KR101989961B1 - Composition for forming eco-friendly polyurethane foam with improved storage stability and antioxidant property and method for preparing the polyurethane foam - Google Patents

Abstract

The present invention relates to a composition for forming an environmentally friendly polyurethane foam having improved storage stability and antioxidation properties and a process for preparing the polyurethane foam, and more particularly, to a composition for forming an environmentally friendly polyurethane foam having a specific content of anhydrosugar alcohol-alkylene glycol; And an isocyanate prepolymer prepared by reacting a polyisocyanate with a polyol component including a bio-polyol other than a dihydric alcohol-alkylene glycol, and an eco-friendly polyurethane foam composition having improved storage stability and oxidation- A method for producing the polyurethane foam using the same, and an environmentally friendly polyurethane foam so produced.

Description

TECHNICAL FIELD The present invention relates to a composition for forming an environmentally friendly polyurethane foam having improved storage stability and antioxidation properties and a process for preparing a polyurethane foam,

The present invention relates to a composition for forming an environmentally friendly polyurethane foam having improved storage stability and antioxidation properties and a process for preparing the polyurethane foam, and more particularly, to a composition for forming an environmentally friendly polyurethane foam having a specific content of anhydrosugar alcohol-alkylene glycol; And an isocyanate prepolymer prepared by reacting a polyisocyanate with a polyol component including a bio-polyol other than a dihydric alcohol-alkylene glycol, and an eco-friendly polyurethane foam composition having improved storage stability and oxidation- A method for producing the polyurethane foam using the same, and an environmentally friendly polyurethane foam so produced.

Polyols and isocyanates, which are essential components of polyurethanes, are usually prepared from petroleum-based raw materials. Polyether polyols and polyester polyols are the most popular polyols, and TDI, HDI and MDI are the most common isocyanates. These polyols and isocyanates have a significant influence on the properties of the polyurethanes to be produced and their products. They find applications in a wide variety of industries, such as surface coating materials, adhesives, molding and aerospace, automotive, electronics, construction, furniture, green energy and sporting goods industries. For example, the polyol and isocyanate may be used in two-pack form or prepolymer may be used in one-pack form and may have various properties and properties depending on the application to which they are applied.

On the other hand, due to various reasons such as accelerated depletion of petroleum resources, demand for reduction of greenhouse gas due to climate change, increase of raw material price, increase of need for renewable raw materials, polyether polyol, polyester There is a demand for a method of partially or completely replacing existing petroleum-based raw materials with environmentally friendly components in the polyol field such as polyol and isocyanate field.

Polyols can be produced from renewable biomass such as vegetable natural oils, cellulose and lignin, and bio-polyols derived from vegetable natural oils have already been produced on a commercial scale. The physical properties of the produced bio-polyol depend on the type of biomass used in the production. In general, castor oil, coconut oil and the like are used in the production of soft and hard polyurethanes and synthetic polyols, and soybean oil is used in the production of polyols for flexible polyurethanes. However, biopolyols based on biomass currently being manufactured have a disadvantage of high viscosity.

There have been few studies on the production of diisocyanates using biomass. While the isocyanates used in the industry are aromatic such as TDI, the isocyanates of the vegetable natural oils are essentially aliphatic compounds. In order to form a polyurethane foam, very high reactivity is required, which is disadvantageous in that the aliphatic diisocyanate is less reactive than the aromatic diisocyanate. On the application side, most polyurethanes utilizing aliphatic diisocyanates are used for coating. In order to overcome this disadvantage, a process for producing a polyurethane foam in which a bioisocyanate prepolymer is prepared by synthesizing a biopolyol and an isocyanate and used as a component in the production of a polyurethane foam has been developed. However, when this production method is used, the viscosity of the biopolyol is too high to lower the process stability, and crystals are precipitated after the production of the isocyanate prepolymer, and it has been confirmed that there is a problem in the storage stability.

Korean Patent Laid-Open Publication No. 10-2015-0123583 discloses a low density urethane foam composition comprising a bio-polyol and a diisocyanate produced from biomass resources. The polyurethane foam produced from this composition easily oxidizes There is a problem that yellowing occurs.

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 it is an object of the present invention to provide a composition containing a specific amount of anhydrosugar alcohol- And an isocyanate prepolymer prepared by reacting a polyisocyanate with a polyol component including a bio-polyol other than a dihydric alcohol-alkylene glycol, and an eco-friendly polyurethane foam composition having improved storage stability and oxidation- A method for producing the polyurethane foam using the same, and an environmentally friendly polyurethane foam so produced.

