agent may be used in an amount of 0.1 to 30 parts by weight, more specifically 0.5 to 25 parts by weight, based on 100 parts by weight of the polyol It does not. According to one embodiment of the present invention, 0.8 to 5.0 parts by weight of water, or 0.8 to 5.0 parts by weight of water and 0.1 to 18 parts by weight of methylene chloride may be used as a foaming agent based on 100 parts by weight of the polyol.

The polyol premix composition of the present invention may further contain an auxiliary additive selected from the group consisting of a flame retardant, a colorant, a UV stabilizer, a thickener, a foam stabilizer, a filler, and combinations thereof, have.

The content of the auxiliary additive is not particularly limited and may be selected within a range that does not impair the object physical properties of the polyol premix composition. In one embodiment, the content of the auxiliary additive may be 0.01 to 5 parts by weight based on 100 parts by weight of the polyol, More preferably 0.1 to 2 parts by weight.

According to another aspect of the present invention, there is provided a composition comprising the polyol premix composition as a first component; And a polyisocyanate as a second component. The composition for forming a two-component type polyurethane foam is provided.

In the present invention, the polyisocyanate can be used without any particular limitation as long as it can be used in the production of a polyurethane foam. Thus, for example, polyisocyanates selected from the group consisting of aliphatic polyisocyanates, cycloaliphatic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, heterocyclic polyisocyanates, and combinations thereof may be used, Both isocyanate or modified polyisocyanate may be used.

Specifically, the polyisocyanate is at least one compound selected from the group consisting of methylene diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1-12-dodecane diisocyanate, cyclobutane- Cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 2-4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, dicyclohexylmethane-diisocyanate, 4,4'-diisocyanate (HMDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane- , 4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, polydiphenylmethane diisocyanate (PMDI), naphthalene-1,5-diisocyanate and combinations thereof Luer binary may be selected from the group. In one embodiment, as the polyisocyanate, toluene diisocyanate (2,4- / 2,6-isomer ratio = 80/20) in which 2,4-toluene diisocyanate and 2,6-toluene diisocyanate are mixed can be used have.

In the present invention, the amount of polyisocyanate to be used is preferably 70 to 130 in terms of isocyanate index, more preferably 80 to 120, and even more preferably 100 to 120. The isocyanate index refers to the amount of isocyanate used relative to the theoretical equivalent, as a ratio of the number of hydroxy equivalents present in the polyol to the number of equivalents of isocyanate in the urethane reactant. An isocyanate index of less than 100 means that an excess of polyol is present, and an isocyanate index of more than 100 means that an excess of isocyanate is present. If the isocyanate index is less than 70, There is a problem in that the reaction is delayed to prevent curing. When the isocyanate index is more than 130, the hard segment is excessively increased, causing a shrinkage phenomenon.

In the composition for forming a two-component type polyurethane foam of the present invention, the first component and the second component may be present separately without contact, and they may be mixed immediately before use or in situ .

According to another aspect of the present invention, there is provided a process for producing a polyurethane foam, which comprises mixing and reacting the polyol premix composition and a polyisocyanate, and a polyurethane foam, such as a flexible polyurethane foam, .

When the polyol premix composition of the present invention is used in the production of the polyurethane foam, a polyisocyanate is added to the polyol premix composition and stirred, and then the mixture is poured into a mold to allow curing and foaming to proceed. have.

When the composition for forming a two-component polyurethane foam of the present invention is used for the production of the polyurethane foam, the first component and the second component contained in the composition are mixed and stirred, And the foaming proceeds, whereby a polyurethane foam can be produced.

There are no particular restrictions on equipment or conditions (temperature, time, etc.) used in the production of the polyurethane foam, and the equipment or conditions that are usually employed may be used as is or modified appropriately.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited by these examples.

[ Example ]

Example  And Comparative Example

The polyol, isosorbide, catalyst, silicone foaming agent and foaming agent were mixed according to the components and the content ratios shown in Tables 1 to 3 below, and thoroughly mixed for 1 minute to 3 minutes at a stirring speed of 3000 rpm to prepare a polyol premix composition .

Polyisocyanate was added to the prepared polyol premix composition and stirred at a stirring speed of 3000 rpm for 7 to 10 seconds to prepare a composition for forming polyurethane foam.

