KR100893355B1 - Synthetic method of recycling polyol from wasted polyurethane foam and composition of polyurethane foam using this - Google Patents

Abstract

A synthetic method of recycling polyol from waste polyurethane foam is provided to secure competitive price by recycling high-priced polyurethane foam and reducing the quantity of amine catalysts consumed. A synthetic method of recycling polyol from waste polyurethane foam comprises the following steps. The 100 parts of waste polyurethane foam is mixed to the 100-300 parts of polyether polyol or polyester polyol by weight to be decomposed at a temperature range of 120-300°C. The mixture is added to the following compositions of: amine-based oligomer selected from the group consisting of di(2,6-dimethylmorpholinoethyl)ether, bisoxazolidine, diethylated toluene diamine, N-methyl-2-pyrrolidone, morpholine and tetramethyl propylene diamine; animal or plant oil selected from the group consisting of palm oil, soybean oil, olive oil, castor oil, rape oil and rice oil; and organometallic catalyst or tertiary amine-based catalyst selected from the group consisting of triethylenediamine, 5-methyl-diethylene triamine, di-(N,N-dimethyl aminoethyl)ether and dimethylcyclohexylamine to react the mixture at 170-400°C for a predetermined time.

Description

Synthetic Method of Recycling Polyol from Wasted PolyUrethane Foam and Composition of Polyurethane Foam Using This}

The present invention relates to a method for synthesizing recycled polyol from waste polyurethane foam and to a polyurethane foam composition comprising recycled polyol synthesized by the above method.

Porous material is composed of independent bubble structure and open bubble structure, with independent bubble type cellutype = expended materials and open bubble type noncellutype = sponge materiais. The distinction between sponges and foams coated with rubber-based foam materials or plastic packaging materials is vague, and foams and sponges are difficult to clearly distinguish, like coriander or other plastic porous materials, and are confused with foams or sponges. The porous material is collectively called a sponge.

Currently, plastic porous materials are just called foams and sponges. At present, foam is manufactured in all polymer gases, but it is a liquid phase with high fluidity, and it is the biggest feature of urethane foam to be molded by a simple operation which is hardened as it is injected or discharged at room temperature in an arbitrary space.

Polyurethane foam production principle is that the polymer of the hydroxyl end group and the diisocyanate cause crosslinking crosslinking network reaction according to the formation reaction of the elastomer by the water crosslinking to enlarge the molecules and expand by the gas generated at this time. Spherical or hemispherical or polygonal cellular structures are formed and cured to form polyurethane foams. The mainstream of the foaming reaction is the reaction of isocyanate groups with water and various developments.

Uniformity of Foam Products Recently Differences in Bubble Opening or Independent Phases In order to obtain reproducible properties such as chemical physical properties, changes in the reaction process such as polyol diisocyanate water or blowing agent catalyst additives, etc. As the self-entanglement affects, continuous obtaining of certain properties of the foam requires accurate raw materials and reliable operation methods. The size of the cell depends on the speed of the stirring, the discharge pressure and the air injection amount, and the method thereof, and attention is required.

Polyurethane obtained by the reaction of isocyanate salt and glycol is used as a constituent material, and foamed product made by mixing volatile solvent such as carbon dioxide and freon produced by reaction of isocyanate salt and water used as bridge binder as foaming agent. It is called. The apparent density of the foam can be controlled relatively freely, allowing for easy foaming anywhere on site.

Depending on the type of raw materials and glycol used, it can be divided into polyether foam and polyester foam. The former is flexible and the latter is suitable for use as an industrial foam. The foam made in this way has a rigidity such as super soft soft semi-hard hard. The super soft and soft cushions are used for mattresses, and the rigid foams are used for refrigerator insulation and waterproof insulation of refrigerators because of their rigidity and good thermal insulation and low temperature. There are two foam molding methods, one-shot method and prepolymer method. The one-shot method is economical because the raw material components are mixed and reacted at once, so that the foam is mostly made by this method. The prepolymer method is a method of preparing a prepolymer (partial polymerizer) by reacting a part of glycol and a diisocyanate salt in advance, and mixing the remaining glycol blowing agent catalyst with the foam, and since the foam is uniform, it is used for industrial purposes such as semi-rigid foam or rigid foam. Use this method to create a form that values. Recently, non-freon foams that only foam with water have been developed in Japan, and rigid urethane foams using water-repellent foams that do not use alternative freons, such as Hcfc 141b, which are scheduled to be closed in 2004, have also been developed by Nishi Nishi paint industry. .