To achieve the above object, according to a first aspect of the present invention, there is provided a process for producing an alcohol-free alcohol-alkylene glycol; And a polyol containing a bio-polyol other than anhydrosugar alcohol-alkylene glycol and a polyisocyanate compound, wherein the content of the anhydropoly alcohol-alkylene glycol is 1 to 99 parts by weight based on 100 parts by weight of the total amount of the polyol , And the content of the bio polyol other than the anhydropoly alcohol-alkylene glycol is 1 to 99 parts by weight based on 100 parts by weight of the total amount of the polyol.

According to a second aspect of the present invention, there is also provided a polyol premix composition which is a first component; And a second component polyisocyanate, wherein the polyisocyanate comprises an isocyanate prepolymer according to the present invention. The present invention also provides a composition for forming a two-component polyurethane foam.

According to a third aspect of the present invention, there is provided a method for producing a polyisocyanate composition, which comprises mixing and reacting a polyol premix composition as a first component and a polyisocyanate as a second component, wherein the polyisocyanate is an isocyanate prepolymer A process for producing urethane foam is provided.

According to a fourth aspect of the present invention, there is provided a polyurethane foam produced by mixing and reacting a polyol premix composition as a first component and a polyisocyanate as a second component, wherein the polyisocyanate comprises an isocyanate prepolymer according to the present invention , Polyurethane foam are provided.

The isocyanate prepolymer of the present invention is advantageous as a raw material for a polyurethane foam which can be applied to various fields as well as being able to realize environmentally friendly properties using a biopolyol and a polyisocyanate as main raw materials. The composition for forming a two-component polyurethane foam of the present invention comprising the isocyanate prepolymer of the present invention can prevent the viscosity rise caused by the bio-polyol and prevent the solid from being precipitated from the isocyanate prepolymer during long- , Process stability and productivity, and it is possible to secure an improved antioxidation characteristic, thereby making it possible to produce an environmentally friendly polyurethane foam which can be applied to various fields.

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

The isocyanate prepolymer of the present invention can be prepared by reacting an anhydrosugar alcohol-alkylene glycol; And a polyol containing a bio-polyol other than anhydrosugar alcohol-alkylene glycol and a polyisocyanate compound, wherein the content of the anhydropoly alcohol-alkylene glycol is 1 to 99 parts by weight based on 100 parts by weight of the total amount of the polyol , The content of the bio-polyol other than the anhydropoly alcohol-alkylene glycol may be 1 to 99 parts by weight based on 100 parts by weight of the total amount of the polyol.

The content of the alcohol-free alkylene glycol is 1 to 99 parts by weight, preferably 1 to 97 parts by weight, more preferably 5 to 97 parts by weight or 5 to 70 parts by weight, based on 100 parts by weight of the total amount of polyol, Still more preferably 5 to 50 parts by weight, still more preferably 30 to 50 parts by weight. When the content of anhydrosalcohol-alkylene glycol is less than 1 part by weight based on 100 parts by weight of the total amount of the polyol, a solid is precipitated from the isocyanate prepolymer during storage at room temperature, resulting in deterioration of the storage stability and making polyurethane foam , Foaming of the foam may be impossible, and the physical properties (hardness, tensile strength, elongation and antioxidation characteristics, etc.) of the polyurethane foam may be poor.

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 a reducing end group of a saccharide, generally HOCH ₂ (CHOH) _n CH ₂ OH (where 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 1,4,3,6-dianhydro- mannitol), isoidide (1,4-3,6-dianhydroiditol), or a mixture thereof, and most preferably, isosorbide is used .

Anhydrosugar alcohol-alkylene glycol used in the present invention is an adduct obtained by reacting an alkylene oxide with a hydroxyl group at both terminals or one terminal (preferably both terminals) of anhydrosugar alcohol.

In one embodiment, the alkylene oxide may be linear or branched alkylene oxide having from 2 to 8 carbon atoms, and more specifically, ethylene oxide, propylene oxide, or a combination thereof.

In one embodiment, the anhydride alcohol-alkylene glycol may be a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ and R ² each independently represent a linear or branched alkylene group having 2 to 8 carbon atoms and a branched alkylene group having 3 to 8 carbon atoms,

m and n each independently represent an integer of 0 to 15,

m + n represents an integer of 1 to 30;

More preferably, in Formula 1,

R ¹ and R ² each independently represent an ethylene group, a propylene group or an isopropylene group, and preferably, R ¹ and R ² are the same as each other,

m and n each independently represent an integer of 1 to 14,

m + n represents an integer of 2 to 15;

In one embodiment, the anhydrosugar alcohol-alkylene glycol may include the following isosorbide-propylene glycol, isosorbide-ethylene glycol, or mixtures thereof.

