KR101772523B1 - Rigid Polyurethane Foams for Construction-Insulator Containing Biopolyol - Google Patents

Abstract

More particularly, the present invention relates to a rigid polyurethane foam for building insulation comprising a biopolyol, which comprises a natural oil, a polyfunctional active hydrogen-containing compound, a catalyst and an alkylene oxide, wherein the number of functional groups is 3 or more, Dimensional stability, moldability, heat resistance, environmental friendliness, compressive strength and bending strength, and the like, by containing a polyol having a value of 200 to 600 mgKOH / g and a viscosity (25 DEG C) of 2,000 to 25,000 cps The present invention relates to a rigid polyurethane foam for building insulation which is capable of maintaining physical properties as a heat insulating material for buildings and being environmentally friendly and recyclable.

Description

TECHNICAL FIELD [0001] The present invention relates to a rigid polyurethane foam for construction insulation containing a bio-polyol,

The present invention relates to a rigid polyurethane foam containing a biopolyol and capable of maintaining physical properties as a heat insulating material for construction.

Polyols, which are essential components of polyurethane, are usually produced from petroleum-based raw materials, and polyether polyols and polyester polyols are especially known as the most popular polyols. These polyols have a significant influence on the properties of the polyurethane or polyurethane foam to be produced.

Generally, a polyol having a high molecular weight and a low functionality is used for producing a soft urethane foam, and a polyol having a small molecular weight and a high number of functional groups is used for producing a rigid urethane foam.

Specifically, the molecular weight of the polyol used in the flexible polyurethane foam is greater than about 1,000. The polyol used in the rigid polyurethane foam has a molecular weight of about 200 to 4,000 and has a modulus of elasticity of at least about 100,000 psi (23 DEG C), a glass transition temperature of 20 DEG C or higher, an elongation of not more than 10% .

On the other hand, due to various reasons such as accelerated depletion of petroleum resources, reduction of greenhouse gas due to climate change, increase of raw material price, increase in need for renewable raw materials, etc., in the urethane field, the regeneration of polyol produced from petroleum- Has been suggested as a substitute for polyol.

Natural oils are generally composed of triglyceride molecules and have a structure in which three fatty acids are bonded to the glycerol junction.

Currently, the production of polyols using natural oils, in particular vegetable oils, can be achieved by: 1) epoxidation-ring opening reaction (incorporating active oxygen into the molecular structure using hydrogen peroxide, ... how to do the ring-opening reaction with an inorganic acid such as; Kandanarachchi et al, J. Mol Catal a: Chem 2002, 184, 65), 2) the hydroformylation reaction (synthesis gas in the presence of a rhodium or cobalt catalyst and the natural oils (3) Ozonolysis reaction (production of a polyol having a hydroxy group at the terminal position by directly decomposing ozone of a natural oil) (Petrovic et al ., Polyurethanes from vegetable oils. Polymer Reviews 48: 1 109-155) ); And Petrovic et al ., Biomacromolecules 2005, 6, 713), 4) an esterification reaction (Vilar et al. , 2002), and the like.

It has been reported that polyurethane foams using bio-polyols prepared from natural oils can secure properties comparable to polyurethane foams produced from petroleum-based products. However, there is a problem that the physical properties of the polyurethane foam are lowered due to the low reactivity of the actual bio-polyol.

The low reactivity of biopolyols is due to the presence of secondary alcohols and the presence of a large number of nonfunctional branches.

On the other hand, polyurethane foam, especially rigid polyurethane foam, is used in various fields, and there is a difference in physical properties required depending on the application field. In particular, when used as a heat insulating material for interior and exterior materials, flame retardancy, dimensional stability, moldability, heat insulation and environment friendliness are required.

However, the rigid polyurethane foam to which the conventional bio-polyol is applied may be deteriorated in physical properties such as dimensional stability, flame retardancy, heat insulation, compressive strength and flexural strength owing to a low functional group number of the bio-polyol. The moldability may be deteriorated due to the unreacted natural oil which interferes with growth, and thus it has been limited to be applied as a raw material for a heat insulating material foam for building interior and exterior materials.

In addition, the conventional bio-polyol has a high risk of degradation of storage stability due to the nature of natural oil, and the viscosity of the bio-polyol is high while the number of functional groups is not sufficiently high. Therefore, problems such as reactivity and handling during hard polyurethane foam production may occur There is a limit. Thus, it is possible to apply castor oil or soybean oil having a proper functional group number to hard polyurethane foam easily, but they are mainly used as food resources or have a relatively high price, which has a low economic efficiency.

Therefore, there is a need for a rigid polyurethane foam for building insulation using a bio-polyol that can provide a physical property equal to or higher than that of a polyurethane foam for building insulation using a petroleum-based polyol.

The present invention relates to a rigid polyurethane foam for building insulation using a biopolyol having a specific number of functional groups, a hydroxyl value (mgKOH / g), viscosity, etc., as flame retardancy, dimensional stability, moldability, heat insulation, environment friendliness, And a hard polyurethane foam capable of maintaining the physical properties of the polyurethane foam.

The present inventors have found that the use of a bio-polyol containing a polyfunctional active hydrogen-containing compound and an alkylene oxide in a natural oil to lower the number of secondary alcohols and a large number of non-functional branches present in the bio- It has been found that it is possible to maintain physical properties such as flame retardancy, dimensional stability, moldability, heat insulation, environment friendliness, compressive strength and bending strength for building insulation.

Accordingly, the present invention relates to a process for the preparation of polyfunctional olefins, which comprises 10 to 60% by weight of a natural oil, 10 to 60% by weight of a polyfunctional active hydrogen-containing compound, 0.1 to 1.5% by weight of a catalyst and 20 to 70% by weight of an alkylene oxide, A polyol having a hydroxyl value of 200 to 600 mgKOH / g and a viscosity (25 DEG C) of 2,000 to 25,000 cps; And isocyanates,

A bulk density of 25 kg / m 3 or more, a thermal conductivity of 0.025 W / m · K or less, a flexural strength of 15 N / cm 2 or more, a compressive strength of 10 N / Or less, a combustion time of 120 seconds or less, and a combustion length of 60 mm or less (self-extinguishing).

Wherein the polyfunctional active hydrogen compound is a polyfunctional alcohol, a polyfunctional amine or a mixture thereof, wherein the polyfunctional alcohol is at least one selected from the group consisting of ethylene glycol, diethylene glycol, glycerin, trimethanolpropane, pentaerythritol, dipentaerythritol, alphamethyl glucoside , Xylitol, sorbitol, sugar or a mixture thereof, and the polyfunctional amine may be ethylenediamine, diethylenetriamine, triethanolamine, ortho-toluenediamine, diphenylmethanediamine, diethanolamine or a mixture thereof.

The catalyst may be potassium hydroxide, sodium hydroxide, cesium hydroxide, dimethyllauamine, dimethylpolymethylamine, N, N-dimethyldodecane-1 -amine, 1-octadecaneamine or mixtures thereof.

The alkylene oxide may be ethylene oxide, propylene oxide or a mixture thereof.

The biopolyol may be prepared by a) exchanging a natural oil with a polyfunctional active hydrogen-containing compound in the presence of a catalyst; And b) subjecting the product of the exchange reaction to an addition reaction with alkylene oxide.

In addition, the bio polyol may further include c) removing the catalyst from the addition reaction product of the alkylene oxide compound, wherein the step c) is performed by adding a catalyst adsorbent and water, stirring the mixture, .

The bio polyol may be contained in an amount of 10 to 60 parts by weight based on 100 parts by weight of the polyol.

The isocyanate may contain polymeric MDI (diphenylmethane diisocyanate), wherein the number of functional groups is in the range of 2.7 to 3.0, the NCO% value is in the range of 25 to 35, and the isocyanate index is in the range of 90 to 160.

0.1 to 10 parts by weight of a urethane catalyst, 0.1 to 35 parts by weight of a blowing agent and 0.1 to 5.0 parts by weight of a surfactant based on 100 parts by weight of the polyol.

Wherein the rigid polyurethane foam has a viscosity (20 ° C) of 150 to 1500 cps, a specific gravity (20 ° C) of 1.1 to 1.3, a cream time of 2 to 50 sec and a free density (FD) 55 kg / m < 3 >.