Polyurethane has been used as a very important polymer material in the industrial field in accordance with the excellent physical properties such as chemical resistance, heat insulation, reactivity, and a variety of manufacturing methods, light weight and high quality of products. Polyurethane foams, which are widely used in industrial sites and homes, are often discarded as products when they are used up, and the amount of waste is gradually increasing. These waste polyurethanes are partially recycled, but most of them are incinerated or landfilled by waste disposal companies, despite a fraction of the total. This is a loss of expensive materials that can be recycled, which is a huge loss in terms of national economy.

Therefore, the inventors of the present invention, while devising a method for recycling the waste polyurethane foam, the waste polyurethane foam was synthesized at high temperature by using an amine oligomer, animal and vegetable oil, polyhydric alcohol, and synthesized polyol at high temperature. The present invention has been completed by confirming that the polyurethane can be regenerated to react with.

An object of the present invention is to provide a method for synthesizing recycled polyol using waste polyurethane foam and a polyurethane composition prepared by the above method.

In order to achieve the above object, the present invention comprises the steps of i) adding 100 to 300 parts by weight of polyol which is a polyhydric alcohol to 100 parts by weight of waste polyurethane foam, and decomposing the waste polyurethane foam at a temperature of 120 to 300 ° C .; Ii) di (2,6-dimethylmorpholinoethyl) ether (DMDEE), Bisoxazolidine, diethylated toluene diamine (DETDA), NMP (N, -methyl-2-pyrrolidone), Morpholine and Tetramethyl propylene diamine in the mixture of step iii) Amine oligomers selected from the group consisting of), palm and vegetable oils selected from the group consisting of palm oil, soybean oil, olive oil, castor oil, rapeseed oil, rice bran oil and pig oil, and metal catalysts or organic catalysts based on organic metal (TEDA) or triethylenediamine ), Tertiary amine catalyst selected from the group consisting of 5-methyl-diethylene triamine (PMDETA), di- (N, N-dimethyl aminoethyl) ether (BDMEE) and dimethylcyclohexylamine (DMCHA) Adding a phosphorus amine catalyst and reacting at a temperature of 170 to 400 ° C. for a predetermined time, wherein the sum of the amine oligomer and the animal and vegetable oil is 50 to 150 parts by weight, and the metal or the amine catalyst is 5 to 20 parts by weight.Everything; And iii) a method of synthesizing a recycled polyol from waste polyurethane foam comprising the step of aging and filtering the composition of step ii).

The present invention also provides a polyurethane foam composition comprising a recycled polyol synthesized by the above method.

Hereinafter, the present invention will be described in detail.

The present invention comprises the steps of: i) adding 100 to 300 parts by weight of polyol which is a polyalcohol to 100 parts by weight of waste polyurethane foam, and decomposing the waste polyurethane foam at a temperature of 120 to 300 ° C; Ii) di (2,6-dimethylmorpholinoethyl) ether (DMDEE), Bisoxazolidine, diethylated toluene diamine (DETDA), NMP (N, -methyl-2-pyrrolidone), Morpholine and Tetramethyl propylene diamine in the mixture of step iii) ) Amine-based oligomers selected from the group consisting of amine oligomers, palm oil, soybean oil, olive oil, castor oil, rapeseed oil, rice bran oil, and pig oil selected from the group consisting of animal and vegetable oils, metal catalysts or organic catalysts such as TEDA (triethylenediamine) and PMDETA ( An amine catalyst is a tertiary amine catalyst selected from the group consisting of 5-methyl-diethylene triamine, BDMEE (di- (N, N-dimethyl aminoethyl) ether) and DMCHA (dimethylcyclohexylamine). Reacting at a temperature of 170 to 400 ° C. for a predetermined time, wherein the sum of the amine oligomer and the animal and vegetable oil is 50 to 150 parts by weight, and the metal or amine catalyst is 5 to 20 parts by weight; And iii) a method of synthesizing recycled polyol from waste polyurethane foam, which comprises the step of aging and filtering the composition of step ii).