A polyethylene film was laid in a square shape in a 250 mm x 250 mm square box mold, and the polyurethane foam forming composition prepared above was poured thereon. At this time, the cream time and the maximum rise time were measured and recorded using a stopwatch, and it was observed whether health bubbles occurred. The curing was allowed to proceed at room temperature.

The properties of the foam specimens were measured by the following evaluation methods, and the results are shown in Tables 1 to 3 below.

[Property evaluation method]

(1) Molding density: Measured by KS-M-6672

(2) Tensile strength: Measured according to KS-M-ISO-7214

(3) Elongation: Measured by KS-M-ISO-7214

[Ingredients Used]

1) Polyol

PPG-3022: trifunctional polyether polyol having active hydrogen equivalent of 3000 and hydroxyl value of 54 to 58 mgKOH / g (product of Kumho Petrochemical PPG-3022)

PPG CS-743: a polymer polyol having a vinyl polymer content of 40% by weight or more and a hydroxyl value of 30 to 34 mgKOH / g (PPG CS-743 produced by KKPC)

2) Polyisocyanate

TDI-80: toluene diisocyanate (2,4- / 2,6-isomer ratio = 80/20) in which 2,4-toluene diisocyanate and 2,6-toluene diisocyanate were mixed -80 products)

3) No allowance  Alcohol

80% by weight of isosorbide (Samyang Co.)

4) Catalyst

L-33: amine catalyst, triethylenediamine / dipropylene glycol solution (TEDA L-33, manufactured by Tosoh Corporation) at a concentration of 67 wt%

A-1: An amine-based catalyst, a bis- (20 dimethylaminoethyl) ether / propylene glycol solution (Momentiva, Naikac catta list A-1)

U-28: Organometallic catalyst, tin octylate (U-28 from Nitta Kasei)

5) Foaming agent

L-580K: a silicone foam stabilizer, a polyalkylene oxide methyl siloxane copolymer (Momentive, NIAX L-580K)

L-638: a silicone foam stabilizer, a polyalkylene oxide methyl siloxane copolymer (Momentiva, Nyax silicone L-638)

6) Foaming agent

Methacrine-U: methylene chloride (manufactured by Lotte Fine Chemical Chemical Co., Ltd.-U)

The specimens of Examples 1 and 2 in Table 1 were foamed at a density of 18 kg / m 3, which was foamed without using an organic metal catalyst, U-28, while varying the amount of isosorbide used, and the state and physical properties of the foam were good . On the contrary, in Comparative Example 2, the isosorbide was not used and the U-28, which is an organometallic catalyst, was also foamed without using the foam, and the reaction was slow and the foam was not formed after the reaction. Comparative Example 1 is a specimen foamed in a general manner using an organometallic catalyst.

As shown in the above Table 1, the specimens of Examples 1 and 2 using isosorbide, without using the organometallic catalyst, exhibited foaming characteristics equal to or higher than that of the specimen of Comparative Example 1 using the organometallic catalyst, It can be seen that it improved the quality.

The specimens of Examples 3 and 4 in Table 2 were prepared by using water alone as a foaming agent in place of water and a mixture of methacin-U and using foaming agents without using an organic metal catalyst, U-28, The specimen had a density of 26 kg / m3, and the state and physical properties of the foam were good. On the other hand, in Comparative Example 4, water was used alone as a foaming agent in place of water and a mixture of methacin-U, isosorbide was not used, and a foamed material was used without using the organometallic catalyst U-28. After the reaction was slow, the foam did not form and sagged. Comparative Example 3 is a specimen foamed in a general manner using an organometallic catalyst, while using water alone as a foaming agent in place of water and a mixture of meta-curing-U.

As shown in Table 2, the specimens of Examples 3 and 4 using isosorbide without using an organometallic catalyst were obtained by using water as the foaming agent in place of the mixture of water and methacin- It was found that the catalyst exhibited the foaming property equal to or higher than that of the specimen of Comparative Example 3 using the catalyst, and improved the environmental friendliness.

Table 3 shows the results of comparing physical properties of polyurethane foam specimens having a density of 40 kg / m < 3 > foamed by using a polyol as a polyol together with a polymer polyol. From this, it can be confirmed that the same results as those in Tables 1 and 2 can be obtained regardless of the kind of polyol.

