KR100644998B1 - Processing method of complex degradable additive for polyurethane and complex degragable polyurethane containg the complex degardable additive - Google Patents

Abstract

Provided are a method for preparing a composite decomposer for polyurethane, a composite decomposer for polyurethane prepared by the method which decomposes a widely-used polyurethane completely within a short time, a polyurethane composition containing the composite decomposer, and a polyurethane product using the composition. The method comprises the steps of injecting 20-40 wt% of phosphoric acid, 10-30 wt% of phosphorus acid, 5-15 wt% of sodium perchlorate, and the balance of a saturated fatty acid bisamide into a reactor; increasing the temperature to 120-180 deg.C to melt and react them; and cooling it to prepare the composite decomposer for polyurethane. Preferably the saturated fatty acid bisamide is methylene bisstearamide or ethylene bisstearamide. The polyurethane composition comprises 100 parts by weight of polyurethane; and 0.5-3.5 parts by weight of the composite decomposer.

Description

Processing method of complex degradable additive for polyurethane and complex degragable polyurethane containg the complex degardable additive}

1 is a graph showing the results of measuring the decomposition of the polyurethane film and cellulose prepared according to the present invention.

The present invention relates to a composite disintegrating agent for polyurethane, and more particularly, for polyurethane, which is capable of fully degrading polyurethane in a short period of time by showing excellent complex degradability when added to a general-purpose polyurethane having biodegradability and hydrolyzability. The present invention relates to a method for producing a complex decomposer and a complex degradable polyurethane composition containing the complex decomposer produced by the method.

Generally, polyurethane is a generic term for a polymer compound having a urethane bond (-NHCOO-) in a repeating unit of the main chain, and as is well known, a combination of three components such as isocyanate and polymer polyol constituting the soft part and single phase polyol constituting the hard part It can be seen as a polymer composed of, and can be classified into ester, ether and caprolactam based on the form of the polymer polyol constituting the soft part.

These polyurethanes are not only good in abrasion resistance, abrasion resistance, chemical resistance, solvent resistance, but also excellent in aging resistance and oxygen stability, and are widely used as polyurethane foams, polyurethane rubbers, adhesives, synthetic fibers, paints, and the like. Unlike general polyurethane, the use ratio of Thermoplastic Polyurethane (TPU: Thermoplastic Poly Urethane; This is because thermoplastic polyurethanes are non-toxic, environmentally friendly and thermoformable.

Polyurethane generally has its own degradability such as hydrolysis and biodegradability, but its degradability is so weak that it does not completely decompose upon disposal after use of polyurethane products and is partially decomposed to exist semipermanently It takes a long time to cause environmental pollution. Due to this, the recycling method or incineration method of polyurethane products is used, but there is a problem that harmful substances are generated during incineration, and the recycling method is not only difficult to collect but also has to go through the process of removing impurities mixed separately after collection. have. Therefore, there is an increasing demand for polyurethane that does not change the characteristics of the polyurethane while disposing fast, and various studies have been conducted to prepare a polyurethane having excellent degradability according to such a requirement.

In connection with techniques for improving degradability, Japanese Patent Laid-Open Nos. 4-189822 and 4-189823 produce aliphatic polyesters having a number average molecular weight of about 1.50,000 by reaction of aliphatic dicarboxylic acids and glycols, A method for producing ester-based polyurethanes, that is, polyester urethanes by crosslinking them with diisocyanate (-NHCOO-) has been proposed. However, according to the method proposed by the Japanese Laid-Open Patent, there is a problem in that microgels are generated in the low molecular weight aliphatic polyester, thereby degrading the quality of the polymer. In addition, since the diisocyanate reacts with the aliphatic polyester instantaneously, the remaining diisocyanate does not react and there is a problem that the remaining diisocyanate is present as a new contaminant.

In order to solve such a problem of remaining isocyanate, Korean Laid-Open Patent Publication No. 2001-66970 mixes biodegradable aliphatic polyester and hydrolyzable polyester urethane which is biodegradable resin to have biodegradability and hydrolyzability while The resin composition which is high in this physical property and excellent in the moldability of a product is provided. In this case, since the biodegradability and hydrolyzability are imparted to the aliphatic polyester resin, there is an advantage in that the decomposition rate is improved compared with the case of using the aliphatic polyester alone, but still has a disadvantage in that the decomposition rate is slow.