The rigid polyurethane foam of the present invention is a rigid polyurethane foam for building insulation and has an advantage of being able to maintain physical properties such as flame retardancy, dimensional stability, moldability, heat insulation, environment friendliness, compressive strength and bending strength.

The hard polyurethane foam of the present invention is advantageous in that it is eco-friendly and can be regenerated by using a biopolyol.

In addition, the rigid polyurethane foam of the present invention can be usefully utilized as various kinds of interior and exterior materials for construction such as continuous panel foam, non-continuous panel foam and spray foam.

The present invention relates to a rigid polyurethane foam containing a biopolyol and capable of maintaining physical properties as a heat insulating material for construction.

Hereinafter, the present invention will be described in detail.

The terms used in this specification can be defined as follows.

&Quot; Polyol " means an organic molecule having a hydroxy group per molecule with an average greater than 1.0.

&Quot; Polyurethane foam " refers to a cellular foam product obtained by reacting a di- or polyisocyanate with an isocyanate-reactive hydrogen-containing compound (polyol, amino alcohol and / or polyamine) and a blowing agent . ≪ / RTI >

&Quot; Natural oil " is a concept involving animal and vegetable oils, preferably vegetable oils. Examples of the animal oil may be at least one selected from the group consisting of fish oil, bovine oil, lard oil, sheep oil, and mixtures thereof. Examples of vegetable oils also include vegetable oils such as sunflower seed oil, canola oil, palm oil, corn oil, cottonseed oil, flatland oil, flaxseed oil, safflower oil, oats oil, olive oil, palm oil, peanut oil, rape oil, rice bran oil, Soybean oil, castor oil, and mixtures thereof. The present invention is not limited to the above listed kinds.

Among them, pizza hemp is an oil obtained by squeezing seed of castor bean (Rucinus communis). The seed contains about 45% of this oil and has a higher oil content percentage than other seeds. The fat is made entirely of triester (triglyceride) structure of fatty acid and glycerin. Castor induction Similarly, about 90% of the triester or fatty acid of glycerin is composed of ricinoleic acid and the remainder contains oleic acid, linoleic acid and the like.

The compositional characteristics of typical vegetable oils are shown in Table 1 below.

division Olein Linoleine Linolenine Ricinoleine stearin Palmitin Other Soybean oil 24 54.5 6.8 - 3.2 10.9 0.6 Castor oil 6.0 1.0 - 89.5 1.0 2.0 0.5 Safflower oil 13.1 77.7 - - 2.4 6.5 0.3 Palm oil 45.2 7.9 - - 3.6 40.8 2.5

The "polyol functionality" of the polyol means the average number of hydroxy groups per molecule of the polyol.

"Hydroxyl number" is an index representing the amount of reactive hydroxyl groups capable of participating in the reaction, and means the number of mg of KOH required to neutralize the acetic acid bonded to the acetyl compound obtained from 1 g of the polyol (unit: mg KOH / g).

The term "closed cell foam" refers to a foam in which cells that are not connected by open passages occupy a large proportion, preferably cells that are not open in the cell, independent cells (meaning the percentage of cells closed in the cell ) Is at least about 88%, preferably about 90%, but these figures should be understood by way of example.

"NCO%" means the wt% of NCO contained in the isocyanate sample.

"Isocyanate index" means the amount of isocyanate used relative to the theoretical equivalent, as a ratio of the number of hydroxyl groups (-OH) present in the polyol to the number of equivalents of isocyanate (-NCO) in the urethane reactant. This means that if the isocyanate index is less than 100, excess polyol is present, and if the isocyanate index exceeds 100, excess isocyanate is present.

"Acid number" means the number of mg of KOH required to neutralize the acid present in 1 g of the polyol sample (unit: mg KOH / g).

The rigid polyurethane foam for building insulation of the present invention contains 10 to 60 wt% of natural oil, 10 to 60 wt% of polyfunctional active hydrogen-containing compound, 0.1 to 1.5 wt% of catalyst and 20 to 70 wt% of alkylene oxide A polyol having a functional group number of 3 or more, a hydroxyl value of 200 to 600 mgKOH / g and a viscosity (25 DEG C) of 2,000 to 25,000 cps; And isocyanates.

Natural oils are as defined above and may be used in an amount of from 10 to 60% by weight, preferably from 15 to 40% by weight. If the content is less than 10% by weight, the amount of the other components is excessively large, so that the produced polyol can not be regarded as a bio-polyol. When the content is more than 60% by weight, The physical properties of the hard polyurethane foam to be produced may deteriorate.

The biopolyol may be prepared by a) exchanging a natural oil with a polyfunctional active hydrogen-containing compound in the presence of a catalyst; And b) subjecting the product of the exchange reaction to an addition reaction with alkylene oxide.

Examples of the polyfunctional alcohols include ethylene glycol, diethylene glycol, glycerine, trimethanolpropane, pentaerythritol, dipentaerythritol, At least one selected from the group consisting of α-methylglucoside, xylitol, sorbitol and sucrose can be used. The number of functional groups of the polyfunctional alcohol is shown in Table 2 below.

Polyfunctional alcohol Functionality Carbohydrate system Sugar 8 Sorbitol 6 Almamethylglycoside 4 Aliphatic system Glycols 2 glycerin 3 Trimethanolpropane 3 Pentaerythritol 4

Examples of the polyfunctional amine include ethylenediamine, diethylenetriamine, triethanolamine, ortho-toluenediamine, isomer, diphenylmethanediamine, and the like. Diethanolamine, and the like. The number of functional groups of the polyfunctional amine is shown in Table 3 below.

Polyfunctional amine Functionality Ethylenediamine 4 Diethylenetriamine 5 Toluene diamine 4 Triethanolamine 3

Such a polyfunctional active hydrogen-containing compound may be used in an amount of 10 to 60% by weight, preferably 15 to 40% by weight. When the content is less than 10% by weight, the number of functional groups is low, and the physical properties of the desired bio-polyol are not exhibited, which affects the physical properties of the hard urethane foam and the heat insulating material. When the content is more than 60% by weight, The produced polyol can not be regarded as a bio-polyol.

The catalyst used is a basic catalyst such as KOH, NaOH, CsOH, dimethyl lauramine, dimethyl palmityl amine, At least one selected from the group consisting of N, N-dimethyldodecan-1-amine and 1-octadecanamine can be used.

Such a catalyst is used in an amount sufficient to carry out the exchange reaction, preferably 0.1 to 1.5% by weight, more preferably 0.2 to 1.0% by weight.

The reaction conditions are adjusted so that the exchange reaction is carried out in the range of about 10 to 90% by weight, preferably 20 to 70% by weight, of the natural oil. For example, from 70 to 170 DEG C, preferably from 80 to 120 DEG C, while raising the temperature over a period of from 0.5 to 3 hours, preferably from 1 to 2 hours.

In the above-mentioned natural oil which has not been subjected to exchange reaction, an addition reaction and an exchange reaction are caused in the addition reaction step of alkylene oxide. Since the natural oil is a lipophilic component having a long alkyl chain and the polyfunctional active hydrogen-containing compound is a hydrophilic component, when the alkylene oxide is added after a part of the natural oil is exchanged, the addition reaction with the alkylene oxide And a homogeneous bio-polyol can be obtained. As a result, the storage stability of a composition for producing a rigid polyurethane foam (polyol containing a bio-polyol and other additives, etc.) can be enhanced.

The present invention can perform a pretreatment step of purifying natural oil prior to the exchange reaction. During this pretreatment, gums or other non-sparing impurities (such as phospholipids) can be removed by submersion. In addition, the separated natural oil layer may be treated with an alkali or the like to remove the remaining free fatty acid component.

The exchange reaction will be described in more detail as follows.

When a polyhydric alcohol is used as the polyfunctional active hydrogen-containing compound, the triglyceride present in the natural oil as shown in the following reaction formula 1 reacts with a polyhydric alcohol to cause a fatty acid group to be lost and a di- and monosubstituted hydroxyglyceride And the polyhydric alcohol may form a fatty acid ester with the separated fatty acid group.

[Reaction Scheme 1]

In the case of a polyhydric amine having a hydroxyl group in a molecule such as diethanolamine in the polyhydric amine, an exchange reaction can be carried out according to the reaction mechanism of the following reaction formula (2).

