KR100830148B1 - Polyurethane block foam, polyurethane board using recycling polyurethane block foam and manufacturing thereof - Google Patents

Abstract

A recycled polyurethane block foam, a polyurethane board using the same and a manufacturing method thereof are provided to improve usage of waste polyurethane and to manufacture an inexpensive high-quality product by utilizing improved recyclate polyol to fill an empty space between the wastes. A manufacturing method of a polyurethane board comprises the steps of: throwing waste polyurethane as a disused shape in a mold without a treating process like pulverizing; pouring a mixture of resin premix(a first solution) and isocyanate compound(a second solution) at a weight ratio of 1: 1~2 in the mold, to fill an empty space between the wastes; foaming and hardening the mixture, manufacturing a block foam whose empty space between the wastes is filled, and taking out from the mold; maturing at a room temperature; and cutting the polyurethane block foam to the thickness desired by a user using a skiving machine. The resin premix is made by mixing an additive to a mixture of improved recyclate polyol and pure polyol. The improved polyol is made by esterifying at high pressure vacuum of recyclate polyol glycolysis using waste polyurethane foam and glycol, added with more than one among adipic acid, adipic salt, adipic ester, and dioctyl adipate.

Description

Waste Polyurethane Block Foam, Polyurethane Board Using the Same and Manufacturing Method Thereof {POLYURETHANE BLOCK FOAM, POLYURETHANE BOARD USING RECYCLING POLYURETHANE BLOCK FOAM AND MANUFACTURING THEREOF}

The present invention relates to a polyurethane board manufacturing technology of a new method that combines the physical recycling technology and chemical recycling technology of polyurethane waste, and through the present invention to process a large amount of waste polyurethane waste and productivity through a simple process The present invention relates to the development of polyurethane boards that secure the marketability and economic feasibility using polyurethane waste.

Hereinafter, in the present invention, the regenerated polyol means a polyol prepared by depolymerization of waste polyurethane waste.

Polyurethane waste is released in various forms. In particular, since polyurethane is capable of a wide range of physical properties, ranging from the properties of rubber elastomers to very hard properties such as artificial wood, among various polymers, there are also various applications, and various physical wastes are emitted therefrom. Of these, the highest emissions and the most difficult for waste disposal are rigid polyurethane foams used as insulation. Rigid polyurethane foams used as insulation are very widely used in refrigerators, building panels, district heating coolers, LNG ships and storage tanks, and other thermal insulation materials. Polyurethanes are often produced by users reacting directly on site, and reactions are sensitive, resulting in high defect rates, resulting in a large amount of waste discharged from related industries. In addition, most polyurethanes are thermosetting polymers, which have been difficult to recycle.

Many studies have been conducted due to such an urgent problem. For example, in Korean Patent Laid-Open Publication No. 2001-0008243, the waste foamed urethane was pulverized to a predetermined size of 10 mm or less, and then mixed for about 1 minute using an adhesive in a hopper. The obtained mixture is put into a preheated mold at 55 to 60 ° C., and then compressed to a press pressure of about 50 kg / cm 2 G or less, and then demolded to describe a method for making a desired building material. Korean Patent Publication No. 1996-0040602 The waste polyurethane is crushed to a size of 5 mm or less, and per 100 wt% of the waste polyurethane pulverized by the above crushing process, 8 to 5 wt% of the polyurethane stock solution, 4 to 1 wt% of the curing agent, and a liquefaction freon are mixed. A mixing process and a molding process of filling the jig with the mixed waste polyurethane mixed by the mixing process, and filling the mixed waste polyurethane by 50 to 30% of the total volume of the jig; The mixed waste polyurethane filled in the jig by the molding process is heat treated with dry heating air at 30-40 ℃, and then expanded to 200 ~ 300% of the volume of waste polyurethane injected into the jig and then cooled at 10 ~ 30 ℃. A method for producing a heat insulating material using waste polyurethane as a raw material is described. The publication No. 2003-0055420 discloses waste polyurethane obtained by grinding waste polyurethane into a particle size of 1-5 mm powder. The mixture was added to a mixing tank so as to be regenerated by the filling method, followed by mixing and stirring the polypropylene glycol in a volume ratio of 1: 1. Then, methyl diisocyanate was added thereto in a ratio of weight ratio of 1: 1 with respect to the polypropylene glycol. Waste polyure produced by filling and stirring to make foaming, and injecting it into molding mold Although a technique for making a urethane board for building panels using the same has been disclosed, all of the conventional techniques include a process of pulverizing the waste polyurethane into a powder form, resulting in inferior workability due to a large amount of dust during the crushing operation, and required in the recycling process. There is a problem that the processing cost is high as a facility for establishing the condition, there is a problem that the amount of the produced polyurethane is limited because the form of the product to be made is limited.

