KR20110064911A - Polyisocianurate foam comprising polyester-polyether hybrid polyol and a manufacturing method thereof - Google Patents

Abstract

PURPOSE: Polyester-polyether hybrid polyol is provided to form polyisocianurate foam with low viscosity of a resin premix and excellent adhesive force to a steel plate. CONSTITUTION: Polyester-polyether hybrid polyol includes 5-50 weight% of dicarboxylic acids, 5-50 weight% of diols, 5-50 weight% of polyfunctional poly(alkyleneoxide)polyols, and 0-5 weight% of polyfunctional compound. The polyfunctional compound is such that polyvalent poly(alkyleneoxide)polyols and polyfunctional compounds are bonded with ester compounds consisting of dicarboxylic acids and diols.

Description

POLYISOCIANURATE FOAM COMPRISING POLYESTER-POLYETHER HYBRID POLYOL AND A MANUFACTURING METHOD THEREOF

The present invention relates to a polyester-polyether hybrid polyol and a polyisocyanurate foam prepared using the same, and more particularly, to a thermosetting plastic foamed with a low viscosity polyester-ether hybrid polyol having chemically stable properties with a curing agent. Polyisocyanurate foam with excellent flame retardancy, heat resistance and low smokeability and its polyisocyanurate foam as foams are provided as intermediate materials for building panels.As a structural panel with excellent dimensional stability while increasing adhesive strength on the upper and lower surfaces It is about.

The present invention relates to a flame retardant insulation panel used as a material for insulation construction of various buildings, including refrigerated warehouses, industrial buildings, insulated houses, container boxes and ship interiors.

Polyisocyanurate foams used as internal insulation are generally prepared by reacting the polyol component in the presence of isocyanate components and blowing agents, catalysts, foam stabilizers and other additives. Conventionally, there has been a heat insulating material in which a flame retardant formed of a modified polyisocyanurate foam is filled between a surface material formed of a metal plate or the like, which generally has a high crosslinking density, but has a problem in that a heat insulating material made of a polyisocyanurate foam breaks.

Japanese Patent Publication No. 46-4591 discloses a method for producing a modified polyisocyanurate foam in which an organic polyisocyanate and a polyol are used as a heat insulating material using a trimerization catalyst and a carbodiimide catalyst in the presence of a blowing agent. Known.

Korean Patent No. 278,365 discloses a technique for a polyisocyanurate foam in which a polyol obtained by adding propylene oxide and ethylene oxide to polymeric MDI and terephthalic acid and a heat insulating material using the same are disclosed.

US 5164422 describes the use of isocyanate prepolymers with CFC-11 as blowing agent to improve the thermal insulation of foams.

EP 320134 describes the use of isocyanate prepolymers with R-11 as blowing agent to improve the compatibility of component A and component B.

Likewise, US 5254600 shows improved processability as a result of the use of isocyanate prepolymers.

Improved thermal conductivity of rigid foams as a result of the use of isocyanate prepolymers is given in EP 394736. JP 2000-264945 describes sandwich surfaces of good surfaces produced using isocyanate prepolymers.

WO 240566 describes the use of isocyanate prepolymers and the dynamics of rigid polyurethane and polyisocyanurate foams to improve flame retardancy.

However, this is only a method for overcoming the poor adhesion of the polyisocyanurate foam and the low miscibility of the ether polyol and the ester polyol, which is a disadvantage of the ester polyol system, and the low viscosity and excellent adhesion of the resin premix to be proposed in the present invention. There is a limit to granting

Accordingly, there is a continuing need for a new isocyanurate foam having a low viscosity of resin premix and excellent adhesion to an iron plate, and a polyol capable of manufacturing the same.

The problem to be solved by the present invention is to provide a method for producing a new polyester-ether hybrid polyol capable of forming an isocyanurate foam having a low viscosity of the resin premix and excellent adhesion to an iron plate.

Another problem to be solved by the present invention is to provide a novel polyester-ether hybrid polyol capable of forming an isocyanurate foam having a low viscosity of the resin premix and excellent adhesion to an iron plate.

Another problem to be solved in the present invention is to provide a resin premix having a low viscosity capable of producing isocyanurate foam.

Another problem to be solved by the present invention is to provide an isocyanurate foam having high adhesion.

In order to achieve the above object, the polyisocyanurate foam according to the present invention is 5-50% by weight of dicarboxylic acid, 5-50% by weight of diol, 5-50% by weight of polyhydric poly (alkylene oxide) polyol and A polyol comprising a polyester-ether hybrid polyol consisting of 0-5% by weight of a multifunctional compound is prepared by reacting with a polyisocyanate and a blowing agent.