[Reaction Scheme 2]

Further, in the case of a polyhydric amine which does not contain a hydroxyl group in the molecule, an exchange reaction can be carried out according to the reaction mechanism of the following reaction formula 3 (a kind of transamidation reaction).

[Reaction Scheme 3]

The exchange reaction can be carried out with a dehydration process, for example a vacuum dehydration process, in which a trace or small amount of water is contained in the natural oil as the reactant, or the catalyst is in the form of an aqueous solution (for example an aqueous solution of an alkali hydroxide) It is also possible to use it as.

The reaction conditions and the selection of the polyfunctional active hydrogen-containing compound can be determined in consideration of the degree of the alkylene oxide addition reaction, the degree of expansion to be achieved in the final hard polyurethane foam, and the curing time .

The present invention causes addition reaction of alkylene oxide to the product of the exchange reaction (first step reaction).

When the addition reaction is carried out with the alkylene oxide in a specific amount to the product obtained by the exchange reaction, the storage stability can be increased while having a high functional group, the viscosity can be kept low, and then the rigid polyurethane foam for building insulation It is possible to improve the physical properties.

The alkylene oxide is a compound having at least one alkylene oxide group such as ethylene oxide, propylene oxide (1,2-epoxypropane), butylene oxide (1,4-epoxybutane), 1,2- , 2,3-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, amylene oxide and styrene oxide may be used. In view of commercialization, ethylene oxide, propylene oxide and butylene oxide can be preferably used, and ethylene oxide and propylene oxide can be more preferably used in consideration of cost and physical properties.

In this case, when a plurality of alkylene oxides are used in combination, the respective alkylene oxides may be continuously introduced or simultaneously introduced, and the physical properties may be changed by controlling the mixing ratio of the alkylene oxide.

In addition, a catalyst used in the exchange reaction, such as a basic catalyst (especially an alkali hydroxide catalyst), can be used to promote the alkylene oxide addition reaction.

Increasing the amount of natural oil used in a given amount of total reactant reduces the amount of alkylene oxide used in the addition reaction. The present invention can reduce carbon dioxide emissions by reducing the amount of energy input in the course of manufacturing biopolyols by increasing the amount of natural oil used relative to conventional ones.

On the other hand, if the alkylene oxide is added in an amount less than a certain amount, the viscosity of the bio-polyol may be rather increased, resulting in reduced handleability and reduced storage stability.

In addition, when the amount of natural oil used is decreased and the amount of alkylene oxide added is increased, the amount of energy required for the addition reaction is increased. To reduce the amount of natural oil used excessively, There is a problem that it is not matched with the technology trend of.

Thus, there is a need to appropriately control the composition of reactants for production of bio-polyols, particularly the addition amount of alkylene oxide compounds, in order to maximize advantages of using natural oil and to alleviate problems caused by use of natural oil.

In this connection, the alkylene oxide added to the exchange reaction product between the natural oil and the polyfunctional active hydrogen-containing compound contains at least 20% by weight, preferably from 20 to 70% by weight, more preferably from 30 to 60% can do.

The alkylene oxide addition reaction may be carried out at a temperature of from 80 to 140 DEG C, preferably from 100 to 120 DEG C over a period of from 1 to 40 hours, preferably from 5 to 15 hours. Also, the pressure can be performed at 5.0 kgf / cm 2 or less, preferably 3 to 4 kgf / cm 2.

The present invention may further comprise, after the addition reaction step of the alkylene oxide, selectively removing the catalyst component present in the product. In the case of remaining in the bio-polyol, it is preferable to carry out the above step since the foam may be degraded in the formability and cross-linking reaction of the foam during the polyurethane synthesis process.

The removal of the catalyst component can be carried out using a catalyst adsorbent. Specifically, a catalyst adsorbent and water may be introduced into the alkylene oxide addition reaction product and then filtered. At this time, it is preferable that the catalyst removal step is carried out under stirring.

As the catalyst adsorbent, for example, silicates such as aluminum silicate and magnesium silicate may be used, and these catalysts may be used singly or in combination. The catalyst adsorbent may be used in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 2.0% by weight.

In addition, the catalyst removal step (catalyst adsorbent injection and adsorption treatment) may be carried out at 50 to 140 ° C, preferably at 70 to 100 ° C over 1 to 15 hours, preferably 2 to 10 hours.

The biopolyol produced by the above reaction (exchange reaction and addition reaction of alkylene oxide) has a functional group number of 3 or more (preferably 3 to 7) and a hydroxyl value of 200 to 600 mgKOH / g (preferably 300 to 500 MgKOH / g), and the viscosity (25 DEG C) may range from about 2,000 to 25,000 cps (preferably 3,000 to 15,000 cps).

As described above, the bio-polyol prepared according to the present invention exhibits excellent physical properties by decreasing the number of functional groups and the content of residual natural oil, and in particular, by adding a considerable amount of alkylene oxide into the molecular structure, , And the storage stability is improved. Such properties are unexpected in the prior art, and are easy to handle and have the advantage of being able to inhibit changes in the physical properties of the polyol even during long-term storage. In addition, the properties of the rigid polyurethane foam to be produced can be easily changed by selecting the reactants, controlling the ratio, density, reactivity, etc. between the reactants.

Due to these improvements, the rigid polyurethane foam produced using the bio-polyol is particularly suitable for use as a thermal insulation material for construction purposes.

On the other hand, a rigid polyurethane foam can be prepared by reacting polyol including the bio-polyol prepared above with isocyanate and urethane.

Such mechanism of urethane reaction is well known in the art and various additives (for example, a catalyst, a foaming agent, a surfactant, a flame retardant, etc.) are mixed so that the rigid polyurethane foam to be produced exhibits physical properties suitable for use as a thermal insulation for construction .

The method of producing the rigid polyurethane foam is not particularly limited, and the urethane reaction may be performed by mixing the additives, polyol, and isocyanate at the same time, or the additive may be first added to the polyol, and the polyol containing the additive and the isocyanate may be urethane-reacted. When the additive, polyol and isocyanate are mixed at the same time, it is difficult to form uniform urethane foam due to the local unevenness of the concentration, and handling properties of the polyol and moldability of the urethane foam may not be easy. Method is preferable.

The polyol and isocyanate are reacted at a stoichiometric ratio, but 80 to 180 parts by weight, preferably 90 to 150 parts by weight of isocyanate may be used relative to 100 parts by weight of the polyol in consideration of the reaction efficiency and the like.

Also, considering the characteristics of the rigid polyurethane foam to be produced, the isocyanate index may be in the range of 60 to 400, preferably 90 to 200, and more preferably 90 to 160 in view of the construction.

Hereinafter, the reactants (polyol, isocyanate and additives) for preparing the rigid polyurethane foam will be described in detail.

The polyol of the present invention necessarily comprises a biopolyol and may additionally comprise an ether polyol, an ester polyol or a mixture thereof.

Examples of the ether polyols include glycerine, trimethanolpropane, pentaerythritol, dipentaerythritol, alpha-methylglucoside, xylitol, sorbitol, Polyfunctional alcohols such as sucrose and the like; (For example, ethylene oxide, propylene oxide, and the like) with a polyfunctional amine, such as ethylene oxide, propylene oxide and / or ortho-toluene diamine, ethylene diamine, triethanol amine, Oxides, butylene oxides, or mixtures thereof). The method of synthesizing such an optionally containing ether polyol is known in the art, and the basic reaction mechanism is shown in the following reaction formula (4).

[Reaction Scheme 4]

Examples of ester polyols include reaction products of polyhydric alcohols with polyhydric acids (especially polyhydric carboxylic acids). At this time, an anhydride thereof, an ester compound with a lower alcohol or a mixture thereof may be used instead of the polyvalent acid. More specifically, it is possible to use a polyhydric alcohol such as dicarboxylic acid (e.g., phthalic anhydride, terephthalic acid, suberic acid, sebacic acid, isophthalic acid, trimellitic acid, succinic acid, adipic acid, fumaric acid, , Diethylene glycol, 1,4-butanediol, glycerin, trimethylol propane, propylene glycol, etc.) can be used. Further, a single ester polyol may be used, or two or more ester polyols may be used in combination. The reaction mechanism for synthesizing such an ester polyol is shown in the following reaction formula (5).