[Isosorbide-propylene glycol]

In the above formula, a + b may be an integer of 1 to 30, and more preferably an integer of 2 to 15.

[Isosorbide-ethylene glycol]

In the above formula, c + d may be an integer of 1 to 30, more preferably an integer of 2 to 15.

The polyol component used in the preparation of the isocyanate prepolymer of the present invention may include a bio-polyol other than the anhydropoly alcohol-alkylene glycol, and the bio-polyol content may be 1 to 99 parts by weight, More preferably 30 to 95 parts by weight, still more preferably 50 to 95 parts by weight, still more preferably 50 to 70 parts by weight. If the content of the bio polyol is less than 1 part by weight based on 100 parts by weight of the total amount of the polyol, the biocompatibility of the isocyanate prepolymer may decrease and the effect of improving the environment friendliness may be insignificant.

The bio-polyols other than the anhydrous alcohol-alkylene glycol used in the present invention may be selected from dimeric acid-based bio-polyols (e.g., Priplast 3192, 3162, 3172, 2033, 1837, 1838, 3238, 1839, 3196, 3187, 3186 2828, 5000, 5100, 5300, 5450, 2300, 2828 or the like manufactured by Mitsui Chemicals & SKC polyurethanes) B-1350, B-1500, EBT-509, etc.), and the like.

To prepare the isocyanate prepolymer of the present invention, a polyol containing an anhydrosugar alcohol-alkylene glycol (preferably a polyol mixture comprising an anhydrosugar alcohol-alkylene glycol, and an anhydride alcohol-a polyol other than an alkylene glycol) Can be used without particular limitation as long as they can be used in the production of polyurethane foam. Thus, for example, polyisocyanates selected from aliphatic polyisocyanates, cycloaliphatic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, heterocyclic polyisocyanates, or combinations thereof may be used, and also unmodified polyisocyanates or modified Can be used as the polyisocyanate.

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 or a combination thereof ≪ / RTI > 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.

According to another aspect of the present invention, there is provided a composition comprising a first component, a polyol premix composition; And a second component polyisocyanate, wherein the polyisocyanate comprises the above-mentioned isocyanate prepolymer. The present invention also provides a composition for forming a two-component polyurethane foam.

The polyol premix composition contained as the first component in the composition for forming a two-component polyurethane foam of the present invention comprises a polyol, a catalyst, a foam stabilizer and a foaming agent.

The polyol contained in the polyol premix composition of the present invention is a polyol commonly used in the production of a polyurethane foam having an average number of active hydrogen atoms of 2 or more (preferably 2 to 4) and an active hydrogen equivalent of 600 to 7,000 . More specifically, a polyether polyol, a polyester polyol, a polymer polyol obtained by polymerizing the polyol and the 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 can be obtained in the form of a stable suspension 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%.

As the catalyst included in the polyol premix composition of the present invention, an organic metal catalyst, an amine catalyst, or a combination thereof may be used.

As the organometallic catalyst, an organometallic catalyst commonly used in the production of a polyurethane foam can be used. For example, an organotin catalyst (more specifically, dibutyltin dilaurate (DBTDL) or tin bis [2- Hexanoate]), but is not limited thereto.

The amine catalyst used in the present invention promotes the reaction between the polyol of the first component and the isocyanate prepolymer of the second component. In the present invention, the kind of the amine catalyst is not particularly limited, but one or a mixture of two or more thereof may be used in the tertiary amine catalyst. More specifically, triethylene diamine, triethylamine Triethylamine, N-methyl morpholine, N-ethyl morpholine, or a combination thereof may be used.

In the polyol premix composition of the present invention, the organometallic catalyst and the amine catalyst may be independently included 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 these catalysts to be 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 contrary, 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 commonly used in the production of polyurethane foam foam, and for example, silicon based foam stabilizer can be generally 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, as the foaming agent, water is typically used. 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, as a foaming agent based on 100 parts by weight of polyol, 0.8 to 5.0 parts by weight of water alone or a mixture of this and 0.1 to 18 parts by weight of methylene chloride may be used.

The polyisocyanate, which is the second component included in the composition for forming a two-component polyurethane foam of the present invention, may include the above-mentioned isocyanate prepolymer and other polyisocyanate compounds, and the polyisocyanate described above, which is used in the production of the isocyanate prepolymer, The same isocyanate compound as the isocyanate compound can be used.