In order to solve such a conventional problem, the present invention, when used in addition to the existing general-purpose polyurethane, that is, a general-purpose polyester urethane having biodegradability and hydrolyzability, exhibits the decomposition properties such as oxidative decomposability in addition to biodegradability and hydrolysis. It is an object of the present invention to provide a method for preparing a composite disintegrating agent for polyurethane, which can significantly shorten the decomposition time of polyurethane because of its complex degradability.

In addition, the present invention has another object to provide a composite decomposition agent for polyurethane produced by the above production method.

In addition, the present invention contains a complex decomposition agent for polyurethane, and significantly shortens the decomposition period of the polyurethane, and has a complex degradability having reworkability while maintaining the stability of the wear resistance, chemical resistance, solvent resistance, etc. of the polyurethane as it is. It is another object to provide a polyurethane composition.

In another aspect, the present invention is to provide a polyester urethane product having a multi-degradability as being prepared by extrusion or injection molding the polyurethane composition.

In order to achieve the above object, the present invention provides a reaction vessel with 20-40% by weight of phosphoric acid, 10-30% by weight of phosphoric acid, 5-15% by weight of sodium perchlorate and saturated fatty acid bis The present invention provides a method for producing a composite disintegrating agent for polyurethane, which is characterized by cooling the amide by adding a residual amount of amide to 100 wt%, then heating to 120-180 ° C. to melt the reaction.

In another aspect, the present invention provides a composite decomposer for polyurethane, characterized in that prepared by the above production method.

Furthermore, the present invention provides a polyurethane composition having a complex degradability, which is obtained by adding and mixing the complex decomposition agent for polyurethane to a polyurethane.

In addition, the present invention provides a polyurethane product, characterized in that prepared by extruding or injection molding the multi-decomposable polyurethane composition.

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

Polyurethane complex disintegrator according to the present invention 100 to 20% by weight of phosphoric acid, 10 to 30% by weight of phosphorus acid, 5 to 15% by weight of sodium perchlorate and saturated fatty acid bisamide in the reaction vessel It is prepared by adjusting to% and then heating to 120-180 ° C. to melt the reaction.

Polydegradation agent for polyurethane prepared in this way, when used in combination with polyurethane, not only biodegradability and hydrolyzability but also oxidatively decomposable in combination with the existing polyurethane to improve the biodegradability and hydrolyzability of the polyurethane to decompose It will increase the speed considerably.

Here, the phosphoric acid is added to promote the biodegradability as well as to enhance the decomposability by promoting the oxidation of the prepared complex decomposer with polyurethane. At this time, the phosphoric acid has a problem in that when the total weight of the total ingredients added to the composite decomposition agent is 100% by weight, if the amount is less than 20% by weight, sufficient degradability enhancement effect cannot be obtained, and the amount is 40% by weight. If it exceeds%, there is a problem that the decomposability-promoting effect is halved because it is difficult to exhibit the complex decomposition properties because the other components are added relatively less. Therefore, the phosphoric acid is preferably added so that 20 to 40% by weight.

10-30% by weight of phosphorus acid is added together with the phosphoric acid, and the phosphorus acid is added to enhance the hydrolyzability when the prepared complex decomposition agent is added to the polyurethane. Here, when the amount of phosphorus acid added is less than 10% by weight, there is a problem in that the hydrolyzable effect is not sufficiently enhanced. When the amount of the phosphorus acid is added in excess of 30% by weight, the content of other components is relatively reduced, so that it is difficult to exhibit complex degradability, thereby improving degradability. Since there is a problem that the effect is halved, it is preferable to add phosphorus acid within the above range.

Sodium perchlorate is added to impart oxidative degradability when the prepared complex decomposer is added to the polyurethane. If the added amount is less than 5% by weight, there is a problem in that the effect of enhancing the oxidative decomposability is lowered. In this case, since the content of other components is relatively reduced, it is difficult to exert complex decomposition properties, so that there is a problem of inferior degradability. Sodium perchlorate is preferably added by 5 to 15% by weight.

Saturated fatty acid bisamide acts as a binder and is added to make the mixing evenly by mixing with polyurethane. When the remaining amount of bisamide is added to the total reactor, do.

The saturated fatty acid bisamide may be a variety of known ones, but it is preferable to use methylene bis stearamide or ethylene bis stearamide as the saturated fatty acid bisamide.

After adding the phosphoric acid, phosphorus acid, sodium perchlorate and saturated fatty acid bisamide to the reactor as described above, the temperature of the reactor is increased to 120-180 ° C, melted, and then reacted for 20 minutes and cooled. Degradants can be obtained. If necessary, it may be used by cutting to a predetermined size or preparing a pellet to facilitate the handling of the complex decomposition agent prepared in the cooling and solidification process after the melting reaction, which can be selectively made as needed.