[Reaction Scheme 5]

The hydroxyl value of the polyol (ether polyol and / or ester polyol) usable in combination with the biopolyol may be in the range of 50 to 600 mgKOH / g to satisfy various physical properties required for thermal insulation such as thermal conductivity, compressive strength and the like. The physical properties (e.g., thermal conductivity and strength properties (compressive strength, flexural strength, etc.) of the rigid polyurethane foam can be controlled through appropriate selection of the hydroxyl value.

The polyol may comprise 10% by weight or more, preferably 10 to 60% by weight of the bio-polyol. The ether polyol which may be added may be used in an amount of 80 wt% or less (preferably 20 to 70 wt%) and the ester polyol may be used in an amount of 40 wt% or less (preferably 20 wt% or less).

For example, the ether polyol may be selected from the group consisting of (i) 60 to 100% by weight of an ether polyol having a number of functional groups of about 5.5 to 7, a hydroxyl value of 350 to 500 mg KOH / g, and (ii) And 0 to 40% by weight of an ether polyol having a hydroxyl value of KOH / g. The ester polyol having a functional group number of 2 to 4 and a hydroxyl value of 50 to 400 mgKOH / g can be used.

As another example, the ether polyol may be selected from (i) 60 to 100% by weight of an ether polyol having a number of functional groups of 5 to 6.5, a hydroxyl value of 300 to 550 mgKOH / g, and (ii) And 0 to 40% by weight of an ether polyol having a hydroxyl value of mgKOH / g. The ester polyol having a functional group number of 2 to 3 and a hydroxyl value of 50 to 400 mgKOH / g can be used.

The isocyanate of the present invention reacts with a polyol to form a urethane bond in the foam, and includes a compound in which an isocyanate group is bonded with an aromatic, alicyclic, and / or aliphatic group.

The isocyanate compounds are known in the art and include, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, Diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane ( 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI or HMDI), 1,3-hexanediol diisocyanate, Phenylenediisocyanate, 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate (TDI), diphenylmethane-2,4'-diisocyanate, diphenylmethane- Diisocyanate (MDI), naphthylene-1,5-diisocyanate , Triphenylmethane-4,4 ', 4 "-triisocyanate, polyphenyl-polymethylene-polyisocyanate (crude MDI), norbornane diisocyanate, m- isocyanatophenylsulfonyl isocyanate, p-iso Modified polyisocyanate, urethane-modified polyisocyanate, urethane-modified polyisocyanate, urethane-modified polyisocyanate, isocyanurate-modified polyisocyanate, urea-modified polyisocyanate, urea-modified polyisocyanate, urea-modified polyisocyanate , Buret-containing polyisocyanates, isocyanate-terminated prepolymers, or mixtures thereof.

The isocyanate may have a number of functional groups of 2.5 to 3.5 and an NCO% of 25 to 35. Suitable isocyanates for architectural insulation are MDI, polymeric MDI or crude MDI having a number of functional groups of 2.6 to 3.0 (preferably about 2.7), an NCO% value in the range of 25 to 35 (preferably an NCO% value of 27 to 32) MDI (p-MDI, typically weight average molecular weight (M _w ): about 350 to 420). The p-MDI is typically in the form of a brown liquid at room temperature, and the viscosity range may range from 100 to 3,000 cps (more specifically, from 100 to 300 cps).

The reaction between the polyol and the isocyanate can be carried out in the presence of a urethane catalyst in order to shorten the curing time and the like. The catalyst is not particularly limited, but typically at least one selected from the group consisting of an amine-based catalyst such as a secondary or tertiary amine compound and a metal catalyst such as an organic metal may be used.

Examples of the amine catalyst include triethylenediamine, triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexadecyldimethylamine, tetramethylethylenediamine, 3-methoxy-N-dimethyl N-dimethylaminopropylamine, N, N-diethyl-3-diethylaminopropylamine, tris (3-dimethylamino) propylhexahydrotriamine, N-methylmorpholine, N- N, N ', N', N'-tetramethylethylenediamine, diethylenetriamine, diethylenetriamine, diethylenetriamine, diethylenetriamine, diethanolamine, diethanolamine, N, N'-dimethylcyclohexylamine, N, N'-dimethylcyclohexylamine, N, N'-dimethyldicyclohexylamine, N ', N', n'-pentamethyldiethylenetriamine, and triethylenediamine. Can be used. In this case, Polyact 8, N, N, N ', N', N'-pentamethyldiethylenetriamine, trade name Polyact 5 in the case of N, N-dimethylcyclohexylamine and trade name TEDA-33P in the case of triethylenediamine, .

The metal catalyst may be one selected from the group consisting of potassium octoate, potassium acetate, bismuth-based gel catalyst, and tin-type catalyst. More than species can be used.

The gel catalyst mainly promotes a gel reaction to form a urethane chain in a urethane foam. Examples of the tin catalyst include tin salts of carboxylic acid, tin acrylate, trialkyltin oxide, dialkyltin dihalide, dialkyltin oxide (dibutyltin (IV) oxide and the like), dibutyltin diaurate, At least one selected from the group consisting of dibutyltin diacetate, diethyltin diacetate, dihexyltin diacetate, di-2-ethylhexyltin oxide, dioctyltin dioxide and tin octoate may be used.

The urethane catalyst may be used in an amount of 0.1 to 10 parts by weight, preferably 0.2 to 7.0 parts by weight based on 100 parts by weight of the polyol. Generally, as the amount of the catalyst is increased, the reaction rate for forming the polyurethane foam increases. However, if the reaction rate is too high, the polyol and isocyanate may be changed into a solid phase before filling the thermal insulation space of the panel structure, And there may be a problem that workability is bad, so it is desirable to adjust it appropriately.

The foaming agent acts to generate bubbles during the urethane reaction. The foaming agent is a physical foaming agent that does not participate in the urethane reaction but is vaporized (sublimed) by the reaction heat to form bubbles and water (which reacts with isocyanate to generate carbon dioxide) as a chemical foaming agent These two types can be used singly or in combination.

In the physical blowing agent, the foaming agent is vaporized (sublimated) by the heat of reaction, and the resulting gas is accumulated by the cells surrounded by the foam, so that the foam produced can exhibit a low thermal conductivity. In addition, the physical foaming agent can control the required properties (density, etc.) of the polyurethane foam.

HFC-245fa (1,1,1,3,3,3-pentafluoropropane), which is a hydrocarbonsystem, CFC-pentane, hydrofluorocarbon-based HCFC-141b (1,1-dichloro-1-fluoroethane) and hydrofluorocarbon - pentafluoropropane), HFC-365mfc, mixed HFC-365mfc / 227ea, mixtures thereof, and the like may be preferably used as a foaming agent. The use of the CFC foaming agent conventionally used is not excluded, but it may cause an environmental problem and it may be preferable to exclude the use as much as possible. Preferably, a more environmentally friendly component such as C-Pentane, HFC, or the like can be used. In particular, HFC-245fa may be used as the HFC-based blowing agent used in the production of the closed-cell insulating foam.

The blowing agent may include 0.1 to 35 parts by weight based on 100 parts by weight of the polyol. Specifically, the physical blowing agent may range from 0.1 to 35 parts by weight, and preferably from 10 to 30 parts by weight, based on 100 parts by weight of the polyol. The chemical foaming agent may be used in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 6 parts by weight, based on 100 parts by weight of the polyol.

The present invention can use a surfactant that affects the cell structure in the polyurethane foam. The surfactant may act to stabilize the mixing of the reaction raw materials, to generate bubbles, and to stabilize the bubbles. For example, it is possible to increase the surface area by reducing the surface tension by decreasing the cell size, and by increasing the surface elasticity, it is possible to restore the critical expanding film before cell destruction occurs, And increase the surface viscosity which reduces deformation of the cell structure.

As such, the kind of the surfactant can be appropriately selected in consideration of the cell structure in the foamed polyurethane, and specific examples thereof include a silicone surfactant or a foam stabilizer. Examples thereof include B-8404, product name of Evonik, B-8462 and the like. In this connection, a polysiloxane ether system having a molecular weight of 1,000 to 10,000 g / mol, more preferably 3,000 to 7,000 g / mol may be used to facilitate the formation of a closed cell. In particular, when water is used as the foaming agent, the use of a silicone surfactant may be preferable.