In the present invention, the polyfunctional compound is prepared by combining a polyhydric poly (alkylene oxide) polyol and a polyfunctional compound with an ester compound consisting of dicarboxylic acid and diol. In the practice of the present invention, the ester compound has an acid value of 15-30 to sufficiently lower the viscosity of the resin premix, and an acid value of 1 or less after the polyvalent poly (alkylene oxide) polyol and the polyfunctional compound are combined. good.

In one aspect, the present invention is prepared by reacting a polyol comprising a polyester-ether hybrid polyol and a polyisocyanate together with a blowing agent, wherein the hybrid polyol is a dicarboxylic acid, a diol and a polyhydric poly (alkylene oxide) polyol. It consists of a polyisocyanurate foam, characterized in that it further comprises a multifunctional compound.

In another aspect, the present invention comprises a polyester-ether hybrid polyol for producing isocyanurate foam consisting of a dicarboxylic acid, a diol, a polyvalent poly (alkylene oxide) polyol, and a polyfunctional compound.

The present invention is to prepare a polyester-ether hybrid polyol, dicarboxylic acid, diol, and ether composition of the polyhydric poly (alkylene oxide) polyol in the final polyol composition by mixing a dicarboxylic acid content of 5 It is prepared by condensation reaction to ˜50 wt%.

Meanwhile, the polyester-ether hybrid polyol according to the present invention is prepared by condensation polymerization of a dicarboxylic acid component, a polyvalent poly (alkylene oxide) polyol, a diol, a polyfunctional compound, and the like, as the dicarboxylic acid component. For example, phthalic acid, naphthalene carboxylic acid, sodium dicarboxylic benzene sulfonic acid, adipic acid, suberic acid, sebacic acid, aliphatic cyclo 11 carboxylic acid, or a mixture thereof may be used, and polyhydric poly ( Alkylene oxide) polyols include, for example, ethylene oxide, propylene oxide, styrene oxide, butylene oxide and epichlorohydrin as alkylene oxides.

As the diol component, ethylene glycol, 1,2-propylene glycol, triethylene glycol, butanediol, neopentylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimentanol, diethylene glycol, 1,5- Pentanediol, polyethyleneglycol, etc. are mentioned.

The polyfunctional compound is a compound containing two or more active hydrogens, for example, trimethylolpropane, triglycidyl ether, trimethylolpropane, diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, Sorbitol polyglycidyl ethers such as sorbitol diglycidyl ether, triglycidyl ether, tetraglycidyl ether, triepoxypropyl isocyanurate, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl And compounds containing glycidyl ether ends, such as ether, polyethyleneglycol diglycidyl ether and the like. The polyfunctional compound including the glycidyl ether terminal is not only excellent in reactivity with the carboxyl terminal than the hydroxyl terminal, but also advantageous in terms of physical properties of the final polymer.

As the catalyst used in the present invention, tetraalkyl titanate may be used or mixed with magnesium or calcium acetate. In addition, Mg [HTi (OR) 5] 2 produced from an alcohol side compound of an alkali earth metal and an ester compound of titanate may be used. Titanate complexes such as titanium or inorganic titanate compounds such as titanium titanate, mixtures of calcium acetate and antimonytrioxide, lithium or magnesium acetate, organotin compounds, or mixtures of organotin compounds and organotitanium compounds Excellent performance as a catalyst.

The polyester-ether hybrid polyol prepared in the present invention is preferably impregnated with chemical crosslinking to improve thermal stability and mechanical properties.

In one embodiment of the invention, a trifunctional or higher poly (alkylene oxide) polyol can be obtained by an ester reaction or a polycondensation reaction with a bifunctional acid. In a preferred embodiment of the present invention, a polyfunctional poly (alkylene oxide) polyol is prepared by addition polymerization of an alkylene oxide and an organic compound having two or more active structures, wherein two or more active hydrogen atoms are present. Examples of the initial material to be mentioned are propylene glycol, glycerin, pentaerythritol, ethylenediamine and sorbitol. Examples of alkylene oxides include ethylene oxide, propylene oxide, styrene oxide, butylene oxide and epichlorohydrin. Etc.