In the method for synthesizing recycled polyol from the waste polyurethane foam of the present invention, the polyhydric alcohol is preferably polyether polyol or polyester polyol, and the organometallic catalyst is DBTDL (dibutyltindilaurate). It is preferable.

In addition, in the method for synthesizing recycled polyol from the waste polyurethane foam of the present invention, the decomposition temperature of step iii) and the reaction temperature of step ii) are preferably 180 to 190 ° C, and the reaction of step ii) is 4 It is preferably done for ˜8 hours.

In addition, in the method for synthesizing the recycled polyol from the waste polyurethane foam of the present invention, the iii) aging and filtration step is aged for 1 to 3 hours, and then filtered through a filter having a pore size of 180 μm or less. Do.

Referring to the synthesis process of the regenerated polyol synthesized by the above method of the present invention step by step.

1) Raw material input and decomposition step

The waste polyurethane foam and polyhydric alcohol (polyol) are put together, and then raised to 120 ° C. or higher to decompose the waste polyurethane foam.

In this case, polyol is an organic compound having two or more hydroxyl groups (-OH) at the terminal of the molecule and forms a main component together with isocyanate during PU production. For the production of PUF, polyether polyol, polyester polyol, and the like are mainly used. Polyether polyol is a kind of polyol in which ether group (Ether, -O-) is repeatedly bonded to molecular structure, and polyester polyol is polyol in which ester group (Ester, -COO-) is repeatedly bonded to molecular structure Polymer polyol (POP) is an abbreviation of Polymer Polyol, also called copolymer polyol (PPP), and is a polyol prepared by dispersing and polymerizing an acrylic monomer in a polyether polyol. It is mainly used for the purpose of increasing hardness and breathability (applied to soft and semi-rigid foam).

2) the reaction step of the material

An amine oligomer, animal and vegetable oils, and a metal or amine catalyst are added to the decomposed waste polyurethane and polyhydric alcohol and reacted for 4 hours or more at a temperature of 170 ° C or higher.

As the amine oligomer, DMDEE (di (2,6-dimethylmorpholinoethyl) ether), Bisoxazolidine, DETDA (diethylated toluene diamine), NMP (N, -methyl-2-pyrrolidone), Morpholine, TMPDA, etc. can be used. Vegetable oils may be used, such as palm oil, soybean oil, olive oil, castor oil, rapeseed oil, vegetable such as rice bran oil and animal such as pig oil. The amine oligomer and animal and vegetable oils may contain 50 to 150 parts by weight, preferably 90 parts by weight, based on 100 parts by weight of the waste polyurethane.

It is preferable to use an organometallic catalyst as the metal catalyst, for example DBTDL (dibutyltindilaurate), tin compounds containing other organic substances, lead compounds and the like can be used. Tertiary amine (Tertiary Amine) catalyst is preferably used as the amine catalyst, such as TEDA (triethylenediamine), PMDETA (5-methyl-diethylene triamine) and BDMEE (di- (N, N-dimethyl aminoethyl) ether) , DMCHA (dimethylcyclohexylamine; dimethylcyclohexylamine) may be used. The catalyst may contain 5 to 15 parts by weight, preferably 10 parts by weight based on 100 parts by weight of waste polyurethane.

3) Ripening and Filtration Steps

When the reaction is completed, it is aged slowly for 1 to 3 hours while slowly lowering the temperature. After aging is completed, the filter is filtered through a filter having a pore size of 180 μm or less. Finally wrap this.