The amount of the surfactant to be used may be in the range of 0.1 to 5.0 parts by weight, more preferably 0.5 to 3.0 parts by weight, based on 100 parts by weight of the polyol.

In addition, the present invention can be suitably added and reacted with a chain extender, a flame retardant, a colorant, a filler, an internal release agent, an antistatic agent, an antibacterial agent, a cell control agent and a reaction inhibitor.

The chain extender may be selected from the group consisting of low molecular weight polyhydric alcohols (e.g., ethylene glycol, 1,4-butanediol, glycerin and the like), low molecular weight amine polyols (diethanolamine, triethanolamine and the like), polyamines (ethylene diamine, Diamine, etc.) can be used.

The flame retardant is a component used for imparting flame retardancy to the polyurethane foam to be finally produced, and may be used in an appropriate amount in consideration of the level required when necessary. For example, a phosphorus flame retardant (TCPP, TCEP, Phosphorus ester, etc.) can be used.

Other additives may be appropriately selected depending on the type and amount used in the art.

The urethane reaction of the present invention may utilize conventional foam forming principles and associated equipment, and it may be desirable to form a closed cell foam to suit the particular use of building insulation. For example, the polyol, isocyanate and additives can be contacted and mixed and then expanded / cured in the form of a cellular polymer (specifically, the foaming step). As another example, the polyol and the additive may be first mixed and then subjected to an expansion / cure reaction by mixing with the isocyanate for the reaction.

Further, a foaming machine may be used for foam formation, and the foaming temperature may be in the range of 15 to 30 DEG C (more preferably 18 to 28 DEG C) and the foaming pressure may be in the range of 90 to 160 bar (more preferably 110 to 140 bar) have. Further, in one embodiment, the temperature of the mold is preferably 25 to 70 DEG C (more preferably 30 to 50 DEG C) and the demolding time is 2 to 60 minutes (more preferably, 2 to 60 DEG C) so as to be particularly suitable for rigid urethane foam for building insulation. To 40 minutes).

The rigid polyurethane foam produced according to the embodiment of the present invention is a heat insulating material for a building panel, in which a steel plate is attached to both sides of a core polyurethane foam (continuous panel and non-continuous panel).

In addition, the spray-type polyurethane foam is manufactured by spraying directly on the surface of a target with a spray gun of a specially manufactured blower, and laminating it in multiple layers.

The hard polyurethane foam composition has a viscosity (20 ° C) of 150 to 1500 cps, a specific gravity (20 ° C) of 1.1 to 1.3, a cream time of 2 to 50 sec, and an apparent density 20 to 55 kg / m < 3 >. Here, the viscosity and specific gravity are the physical properties of the mixture in which the isocyanate is excluded in the composition for producing a rigid polyurethane foam.

The composition of the rigid polyurethane foam for continuous panel has a viscosity (20 ° C) of 300 to 1,200 cps, a specific gravity (20 ° C) of 1.0 to 1.25, a cream time of 5 to 20 sec, gel time of 30 to 80 sec, a tack free time of 55 to 120, and a free density (F / D) of 20 to 60 kg / m < 3 >. Here, the viscosity and specific gravity are the physical properties of the mixture in which the isocyanate is excluded in the composition for producing a rigid polyurethane foam.

Further, the composition of the rigid polyurethane foam for a discontinuous panel has a viscosity (20 ° C) of 150 to 900 cps, a specific gravity (20 ° C) of 1.0 to 1.25, a cream time of 10 to 50 sec, The gel time may be 80 to 600 sec and the free density (F / D) may be 20 to 50 kg / m < 3 >. Here, the viscosity and specific gravity are the physical properties of the mixture in which the isocyanate is excluded in the composition for producing a rigid polyurethane foam.

The composition of the rigid polyurethane foam for spray has a viscosity (20 DEG C) of 150 to 1,000 cps, a specific gravity (20 DEG C) of 1.0 to 1.25, a cream time of 2 to 7 sec, and a rise time rise time of 5 to 40 sec and a free density (F / D) of 10 to 45 kg / m < 3 >. Here, the viscosity and specific gravity are the physical properties of the mixture in which the isocyanate is excluded in the composition for producing a rigid polyurethane foam.

Typical physical properties (2 kind 2) of rigid polyurethane foam for architectural panel have an apparent density of not less than 35 kg / ㎥ to less than 45 kg / ㎥, a thermal conductivity of not more than 0.023 W / m · K, a flexural strength of 25 N / Or more, a compression strength of 10 N / cm 2 or more, an absorption amount of 3.0 g / 100 cm 2 or less, a combustion time of 120 seconds or less, and a combustion length of 60 mm or less (self-firing).

The standard physical properties (No. 3) of the rigid polyurethane foam for spraying have an apparent density of not less than 25 kg / m 3 to less than 35 kg / m 3, a thermal conductivity of not more than 0.025 W / m · K, a flexural strength of 15 N / Or more, a compression strength of 10 N / cm 2 or more, an absorption amount of 3.0 g / 100 cm 2 or less, a combustion time of 120 seconds or less, and a combustion length of 60 mm or less (self-firing).

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. , And it is natural that such variations and modifications fall within the scope of the appended claims.

1) Natural oil

Palm oil: molecular weight (Mw) of Sigma-Aldrich: about 950; Cas. No .: 8002-75-3

Soybean oil: molecular weight (Mw) of Sigma-Aldrich of about 968.7; Cas. No .: 8001-22-7

Castor oil: molecular weight (Mw) of Sigma-Aldrich 946.7; Functional group: 2.7; Cas No .: 8001-79-4

2) Multifunctional active hydrogen-containing compound

Sucrose: molecular weight (Mw) of Sigma-Aldrich 342.3; Functional group: 8; Cas No .: 57-50-1

Sorbitol: molecular weight (Mw) of Sigma-Aldrich 178.1; Functional group: 6

Pentaerythritol: Molecular weight (Mw) of Sigma-Aldrich, 136.2; Functional group: 4

Glycerin: molecular weight (Mw) of Sigma-Aldrich 92.1; Functional group: 3; Cas. No .: 56-81-5

o-TDA: molecular weight (M _w ) of KPX Fine Chemical Co., Ltd. 122.2; Functional group: 4

Triethanolamine: Molecular weight (Mw) of Sigma-Aldrich 149.2

Ethylene diamine: Molecular weight (Mw) of Sigma-Aldrich 60.1

3) The exchange catalyst

KOH catalyst: KOH solution of Sigma-Aldrich (concentration: 45% solution, Cas. No .: 1310-58-3) Molecular weight (Mw) 56.1

Dimethyllauramine: product name of Kao Corporation: DM-2098; Cas. No: 112-18-5

4) alkylene oxide

Propylene oxide (PO): Molecular weight (Mw) of SKC Co., Ltd. 58.08; Cas. No: 75-56-9

Ethylene oxide (EO): molecular weight (Mw) of Honam Petrochemical Co., Ltd. 44.05; Cas. No75-21-8

5) Isocyanate

Cosmonate M-200 (compound name: p-MDI, functional group: 2.7, NCO%: 31) manufactured by KUMHO MITSUI CHEMICAL Co.,

6) Urethane catalyst

Amine catalysts: Polyact5 (Pentamethyldiethylenetriamine) and Polyact8 (Dimethylcyclohexylamine), products of Air Products, KPX Chemical Co., Ltd. TEDA-33P (Triethylenediamine / DPG)

7) Surfactants

Silicon surfactant: product names of Evonik, B-8462, B-8404

8) Foaming agent

HCFC-141b (compound: 1,1-dichloro-1-fluoroethane; Cas. No. 1717-00-6) manufactured by Zhejiang Juhua Calcium Carbide Co.,

9) Flame retardant

The compound Fyrol PCF (compound: Tris (2-chloroisopropyl) phosphate; Cas. No .: 13674-84-5)

Polyol manufacturing

Example 1

The reaction was carried out by adding sugar, palm oil and KOH (45% by weight) catalyst to a 20 L high-pressure vessel and stirring under a nitrogen atmosphere (reduced pressure substitution), followed by vacuum dehydration at about 120 ° C for about 1 hour. Then, propylene oxide was added at about 115 캜 and reacted for 15 hours.