In another embodiment of the present invention, the chemical crosslinking of the polyester-ether hybrid polyol has no chemical crosslinking point when a bifunctional ether and a bifunctional ester are used. By adding a multifunctional mixture having three or more functional groups capable of reacting, chemical crosslinking of the polyester-ether hybrid polyol can be induced to improve not only thermal stability but also mechanical properties of the final polymer.

In a preferred embodiment of the present invention, the polyfunctional compound as described above capable of inducing a chemical bond to the polyester-ether hybrid polyol is used at an amount of 0.1 to 5.0 wt% based on the acid component of the polyester-ether hybrid polyol. When the polyisocyanurate foam with improved thermal stability and mechanical properties can be prepared. In this case, when the polyfunctional compound is added in an amount of 0.1 wt% or less, it is impossible to prepare a polyisocyanurate foam in which desired thermal stability and physical properties are improved, and when using 5.0 wt% or more of polyester-ether, As the viscosity of the hybrid polyol rises rapidly, it is not preferable because the workability is very bad and the mechanical properties are degraded.

On the other hand, the polymerization of the polyester-ether hybrid polyol according to the present invention may be prepared using a conventional method of reacting by simultaneously adding a polymerization component, a catalyst, and a reaction aid including the multifunctional compound, but the present invention as follows. By using the production method according to the present invention, it is possible to prepare a polyester-ether hybrid polyol having low viscosity and more excellent compatibility.

According to the present invention, the dicarboxylic acid component and the diol are first added to the reaction flask, pressurized and reacted at a temperature of 190 ° C. for 4 hours, and then reacted by adding a reaction catalyst, and when the acid value is 20 or less, poly (alkylene) A polyfunctional compound having an acid value of 1 or less is synthesized by further adding a polyfunctional compound including an oxide) glycol and a glycidyl ether terminal. Using this method, the polyfunctional component reacts with the dicarboxylic acid to reduce the viscosity of the polyol, and due to trace chemical crosslinking, it is possible to prepare a polyester-ether hybrid polyol having excellent thermal stability and adhesion. Can be.

After the completion of the esterification or transesterification reaction as described above, the reaction tube was gradually heated to 200 to 220 ° C. by applying a vacuum to 0.7 mmHg or less gradually over about 1 hour to stop the reaction under moderate agitation. And then discharged to obtain a polyester-ether hybrid polyol.

In general, polyester polyols are very poor in flowability because they have a very high degree of crystallinity. However, the polyester-ether hybrid polyol according to the present invention has a very low crystallinity and a very low crystallinity and viscosity than the polyester polyol alone due to the high flowability of the polyether component. In addition, even when a small amount of chemical crosslinking is induced, the tendency of crystallinity and viscosity to rise is higher than that of the polyester polyol alone.

In addition, since the polyol structure has both a polyether portion and a polyester portion, compatibility with existing polyether polyols and polyester polyols is very excellent. Therefore, very good compatibility with existing polyether polyols or polyester polyols can be shown and used by mixing.

In the present invention, the hybrid polyol is preferably used as the main component of the polyol, and for example, 50 wt% or more, more preferably 60 wt% or more, and most preferably 80 wt% or more.

In the present invention, the polyol is a variety of known polyols, such as polyether polyol, polyester polyol, or mixtures thereof in order to supplement the dimensional stability, flame retardancy, or viscosity performance of the polyisocyanurate foam Polyols.

In the practice of the present invention, the polyetherpolyol may be prepared in a conventional manner to add alkylene oxides such as ethylene oxide or propyline oxide to the polyol, preferably obtained by adding propylene oxide to sorbitol or Ether polyols obtained by adding propylene oxide and ethylene oxide to the loose can be used, and commercially available from polyol manufacturers, for example, PPG-482 grade of Kumho Petrochemical.

In the practice of the present invention, the polyester polyol may be prepared in a conventional manner by adding diethylene glycol or propylene glycol to phthalic anhydride, and may be purchased commercially. Preferably, it is AK-3001 grade of Aekyung Chemical.

In a preferred embodiment of the invention, the polyol is a polyol comprising 5-50 parts by weight of polyol selected from 50-95% by weight of polyether-ester mixed polyol, polyetherpolyol, polyesterpolyol, or mixtures thereof, and Preferably it is a mixture of 80 weight part of polyether ester interpolyols and 20 weight part of polyether polyols.

In the present invention, in order to maintain the mechanical strength of the product of the polyol and the dimensional stability at low temperature, it is preferable to use a polyol having an average OH value of 150 to 300. If the average OH value of the polyol composition is 150 or less, the mechanical strength and low-temperature dimensional stability of the product is inferior, and if the average OH value exceeds 300, the flame retardancy and heat insulation are lowered, resulting in a failure of the product and productivity is lowered.

