KR100381693B1 - The method and its products of used polyuretane foam - Google Patents

Abstract

The present invention is to develop a boiler flooring material and prefabricated blocks for building by separately recycling the rigid urethane foam used for refrigerators and building insulation, glass fiber-containing rigid urethane foam used as reinforcement, and SMC (Sheet Molding Compound) waste. .

That is, the hard polyurethane foam, glass fiber-containing hard urethane foam and SMC waste obtained by the separate collection are crushed to a certain size, and then mixed with the adhesive in a hopper, and then discharged into a mold of a certain size and shape to be heated. The present invention relates to a regeneration method using waste polyurethane foam, and a regenerated product, which are produced by compressing a press for a predetermined time, and then demolding and aging at room temperature.

Description

Recycling method using waste polyurethane foam and its regenerated product {The method and its products of used polyuretane foam}

The present invention relates to a recycling method using the waste polyurethane foam and its regenerated product, which will be described in detail, a rigid urethane foam used as a refrigerator and a building insulation material, a glass fiber-containing rigid urethane foam used as a reinforcing material, and SMC (Sheet Molding Compound) waste. It relates to a regeneration method using the waste polyurethane foam to be recycled without separate and its regenerated product.

Since 1957, when polyurethane material was introduced to Korea, the polyurethane industry has grown remarkably and now has reached the level of developed countries in terms of quantity and quality. In other words, polyurethane is widely applied in all industries due to its excellent physical properties and processability such as automobile interior, building insulation, home appliances, shoes, artificial leather, and man-made fiber, and it was reported to have produced more than 220,000 M / T as of 1998. .

On the other hand, the glass fiber used together as a reinforcement and some flame retardant effect in the production of polyurethane foam is also a carcinogenic material, there is a lot of difficulties in the work environment and its separate collection is also a very urgent problem.

In addition, SMC, which is applied to various industrial materials such as interior and exterior materials such as Fender of automobiles, and water tanks of apartments, is also attracting attention as its environmental pollutant as well as the aforementioned polyurethane materials. There is much interest in the development of complex materials that make full use of.

SMC is a polymer material having a composition of unsaturated polyester, calcium carbonate and glass fiber, and particularly, it is widely used in water tanks in automobiles, exterior materials, apartments, and large buildings because of its excellent strength and elasticity, and is mainly processed by extrusion and injection.

The recycling of waste polyurethane is largely done by crushing the waste polyurethane and rebonding it with adhesive, recycling it to polyurethane raw material by thermal depolymerization, and incineration by simply using a heat source. In the case of chemical recycle, it is impossible to recover the raw material itself due to various chemical bonds of polyurethane, and incineration has become a major culprit of environmental pollution due to the emission of harmful gases and their disposal.

In Korean Patent Application Publication No. 2000-6549, the waste foamed plastic material is mixed with an adhesive and solidified, or the waste foamed plastic material is pulverized and tied with a net, or tied with a net as it is. After forming, the polyurethane foam composition is sprayed on the surface of the manufactured inner member by a predetermined thickness and then solidified, or the inner member is poured into a mold of a predetermined shape, and then the urethane foam composition is poured and then solidified. By using the waste foam plastic as an internal filler in the buffer structure, the waste foam plastic which overcomes the disadvantages such as insufficient shock absorption of the existing waste tire, high processing cost of the pure urethane foam, and low physical properties of Schiropol Buffer structure is described,

Korean Patent Publication No. 2000-35765 discloses a fluidization means for hydrolyzing a polyurethane resin to fluidize it as a target compound, and hydrolyzing the fluidized target compound for decomposition into a decomposition product mixture using supercritical water or high temperature and high pressure water. Decomposition of polyurethane resin, including water supply means for supplying the reactor, supercritical water or high temperature and high pressure water to the reactor, and post-treatment means for introducing the decomposition product mixture discharged from the reactor into the post-treatment process to recover the polyamine compound or polyol compound. And a device for recovery is described,

Korean Patent Publication No. 98-32323 discloses a powder obtained by pulverizing a polyurethane foam, and then injecting glycol and a catalyst into a reactor equipped with a cooler, and heating to 120-300 ° C. in nitrogen gas to prepare a regenerated polyol, followed by a pure polyol. And a method for preparing a polyurethane foam by mixing a regenerated polyol and preparing a mixture, and then reacting with the diisocyanate in the mixture.

Publication No. 2000-28780 discloses a varnish composition for laminated plates, a thermosetting or thermoplastic resin composition kneaded with a single screw extruder in a crushed scrap containing thermosetting resin, followed by injection molding to coat a paint composition, an adhesive composition, a brick cement mortar composition for construction, and a synthetic resin flooring composition. Technology to use as an additive in the

Korean Patent Publication No. 97-65462 discloses a thermal insulating material manufactured by mixing a foam molding agent, a stabilizer, a natural fiber chip, a flame retardant material, and an ABS resin based on recycled styropol and polystyrene.