In addition, Korean Patent Publication No. 10-2005-0078165 discloses one or more selected from mesh type paper, gypsum board, ocher panel or iron plate on one or both sides of a foamed urethane board made by reacting isocyanate and polyol with waste urethane chips cut to a suitable size. The present invention relates to a laminated urethane foam for building materials, in which the general pure resin premix is applied to a board, and thus, due to the waste urethane chip when forming a block foam, flowability is reduced and pores are largely formed, resulting in poor thermal insulation.

The present invention has been made in accordance with the technical request, the object of the present invention is to put the recycled polyol and pure polyol and additives modified by the secondary reaction to 10 to 80% by weight in the mold in the form of the discharge of polyurethane waste The mixed resin premix and polymethylenediphenylisocyanate (MDI) are mixed in a 1: 1 to 2 weight ratio and injected into the mold to foam new polyurethane between the polyurethane waste in the mold to provide a new polyurethane block foam that fills the voids. I would like to. In particular, the present invention provides a new polyurethane block foam that can lower the manufacturing cost and increase the amount of waste by using recycled polyol that recycles polyurethane waste as well as using polyurethane waste to lower the manufacturing cost. I would like to.

In addition, the present invention, when using a recycled polyol using depolymerization, which is a general chemical regeneration method, the reactivity is not controlled in the production of polyurethane block foam because the reactivity is not controlled when the polyurethane foaming due to residual glycol in the polyol is not suitable for the production of recycled polyol Modified regeneration to adjust the OH value of the regenerated polyol to 75 to 120 mgKOH / g by carrying out a second high pressure esterification reaction using adipic acid in a molar ratio of 1: 0.5 to 0.8 to remove residual glycol. It is intended to provide a method for producing a polyurethane block foam having a polyol to increase heat insulation and strength, and excellent adhesiveness and filling with waste.

In addition, the present invention is to manufacture the polyurethane board by skiving the polyurethane block foam, according to the characteristics of the polyurethane board required asbestos, plywood, paper, iron plate, gypsum board on one or both sides of the skied polyurethane board It is an object of the present invention to provide a polyurethane board having a brick or the like attached thereto.

The present invention for achieving the above object relates to a polyurethane board manufacturing technology of a new method that combines the physical recycling technology and chemical recycling technology of the polyurethane waste, as it is discharged without processing such as grinding the polyurethane waste The present invention relates to a new polyurethane block foam and a method for producing the same, which increase the amount of waste used by recycling waste physically and chemically by using recycled polyol using waste.

In particular, the present invention is to put the polyurethane waste into the mold as it is discharged without processing such as pulverization, the empty space between the waste is to fill by filling with a mixture of the resin premix and isocyanate compound using recycled polyol In particular, the flowability of the resin premix is important to completely fill the void space, and sufficient strength must be expressed so that shrinkage does not occur even after the void space is filled, and in order to be used as a board, it must be excellent in thermal insulation.

Therefore, the present invention used a resin premix using a recycled polyol to achieve this, in particular, in order to improve the flowability of the recycled polyol and adhesion with waste to prepare and use a second modified modified polyol by using adipic acid. Reached.

That is, the present invention can produce a block foam in which the wastes are bonded while filling with a mixture of a resin premix and an isocyanate compound using a modified regenerated polyol and foaming, and shrinkage does not occur. It was also confirmed that the empty spaces between the wastes were filled.