In the embodiment of the present invention, the preparation of the recycled polyol is performed by pulverizing the polyurethane foam, putting it in DEG and raising it to high temperature, and then adding an amine catalyst (DMCHA) or an organometallic catalyst (DBTDL), palm oil or soybean oil, DMDEE or DETDA. The reaction was carried out to synthesize a polyol. The recycled polyol of the present invention has a characteristic of having an average functional group of 2 to 5, a hydroxyl group of 440 to 500 mg KOH / g, a viscosity (cps / 25 ° C) of 2,200 to 2,500, and a water content (%) of 0.3% or less. .

In addition, the present invention provides a polyurethane foam composition comprising a recycled polyol.

In the polyurethane foam foam composition of the present invention, the polyurethane foam foam composition is i) 100 parts by weight of regenerated polyol, 0.5 to 5 parts by weight of water, 0.5 to 5 parts by weight of silicone foam stabilizer, DMCHA (dimethylcyclohexylamine; dimethylcyclohexylamine A system polyol comprising from 0.1 to 2 parts by weight and from 10 to 100 parts by weight of 141B (1,1-dichloro-1-fluoroethane); And ii) MDI (Methylene diphenyl diisocyanate), wherein the system polyol is 100 parts by weight of recycled polyol, 1.5 parts by weight of water, 1.5 parts by weight of silicone foam stabilizer, 0.5 parts by weight of DMCHA and 33 parts by weight of 141B. desirable.

Moreover, in the polyurethane foam foam composition of this invention, it is preferable that the said system polyol: MDI = 1: 0.5-2, and it is more preferable that the said system polyol: MDI = 1: 1.

In addition, in the polyurethane foam foam composition of the present invention, the composition is preferably used for the use selected from the crowd consisting of a thermal insulation agent and spray foam raw materials, such as for refrigerators, automobiles, LNG vessels, freezers, sandwich panels.

Referring to each component of the polyurethane foam composition of the present invention in more detail as follows.

The amine catalyst used in the present invention plays a role as a foaming catalyst, and DMCHA is a type of balance catalyst, which is a catalyst that properly promotes both resination and saturation reactions. Since the DMCHA uses an amine base polyether polyol, it is possible to reduce the amount of amine catalyst used. The amount of the catalyst is used in the range of 0.1 to 2 parts by weight based on 100 parts by weight of the polyol, and when the content is less than 0.1 parts by weight, the reaction is delayed. The problem that cracking of the foam occurs occurs, and also the amount of residual amine catalyst in the cell increases. As the content of the catalyst increases, the degree of odor generation tends to increase.

Surfactant (Surfactant) is a kind of additive that affects the cell structure in the foam by the effect of the surface active effect and functions as the mixing of the raw materials, stability, bubble generation, bubble stability, etc. The foam stabilizer serves to prevent the resulting cells from coalescing and breaking when the cells are formed in the foam and to control the formation of a uniform cell. The type of foam stabilizer is not particularly limited to those used in the art. In terms of dispersibility of the reactants, a silicone foam stabilizer is used, and the use range is 0.5 to 5 parts by weight based on 100 parts by weight of the polyol. If more than 5 parts by weight, the problem that the foam formability is slow.

When the blowing agent used in the present invention reacts with the isocyanate when the polyol and the isocyanate react to generate a gas to have a foam structure, the kind is not particularly limited to those used in the art, but in particular, 141B is a physical blowing agent It is a substance that is vaporized by heat of reaction to form bubbles, and does not participate in polymer reaction. The amount of the polyol is used in the range of 10 to 100 parts by weight based on 100 parts by weight of the polyol, and when the content is less than 10 parts by weight, foam cell formation is insufficient. .