The prior art is mainly a material recycle, which is a rudimentary step of pulverizing waste polyurethane and re-bonding it with an adhesive and recombining by a press, and is simply a technology for recycling foams, and the recycling process is complicated, resulting in processing cost. There has been a lot of trouble.

In order to solve the above problems, the present invention separates and collects rigid polyurethane foam, glass fiber-containing rigid polyurethane foam, and SMC waste generated from discarded home appliances or buildings, and grinds them to a predetermined size without separating them separately. It is an object of the present invention to provide a regeneration method using waste polyurethane foam that recycles waste by recombining it again into a press using an adhesive, and a regenerated product thereof.

In order to achieve the above object, the present invention is to crush the rigid urethane foam obtained from the insulation of the refrigerator and the building, the rigid urethane foam including glass fiber and SMC waste to a certain size of 10mm or less, and then using an adhesive in the hopper Mix well for about 1 minute.

The mixture thus obtained is placed in a mold preheated to 55-60 ° C. and then compressed to a press pressure of about 50 kg / cm 2 G or less. On the other hand, after 5 minutes, it can be demolded to obtain the desired building materials.

The adhesive used in the present invention uses a urethane adhesive, an epoxy adhesive and an acrylic adhesive,

Urethane-based adhesives include Toluene Diisocyanate (TDI), Methylene Diphenyl Diisocyanate (MDI), Isophorone Diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), and m-Xylene Diisocyanate (MXDI).

Epoxy-based adhesives are bisphenol A type epoxy resins,

Bisphenol F type epoxy resin,

Noble type epoxy resin,

Polyol modified epoxy resins,

Acrylic adhesives have a molecular weight of 1,000 to 100,000 and a glass transition temperature (Tg) of 0 to 100 ℃. The monomers are MMA (Methylmeth Acrylate), 2-EHA (2-Ethyl hexyl Acrylate), and 2-HEMA. (2-Hydroxyl ethylmeth Acrylate), Butyl Acrylate (BA), Ethyl Acrylate (EA), and Styrene Monomer (SM) are used.

Polypropylene Glycol (PPG), Polyethylene glycol (PEG), Polytetramethylene Glycol (PTMG), Polyester Polyol, Polyamide, Primary, Secondary, Tertiary Amines and Isocyanate Compounds are used as the curing agent for the adhesive.

Through the following examples will be described in detail the present invention.

Example 1

840 parts by weight and 80 parts by weight of rigid polyurethane foam or glass fiber-containing rigid polyurethane foam and SMC waste, which were previously ground to a diameter of 10 mm or less, respectively, with 360 parts by weight of toluene diisocyanate and polypropylene glycol and catalyst beforehand After mixing the urethane adhesive composed of the compound mixed with other additives sufficiently, put it in the flooring mold pre-heated to 55-60 ℃ and compressed to about 50kg / ㎠G press pressure. At this time, the jig of the boiler flooring mold was 0.5 m (W) X 0.4 m (L) X 0.06 m (T). After 5 minutes demolding, it is possible to obtain a flooring material for a boiler after fully aging at room temperature for 1 day and a product having various physical properties according to the density as shown in Table 1.

Example 2

700 parts by weight of methylene diphenyl diisocyanate, polyethylene glycol, catalyst, etc. in a ratio of 2,570 parts by weight and 240 parts by weight of hard polyurethane foam or glass fiber-containing hard polyurethane foam or SMC waste, which were previously ground to a diameter of 10 mm or less; After mixing the urethane adhesive composed of the compound mixed with the additives sufficiently, put it in the flooring mold pre-heated to 55-60 ℃ and then compressed to about 50kg / ㎠G press pressure.

At this time, the jig of the boiler flooring mold was 0.5 m (W) X 0.4 m (L) X 0.06 m (T). After 5 minutes demolding, it is possible to obtain a flooring material for a boiler after fully aging at room temperature for 1 day and a product having various physical properties according to the density as shown in Table 1.

Example 3

A composition of 800 parts by weight of bisphenol A-type epoxy resin and polyamide was prepared in a ratio of 2,930 parts by weight and 270 parts by weight of hard polyurethane foam or glass fiber-containing rigid polyurethane foam and SMC waste, which were previously ground to a diameter of 10 mm or less. The mixed epoxy-based adhesive is sufficiently mixed and then placed in a flooring mold preheated to 55-60 ° C., and then compressed to about 50 kg / cm 2 G press pressure.

At this time, the jig of the boiler flooring mold was 0.5 m (W) X 0.4 m (L) X 0.06 m (T). After 5 minutes demolding, it is possible to obtain a flooring material for a boiler after fully aging at room temperature for 1 day and a product having various physical properties according to the density as shown in Table 1.

Example 4

An acrylic adhesive containing 960 parts by weight of methyl methacrylate as a monomer in a ratio of 3,520 parts by weight and 320 parts by weight of hard polyurethane foam or glass fiber-containing hard polyurethane foam or SMC waste, which was previously ground to a diameter of 10 mm or less. After sufficient mixing, it is placed in a flooring mold preheated to 55-60 ° C. and compressed to about 50 kg / cm 2 G press pressure.