Therefore, the polyurethane block foam prepared according to the present invention can recycle waste in large quantities, and can be used as it is in the form of uncrushed waste, thereby reducing the manufacturing cost, and also in the resin premix for filling the voids of the waste. In addition, the use of modified regenerated polyols not only reduces manufacturing costs but also increases the amount of waste recycled compared to using pure polyols. Polyurethane blocks having excellent flame retardancy, heat insulation and strength due to aromatic groups present in the regenerated polyols Can provide form

Although not limited in the present invention, it is preferable to use a mold having a width of 2 to 3 m, a length of 1 to 2 m, and a height of 0.1 to 1 m. Provide urethane block foam. However, the mold is not limited to the above range and it will be apparent to those skilled in the art that the mold can be easily changed and used. However, the present invention requires a mold size that can be used without grinding the polyurethane waste. In addition, it is important to select and use a resin premix so that the heat of foam can be controlled in a mold of this size.

More specifically, the present invention

A) injecting the polyurethane waste into the mold as it is discharged without processing such as grinding;

B) In order to fill the empty space between the wastes, a resin premix (first liquid) and an isocyanate compound (second liquid) in which an additive is added to a mixed polyol component in which a modified regenerated polyol and a pure polyol are mixed are mixed. Injecting into the mold;

C) demolding after foaming and curing of the mixture;

D) aging at room temperature;

Characterized in that it comprises a.

The reason for the aging step in the present invention is to ensure that the latent heat inside the block foam is completely removed so that the shrinkage of the block foam does not occur, and if this process is not performed, adhesion to the waste is not good and cracks are generated in the block. Or shrinkage may occur.

In addition, in the present invention, the polyurethane block foam can be manufactured by cutting the foam using a skiving machine, and the skiving machine has an effect of cutting the foam to have a predetermined cross section according to a desired thickness. An example of such skiving is WINTECH's FAST-WIRE CONTOUR CUTTER.

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

In the present invention, the mold is a box-type mold having a cover that is open at the top and opened and closed by a hinge portion, and the size thereof is not limited, but in the present invention, it is possible to use the polyurethane without being crushed. The dimension of the mold produced and used 2.4 m (width) x 1.2 m (length) x 0.6 m (height). According to the present invention, after the mold is demoulded, the form of the foam is manufactured in the form of a block, and the user can use it by cutting it to a desired thickness. Thus, a manufacturing process such as using multiple layers of boards by using an adhesive is used. Without the cutting, such as skiving can be produced by cutting the board as needed to adjust the thickness.

In the present invention, the polyurethane waste is discharged from waste refrigerators, LNG vessels, etc. It is possible to put up to 10 ~ 80% by mold volume ratio in the mold as it is without going through the waste pretreatment process and the crushing process to discharge the polyurethane waste when discarded. Do.

After filling the mold with the waste, the voids are filled by foaming a new polyurethane foam, which is controlled by controlling the reaction rate of the cream time and the gel time when the polyurethane foam has flowability and the foam starts to swell. It is possible to prepare a resin premix having excellent properties, and the present invention is to reformate the regenerated polyol to achieve this.

In the present invention, the regenerated polyol is depolymerized using waste polyurethane and glycol, which can be prepared by a known method. Recycled polyols have excellent thermal insulation and strength because of “The Effects of Recyclate Polyols on Polyurethane Foam Properties”, J. There is a previous study in Cellular Plastics, 34 (March), pp111-123, because the structure of the regenerated polyol has a structure that is well mixed with polyisocyanate (MDI). When foamed by mixing polyurethane, the cell size of the foam becomes more fine, which improves the insulation and strength.

However, since the residual glycol remains in the regenerated polyol, the reaction is relatively quick, which is not suitable for block resin premixes in which flowability and reactivity are important as in the present invention. Therefore, in the present invention, the flowability and reactivity were controlled by applying the recycled polyol in which the recycled polyol was secondarily reacted to remove residual glycol.

The present invention relates to one or more selected from adipic acid, adipic acid salt, adipic acid ester, adipic acid dioctyl with respect to the depolymerized regenerated polyol in the range of 1: 0.5 to 0.8 mol. After the addition, the esterification reaction under high pressure vacuum reaction for 3 to 12 hours at 150 to 250 ℃. At this time, when any one or more selected from adipic acid, adipic acid salt, adipic acid ester, and adipic acid dioctyl is used in less than 0.5 molar ratio, the residual glycol content increases, so that the reactivity is increased 0.8. In the case of using more than mole, since the viscosity is high and it is not suitable to use, it is preferable to use it in the said range.