The catalyst adsorbent and water were added to the reaction product thus obtained, stirred at about 80 캜 for about 1 hour, and then filtered to synthesize a bio-polyol. The composition ratios of the reactants are shown in Table 4 below.

Examples 2 and 3

A bio-polyol was synthesized in substantially the same manner as in Example 1 except that the type of natural oil was changed in the reactants. The composition ratios of the reactants are shown in Table 4 below.

Classification (parts by weight) Example 1 Example 2 Example 3 Natural oil palm oil 200 - - Soybean oil - 200 - Castor oil - - 200 Multifunctional active hydrogen-containing compound Sugar 300 300 300 Sorbitol - - - Pentaerythritol - - - glycerin - - - o-TDA - - - Triethanolamine - - - Ethylenediamine - - - Water (reaction) 10 10 - catalyst KOH (45%) 3.5 3.5 3.5 Alkylene oxide PO 488 488 498 Water (disposal) handful handful handful Catalyst adsorbent Magnesium silicate handful handful handful Sum 1001.5 1001.5 1001.5

Examples 4 to 9

In this example, palm oil was used as the natural oil, the type of the polyfunctional active hydrogen-containing compound was changed, and a bio-polyol was synthesized in substantially the same manner as in Example 1 according to the composition ratio shown in Table 5 below.

Classification (parts by weight) Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Natural oil palm oil 200 200 200 200 200 200 Multifunctional active hydrogen-containing compound Sugar 300 - - - - - Sorbitol - 240 - - - - Pentaerythritol - - 280 - - - glycerin - - - - - - o-TDA - - - 275 - - Triethanolamine - - - - 300 - Ethylenediamine - - - - - 150 Water (reaction) 10 - - - 20 - catalyst KOH (45%) 3.5 3.5 3.5 3.5 3.5 3.5 Alkylene oxide PO 488 560 520 520 480 650 Water (disposal) handful handful handful handful handful handful Catalyst adsorbent Magnesium silicate handful handful handful handful handful handful Sum 1001.5 1003.5 1003.5 998.5 1003.5 1003.5

Examples 10 to 13

In this example, castor oil was used as a natural oil, the kind of the polyfunctional active hydrogen-containing compound was changed, and a bio-polyol was synthesized in substantially the same manner as in Example 1 according to the composition ratio shown in Table 6 below.

Classification (parts by weight) Example 10 Example 11 Example 12 Example 13 Natural oil Castor oil 200 200 200 200 Multifunctional active hydrogen-containing compound Sugar 300 - - - Sorbitol - 230 - - Pentaerythritol - - 260 - glycerin - - - 230 Water (reaction) - - - - catalyst KOH (45% by weight) 3.5 3.5 3.5 3.5 Alkylene oxide PO 498 570 540 570 Water (disposal) handful handful handful handful Catalyst absorbent Magnesium silicate handful handful handful handful Sum 1001.5 1003.5 1003.5 1003.5

Examples 14 to 16

In this Example, a bipolyol was synthesized in substantially the same manner as in Example 1 by using palm oil as a natural oil and varying the ratio between a plurality of polyfunctional active hydrogen-containing compounds according to the composition ratio shown in Table 7 below.

Classification (parts by weight) Example 14 Example 15 Example 16 Natural oil palm oil 200 250 300 Multifunctional active hydrogen-containing compound Sugar 300 200 150 glycerin - 100 100 Water (reaction) 10 - 10 catalyst KOH (45% by weight) 3.5 3.5 3.5 Alkylene oxide PO 488 450 440 Water (disposal) handful handful handful Catalyst absorbent Magnesium silicate handful handful handful Sum 1001.5 1003.5 1003.5

Examples 17 to 20

In this Example, the type and proportion of the alkylene oxide and the kind of the catalyst were changed, and a bio-polyol was synthesized in substantially the same manner as in Example 1 according to the composition ratios shown in Table 8 below.

Classification (parts by weight) Example 17 Example 18 Example 19 Example 20 Natural oil palm oil 200 200 200 200 Multifunctional active hydrogen-containing compound Sugar 300 300 300 300 Water (reaction) 10 10 10 10 catalyst KOH (45% by weight) 3.5 3.5 - - Dimethyllauamine - - 10.0 - Dimethylpalmitylamine - - - 10.0 Alkylene oxide PO 488 300 480 480 EO 190 - - Water (disposal) handful handful - - Catalyst absorbent Magnesium silicate handful handful - - Sum 1001.5 1003.5 1000 1000

Comparative Example 1

563.3 parts by weight of sorbitol and ₂ parts by weight of KOH were added to a 2000 mL round bottom flask, stirred in a nitrogen atmosphere, and dehydrated in vacuo at 110 ° C. 565.3 parts by weight of castor oil was added to the mixture, and the mixture was reacted at 200 ° C for about 4 hours. Then, 127.2 parts by weight of glycerin and 49.5 parts by weight of diethylene glycol were added, followed by further reaction for 3 hours. Finally, 176.7 parts by weight of phthalic anhydride and 0.1 part by weight of tetraisopropyltitanate (TPT) were added for the ester reaction, and the reaction was carried out at 230 DEG C for about 15 hours.

A small amount of magnesium silicate and water was added to the reaction product as a catalyst adsorbent, stirred at 80 ° C for 1 hour, and filtered to synthesize a bio-polyol.

Example 21 and Comparative Example 2

The biopolyol was synthesized in substantially the same manner as in Example 1 while varying the addition amount of alkylene oxide. The composition of each reactant is shown in Table 9 below.

Classification (parts by weight) Example 21 Comparative Example 2 Natural oil palm oil 105 550 Multifunctional active hydrogen-containing compound Sugar 150 150 glycerin 100 100 (reaction) 10 10 catalyst KOH (45%) 3.5 3.5 Alkylene oxide PO 635 190 Water (disposal) handful handful Catalyst absorbent Magnesium silicate handful handful Sum 1003.5 1003.5

Test Example

The physical properties of the polyol prepared in the above Examples were measured by the following methods and are shown in Tables 10 to 15.

1) Color : Measured by the Gardner Color test method.

2) Measurement of hydroxyl value : The hydroxyl value of the bio-polyol synthesized in Examples 1 to 20 was measured according to the acetic anhydride-pyridine method (JISK 8004-1961, JISK 3342-1961, JISK 3361-1963).

<Measuring Mechanism>

(200 ml), air cooling tube (30 cm), pipette (5 ml, 10 ml), buret (50 ml) and oil bath

<Measurement method>

(1) In a Erlenmeyer flask, the polyol synthesized in Examples 1 to 20 and a 5 ml anhydrous acetic acid-pyridine solution were added and shaken for 5 times or more, followed by cooling with a cooler and reacting in a oil bath for 1 hour and 30 minutes.

(2) 1 ml of distilled water was added, and the mixture was shaken 5 times or more. Then, the mixture was allowed to stand for 10 minutes in the oil bath for accelerating the hydrolysis.

(3) After taking out from the oil bath and keeping it at room temperature for 10 minutes, the inner wall of the cooler was washed with 10 ml of acetone and then shaken 5 times or more, 3 to 4 drops of phenolphthalein indicator were added and titrated with 0.5N KOH standard solution.

The hydroxyl value was calculated by the following equation (1).

S: Amount of sample

B: 0.5N KOH (ml) required for blank

A: 0.5 N KOH (ml)

B: The acid value of the sample used in this test

3) Viscosity

And measured at 25 캜 using DV-III from Brookfield.

4) Functional group

The functional groups of the prepared bio-polyol were calculated by the following formula (2) using the molar number of the polyfunctional active hydrogen-containing compound and the natural oil and the number of functional groups.

- A (a ₁ + a ₂ + a ₃ + a ₄ + ... + a _n ): Sum of polyfunctional active hydrogen-

- a _n : the number of moles of each of the polyfunctional active hydrogen-containing compound and the natural oil

- f _n : the number of functional groups of each polyfunctional active hydrogen-containing compound and natural oil

5) Storage stability

The synthesized polyol was placed in a 500 ml sample bottle and evaluated by confirming whether or not the layer was separated for 100 days in an oven at 30 ° C.