The first component or the second component contained in the composition for forming a two-component polyurethane foam of the present invention may contain, in addition to the above components, a flame retardant, a colorant, a UV stabilizer, a thickener, a foam stabilizer, a filler, An auxiliary additive selected from the group consisting of

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 method for producing a polyurethane foam, which comprises mixing and reacting a polyol premix composition as a first component with a polyisocyanate as a second component, wherein the polyisocyanate comprises an isocyanate prepolymer as described above Method, and a polyurethane foam, for example, a flexible polyurethane foam, so prepared.

In the preparation of the polyurethane foam, a polyisocyanate, which is a second component, is added to a polyol premix composition which is a first component of the composition of the present invention, and the mixture is stirred and then cured and foamed so that a polyurethane foam can be prepared have.

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.

In one embodiment, the polyurethane foam can be cured at elevated temperatures due to the urethane foaming reaction heat, and can be cured preferably at from 100 ° C to 180 ° C or from 120 ° C to 180 ° C, preferably from 160 ° C to 180 ° C It is not limited.

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 ]

<Isocyanate Prepolymer  Manufacturing>

Example  A-1

(IC52, manufacturer: IC chemical, molecular weight: 3,000, weight ratio: 83% by weight) and diisocyanate-based bifunctional polyol (trade name: Priplast 1838 : 365.47) at a weight ratio of 50:50 and 368 parts by weight of TDI as a polyisocyanate, the reaction was carried out at a temperature of 60 ° C for 2 hours under the conditions of adjusting the NCO content to 35 to obtain an isocyanate prepolymer . The prepared isocyanate prepolymer was transferred into a 30 ml vial bottle and stored in an oven at 25 ° C. for 1 month, and it was confirmed whether a white solid precipitated. The results are shown in Table 1 below.

Example  A-2

(Trade name: IC102, manufactured by IC chemical, molecular weight: 20,000), a bifunctional dimer acid bifunctional polyol (trade name: Priplast 3196, manufacturer: Croda, molecular weight: 3,000, bio content 82 wt.%) And isophorone diisocyanate 578.05) at a weight ratio of 60:40 and 321 parts by weight of TDI as a polyisocyanate, the reaction was carried out at a temperature of 70 ° C for 1.5 hours under the conditions of setting the NCO content at 35, thereby obtaining an isocyanate prepolymer . The prepared isocyanate prepolymer was transferred into a 30 ml vial bottle and stored in an oven at 25 ° C. for 1 month, and it was confirmed whether a white solid precipitated. The results are shown in Table 1 below.

Example  A-3

(Trade name: ICP910, manufactured by IC Chemical, molecular weight: 1,000), a bi-polyol having a bifunctional dimer acid system (trade name: Priplast 3238, manufactured by Croda, molecular weight 3,000, a biocompatibility of 100% by weight) and a propylene oxide 5 mol adduct of isosorbide 432.37) at a weight ratio of 50:50 and 480 parts by weight of TDI as a polyisocyanate were reacted at a temperature of 60 占 폚 for 2 hours under the condition of setting the NCO content to 35 to prepare an isocyanate prepolymer . The prepared isocyanate prepolymer was transferred into a 30 ml vial bottle and stored in an oven at 25 ° C. for 1 month, and it was confirmed whether a white solid precipitated. The results are shown in Table 1 below.

Example  A-4

(Trade name: IC89 manufactured by IC89, manufactured by Mitsui Chemicals, Inc., trade name: Mitsui chemicals & SKC polyurethanes, molecular weight: 2,500) of isophorone diisocyanate, caster oil based trifunctional bio- IC chemical, molecular weight 618.52) at a weight ratio of 70:30 and 618 parts by weight of MDI as a polyisocyanate were reacted at a temperature of 60 ° C for 2 hours under the conditions of setting the NCO content to 28 To prepare an isocyanate prepolymer. The prepared isocyanate prepolymer was transferred into a 30 ml vial bottle and stored in an oven at 25 ° C. for 1 month, and it was confirmed whether a white solid precipitated. The results are shown in Table 1 below.

Example A -5

100 parts by weight of a bifunctional difunctional biopolyol (trade name: Priplast 1838, manufacturer: Croda, molecular weight: 2,000, bio content: 83% by weight) based on dimeric acid and 575 parts by weight of MDI as polyisocyanate were used to adjust the NCO content to 28 The reaction was carried out at a temperature of 60 占 폚 for 2 hours to prepare a first isocyanate prepolymer.