In the present invention, the polyisocyanate may be of any form such as aliphatic, aromatic, and mixtures thereof, but preferably includes urethane.

In more detail, the aliphatic polyisocyanate includes hexamethylene diisocyanate, dimethyl diisocyanate, isophorone diisocyanate, methylene biscyclohexyl isocyanate, methyl isocyanate, and the like, and the aromatic polyisocyanate is 2,4-toluene diisocyanate, 2 Diisocyanates such as, 6-toluene diisocyanate and methylene diphenyl diisocyanate, and aromatic isocyanates such as 4,4 ', 4-triphenylmethane triisocyanate and 2,4,6-tolylene triisocyanate. Preferably it is polymeric MDI.

In the present invention, the polyisocyanate component to be reacted with the polyol composition is a polymeric MDI having 2 or more functional groups and preferably 2.5 to 3.0. If the average number of functional groups of the isocyanate component is 2.5 or less, the dimensional stability is poor at the time of forming the polyisocyanurate foam, and if the number of the functional groups is 3.0 or more, the viscosity is greatly increased and fluidity is inferior. Therefore, the average number of functional groups of the isocyanate component is preferably 2.5 to 3.0 for producing a stable polyisocyanurate foam.

In the present invention, the isocyanate component preferably has an average NCO% of 29 to 32%. At this time, fluidity | liquidity falls that the average NCO% of the said isocyanate component is 29% or less, and low temperature dimensional stability falls when it is 32% or more. Therefore, the average NCO% of the isocyanate component is preferably 29 to 32 for producing a stable polyisocyanurate foam.

The reaction ratio of the polyisocyanate component and the polyol component should have an equivalent ratio of polyisocyanate and polyol of 1: 2.0 to 1: 4.0. The equivalent ratio of 1: 2.0 means that the NCO of the polymeric MDI is 200% of the OH component in the polyol system.As the average NCO% is lower, the adhesion and the compressive strength increase to a certain range, but the polyisocyanurate foam is unique. The flame retardancy of the resin is reduced, and the higher the average NCO%, the higher the polyisocyanurate synthesis, the more the foam is brittle, the low temperature dimensional stability is lowered, and the adhesive strength with the iron plate is reduced. It is preferable to adjust to 1: 4.0.

In the present invention, the polyol is mixed with a catalyst, foam stabilizer, flame retardant or other additives, for example, a nucleating agent or a surfactant to form a resin solution, blended with a polyisocyanate component, foamed with a foaming agent, and adhesive performance and flame retardancy It is made from this excellent polyisocyanurate foam.

In the present invention, the resin stock solution may include a flame retardant for the flame retardancy of the final product. The flame retardant may be a non-halogen type, a halogen type, a mineral type, or the like. Preferably, a phosphorus flame retardant, a bromine flame retardant, or a mixture thereof is suitable. In particular, it is preferable to use phosphorus-based flame retardants because phosphorus-based flame retardants containing phosphorus compounds are less harmful to the human body, have excellent environmental friendliness and have high flame retardant efficiency.

In the case of the polyisocyanurate foam, the phosphorus-based flame retardant functions to prevent the conversion of the combustible material into a gas in a combustible state because the phosphorus-based compound increases the carbon yield.

Inorganic phosphorus flame retardants include tricresyl phosphate, ammonium phosphate, ammonium poly phosphate, and the like, and organophosphorous flame retardants include melamine phosphate, dimelamine phosphate, triethylene phosphate, and the like, and halogen phosphate includes bromine phosphate. In comparison to other flame retardants, phosphorus-based flame retardants are generally known to be harmless or exhibit only slight toxicity.

The brominated based flame retardants include tribromer neopentyl alcohol, dibromer neopentyl glycol, decabromer diphenyloxide, penta bromer diphenyl oxide, and the like, and liquid brominated is particularly preferable. Do.

As for the flame retardant total amount used for this invention, 1-40 weight part is preferable with respect to 100 weight part of polyol components, More preferably, it is 5-25 weight part. If the amount is less than 1 part by weight, the flame retardant effect of the addition of the flame retardant is insignificant. If it is more than 40 parts by weight, the flame retardant effect of the flame retardant is not observed. Deformation, flowability, processability, and the like have a problem of deterioration. Therefore, it is preferable that it is 5-40 weight part of phosphorus flame retardants, a bromine flame retardant, or the mixture of a phosphorus flame retardant and a bromine flame retardant with respect to 100 weight part of polyol and polyisocyanate mixtures.