In this case, calcium carbonate may be additionally added in the process of preparing the complex decomposer, and the calcium carbonate is added to give the decomposability by photodegradation, that is, by ultraviolet rays when the prepared complex decomposer is mixed with polyurethane. Calcium carbonate has the disadvantage that the UV decomposition performance is insignificant when the addition amount is less than 0.1% by weight, and when the addition amount is more than 2% by weight, the content of other components is relatively reduced, which is difficult to show the complex degradability. Since there is a problem, calcium carbonate may be added at an additional 0.1 to 2% by weight during the preparation of the composite decomposition agent.

 The composite decomposer prepared as described above has a complex degradability which simultaneously exhibits biodegradability, hydrolyzability and oxidative degradability, thereby significantly shortening the decomposition period of the polyurethane when mixed with polyurethane, and when calcium carbonate is additionally added. In addition to biodegradability, hydrolyzability and oxidative degradability, the complex decomposer can further exhibit photodegradability, which can significantly shorten the decomposition period of the polyurethane, thereby greatly contributing to the prevention of environmental pollution.

As described above, the complex decomposer for polyurethane according to the present invention can be used by adding and mixing a general purpose polyurethane, and accordingly, in the present invention, the complex decomposability is characterized by adding and mixing a complex decomposing agent to a polyurethane. It provides a polyurethane composition having.

Here, the polyurethane may be applied to a general purpose, it is applicable to all ester-based, ether-based and lactone-based polyurethane. Preferably, among the polyurethanes, it is preferable to use an ester polyurethane having high biodegradability and hydrolyzability, that is, polyester urethane. As is well known, polyester urethane is prepared by reacting an aromatic polyester with a diisocyanate, and can be easily prepared through known techniques. If necessary, polyester urethanes commonly used in the art may be purchased and used, and for example, may be selected from those sold in SK Chemicals, Kolon, Songwon Industries, Hosung Chemicals, and the like.

At this time, when the polyester urethane has a melting point of 120 to 220 ° C., a number average molecular weight of 1,000 to 150,000, a weight average molecular weight of 1,500 to 300,000, and a surface strength (type A) of 50 to 100, an excellent decomposition effect. Since it can be obtained, it is preferable to select and use a polyester urethane in consideration of this.

The complex disintegrating agent mixed with the polyester urethane is preferably mixed at a ratio of 0.5 to 3.5 parts by weight with respect to 100 parts by weight of polyester urethane. However, when the mixing ratio is less than 0.5 parts by weight, there is a problem in that the degradation performance is lowered. If the ratio exceeds 3.5 parts by weight, it may lead to a change in physical properties of the polyester urethane to be mixed, so that the complex decomposition agent is mixed with the polyester urethane in a ratio within the above range.

The composition obtained by mixing the polyester urethane and the composite decomposition agent can be applied to various products according to a known extrusion or injection molding method, for example, injection of commercial films such as packaging materials, horticulture and agricultural, industrial, textile materials, etc. It can be applied to molded products and extruded products.

Such products exhibit superior decomposability compared to conventional polyurethane products because they exhibit complex decomposability upon disposal after use, and can significantly reduce the decomposition period. Therefore, the complex decomposition agent according to the present invention in order to prevent environmental pollution will have an important significance.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are only presented to aid the understanding of the present invention, but the present invention is not limited thereto.

<Examples 1 to 4 and Comparative Examples 1 and 2>

To the 40000 g of polyester urethane (TPU) having a number average molecular weight of 78000, a weight average molecular weight of 164000, and a melting point of 185 ° C., a composite decomposition agent was added and mixed as shown in Table 1 below, followed by L / with hopper dry. It was put into an extrusion molding machine of D 30 to prepare a film according to a conventional film forming method. The physical properties of the prepared film were measured using a UTM (Universal Testing Machine), and measured 10 times for each item, and the average values of the remaining values except for the maximum and minimum values are shown in Table 1 below.

division Compound Degradation Amount (g) Addition amount of complex degradant per 100g of TPU (g) Tensile Strength (Kgf / ㎠) Elongation (%) Tear strength (Kgf / ㎠) Comparative Example 1 0 0 700 800 450 Example 1 200 0.5 665 753 412 Example 2 600 1.5 654 723 354 Example 3 1000 2.5 652 721 340 Example 4 1400 3.5 650 688 335 Comparative Example 2 1800 4.5 638 585 326

As shown in Table 1 above, in the case of adding the complex decomposition agent to the polyurethane within the preferred range of the present invention, that is, Examples 1 to 4 in which the complex decomposition agent per 100 g of TPU is added within the range of 0.5 to 3.5 g It can be seen that the change in physical properties is not large when compared with Comparative Example 1 without adding a complex decomposition agent. However, in the case of Comparative Example 2 in which the complex decomposition agent was added at a ratio of 4.5 g per 100 g of TPU, it can be seen that the physical properties dropped sharply.