Using 100 parts by weight of an ethylene oxide 5 mole adduct of isosorbide (trade name: IC52, manufacturer: IC chemical, molecular weight: 365.47) and 911 parts by weight of MDI as polyisocyanate, For 2 hours to prepare a second isocyanate prepolymer.

Then, the prepared first isocyanate prepolymer and second isocyanate prepolymer were mixed at a weight ratio of 50:50 to prepare an isocyanate prepolymer composition. The isocyanate prepolymer composition was transferred into a 30 ml vial bottle and stored in an oven at 25 ° C. for 1 month. It was then confirmed whether a white solid precipitated. The results are shown in Table 1 below.

Example A -6

100 parts by weight of difunctional biopolyol (trade name: Priplast 3196, manufacturer: Croda, molecular weight: 3,000, bio content 82% by weight) based on dimeric acid and 581 parts by weight of MDI as polyisocyanate were used to prepare 60 C for 2 hours to prepare a first isocyanate prepolymer.

Further, 100 parts by weight of an ethylene oxide 10-mole adduct of isosorbide (trade name: IC102, manufacturer: IC chemical, molecular weight: 578.05) and 802 parts by weight of MDI as polyisocyanate were used to adjust the NCO content to 28, For 2 hours to prepare a second isocyanate prepolymer.

Then, the prepared first isocyanate prepolymer and second isocyanate prepolymer were mixed at a weight ratio of 50:50 to prepare an isocyanate prepolymer composition. The isocyanate prepolymer composition was transferred into a 30 ml vial bottle and stored in an oven at 25 ° C. for 1 month. It was then confirmed whether a white solid precipitated. The results are shown in Table 1 below.

Example A -7

100 parts by weight of a difunctional biopolyol (trade name: Priplast 1838, manufacturer: Croda, molecular weight: 2,000, bio content 83% by weight) based on dimeric acid and 4 parts by weight of TDI 413 as polyisocyanate were mixed under conditions of an NCO content of 35 The reaction was carried out at a temperature of 60 占 폚 for 2 hours to prepare a first isocyanate prepolymer.

Further, 100 parts by weight of an ethylene oxide 5-mole adduct of isosorbide (trade name: IC52, manufacturer: IC chemical, molecular weight: 365.47) and 597 parts by weight of TDI as polyisocyanate were used to prepare 60 Lt; 0 &gt; C for 2 hours to prepare a second isocyanate prepolymer.

Then, the prepared first isocyanate prepolymer and second isocyanate prepolymer were mixed at a weight ratio of 99: 1 to prepare an isocyanate prepolymer mixture. The isocyanate prepolymer mixture was transferred into a 30 ml vial bottle and stored in an oven at 25 ° C. for 1 month, and it was confirmed whether a white solid precipitated. The results are shown in Table 1 below.

Example A -8

100 parts by weight of an ethylene oxide 5-mole adduct of isosorbide (trade name: IC52, manufacturer: IC chemical, molecular weight: 365.47) and 911 parts by weight of MDI as polyisocyanate were mixed at 60 DEG C For 2 hours to prepare an isocyanate prepolymer. The prepared isocyanate prepolymer was transferred into a 30 ml vial bottle and stored in an oven at 25 ° C for 1 month, and it was confirmed whether a white solid precipitated. The results are shown in Table 1 below.

Comparative Example  A-1

100 parts by weight of a difunctional biopolyol (trade name: Priplast 1838, manufacturer: Croda, molecular weight 2,000, bio content 83% by weight) based on dimeric acid and 296 parts by weight of TDI as polyisocyanate were used to adjust the NCO content to 35, For 2 hours to prepare an isocyanate prepolymer. The prepared isocyanate prepolymer was transferred into a 30 ml vial bottle and stored in an oven at 25 ° C for 1 month, and it was confirmed whether a white solid precipitated. The results are shown in Table 1 below.

Comparative Example  A-2

100 parts by weight of difunctional biopolyol (trade name: Priplast 3238, manufacturer: Croda, molecular weight: 3,000, bio content 100% by weight) based on dimeric acid and 286 parts by weight of TDI as polyisocyanate were used to prepare 60 C for 2 hours to prepare an isocyanate prepolymer. The prepared isocyanate prepolymer was transferred into a 30 ml vial bottle and stored in an oven at 25 ° C for 1 month, and it was confirmed whether a white solid precipitated. The results are shown in Table 1 below.