More specifically, the waste polyurethane foam used to prepare the recycled polyol in the present invention can be used as long as it is a waste hard polyurethane without limitation, and the waste polyurethane foam used to manufacture the recycled polyol is used finely ground It is desirable to. It is preferable to use 15 to 100 parts by weight of glycol with respect to 100 parts by weight of the waste hard polyurethane foam powder pulverized in the depolymerization step. If the OH value of the regenerated polyol produced outside the above range is too high or low, it is difficult to apply to the resin premix which is a raw material for synthesizing polyurethane foam.

The glycol used in the depolymerization is ethylene glycol, diethylene glycol, 1,2-propane diol, 1,3-propane diol, dipropylene glycol, 1,4-butane diol, 1,3-butane diol, 1,2 -Butane diol, neopentyl glycol, 1,5-pentanediol, hexylene glycol, bisphenol A, 2,2-di (4-hydroxypropoxyphenyl) propane, 2,2-di (4-hydroxyethoxy Preference is given to using one or more selected from trivalent or higher glycols such as dihydric glycols such as phenyl) propane, glycerin, trihydroxy methylpropane, trimethylol ethane, pentaerythritol and the like.

The depolymerization catalyst used in the depolymerization step of the present invention is a zinc acid catalyst such as zinc chloride, iron chloride, aluminum chloride, mercury chloride, acetic acid, formic acid, propionic acid, butyric acid, carboxylic acid such as benzoic acid, magnesium acetic acid, lead acetic acid, calcium Preference is given to using at least one selected from the group consisting of inorganic acetates such as acetic acid, potassium acetic acid, zinc acetic acid, sodium acetic acid, phosphorus acetic acid and the like and alkali catalysts such as sodium carbonate, sodium bicarbonate, calcium hydroxide, potassium hydroxide or sodium hydroxide, It is preferable to use 0.1 to 10 parts by weight based on the polyurethane foam content. If the amount is less than 0.1 part by weight, the reaction time is long, and even if it is used more than 10 parts by weight, no special effect on the reaction can be expected.

The depolymerization reaction is generally reacted at 120 to 250 ° C. for 30 minutes to 15 hours.

Next, in order to remove residual glycol produced in the depolymerization step, adipic acid and its derivatives are added to perform esterification. If the amount of anhydrous compound is used more than 0.8 mole, the viscosity becomes high at room temperature, and when used less than 0.5 mole, the reactivity is faster due to the influence of residual glycol.

The reaction temperature of the esterification reaction is 150 to 250 ℃ and for 3 to 12 hours it is preferable to perform a vacuum reaction under 600 ~ 800kg / ㎠ pressure.

In addition, the polymerization catalyst used in the esterification reaction of the present invention is tin octylate, monobutyltin triacetate, monobutyltin monooctylate, monobutyltin monoacetate, monobutyltin maleate, dibutyltin diacetate, dibutyl Organic tin compounds such as tin dioctanoate, dibutyltin distearate, dibutyltin dilaurate and dibutyltin maleate, organic titanium compounds such as tetraisopropyl titanate and tetra-n-butyl titanate, and It is preferable to use at least one selected from tertiary amines such as triethylamine, N, N-diethylcyclohexylamine, N, N, N ', N'-tetramethylethylenediamine and triethylenediamine. It is preferable to use 0.001 to 10 parts by weight based on the content of the silver regenerated polyol. The reaction time and yield were the best in this range.

The modified regenerated polyol according to the present invention preferably has an OH value of 75 to 120 mgKOH / g and a viscosity of 15000 to 22000 cps / 25 ° C. This is because when the OH value is out of the above range, the viscosity becomes relatively high and is not suitable for use at room temperature.

In the present invention, the resin premix is a reaction catalyst with an additive based on 100 parts by weight of the mixed polyol component in which 10 to 70% by weight of the modified regenerated polyol, 30 to 90% by weight of polyether, polyester or mixed polyols thereof is mixed. 0.1 to 3 parts by weight, 0.5 to 5 parts by weight of surfactant, 5 to 10 parts by weight of flame retardant and 15 to 25 parts by weight of blowing agent are used.

When the content of the modified regenerated polyol is less than 10% by weight, the flowability is lowered, and when the content of the modified regeneration polyol is more than 70% by weight, the viscosity of the system is high.