MDI used in the present invention refers to the most commonly used types of isocyanate which is commercialized, and is an organic compound containing an isocyanate group (-NCO) in a molecule and forms a main component together with a polyol during PU production. The system polyol and MDI are mixed in a 100: 100 weight ratio, the content of isocyanate is lower when the content is less than 100: 50 weight ratio, the cell stability of the foam is lowered, and when the 100: 200 weight ratio is higher than the content of isocyanate, foam foam molding is not normal Problem occurs.

In the present invention, as a result of examining the effect of the structure of the scrap on the synthesis of the recycled poly, as the crosslinking degree of the scrap used for the synthesis of the recycled poly increased the hydroxyl value and viscosity of the recycled polyol, the total amine group was greatly improved.

The reaction rate, compressive strength, glass transition temperature, thermal conductivity, etc. were measured by synthesizing the polyurethane foam using the recycled polyol. As a result, the reaction rate was influenced by the amine contained in the recycled polyol compared to the polyurethane foam using only the new polyol. Faster and increased crosslinking resulted in improved glass transition temperature and improved thermal conductivity by forming fine cells at the beginning of the reaction.

Since the system polyol of the present invention can reduce the amount of the amine catalyst using recycled polyol and has excellent moldability and heat insulation effect compared to the existing polyurethane foam, the composition is for sandwich panels, refrigerators, spray foam raw materials and refrigeration. It can be widely used for warehouse.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are only for illustrating the present invention, and the present invention is not limited to the following examples and may be changed to other embodiments equivalent to substitutions and equivalents without departing from the technical spirit of the present invention. Will be apparent to those of ordinary skill in the art.

Example 1 Synthesis of Regenerated Polyol 1

50 g of commercial polyurethane foam were prepared from waste rigid polyurethane foam scrap having a constant size using a grinder. A four-necked flask equipped with a condenser, a mechanical stirrer, and a thermostat was attached to the heating mantle, and 100 g of a polyhydric alcohol DEG (diethylene glycol) was added to the flask, and a portion of the waste hard polyurethane scrap was slowly added to the reactor. After that, the temperature was raised to 200 ° C. When the reaction temperature reaches 200 ° C., 5 g of an amine catalyst (TEDA), 20 g of palm oil, and 25 g of DMDEE, an amine oligomer, are added, and when the waste hard polyutethane scrap is depolymerized, the remaining scrap is added. Repeat until all the scraps. After adding the scrap, check whether there is any unreacted scrap in the reaction solution by using a water dispenser, etc., and after 6 hours of reaction at 230 ° C., if the unreacted scrap is not seen, the reaction was terminated. Then, the temperature was slowly lowered and aged for 2 hours, and then filtered through a filter having a 150 μm pore size.

Example 2 Synthesis of Regenerated Polyol 2

Regenerated polyol was synthesized in the same manner as in Example 1, except that 5 g of DBTDL organometallic catalyst, 20 g of soybean oil instead of palm oil, and 25 g of DETDA instead of DMDEE were added instead of the amine catalyst.

Example 3 Physical Properties of Recycled Polyol

In Example 1 and Example 2, a recycled polyol of uniform quality was synthesized by depolymerization of waste polyurethane scrap, and the physical properties of the synthesized polyol are shown in Table 1 below.

Example 1 Example 2 OH value (mg KOH / g) 450-500 440-480 Viscosity (cps / 25 ℃) 2.300 ~ 2,500 2.200 ~ 2,400 Moisture content (%) 0.3% or less 0.3% or less

Example 4 Preparation of Polyurethane Foam Foam Composition

1.5 parts by weight of water, 1.5 parts by weight of silicone foam stabilizer, 0.5 parts by weight of dimethylcyclohexylamine (DMCHA), and 33 parts by weight of 141B (1,1-dichloro-1-fluoroethane) in 100 parts by weight of the recycled polyol prepared in Example 1 Addition made system polyols. Based on 100 parts by weight of the system polyol, the same parts by weight of MDI were added and stirred vigorously for 50 to 100 seconds, and then injected into a 200 × 200 × 100 mm 3 mold to confirm reactivity and appearance of the foam.