(Layer separation:?, No layer separation:?, Slight haziness and unstable:?)

division Example 1 Example 2 Example 3 color Yellow liquid Yellow liquid Yellow liquid Hydroxyl value
(mg KOH / g) 440 445 420 Viscosity (25 ℃) 6,500 6,320 6,720 Functional group About 6.5 About 6.5 Approximately 6.9 Storage stability × × ×

division Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 color Yellow liquid Yellow liquid Yellow liquid Red liquid phase Red liquid phase Yellow liquid Hydroxyl value
(mg KOH / g) 440 450 455 460 440 520 Viscosity (25 ℃) 6,500 5,210 3,890 - - - Functional group About 6.5 About 5.2 About 3.6 About 3.7 About 3.0 About 3.0 Storage stability × × × × × ×

division Example 10 Example 11 Example 12 Example 13 color Yellow liquid Yellow liquid Yellow liquid Yellow liquid Hydroxyl value
(mg KOH / g) 420 455 450 445 Viscosity (25 ℃) 6,720 5,750 - - Functional group Approximately 6.9 About 5.6 About 4.3 About 3.4 Storage stability × × × ×

division Example 14 Example 15 Example 16 color Yellow liquid Yellow liquid Yellow liquid Hydroxyl value
(mg KOH / g) 440 435 430 Viscosity (25 ℃)  6,500 5,920 5,330 Functional group About 6.5 About 6.5 About 6.5 Storage stability × × ×

division Example 17 Example 18 Example 19 Example 20 color Yellow liquid Yellow liquid Yellow liquid Yellow liquid Hydroxyl value
(mg KOH / g) 440 420 435 430 Viscosity (25 ℃) 6,500 6,380 6,350 6,350 Functional group About 6.5 About 6.5 About 6.5 About 6.5 Storage stability × × × ×

division Example 16 Example 21 Comparative Example 1 Comparative Example 2 color Yellow liquid Yellow liquid bitumen Yellow liquid Hydroxyl value
(mg KOH / g) 430 427 325 425 Viscosity (25 ℃) 5,330 3,620 29,000 32,000 Functional group About 6.5 About 4.2 About 4.0 About 4.2 Storage stability × × △ △

As can be seen from the above table, when the addition reaction of the alkylene oxide was not carried out (Comparative Example 1), the storage stability and appearance characteristics were poorer than the biopolyol obtained according to the Example under the same conditions, It can be seen that the handling property is low.

In addition, when the amount of the alkylene oxide used was less than a certain amount (Comparative Example 2), the viscosity was so high that the handling property in the urethane reaction was lowered.

Rigid polyurethane foam manufacturing

Examples 22 to 23

The hard polyurethane foam was prepared according to the composition shown in the following Table 18 and the conventional method for producing a continuous panel foam while varying the amount of the bio-polyol synthesized in Example 15.

At this time, a mechanical foaming machine was used for foaming for foam formation. In the production of foam, the urethane foaming temperature between the polyol and the isocyanate was about 20 ° C, the foaming pressure was about 120 bar, the mold temperature was about 45 ° C, Min.

Comparative Examples 3 to 4

Using the conventional polyol and the bio-polyol synthesized from Comparative Example 1, foams for rigid continuous panels for construction were prepared in the same manner as in Example 22, according to the compositions shown in Table 16 below.

Classification (parts by weight) Example 22 Example 23 Comparative Example 3 Comparative Example 4 Polyol A 45.5 26.0 65.0 45.5 Polyol B 24.5 14.0 35.0 24.5 The bio-polyol according to Comparative Example 1 - - - 30.0 The biopolyol of Example 15 30.0 60.0 - - Flame retardant (TCPP) 17.5 17.5 17.5 17.5 water 2.0 2.0 2.0 2.0 Surfactants 1.5 1.5 1.5 1.5 Amine catalyst A 2.8 2.7 2.8 About 2.7 Amine catalyst B 0.55 0.50 0.6 About 0.55 HCFC-141b 12.0 12.0 12.0 12.0 Sum 136.35 136.2 136.4 136.25 Viscosity (20 ℃) 760 735 785 1125 Specific gravity (20 ℃) 1.129 1.130 1.128 1.130 p-MDI 149.2 149.0 149.3 145.0 - Polyol A: Polyol for continuous panel produced by KPX Chemical Co., KONIX HD-402
- Polyol B: Polyol for continuous panel produced by KPX Chemical, KONIX HD-401
- Amine catalyst A: Polycat8
- Amine catalyst B: Catalyst for continuous panel used in KPX Chemical Co., Ltd.

Examples 24 to 25

A hard polyurethane foam was prepared according to the composition shown in the following Table 17 and a conventional method for producing a foam for a discontinuous panel while varying the amount of the bio-polyol synthesized in Example 15.

At this time, a mechanical foaming machine was used for foaming for foam formation. During the production of the foam, the urethane foaming temperature between the polyol and the isocyanate was about 20 ° C, the foaming pressure was about 120 bar, the mold temperature was about 45 ° C, Min.

Comparative Examples 5 to 6

Using the conventional polyol and the bio-polyol synthesized from Comparative Example 1, a foam for a rigid non-continuous panel for construction was manufactured in the same manner as in Example 24 according to the composition shown in Table 17 below.

Classification (parts by weight) Example 24 Example 25 Comparative Example 5 Comparative Example 6 Polyol B 60.0 40.0 80.0 60.0 Polyol C 15.0 10.0 20.0 15.0 The bio-polyol according to Comparative Example 1 - - - 25.0 The biopolyol of Example 15 25.0 50.0 - - Flame retardant (TCPP) 13.0 13.0 13.0 13.0 water 2.2 2.2 2.2 2.2 Surfactants 1.5 1.5 1.5 1.5 Amine catalyst A 1.3 1.3 1.3 1.3 HCFC-141b 20.0 20.0 20.0 20.0 Sum 138.0 138.0 138.0 138.0 Viscosity (20 ℃) 205 200 225 560 Specific gravity (20 ℃) 1.126 1.126 1.125 1.128 p-MDI 140.0 145.0 140.0 140.0 - Polyol B: Non-continuous panel polyol produced by KPX Chemical, KONIX HD-401
- Polyol C: Non-continuous panel polyol produced by KPX Chemical, Sucrose base ether polyol
- Amine catalyst A: Polycat8

Examples 26 to 27

The hard polyurethane foam was prepared according to the composition shown in the following Table 18 and the usual method for producing foam for spraying while varying the amount of the bio-polyol synthesized in Example 15.

At this time, a mechanical foaming machine for spraying was used for foaming for foam formation, and the urethane foam temperature between the polyol and the isocyanate was about 20 ° C and the foaming pressure was about 130 bar.

Comparative Examples 7 to 8

Using the conventional polyol and the bio-polyol synthesized from Comparative Example 1, a foam for hard spray for construction was manufactured in the same manner as in Example 26, according to the composition shown in Table 18 below.

Classification (parts by weight) Example 26 Example 27 Comparative Example 7 Comparative Example 8 Polyol D 30.0 20.0 40.0 30.0 Polyol E 45.0 30.0 60.0 45.0 The bio-polyol according to Comparative Example 1 - - - 25.0 The biopolyol of Example 15 25.0 50.0 - - Flame retardant (TCPP) 10.0 10.0 10.0 10.0 water 1.9 1.9 1.9 1.9 Surfactants 1.0 1.0 1.0 1.0 Amine catalyst A 2.5 2.5 2.5 2.5 Amine catalyst C 2.0 2.0 2.0 2.0 Amine catalyst D 1.0 1.0 1.0 1.0 HCFC-141b 22.0 22.0 22.0 22.0 Sum 140.4 140.4 140.4 140.4 p-MDI 147.42 147.42 147.42 143.0 Viscosity (20 ℃) 265 252 280 610 Specific gravity (20 ℃) 1.186 1.188 1.186 1.189 - Polyol D: Spray polyol, Glycerine base ether polyol produced by KPX Chemical
- Polyol E: Polyol for spraying produced by KPX Chemical Co., Amine base ether polyol
- Amine catalyst A: Polycat8
- Amine catalyst C: TEDA-33P
-Amine Catalyst D: DABCO T-12

Test Example

The properties of the prepared continuous panel, the non-continuous panel and spray composition and the rigid polyurethane foam were measured by the following methods, and the results are shown in Tables 19 to 20.