In addition, the polyether-based, polyester-based or mixed polyols thereof may be used without limitation as long as it is a normal pure polyol used in the art. By pure polyol is meant pure polyol that has not been recycled. More preferably, the pure polyol has an OH value of 300 to 800 mgKOH / g.

In detail with respect to the components used as an additive,

The reaction catalyst in the present invention is a typical catalyst that can be used to obtain a rigid polyurethane foam, for example triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexadecyldimethylamine, N Methyl morpholine, N-ethyl morpholine, N-octadecyl morpholine, monoethanolamine, diethanolamine, dimethylethanolamine, triethanolamine, N-methyl diethanolamine, N, N-dimethylethanolamine, diethylene Triamine, N, N, N ', N'-tetramethylbutanediamine, N, N, N', N'-tetramethyl-1,3-butanediamine, N, N, N ', N'-tetraethyl Hexamethylenediamine, 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, N, N-dialkylpi Amine-type urethanization catalysts, such as azacyclic compounds, such as a perazine, and (beta) -aminocarbonyl catalyst of various N, N ', N "-trialkylaminoalkylhexahydrotriazines, can be used.

It is preferable to use these catalysts individually or in mixture, and the usage-amount may use 0.1-3 weight part with respect to resin premix. If the amount is less than 0.1 part by weight, it is difficult to form the foam, and if it exceeds 3 parts by weight, it is difficult to crack and workability is used in the above range.

In the present invention, it is preferable to use the organosilicon compound generally used in the preparation of the polyurethane foam, and more preferably to use the polyalkylene glycol silicone copolymer for homogenization of the cell. For example, F-220, F-230, F-260, F-305, F-307 (Japanese Shin-Etsu Chemical Co., Ltd. brand name), L-520, L-540, L-5,340, L-5,420 (Union Carbicle company name), DC-5604, DC-192, DC-193, DC-194, DC-195, (Dow Corning company name), etc. can be used. The amount of the surfactant used is preferably 0.5 to 5 parts by weight based on the resin premix. If the amount is less than 0.5 parts by weight, the cell of the foam is large, the thermal conductivity is lowered, and if it exceeds 5 parts by weight, the reactivity is lowered, so it is used in the above range.

In the present invention, the flame retardant is to impart flame retardancy, for example, the flame retardant is trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tris (isopropylphenyl) phosphate, tris ( 2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (1,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tetrakis (2-chloroethyl) ethylenedi Phosphate, tetrakis (2,3-dichloropropyl) ethylenediphosphate, tetrakis (2-chloropropyl) ethylenediphosphate, tetrakis (2-chloroethyl) phenylenediphosphate, tetrakis (chloroethyl) tetrachlorophenyl Rendiphosphate, bis [di (chloropropyl)] phosphate diethylene glycol, bis [di (chloroethyl)] phosphate diethylene glycol, 2,2-bis ( Chloromethyl-1,3-propylene-bis [bis (2-clopinethyl) phosphate] poly (chloroethylethyleneoxy) phosphoric acid, 2- [bis (2-chloroethoxy) phosphinyl] -isopropyl- Bis (2-chloroethylphosphate, 2-bis (2-chloroethyl) phosphinyl-isopropyl-2-chloroethyl, 1,3-dichloropropylphosphate and the like.

The amount of flame retardant is preferably used 5 to 10 parts by weight based on the resin premix. If the amount is less than 5 parts by weight, the flame retardant effect is insignificant, and if it exceeds 10 parts by weight, the reactivity of the foam is lowered, so use within the above range.

In the present invention, the blowing agent may generally use water, a carboxylic acid, a fluorocarbon blowing agent or an inert gas such as carbon dioxide or air as the blowing agent used in the rigid polyurethane foam. More specifically, trichloromonofluoromethane (CFC-11) or dichloromonofluoroethane (HCFC-141b) or a mixture thereof is used as water or a fluorocarbon blowing agent. At this time, the organic foaming agent is preferably used 15 to 25 parts by weight based on the resin premix. If the amount is less than 15 parts by weight, the viscosity of the resin premix is lowered, and if it exceeds 25 parts by weight, the foam of the foam becomes weak, so it is used in the above range. At this time, the water may be used as an auxiliary foaming agent, it is preferable to use a small amount within the range of 0.5 to 3 parts by weight.