In addition, the reaction catalyst used in the present invention is a typical catalyst that can be used to obtain a polyisocyanurate foam, for example triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexa Decyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, diethanolamine, dimethylethanolamine, triethanolamine, N-methyldiethanolamine, N, N-dimethyl Ethanolamine, diethylenetriamine, N, N, N ', N'-tetramethylbutanediamine, N, N, N', N'-tetramethyl-1.3-butanediamine, N, N, N ', N' Tetraethylhexamethylenediamine, bis [2- (N, N-dimethylamino) ethyl] ether, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N, N ', N', N-pentamethyldiethylenetriamine, triethylenediamine, formic acid and other salts of triethylenediamine, amino groups and oxyalkylene adducts of the first and second amines, Amine-type urethanization catalysts, such as azacyclic compounds, such as N, N- dialkyl piperazine, and the aminocarbonyl catalyst of various N, N ', N "-trialkylaminoalkylhexahydrotriazines.

In particular, the isocyanate trimerization catalyst used in the present invention is a hydroxy alkyl ammonium compound, 1,3,5-tris (N, N-dimethylaminopropyl) -S-triazine, 2,4,6-tris (dimethyl amino Amines such as methyl) phenol, and aliphatic monocarboxylic acid alkali metal salts.

Tertiary amine catalysts include dimethylcyclohexylamine (DMCHA), dimethylethanol amine (DMEA), pentamethyldiethylenetriamine (PMDETA), tetramethylhexamethylenediamine (TMHMDA), and the like.

The catalyst controls the trimer primary and secondary reactions and affects the productivity, processability, and polyisocyanurate conversion of the polyisocyanurate, in particular by mixing the trimerization catalyst with the tertiary amine catalyst. It is desirable to.

These catalysts are used individually or in mixture, The usage-amount is preferable 0.5-10 weight part with respect to 100 weight part of polyol components, More preferably, it is 1-5 weight part. When the total weight of the tertiary amine catalyst, trimerization catalyst or mixture of tertiary amine catalyst and trimerization catalyst is less than 0.5 parts by weight, there is a problem that the rate of the trimerization reaction is slowed. Accelerated effect of the reaction rate is not seen, and because of the cost burden problem is preferably 0.5 to 10 parts by weight.

As the foam stabilizer, a polyalkylene glycol silicone copolymer is used as the organic silicone compound generally used in polyurethane foam production. The amount of foam stabilizer to be used is preferably 0.5 to 5.0 parts by weight, more preferably 1.5 to 3.0 parts by weight based on 100 parts by weight of the polyol component.

The blowing agent includes trichloromonofluoromethane or dichloromonofluoroethane, which is a fluorocarbon blowing agent. Blowing agent affects the density of the density is to be a molding density according to the 3809 rules KMS 35kg / m ³ or more. The total amount of the blowing agent to be used is preferably 5 to 50 parts by weight, more preferably 5 to 40 parts by weight based on 100 parts by weight of the polyol component. When it is 5 parts by weight or less with respect to 100 parts by weight, there is a problem that foaming is difficult, and when it is 40 parts by weight or more, there is a problem that adversely affect the physical properties of the foam such as thickness strain, compressive strength, 5 to 50 parts by weight desirable.

In addition, a nucleating agent may be used to make the size of the cell fine for the purpose of improving the thermal insulation of the polyisocyanurate foam of the present invention. Nucleating agents used in the present invention include perfluorocarbons, titanium oxide, titanium oxide compounds, carbon black and the like. When using a nucleating agent, the usage-amount is 0-10 weight part with respect to 100 weight part of polyol components, More preferably, it is 0-5 weight part. Here, that the amount of nucleating agent is 0 parts by weight with respect to 100 parts by weight of the polyol component indicates that the nucleating agent is not used.

In one aspect, the polyisocyanurate foam obtained by the present invention has a density of 30-50 kg / m 3, a thermal conductivity of 0.0180 kcal / m · hr · ° C. or less, an independent bubble ratio of 90% or more, and low temperature dimensional stability at −40 ° C. -0.1%, room temperature adhesive strength of more than 5kg / ㎠ shows excellent mechanical properties.

The inner plate and the outer plate of the present invention include a zinc iron plate, aluminum plate, colored zinc iron plate, color aluminum zinc alloy plated steel sheet, stainless steel plate, titanium steel plate and the like. The thickness of the steel sheet will be readily determined by one skilled in the art and will vary depending on the use of the panel, but is preferably 0.5 mm.