The properties described in Tables 1 to 3 are as follows.

- Cream Time (sec): This is the time from when the polyurethane foam raw solution is mixed to when the raw solution starts swelling. It is important to find the balance because it is the part to find the optimum reactivity. However, the longer the cream time, the shorter the cream time because foam formation (or cell formation) may become irregular, but if it is too short, the mixing may not be performed properly. Therefore, a suitable cream time (for example, 7 seconds To 14 seconds) is required.

- Rise time (sec): This is the time taken for the foam to swell up to the maximum from the point where the polyurethane foam stock solution is mixed. It is important to balance the gelling and blowing to find the optimum reactivity. It is difficult to say good / bad with only fast and slow. If the rise time is high, the foam will collapse (collapse before the foamed foam is hardened, mainly when the raw fluid ratio is wrong or the raw material mixing is not sufficient), and if it is too slow, the foam will be foamed ), A suitable rise time (for example, 108 to 124 seconds) is required. The " unmeasurable " of the rise time means that the foam does not form because the composition does not swell up.

- Healthy foam: refers to small air bubbles that blow up to the surface of the upper part of the foam immediately after the maximum inflation, and the existence of the health bottle means that the foam is foamed properly.

- Foam status:

1) Good: The foam is in a state of being blown (swollen), and the appearance of collapse or crack due to gelling (phenomenon that the inside of the foam is cracked due to the process of formation of the foam or the external condition after forming) or shrinkage A phenomenon in which the trapped gas in the inside is cooled to be smaller than the original size of the foam) does not occur.

2) Submersion: This means that the foam is not formed due to the cell breaking during the blowing of the foam, and is in a recessed state.

- Meaning of "impossible to measure" in density, tensile strength and elongation: Since the foam is not formed due to low reactivity of the material after the polyurethane foam raw material is mixed, the polyurethane foam raw solution is present in a mixed state, Tensile strength and elongation can not be measured.

Claims (13)

Polyol, anhydrosugar alcohol, an amine catalyst, a foam stabilizer, and a foaming agent. The polyol premix composition according to claim 1, wherein the polyol is selected from the group consisting of a polyether polyol, a polyester polyol, a polymer polyol obtained by polymerizing the polyether polyol or polyester polyol with a vinyl compound, and combinations thereof. The polyol premix composition of claim 1, wherein the anhydrosugar alcohol is selected from the group consisting of isosorbide, isomannide, isoidide, and mixtures thereof. The polyol premix composition according to claim 1, wherein anhydrous alcohol is contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the polyol. The polyol premix composition of claim 1, wherein the amine catalyst is a tertiary amine catalyst. The polyol premix composition according to claim 1, which does not contain an organometallic compound as a catalyst. The polyol premix composition according to claim 1, wherein the foam stabilizer is a silicone foam stabilizer. The polyol premix composition according to claim 1, wherein the blowing agent is selected from the group consisting of water, methylene chloride, n-butane, isobutane, n-pentane, isopentane, dimethyl ether, acetone, carbon dioxide and combinations thereof. The polyol premix composition of claim 1, further comprising an auxiliary additive selected from the group consisting of a flame retardant, a colorant, a UV stabilizer, a thickener, a foam stabilizer, a filler, and combinations thereof. The polyol premix composition of any one of claims 1 to 9 as a first component; And a polyisocyanate as a second component. The composition for forming a two-component polyurethane foam according to claim 1, 11. The composition of claim 10 wherein the polyisocyanate is selected from the group consisting of methylene diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1-12-dodecane diisocyanate, Diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 2-4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, dicyclohexyl Methane-4,4'-diisocyanate (HMDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane Diisocyanate, diphenylmethane-4,4'-diisocyanate, polydiphenylmethane diisocyanate (PMDI), naphthalene-1,5-diisocyanate, and combinations thereof. A two-component type polyurethane foam forming composition is selected from the group eojin. A process for producing a polyurethane foam, which comprises mixing and reacting a polyisocyanate with the polyol premix composition of any one of claims 1 to 9. A polyurethane foam produced by reacting a polyisocyanate with the polyol premix composition of any one of claims 1 to 9.