In the present invention, it is preferable that the isocyanate compound uses polymethylenediphenyl isocyanate (MDI) having a functional group of 2.6 to 3.0.

If the initial reaction time of the foam is too late, the curing may be late and the productivity may decrease. If the reaction time is too fast, the viscosity increase may suddenly increase during foaming, and thermal aging and cracking may occur within the foam.

In the case of the present invention, the foam gelation reaction time is preferably maintained about 130 ~ 170 seconds.

The expandable polyurethane stock solution used in the present invention is flowable after being mixed at room temperature, and a time when clouding occurs, that is, a cream time of about 30 to 50 seconds is appropriate. In addition, the foaming time of the stock solution during the foaming, that is, the gel time (gel time) is suitable for 130 ~ 170 seconds, the time the surface viscosity disappears, that is, the tack free time (200-230 seconds) To ensure good workability and formation of the foam.

Block foam prepared by the present invention is cut to a certain thickness by a skiving method to be used in the form of a board according to the intended use of the product.

In addition, the present invention can be used as a board by attaching asbestos, plywood, paper, iron plate, gypsum board, brick, etc. on one or both sides of the skived polyurethane board with an adhesive according to the material.

Hereinafter, the present invention will be described with reference to Examples in order to provide a detailed description of the present invention, but the present invention is not limited to the following Examples.

[Production Example 1]

Of recycled polyols  synthesis

A four-necked flask was equipped with a reflux condenser, thermometer, mechanical stirrer, and dripping apparatus and a heating mantle with temperature control. 500g of waste polyurethane foam pulverized to a certain size was added, 500g of diethylene glycol and 0.5g of zinc acetic acid were added, and the temperature was adjusted to 130 ° C. and the mixture was slowly stirred. Under nitrogen atmosphere, the reaction temperature was raised to 200 ° C. by 10 ° C. per hour, and stirring was continued for 4 hours until the pulverized waste polyurethane was dissolved. A small amount of the regenerated polyol synthesized by reacting for 2 hours was analyzed to synthesize a polyol having an OH Value of 650 mgKOH / g.

[Production Example 2]

Modified Of recycled polyols  Manufacture (1)

A four-necked flask was equipped with a reflux condenser, a thermometer, a mechanical stirrer, and a dropping device, and a heating mantle capable of temperature control was installed, and an aspirator was installed to reduce the pressure. The regenerated polyol and adipic acid prepared in Preparation Example 1 were added to a four-necked reactor in a 1: 0.5 molar ratio, and the mixture was gradually stirred at an initial temperature of 180 ° C. When reaching 180 ° C, 0.01 g of a dibutyltin dilaurate catalyst was added, and the reaction temperature was increased by 10 ° C. per hour to 230 ° C. in 1 hour through a reduced pressure reaction, and the pressure was reduced to 750 mmHg to give an OH value of 100 mgKOH / g. And polyol having a viscosity of 20000 cps / 25 ° C were synthesized.

[Production Example 3]

Modified Of recycled polyols  Manufacture (2)

A four-necked flask was equipped with a reflux condenser, a thermometer, a mechanical stirrer, and a dropping device, and a heating mantle capable of temperature control was installed, and an aspirator was installed to reduce the pressure. The regenerated polyol and adipic acid prepared in Preparation Example 1 were added to a four-necked reactor at a ratio of 1: 0.8, and the initial temperature was adjusted to 180 ° C., and the mixture was stirred slowly. When reaching 180 ° C., 0.01 g of a dibutyltin dilaurate catalyst was added, and the reaction temperature was increased by 10 ° C. in an hour to 230 ° C. through a reduced pressure reaction, and the pressure was reduced to 750 mm Hg to reduce the OH value to 75 mgKOH / g, A polyol having a viscosity of 22000 cps / 25 ° C. was synthesized.

Comparative Production Example

Reaction polyol and adipic acid were reacted in the same manner as in Preparation Example 2, except that a 1: 1 molar ratio was used. As a result, a polyol having a OH value of 30 mgKOH / g and a viscosity of 30000 cps / 25 ° C was synthesized.

Experimental Example 1

Experiments were conducted to derive a range suitable for the present invention by measuring the flowability and curing time using the modified regenerated polyols prepared in Preparation Examples 2, 3 and Comparative Preparation Examples.