When the polyisocyanurate foam is prepared from the polyester-ether hybrid polyol in the present invention, it is possible to manufacture a polyisocyanurate insulation panel having a low viscosity of the resin premix and excellent adhesion to an iron plate.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are only intended to illustrate specific embodiments, and the scope of the present invention is not limited by the examples, and therefore should not be construed as limiting the protection scope.

Hereinafter, the present invention will be described in detail with reference to Examples.

* Preparation of polyester-ether hybrid polyols

[ Preparation Example 1 . Polyester-ether hybrid polyol (A)]

Condensation polymerization was carried out by adding a mixture of 690.1 g of phthalic anhydride, 600 g of diethylene glycol, and 0.5 g of tetrabutyl titanate to the reaction flask, and then raising the reaction temperature to 170 to 230 ° C. under nitrogen of 5 mm flow. When the acid value is 20, 359 g of polypropylene glycol (Mw: 230, functional group; 3) and 134.6 g of diethylene glycol are added and reacted. The synthesized polyol has a hydroxyl value of 200, an acid value of 0.7, a viscosity of 3,600 cps / 25 ° C (PA / DEG OHV = 200, viscosity = 25,000 cps / 25 ° C), a water content of 0.02%, and a light yellow transparent liquid.

[ Preparation Example 2 . Polyester-ether hybrid polyol (B)]

Condensation polymerization was carried out by adding a mixture of 600.1 g of phthalic anhydride, 600 g of diethylene glycol and 0.5 g of tetrabutyl titanate to the reaction flask, and then raising the reaction temperature to 170-230 ° C. under 5 mm flow of nitrogen. When the acid value is 20, 359 g of polypropylene glycol (Mw: 230, functional group; 3), 134.6 g of diethylene glycol, and 58 g of pentaerythritol are added and reacted. The synthesized polyol has a hydroxyl value of 200, an acid value of 0.7, a viscosity of 7,800 cps / 25 ° C (PA / DEG OHV = 200, viscosity = 25,000 cps / 25 ° C), a water content of 0.02%, and an appearance of a pale yellow transparent liquid.

"Part" and "%" are by weight unless there is particular notice in an Example and a comparative example below.

[ Example  One]

Polyol 20 prepared by condensation of diethylene glycol with adipic acid and terephthalic acid having an average OH value of 450 to 550 and a molecular weight of 700 sorbitol added to a polyol added with propylene oxide and an average OH value of 200 to 250 1 part by weight of water, trichloromono as a blowing agent, in 100 parts by weight of a mixed polyol component consisting of 60% by weight of a polyester-ether mixed polyol having a molecular weight of 600 by an average OH value of 200% prepared by Production Example 1 30 parts by weight of fluoromethane, 3 parts by weight of ammonium salt as trimerization catalyst and 1 part by weight of tertiary amine catalyst, 20 parts by weight of tricresyl phosphate as phosphorus flame retardant and 10 parts by weight of tribromer neopentyl alcohol as bromine-based flame retardant, average here Using 150 parts by weight of polymeric MDI (M-200, Kumho Mitsui Co., Ltd.) with 31% NCO% and 2.7 functional groups, it is discharged to the lower surface of the panel in the molding facility and foamed up to the upper surface. While the polyisocyanurate foam of the present invention was produced, the foam was compression molded to an internal density of 45 kg / m 3 to a 0.5 mm thick stainless steel sheet, and a 50 mm thick polyisocyanurate sandwich panel having a rear plate. Manufactured.

[ Example  2]

Polyol 20 prepared by condensation of diethylene glycol with adipic acid and terephthalic acid having an average OH value of 450 to 550 and a molecular weight of 700 sorbitol added to a polyol added with propylene oxide and an average OH value of 200 to 250 1 part by weight of water and trichloromono as a blowing agent in 100 parts by weight of a mixed polyol component consisting of 60% by weight of a polyester-ether mixed polyol having a molecular weight of 600 by an average OH value of 200% prepared by Production Example 2 30 parts by weight of fluoromethane, 3 parts by weight of ammonium salt as trimerization catalyst and 1 part by weight of tertiary amine catalyst, 20 parts by weight of tricresyl phosphate as phosphorus flame retardant and 10 parts by weight of tribromer neopentyl alcohol as bromine-based flame retardant, average here Using 150 parts by weight of polymer MDI (M-200, Kumho Mitsui Co., Ltd.) with 31% NCO% and 2.7 functional groups, it is discharged to the lower surface of the panel in the molding facility and foamed up to the upper surface. While the polyisocyanurate foam of the present invention was produced, the foam was compression molded to an internal density of 45 kg / m 3 to a 0.5 mm thick stainless steel sheet, and a 50 mm thick polyisocyanurate sandwich panel having a rear plate. Manufactured.