Comparative Example  A-3

100 parts by weight of a trifunctional bio-polyol (trade name: EBT-509, manufactured by Mitsui chemicals & SKC polyurethanes, molecular weight: 2,500) of Caster oil type and 563 parts by weight of MDI as polyisocyanate were used to adjust the NCO content 28, the reaction was carried out at a temperature of 60 DEG C for 2 hours to prepare an isocyanate prepolymer. The prepared isocyanate prepolymer was transferred into a 30 ml vial bottle and stored in an oven at 25 ° C for 1 month, and it was confirmed whether a white solid precipitated. The results are shown in Table 1 below.

Comparative Example  A-4

100 parts by weight of a difunctional biopolyol (trade name: Priplast 3196, manufacturer: Croda, molecular weight: 3,000, bio content: 82% by weight) based on a dimer acid and 399 parts by weight of TDI as a polyisocyanate were used to adjust the NCO content to 35 The reaction was carried out at a temperature of 60 占 폚 for 2 hours to prepare a first isocyanate prepolymer.

Further, 100 parts by weight of an ethylene oxide 10 mole adduct of isosorbide (trade name: IC102, manufacturer: IC chemical, molecular weight: 578.05) and 375 parts by weight of TDI as a polyisocyanate were added at 60 DEG C The reaction was carried out at the temperature for 2 hours to prepare a second isocyanate prepolymer.

Then, the prepared first isocyanate prepolymer and second isocyanate prepolymer were mixed at a weight ratio of 99.5: 0.5 to prepare an isocyanate prepolymer composition. The isocyanate prepolymer composition was transferred into a 30 ml vial bottle and stored in an oven at 25 ° C. for 1 month. It was then confirmed whether a white solid precipitated. The results are shown in Table 1 below.

The content of the bio polyol, isosorbide-alkylene glycol and isocyanate means the total amount of the prepared isocyanate prepolymer or the total amount of the isocyanate prepolymer mixture.

As shown in Table 1, in the case of Examples A-1 to A-8, the content of isosorbide-alkylene glycol was 1 part by weight to 100 parts by weight based on 100 parts by weight of the bio polyol, The bead-alkylene glycol functions as a stabilizer in the isocyanate prepolymer, and no solid precipitation of the isocyanate prepolymer was observed even at the storage at room temperature for a long period (one month).

However, in the case of Comparative Examples A-1 to A-3 in which isosorbide-alkylene glycol was not used, there was no isosorbide-alkylene glycol for carrying out the stabilizer in the isosorbide prepolymer, , 1 day, 2 days, or 5 days, solid precipitation of the isocyanate prepolymer was observed. Also, in the case of Comparative Example A-4, the content of isosorbide-alkylene glycol was less than 1 part by weight based on 100 parts by weight of the bio-polyol, so that the effect of improving storage stability was not exhibited. Respectively. In the case of the isocyanate prepolymers of Comparative Examples A-1 to A-4, a solid was precipitated and it was impossible to use it as an isocyanate component for producing a polyurethane foam.

&Lt; Preparation of polyurethane foam &

Example  B-1 to B-10 and Comparative Example  B-1 to B-6

The polyol, the catalyst, the foaming agent and the foaming agent were mixed according to the components and the content ratios shown in the following Tables 2 and 3 and mixed thoroughly for 1 to 3 minutes at a stirring rate of 3000 rpm to obtain the two-component polyurethane foam Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;

The polyisocyanate component as the second component 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 a two-component polyurethane foam of the present invention.

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, maximum rise time and gel time were measured and recorded using a second watch to observe whether health bubbles occurred. The heat of curing reaction of the polyurethane foam was confirmed by a bar thermometer to be 120 ° C. Physical properties of the foamed specimens were measured by the following evaluation methods, and the results are shown in Tables 2 and 3, respectively.

 [Ingredients Used]

1) Polyol

TF-3000: trifunctional polyether polyol (Mitsui chemicals & SKC polyurethanes, product of TF-3000) having an active hydrogen equivalent of 3,000 and a hydroxyl value of 54, a polyol other than anhydrosugar alcohol,

2) Amine system  catalyst

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

3) Organometallic catalyst

DBTDL: Organometallic catalyst, dibutyltin dilaurate (Sigma Aldrich)

4) Silicon Foaming agent

L-580K: polyalkyleneoxydimethylsiloxane copolymer, Nymex L-580K from Momentive

5) Foaming agent

water

6) Polyisocyanate  ingredient

① T-80 (comparative example)

Toluene diisocyanate (TDI) (2,4- / 2,6-isomer ratio = 80:20), BASF's Loop Lateate T-80 product