15 g of each regenerated polyol prepared in Production Examples 2 and 3 and Comparative Production Example, 55 g of a polyether polyol RP6455 (OH value = 450 mgKOH / g) manufactured by BASF Korea, 33LV (of Air Products) 0.5 g of 33% triethylene diamine, 67% dipropylene glycol), 0.4 g of polycat 8, 1.5 g of foam stabilizer from DOW Corning, DC-5604 1.5, tri 2-chloropropyl phosphate (phosphate flame retardant) Resin premix was prepared using 7 g of Chlorpropyl Phosphate and 1.5 g of water and 24 g of HCFC-141b as a blowing agent.

100 g of BASF Korea MDI Lupranate M20S Co., Ltd. was stirred at 5000 rpm to 100 g of resin premix to synthesize a rigid polyurethane foam (polyisocyanurate). Physical properties are shown in Table 1 below.

TABLE 1

Flowability was observed by pouring the resin premix and MDI mixture on the floor and forming the polyisocyanurate, while the foam flowed and gelated. (Good: The foam spreads widely on the floor. Poor: The foam does not form properly. Not)

2. The blendability was evaluated by evaluating the blendability with other polyols and additives in the preparation of the resin premix and observed whether layer separation occurred after one day of mixing.

3. Reactivity refers to CT for cream time, GT for Gel time, and TFT for Tack free time. The unit is 'second'.

4. Viscosity was measured using a Brookfield viscometer.

As shown in the above table, the molar ratio of regenerated polyol and adipic acid was 1: 0.5 to 0.8 for mixing and flowability with the virgin polyol after the reaction.

Example 1

Preparation of Boards Using Modified Recycled Polyols and Waste Polyurethanes

Polyurethane waste discharged from the waste refrigerator was added up to 30% of the mold volume into the mold as it is discharged without grinding. At this time, the size of the mold was 2.4 m (width) x 1.2 m (length) x 0.6 m (height).

Here, 15 g of regenerated polyol prepared in Preparation Example 2, 55 g of polyether-based polyol RP6455 (OH value = 450 mgKOH / g) manufactured by BASF Korea, 33LV (33% triethylene diamine, 67%, manufactured by Air Product) 0.5 g of dipropylene glycol, 0.4 g of polycat 8, 1.5 g of foam stabilizer from DOW Corning Co., Ltd., DC-5604 1.5 g, as a flame retardant, 7 g of tri 2-chloropropyl phosphate (phosphate flame retardant), foaming agent Furnace was prepared with resin premix (A) using 1.5 g of water and 24 g of HCFC-141b. Resin premix (A) and BASF Korea MDI Lupranate M20S was added to the mixture by stirring at 2000 rpm at a 1: 1 ratio by calculating the input amount to 70% of the mold volume.

Cover the mold and wait until the resin premix is filled between the waste, demolded after 2 hours, aged at room temperature for 2 days and then cut to 100 mm thick with skiving to obtain a polyurethane board, and the physical properties are shown in Table 2. .

Example 2

Except that the polyurethane waste up to 40% of the mold volume, and mixed with the resin premix (A) and MDI up to 60% of the mold volume was the same experiment as in Example 1. Table 2 shows the physical properties.

Example 3

The experiment was performed in the same manner as in Example 1 except that the polyurethane waste was added up to 50% of the mold volume, and the resin premix (A) and MDI were mixed and added up to 50% of the mold volume. Table 2 shows the physical properties.

Comparative Example 1

Polyurethane waste up to 50% of the mold volume, BASF Korea polyether polyol RP6455 (OH value = 450 mgKOH / g) 70g, 33LV (33% triethylene diamine, 67% dipropylene glycol) from Air Products ) 0.5g, polycat 8 0.4g, DOW Corning's foam stabilizer DC-5604 1.5g, flame retardant 7g tri-chloropropyl phosphate (phosphate flame retardant), foam agent Resin premix (B) was prepared using 1.5 g of water and 24 g of HCFC-141b. The resin premix (A) and BASF Korea MDI Lupranate M20S were added at 50 rpm of the mold volume and stirred at 2000 rpm with a 1: 1 ratio. Cover the mold and wait until the resin premix is filled between the wastes, demolded after 2 hours, aged at room temperature for 2 days, and then cut to 100 mm thick with skiving to obtain a polyurethane board, and the physical properties are shown in Table 2. .