[ Example  3]

10 weight percent polyol with propylene oxide added to sucrose with an average OH value of 350 to 450, molecular weight 700, 10 weight polyol with propylene oxide added to a sorbitol having an average OH value of 350 to 450 and molecular weight of 600 %, 20% by weight of a polyol prepared by condensing diethylene glycol to adipic acid and terephthalic acid having an average OH value of 200 to 250, and a poly having an average OH value of 200 according to Production Example 1 and a molecular weight of 600. 100 parts by weight of a mixed polyol component consisting of 20% by weight of a polyol prepared by condensation of diethylene glycol on phthalic anhydride having 40% by weight of an ester-ether mixed polyol and an average OH value of 250 to 350, and 1 part by weight of water and triclo 30 parts by weight of lomonofluoromethane, 3 parts by weight of ammonium salt as trimerization catalyst and 1 part by weight of tertiary amine catalyst, 15 parts by weight of tricresyl phosphate as phosphorus flame retardant, where the average NCO% is 31% and the number of functional groups Using 200 parts by weight of the polymeric MDI (M-200 Kumho Mitsui Co., Ltd.) of 2.7 was discharged to the lower surface of the panel in the molding facility, the polyisocyanurate foam of the present invention was produced while being foamed and filled to the upper surface. The foam was compression molded to an internal density of 45 kg / m 3 to prepare a polyisocyanurate sandwich panel having a thickness of 50 mm in which front and rear plates were formed of a stainless steel plate having a thickness of 0.5 mm.

[ Comparative example  One]

20 weight percent polyol with propylene oxide added to sucrose with an average OH value of 350 to 450, molecular weight 700, 10 weight polyol with propylene oxide added to sorbitol with an average OH value of 450 to 550 %, 60% by weight of polyol prepared by condensing diethylene glycol to adipic acid and terephthalic acid having an average OH value of 200 to 250, and prepared by condensing diethylene glycol to phthalic anhydride having an average OH value of 250 to 350 100 parts by weight of a mixed polyol component consisting of 10% by weight of polyol, 1 part by weight of water as a blowing agent, 30 parts by weight of trichloromonofluoromethane, 3 parts by weight of ammonium salt as a trimerization catalyst and 1 part by weight of tertiary amine catalyst, and tricre as a phosphorus flame retardant. 20 parts by weight of seal phosphate, 31 parts by weight of average NCO%, and 250 parts by weight of polymeric MDI (M-200, Kumho Mitsui Co., Ltd.) having a functional number of 2.7 are discharged to the bottom surface of the panel in the molding facility. The polyisocyanurate foam of the present invention was produced by filling the foam to the top surface, and the foam was compression molded to an internal density of 45 kg / m 3, and then the front and rear plates were made of a stainless steel sheet having a thickness of 0.5 mm. A sociaurate sandwich panel was prepared.

[ Comparative example  2]

10 weight percent polyol with propylene oxide added to sucrose with an average OH value of 350 to 450, and molecular weight 700, 20 weight polyol with propylene oxide added to a sorbitol having an average OH value of 350 to 450 and molecular weight of 600 %, 60% by weight of polyol prepared by condensing diethylene glycol to adipic acid and terephthalic acid having an average OH value of 200 to 250, and prepared by condensing diethylene glycol to phthalic anhydride having an average OH value of 250 to 350 100 parts by weight of a mixed polyol component consisting of 10% by weight of polyol, 1 part by weight of water as a blowing agent, 30 parts by weight of trichloromonofluoromethane, 3 parts by weight of ammonium salt as trimerization catalyst, 1 part by weight of tertiary amine catalyst, and tricre as a phosphorus flame retardant. 20 parts by weight of sil phosphate and 0 parts by weight of tribromer neopentyl alcohol as a bromine-based flame retardant, and an average NCO% of 31% and a polymer MDI (M-200 of Kumho Mitsui Co., Ltd.) having a functional group of 2.7 Part is discharged to the bottom surface of the panel in the molding facility, the polyisocyanurate foam of the present invention was produced while being filled and foamed up to the top surface, the foam is compression molded to an internal density of 45kg / ㎥ and a stainless steel of 0.5mm thickness A polyisocyanurate sandwich panel having a thickness of 50 mm having a front plate and a back plate was manufactured.