(2) MDI: 4,4-methylene diisocyanate (product of Luponate ME, BASF Korea)

? Example A-1: Isocyanate prepolymer prepared in Example A-1

? Example A-2: Isocyanate prepolymer prepared in Example A-2

? Example A-5: Isocyanate prepolymer prepared in Example A-5

? Example A-6: Isocyanate prepolymer prepared in Example A-6

? Example A-7: Isocyanate prepolymer prepared in Example A-7

8) Example A-8: Isocyanate prepolymer prepared in Example A-8

(9) Comparative Example A-1: The isocyanate prepolymer prepared in Comparative Example A-1

(10) Comparative Example A-2: The isocyanate prepolymer prepared in Comparative Example A-2

(11) Comparative Example A-3: The isocyanate prepolymer prepared in Comparative Example A-3

? Comparative Example A-4: Isocyanate prepolymer prepared in Comparative Example A-4

7) Cross-linking agent

Ethylene glycol (Sigma Aldrich)

Properties described in the following Tables 2 and 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 &quot; unmeasurable &quot; 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.

Mold Density: Measured according to ASTM D 1621.

- Hardness: measured according to KS M 6672.

- Tensile strength: Measured according to KS M 6518.

- Elongation: measured according to KS M 6518.

- YI value: Measured according to ASTM E313-96, the lower the YI value, the lower the yellowing phenomenon, which means that the anti-oxidizing property is improved.

The polyurethane foam specimens of Comparative Examples B-1 to B-4 were prepared by using TDI as a petroleum isocyanate as an isocyanate component (Comparative Example B-1), or by using no TDI (Comparative Examples B-2 to B-4) produced by reacting a polyol containing a polyisocyanate with a polyisocyanate (TDI), and the polyurethane foam specimens of Examples B-1 to B- (Examples B-2, B-4 and B-5) prepared by reacting TDI with a bio-polyol containing at least 1 part by weight of anhydrosugar alcohol-alkylene glycol as an isocyanate component, (Examples B-1 and B-3) using a mixture of isocyanate prepolymer and TDI.

In the case of Comparative Example B-1 in which petroleum isocyanate TDI was used as an isocyanate component, the foamed state and physical properties of the polyurethane foam were good, but the yellowing occurred due to the high YI value, Using only isocyanate, environment-friendly properties were poor.

Further, in the case of Comparative Examples B-2 and B-3 in which an isocyanate prepolymer prepared by reacting TDI with a bio-polyol containing no anhydride alcohol-alkylene glycol was used as an isocyanate component and in the case of Comparative Example B- In Comparative Example B-4 where an isocyanate prepolymer prepared by reacting a bio-polyol containing less than 1 part by weight of isocyanate prepolymer with TDI was high in bio content and excellent in environment-friendly properties, a solid precipitated during storage of the isocyanate prepolymer (I.e., poor storage stability), the polyurethane foam prepared using the polyurethane foam was not only inferior in the foaming state, but also failed to form foams, so that hardness, tensile strength and elongation could not be measured, Resulting in poor anti-oxidation properties.

However, in the case of Examples B-2, B-4 and B-5 in which an isocyanate prepolymer prepared by reacting TDI with a bio-polyol containing at least 1 part by weight of an alcohol-free alkylene glycol as an isocyanate component, The foam state and physical properties of the polyurethane foam were good and the YI value was decreased and the yellowing was reduced. As a result, it was confirmed that the antioxidant property was improved, and the non-alcohol-alcohol-alkylene glycol Even in the case of Examples B-1 and B-3 in which a mixture of an isocyanate prepolymer prepared by reacting TDI with a bio-polyol containing not less than 1 part by weight of a polyisocyanate and TDI as an isocyanate component, State and physical properties, as well as decreased YI value and decreased yellowing, and thus the anti-oxidizing property was improved That could be confirmed.

The polyurethane foam specimens of Comparative Examples B-5 and B-6 were prepared using a petroleum-based isocyanate MDI as an isocyanate component (Comparative Example B-5), or a bio polyol and MDI containing no anhydrosugar alcohol- (Comparative Example B-6), and the polyurethane foam specimens of Examples B-6 to B-10 were prepared by dissolving anhydrosugar alcohol-alkylene glycol as an isocyanate component (Examples B-7, B-9 and B-10), or using an isocyanate prepolymer and MDI in combination (Example B-7, B-6 and B-8) foamed polyurethane foam specimens.