1. Viscosity : Measured at 20 캜 using DV-III from Brookfield.

2. Specific gravity : It was measured at 20 캜 using DMA4500 manufactured by Anton Paar.

3. Cream time (CT) : The time when bubbles are generated after foaming and the color of the mixture changes from dark brown to cream color, and the time at which the mixture starts to rise is measured.

4. Gel time (GT) : The time when the urethane, urea, and allophanate reactions occurred and the time at which the fibers were formed was measured.

5. Tack free time (TFT) : The time when the surface of the foam lost its viscosity after foaming was measured.

6. Rise time (RT) : The time at which the growth of the foam stopped after foaming was measured.

7. Apparent density, thermal conductivity (heat insulation), flexural strength, compressive strength, water absorption, combustion time, and combustion length were measured using KS M3809.

8. Free Density (F / D) : Measured according to ASTM D-3574.

9. Independent foaming rate : Measured using ASTM D28566.

10. Dimensional stability : Measured using ASTM D2126.

11. Moldability : The surface of the prepared rigid polyurethane foam was visually inspected and evaluated by the following method.

[Assessment Methods]

1 5 10

Excellent <-------------- Medium ---------------> Poor

Rigid polyurethane foam for continuous panel Example 22 Example 23 Comparative Example 3 Comparative Example 4 Biopolyol content%
(Based on polyol) 25 50 0 25 Isocyanate index 113 111 114 116 Reactivity (CT / GT / TFT, sec) 12/55/80 12/57/83 12/54/80 13/54/85 Apparent density (kg / m ³ ) 41.8 42.2 41.7 42.5 Free density (kg / m ³ ) 37.0 37.3 37.8 37.4 Percentage of closed cells (%) 92.1 91.7 91.5 89.1 Thermal conductivity (W / mK) 0.0177 0.0178 0.177 0.0184 Compressive strength (N / cm ² ) 22.7 22.0 23.4 18.2 Flexural Strength (N / cm ² ) 44.1 43.8 43.6 37.5 Absorption rate (g / cm ² ) 1.20 1.11 1.35 1.23 Dimensional stability (ΔV%) -30 ° C, 24 hr -1.17 -1.07 -1.31 -1.87 70 ° C, 95% RH, 24 hr 2.75 2.65 2.88 3.98 Flammability Self-baking Self-baking Self-baking Self-baking Formability 3 5 3 8

Rigid polyurethane foam for non-continuous panel Example 24 Example 25 Comparative Example 5 Comparative Example 6 Biopolyol content%
(Based on polyol) 25 50 0 25 Isocyanate index 111 111 115 117 Reactivity (CT / GT / TFT, sec) 20/137/209 20/135/205 20/141/215 23/139/300 Apparent density (kg / m ³ ) 38.8 38.5 39.2 39.1 Free density (kg / m ³ ) 30.2 30.0 30.5 29.8 Percentage of closed cells (%) 90.1 90.5 89.9 88.2 Thermal conductivity (W / mK) 0.021 0.021 0.020 0.023 Compressive strength (N / cm ² ) 12.13 12.25 12.01 11.09 Flexural Strength (N / cm ² ) 29.13 27.52 28.80 26.63 Absorption rate (g / cm ² ) 1.88 1.75 1.97 1.89 Dimensional stability (ΔV%) -30 ° C, 24 hr -1.33 -1.48 -1.65 -1.98 70 ° C, 95% RH, 24 hr 2.88 2.73 2.97 3.85 Flammability Self-baking Self-baking Self-baking Self-baking Formability 3 5 3 9

Rigid polyurethane foam for spray Example 26 Example 27 Comparative Example 7 Comparative Example 8 Biopolyol content%
(Based on polyol) 25 50 0 25 Isocyanate index 108 109 107 110 Reactivity (CT / RT, sec) 2/12 2/11 2/11 2/12 Apparent density (kg / m ³ ) 26.8 27.1 27.3 26.7 Free density (kg / m ³ ) 24.2 24.5 24.0 23.7 Percentage of closed cells (%) 91.7 91.0 92.1 90.2 Thermal conductivity (W / mK) 0.0187 0.0188 0.0187 0.0190 Compressive strength (N / cm ² ) 11.02 11.03 11.21 10.04 Flexural Strength (N / cm ² ) 19.88 19.87 20.56 18.25 Absorption rate (g / cm ² ) 2.11 2.05 2.24 2.14 Dimensional stability (ΔV%) -30 ° C, 24 hr -0.98 -0.93 -1.05 -1.15 70 ° C, 95% RH, 24 hr 1.95 2.05 2.11 2.87 Flammability Self-baking Self-baking Self-baking Self-baking Formability 3 3 3 8

Claims (10)

A polyol comprising a bio-polyol having a functional group number of 3 or more, a hydroxyl value of KOH / g of 200 to 600 mg and a viscosity (25 ° C) of 2,000 to 25,000 cps; And
A hard polyurethane foam for building insulation, which is produced by reacting isocyanate with urethane,
Wherein the bio polyol comprises 10 to 60% by weight of a natural oil;
10 to 60% by weight of a polyfunctional active hydrogen-containing compound,
And 20 to 70% by weight of alkylene oxide in the presence of 0.1 to 1.5% by weight of catalyst,
Wherein the polyurethane foam has an apparent density of 25 kg / m 3 or more, a thermal conductivity of 0.025 W / m · K or less, a flexural strength of 15 N / cm 2 or more, a compressive strength of 10 N / A hard polyurethane foam for a building insulation having a fire retardancy of 3.0 g / 100 cm 2 or less, a combustion time of 120 seconds or less, and a combustion length of 60 mm or less.
The method of claim 1, wherein the polyfunctional active hydrogen compound is a polyfunctional alcohol, a polyfunctional amine,
Wherein the polyfunctional alcohol is ethylene glycol, diethylene glycol, glycerin, trimethanolpropane, pentaerythritol, dipentaerythritol, alpha methyl glucoside, xylitol, sorbitol,
Wherein said polyfunctional amine is ethylene diamine, diethylenetriamine, triethanolamine, ortho-toluenediamine, diphenylmethanediamine, diethanolamine or a mixture thereof.
The method of claim 1, wherein the catalyst is selected from the group consisting of potassium hydroxide, sodium hydroxide, cesium hydroxide, dimethyllauamine, dimethylpolymethylamine, N, N-dimethyldodecane- Rigid polyurethane foam.
The rigid polyurethane foam of claim 1, wherein the alkylene oxide is ethylene oxide, propylene oxide or a mixture thereof.
The bio-polyol according to claim 1,
a) exchanging a natural oil with a polyfunctional active hydrogen-containing compound in the presence of a catalyst; And b) subjecting the product of the exchange reaction to an addition reaction with alkylene oxide.
[7] The method of claim 5, wherein the bio polyol further comprises c) removing the catalyst from the addition reaction product of the alkylene oxide compound,
Wherein the step c) is carried out in such a manner that a catalyst adsorbent and water are added, stirred, and then filtered.
The rigid polyurethane foam according to claim 1, wherein the bio polyol is contained in an amount of 10 to 60 parts by weight based on 100 parts by weight of the polyol.
The composition of claim 1, wherein the isocyanate has an isocyanate number in the range of 2.7 to 3.0, an NCO wt.% Value in the range of 25 to 35, an isocyanate index in the range of 90 to 160, and an architecture comprising polymeric MDI (diphenylmethane diisocyanate) Rigid polyurethane foam for insulation.
The rigid polyurethane foam according to claim 1, comprising 0.1 to 10 parts by weight of a urethane catalyst, 0.1 to 35 parts by weight of a blowing agent, and 0.1 to 5.0 parts by weight of a surfactant based on 100 parts by weight of the polyol.
The method of claim 1, wherein the rigid polyurethane foam has a viscosity (20 ° C) of 150 to 1,500 cps, a specific gravity (20 ° C) of 1.1 to 1.3, a cream time of 2 to 50 sec, FD) of 20 to 55 kg / m &lt; 3 &gt;.