Comparative Example 2

Physical properties were measured in the same manner using EPS boards sold as comparative examples, and the physical properties are shown in Table 2.

TABLE 2

1. Density: Foam density of foam (kg / ㎥)

2. Combustibility: Measured according to KS M 3809

3. Pore size of board: Measure pore size between waste and foamed polyurethane

4. Adhesiveness: The adhesiveness between the waste and the newly foamed foam was measured. The separation easily occurred when separating the adhered portion by hand was bad, and the case of being completely adhered without falling was good.

5. Thermal Conductivity: Measured using Enter Corporation's Thermal Conductivity Meter (Model No. 2031) (according to ASTM C-518)

As shown in the above table, the block foam according to the present invention was found to have excellent thermal insulation and low thermal conductivity as compared to Comparative Example 1 by using a regenerated polyol. It was found that the flowability and adhesion to the waste were excellent as using the regenerated polyol modified by using.

The present invention is economically advantageous compared to the existing board by using a rigid polyurethane foam containing waste polyurethane foam on the board for polyurethane interior and exterior by chemical / physical treatment of the waste polyurethane foam, excellent adhesion, heat insulation and combustibility By developing this, the utilization of waste polyurethane can be increased, and the result can be made to make eco-friendly urethane board.

In addition, the present invention was able to provide a resin premix with excellent flowability to completely fill the empty space of the waste by modifying the recycled polyol, and also to produce a board having excellent combustibility and thermal insulation properties due to the nature of the recycled polyol. .

In addition, the present invention is capable of manufacturing a polyurethane foam in the form of a block, so that the user can be cut to the desired size as needed, when used as a conventional board when used as a thick board compared to the use of several layers in contact with the adhesive, etc. With skiving, all you have to do is cut the board, making it easy to manufacture boards of the desired size and thickness.

Claims (8)

A) injecting the polyurethane waste into the mold as it is discharged without processing such as grinding; B) Adipic acid, adipic acid salts, adipic acid esters, adipic acid, in recycled polyols depolymerized using waste polyurethane foam and glycols, to fill the voids between the wastes High pressure vacuum esterification reaction by adding at least one selected from dioctyl Mixing a resin premix (first liquid) and an isocyanate compound (second liquid) in which the additive is added to the mixed polyol component in which the modified regenerated polyol and the pure polyol are mixed at a weight ratio of 1: 1 to 2, and then injected into the mold; C) foaming and curing the mixture to produce block foam filled with voids between the wastes and demolding; D) aging at room temperature; E) cutting the polyurethane block foam to a thickness desired by a user using a skiving machine; Polyurethane board manufacturing method comprising a. The method of claim 1, The polyurethane waste is a polyurethane board manufacturing method, characterized in that used in the range of 10 to 80% of the mold volume. The method of claim 2, The resin premix is 0.1 to 3% by weight of the reaction catalyst as an additive, based on 100 parts by weight of the mixed polyol component in which 10 to 70% by weight of the modified regenerated polyol, 30 to 90% by weight of polyether, polyester or mixed polyols thereof is mixed. Part, 0.5 to 5 parts by weight of surfactant, 5 to 10 parts by weight of flame retardant and 15 to 25 parts by weight of blowing agent, characterized in that the polyurethane board production method. The method of claim 3, wherein The modified regenerated polyol is any one selected from adipic acid, adipic acid salt, ester of adipic acid, and adipic acid dioctyl to a regenerated polyol depolymerized using waste polyurethane foam and glycol. Method for producing a polyurethane board, characterized in that the OH value is 75 ~ 120 mgKOH / g, the viscosity is 15000 ~ 22000cps / 25 ℃ by adding the above 1: 0.5 to 0.8 molar ratio by high pressure vacuum esterification. The method of claim 1, The mold size is a polyurethane board manufacturing method, characterized in that the width 2 ~ 3 m, the length is 1 ~ 2 m, the height is 0.1 ~ 1 m. Polyurethane board produced by the manufacturing method of any one of claims 1 to 5. delete The method of claim 6, The polyurethane board is a polyurethane board, characterized in that laminated one or more exterior materials selected from asbestos, plywood, paper, iron plate, gypsum board, brick after applying the adhesive on one or both sides of the cut polyurethane board.