Example 5 Foam Appearance Evaluation

Foam appearance evaluation was performed by visual evaluation of the molded foam. As a result of visual evaluation, little difference was found between the polyurethane of the molding foam synthesized from the conventional polyol and not the recycled polyol.

Example 6 Foam Formability Evaluation

Foam formability evaluation was evaluated by measuring C / T (cream time; the time when the foam began to swell) and G / T (time when the foam expanded and swelled) and D during foam manufacture. As a result, the foam had a C / T of 12 seconds, a G / T of 60 seconds, and a D of 28. The foam was evaluated to have good moldability. As a result, it was confirmed that the resin composition of the present invention satisfies the foam appearance and foam formability that the existing polyurethane foam should have while maintaining the adhesive strength.

1 is a schematic diagram showing the synthesis of recycled polyol from the waste polyurethane foam of the present invention.

Claims (12)

Iii) adding 100 to 300 parts by weight of polyether polyol or polyester polyol to 100 parts by weight of waste polyurethane foam and decomposing the waste polyurethane foam at a temperature of 120 to 300 ° C; Ii) di (2,6-dimethylmorpholinoethyl) ether (DMDEE), Bisoxazolidine, diethylated toluene diamine (DETDA), NMP (N, -methyl-2-pyrrolidone), Morpholine and Tetramethyl propylene diamine in the mixture of step iii) Amine oligomers selected from the group consisting of), palm and soybean oil, olive oil, castor oil, rapeseed oil, rice bran oil and pig oil selected from the group consisting of animal and vegetable oils, and DBTDL (dibutyltindilaurate) organometallic catalyst or TEDA tertiary amine selected from the group consisting of (triethylenediamine), 5-methyl-diethylene triamine (PMDETA), di- (N, N-dimethyl aminoethyl) ether (BDMEE) and dimethylcyclohexylamine (DMCHA) Adding an amine catalyst as a catalyst and reacting at a temperature of 170 to 400 ° C. for a predetermined time, wherein the sum of the amine oligomer and the animal and vegetable oil is 50 to 150 parts by weight, and the metal or the amine catalyst is 5 to 20 parts by weight.And a gong; And Iii) a method of synthesizing recycled polyol from waste polyurethane foam comprising the step of aging and filtering the composition of step ii). delete delete The method of claim 1, wherein the decomposition temperature of step iii) and the reaction temperature of step ii) are 180 to 190 ° C. The method of claim 1, wherein the reaction of step ii) is carried out for 4 to 8 hours. The method of claim 1, wherein the iii) aging and filtration step is aged for 1 to 3 hours, and then filtered through a filter having a pore size of 180 μm or less. . Polyurethane foam composition comprising a recycled polyol synthesized by the method of any one of claims 1 to 6. The method of claim 7, wherein the polyurethane foam composition Iii) 100 parts by weight of regenerated polyol, 0.5 to 5 parts by weight of water, 0.5 to 5 parts by weight of silicone foam stabilizer, 0.1 to 2 parts by weight of dimethylcyclohexylamine (DMCHA) and 141B (1,1-dichloro-1-fluoro) Roethane) system polyol comprising 10 to 100 parts by weight; And Ii) Polyurethane foam composition comprising MDI (Methylene diphenyl diisocyanate). 9. The polyurethane foam composition according to claim 8, wherein the system polyol is 100 parts by weight of regenerated polyol, 1.5 parts by weight of water, 1.5 parts by weight of a silicon foam stabilizer, 0.5 parts by weight of DMCHA and 33 parts by weight of 141B. 9. The polyurethane foam composition according to claim 8, wherein the system polyol: MDI = 1: 0.5 to 2. 11. The polyurethane foam composition according to claim 8 or 10, wherein the system polyol: MDI = 1: 1. 10. The polyurethane foam according to claim 8, wherein the composition is used for a purpose selected from a crowd consisting of a warming agent selected from the crowd consisting of refrigerators, automobiles, LNG vessels, freezers and sandwich panels, and spray foam raw materials. Foam composition.

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