Comparative Example 3

Polyol 60 prepared by condensing diethylene glycol to adipic acid and terephthalic acid having an average OH value of 350 to 450, a molecular weight of 600, a polyol added with propylene oxide to sorbitol, and an average OH value of 200 to 250. 100 parts by weight of a mixed polyol component consisting of 10% by weight of a polyol prepared by condensing diethylene glycol on phthalic anhydride having a weight% and an average OH value of 250 to 350, and 1 part by weight of water as a blowing agent and 30 parts by weight of trichloromonofluoromethane Parts, 3 parts by weight of ammonium salt as trimerization catalyst and 1 part by weight of tertiary amine catalyst, 20 parts by weight of tricresyl phosphate as phosphorus flame retardant and 0 parts by weight of tribromer neopentyl alcohol as bromine-based flame retardant, with an average NCO% of 31 % By using 250 parts by weight of polymeric MDI (M-200 Kumho Mitsui Co., Ltd.) having a functional number of 2.7 and discharged to the lower surface of the panel in the molding facility, The polyisocyanurate foam of the invention was produced, and the foam was compression molded to an internal density of 45 kg / m 3 to prepare a polyisocyanurate sandwich panel having a thickness of 50 mm, in which a front plate and a back plate were made of a stainless steel plate having a thickness of 0.5 mm. .

Test Methods:

[Adhesion test method] KSM-3718

[Dimensional Stability Test Method] ASTM D2126-99

[Flame retardancy test method] KSF-2271 flame retardant class 3

TABLE 1

As can be seen above, the polyisocyanurate foam building panel using the polyester-ether hybrid polyol used in the polyisocyanurate sandwich panel of Examples 1 to 3 of the present invention is a general poly of the comparative example under the same internal density. Compared to polyisocyanurate building panels using ether polyols and polyester polyols, the resin premix had a lower viscosity and excellent adhesion, and in terms of flame retardancy, the polyisocyanurate foam building panels of the present invention were used through Examples 1 to 3. Passed the KSF-2271 flame retardant class 3, which is a method for testing the flame retardancy of interior materials and structures of buildings, and is a polyisocyanurate foam building panel using the polyester-ether polyol of the present invention. Proved to be excellent and Examples 1 to 3 The conventional polyisocyanurate foam used for the polyisocyanurate building panel using the general polyether polyol and polyester polyol, which are comparative examples, was found to have high viscosity of resin premix and problems in adhesion. It became.

Claims (10)

Polyester-ether hybrid polyol consisting of 5-50% by weight of dicarboxylic acid, 5-50% by weight of diol, 5-50% by weight of polyvalent poly (alkylene oxide) polyol and 0-5% by weight of polyfunctional compound. The polyester-ether hybrid polyol according to claim 1, wherein the polyfunctional compound is a polyhydric poly (alkylene oxide) polyol and a polyfunctional compound bonded to an ester compound consisting of dicarboxylic acid and diol. The polyester-ether hybrid polyol according to claim 1 or 2, wherein the polyfunctional compound is a compound in which glycidyl ether is formed at the terminal. The polyester-ether hybrid polyol of claim 2, wherein the ester compound has an acid value of 15-30. A polyester-ether hybrid polyol in which a polyhydric poly (alkylene oxide) polyol and a polyfunctional compound react with an ester compound consisting of dicarboxylic acid and diol. 6. The polyester-ether hybrid polyol according to claim 5, wherein the ester compound has an acid value of 15-30 and an acid value of the hybrid polyol is less than one. Prepared by reacting a polyol comprising a polyester-ether hybrid polyol with a polyisocyanate together with a blowing agent, Wherein said hybrid polyol is made of dicarboxylic acid, diol and polyvalent poly (alkylene oxide) polyol, and optionally further comprises a polyfunctional compound. The polyisocyanurate foam according to claim 7, wherein the hybrid polyol is prepared by reacting a polyester composed of dicarboxylic acid and diol with a polyhydric poly (alkylene oxide) polyol and a polyfunctional compound. 8. The polyisocyanurate foam according to claim 7, wherein the polyether-ester hybrid polyol in the polyol is a main component. Thermal insulation panel comprising a polyisocyanurate foam according to any one of claims 7 to 9.