At this time, the jig of the boiler flooring mold was 0.5 m (W) X 0.4 m (L) X 0.06 m (T). After 5 minutes demolding, it is possible to obtain a flooring material for a boiler after fully aging at room temperature for 1 day. As shown in Table 1, a product having various physical properties can be obtained according to the density.

Comparative Example 1

Comparative Example 1 of Table 1 shows the characteristics of the molded product produced by different components and different kinds of adhesives.

Table 1 Properties of Boiler Flooring Products

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Rigid Polyurethane Foam or Glass Fiber Rigid Urethane Foam 1,320 parts by weight 2,750 parts by weight 2,930 parts by weight 3,520 parts by weight Expanded Polystyrene SMC Waste 220 parts by weight 240 parts by weight 270 parts by weight 320 parts by weight glue 360 parts by weight 700 parts by weight 800 parts by weight 960 parts by weight Core Density (kg / ㎥) 150 290 330 400 150 Compressive strengthkgf / ㎠ 22 61 73 230 19 Flexural Strengthkgf / ㎠ 49 107 169 350 35 Dimensional stability,% 70 ℃ X 24hr-10 ℃ X 24hr 0.21-0.54 0.19-0.48 0.16-0.30 0.13-0.22 0.25-0.85 Thermal conductivity, kcal / m · hr · ℃ 0.0237 0.0354 0.0372 0.042 0.0452

Examples 5-8

The rigid polyurethane foam or glass fiber-containing rigid polyurethane foam and SMC wastes and adhesives which have been previously ground to a diameter of 10 mm or less are sufficiently mixed in a weight ratio as shown in Table 2. On the other hand, it is put into the prefabricated building mold preheated to 55-60 ℃ and then compressed to about 50kg / ㎠G press pressure. At this time, the jig of the prefabricated block mold for construction was 0.5 m (L) X 0.4 m (W) X 0.06 m (T). After 5 minutes demolding, it is possible to obtain a prefabricated block for construction after sufficiently aging at room temperature for 1 day, and to obtain a product having various physical properties according to the density as shown in Table 2.

Comparative Example 2

The comparative example of Table 2 shows the characteristics of the moldings produced by varying the composition and the amount of adhesive.

Table 2 Properties of Building Blocks

Example 5 Example 6 Example 7 Example 8 Comparative Example 2 Rigid Polyurethane Foam or Glass Fiber Rigid Urethane Foam 840 parts by weight 970 parts by weight 1,320 parts by weight 2,500 parts by weight Hard polyurethane product SMC Waste 80 parts by weight 90 parts by weight 120 parts by weight 230 parts by weight glue Same as Example 1 Same as Example 2 Same as Example 3 Same as Example 4 Core Density (kg / ㎥) 95 110 150 280 50 Compressive strengthkgf / ㎠ 10.1 14.5 23.5 51.6 2.9 Elastic strength kgf / ㎠ 15.9 20.6 49.8 109.6 6.3 Dimensional Stability,% 70 ℃ X 24hr-10 ℃ X 24hr 1.60-1.83 0.95-1.55 0.62-0.55 0.21-0.32 1.75-2.05 Thermal conductivity, kcal / m · hr · ℃ 0.0234 0.0256 0.0275 0.0345 0.021

The present invention as described above has the economical and environmentally friendly advantages of not only fundamentally treating environmental pollution sources such as waste polyurethane foam and glass fiber, but also reusing resources for various building materials and creating new building materials.

Claims (4)

Recycling method of building materials using waste polyurethane foam, 840 ~ 3520 parts by weight of hard polyurethane foam or glass fiber containing hard polyurethane foam pulverized to diameter of 10mm or less, SMC waste 80 ~ 320 parts by weight, adhesive 360 ~ After fully mixing 960 parts by weight, put it in a mold pre-heated at 55-60 ° C., compress it with a press pressure of about 50 kg / cm 2 G, demold after 5 minutes, and mature the product at room temperature for 1 day. Recycling method of building materials using waste polyurethane foam characterized in that. According to claim 1, wherein the adhesive is TDI (Toluene Diisocyanate, MDI (Methylene Diphenyl Diisocyanate), IPDI (Isophorone Diisocyanate), HDI (Hexamethylene Diisocyanate), MXDI (m-Xylene Diisocyanate), Epoxy resin of bisphenol A type having the following structural formula Epoxy resin of bisphenol F type having the following structural formula Noble type epoxy resin, Polyol Modified Epoxy Resin, with molecular weight between 1,000 and 100,000 and a glass transition temperature (Tg) of 0 ~ 100 ℃, MMA (Methylmeth Acrylate), 2-EHA (2-Ethyl hexyl Acrylate), 2-HEMA ( Recycling method of building materials using waste polyurethane foam, characterized in that any one compound selected from 2-Hydroxyl ethylmeth Acrylate), BA (Butyl Acrylate), EA (Ethyl Acrylate), SM (Styrene Monomer). Method of using the recycled building material in claim 1 as a boiler flooring. Method of using the building material recycled in claim 1 in the prefabricated block.