In the case of Comparative Example B-5 in which MDI which is a petroleum isocyanate was used as an isocyanate component, the foaming state and physical properties of the polyurethane foam were good, but yellowing occurred due to a high YI value, Using only isocyanate, environment-friendly properties were poor.

In the case of Comparative Example B-6 in which an isocyanate prepolymer prepared by reacting MDI with a bio-polyol not containing an alcohol-free alcohol-alkylene glycol moiety was used as an isocyanate component, the eco-friendly property was excellent due to high bio content, The polyurethane foam prepared by using the polyurethane foam obtained by the precipitation of solid during the storage of the prepolymer (i.e., poor storage stability) was inferior in the foamed state, and was unable to form a foam, so that it was impossible to measure the tensile strength and elongation, And yellowing property was poor.

However, in the case of Examples B-7, B-9 and B-10 in which an isocyanate prepolymer prepared by reacting MDI with a bio-polyol containing at least 1 part by weight of an alcohol-free alkylene glycol with an isocyanate component, The foam state and physical properties of the polyurethane foam were good and the YI value was decreased and the yellowing was reduced. As a result, it was confirmed that the antioxidant property was improved, and the non-alcohol-alcohol-alkylene glycol Even in the case of Examples B-6 and B-8 in which a mixture of isocyanate prepolymer and MDI prepared by reacting MDI with a bio-polyol containing not less than 1 part by weight of isocyanate was used as the isocyanate component, the foam of polyurethane foam State and physical properties, as well as decreased YI value and decreased yellowing, and thus the anti-oxidizing property was improved That could be confirmed.

Claims (13)

Anhydrosugar alcohol-alkylene glycol; And a polyol comprising a bio-polyol other than anhydrosugar alcohol-alkylene glycol and a polyisocyanate compound,
Wherein the content of the anhydrous alcohol-alkylene glycol is 5 to 50 parts by weight based on 100 parts by weight of the total amount of the polyol,
Wherein the content of the bio-polyol other than the anhydropoly alcohol-alkylene glycol is 50 to 95 parts by weight based on 100 parts by weight of the polyol,
Isocyanate prepolymer. The isocyanate prepolymer according to claim 1, wherein the anhydropoly alcohol-alkylene glycol is an adduct obtained by reacting an alkylene oxide with both terminal or terminal hydroxyl groups of anhydrosugar alcohol. 3. The composition of claim 2, wherein the dihydric alcohol is selected from the group consisting of isosorbide, isomannide, isoidide, or combinations thereof, and wherein the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, , Isocyanate prepolymer. The process of claim 1, wherein the polyisocyanate compound is selected from the group consisting of methylene diisocyanate, ethylenediisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1-12-dodecane diisocyanate, Cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 2-4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, dicyclopentane diisocyanate, cyclohexane-1,3-diisocyanate, Hexyl methane-4,4'-diisocyanate (HMDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, Methane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, polydiphenylmethane diisocyanate (PMDI), naphthalene-1,5-diisocyanate, , The isocyanate prepolymer is selected from the group consisting of. A polyol premix composition which is a first component; And a second component, a polyisocyanate, wherein the polyisocyanate comprises the isocyanate prepolymer of claim 1. 2. A composition for forming a two-component polyurethane foam, comprising: The composition for forming a two-component polyurethane foam according to claim 5, wherein the polyol premix composition comprises a polyol, a catalyst, a foaming agent and a foaming agent. 7. The composition of claim 6, wherein the catalyst is selected from the group consisting of organometallic catalysts, amine catalysts, or combinations thereof. The composition for forming a two-component polyurethane foam according to claim 7, wherein the organometallic catalyst is an organotin catalyst and the amine catalyst is a tertiary amine catalyst. The composition for forming a two-component polyurethane foam according to claim 6, wherein the foaming agent is a silicone foaming agent. 7. The composition of claim 6 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, / RTI &gt; 6. The composition of claim 5, wherein the first or second component further comprises an auxiliary additive selected from the group consisting of a flame retardant, a colorant, a UV stabilizer, a thickener, a foam stabilizer, a filler, A composition for forming a polyurethane foam. A method for producing a polyurethane foam, comprising the steps of mixing and reacting a polyol premix composition as a first component with a polyisocyanate as a second component, wherein the polyisocyanate comprises the isocyanate prepolymer of claim 1. A polyurethane foam produced by mixing and reacting a polyol premix composition as a first component with a polyisocyanate as a second component, wherein the polyisocyanate comprises the isocyanate prepolymer of claim 1 as the polyisocyanate.