Experimental Example 1

The degradability of the resin obtained from the resin composition of the present invention under the controlled composting conditions of the laboratory was evaluated.

① Experimental materials

Compost: 70% food waste, 20% sawdust, and 10% food waste compost were used as raw materials. Composting was carried out in an acrylic reactor with a diameter of 29 cm and a height of 51 cm, and the temperature of the compost was controlled by adjusting the air supply amount. The high temperature fermentation process was about 17 days during the composting process, and the compost after 2 weeks of ripening was used as a compost source for measuring biodegradability.

Sample: Resin in the film state prepared in Example 1 (62.5% carbon content per unit weight) and cellulose (Sigma Co., Ltd.), a natural polymer as a control, was added at a 5% weight ratio of the compost dry weight.

Experimental apparatus: The experimental apparatus was constructed based on US ASTM D5209-92. The reactor (Testing Bottle, 2.5L acrylic reactor) was maintained at 55 ± 2 ℃ for the culture of microorganisms. Two holes were drilled in the reactor to allow for air supply and capture of the generated carbon dioxide. At this time, to remove the carbon dioxide of the air supplied to the reactor 10N aqueous sodium hydroxide solution and 0.025 barium hydroxide aqueous solution was put into a 1L Erlenmeyer flask 700ml each and connected. In addition, in order to capture the generated carbon dioxide 200ml each of 0.4N potassium hydroxide solution and 0.1N barium hydroxide aqueous solution was put in a 250ml Pyrex tube was connected to the reactor. By placing the empty bottle on the top of the reactor to condense the water evaporating from the reactor due to the continuous aeration, and supplying the collected moisture back to the reactor at regular intervals, the moisture content, which is the most important factor in measuring the biodegradability using the compost of the reactor It was kept constant.

② Experiment Method

The biodegradability measurement experiment was carried out using the compost as a solid phase. Care was taken to ensure that the sample was exposed to the surface as much as possible while mixing 5% of the sample by dry weight ratio with respect to 150g of compost (wet weight, moisture content 54.3%). The compost and the sample prepared in the culture bottle (three culture bottles per sample) were prepared, the carbon dioxide collector was connected to each incubator, and the decomposition experiment was started. In each batch experiment, the incubator without the sample was placed, and the amount of carbon dioxide generated in the compost was measured to observe the degree of decomposition. In order to prevent drying of the compost due to continued aeration, the water condensed by condensation was collected and fed back to the reactor.

The generated carbon dioxide was separated from the first carbon dioxide collector 3 to 4 days after the start of the experiment, and then continuously separated and quantified at about 1 week intervals. In order to quantify the amount of carbon dioxide generated, add 2N barium chloride solution and stir well in case of 0.4N potassium hydroxide solution to drop the carbon dioxide of carbon dioxide collected in the solution to precipitate. After titration, the solution was titrated with 0.2 N aqueous hydrochloric acid solution until the color became pink without stirring. In order to quantify the amount of carbon dioxide generated, 0.1 ml of phenolphthalein was added and titrated with 0.2 N aqueous hydrochloric acid solution until the color became colorless while stirring.

③ Analysis

A) Exploded View by CO2 Quantification

The amount of carbon dioxide generated from the sample was obtained by subtracting the amount of carbon dioxide generated from the incubator without the sample from the amount of carbon dioxide generated from the sample. On the other hand, the amount of carbon dioxide generated is a value multiplied by 1.1 after subtracting the amount of hydrochloric acid consumed from the estimated hydrochloric acid consumption as shown in the following reaction formula 1 and equation (1).

Based on the amount of carbon dioxide generated, the degree of decomposition was measured by the following Equation 2, and the result of measuring the degree of decomposition for 80 days is shown in FIG. 1.

As shown in FIG. 1, when comparing the decomposition degree of cellulose known to be excellent in decomposition with the polyurethane according to the present invention, the decomposition degree was similar to each other until 30 days ago, and since the decomposition degree of cellulose was determined according to the present invention. Decomposition is somewhat more advanced. However, as can be seen in Figure 1 it can be seen that the polyurethane according to the present invention exhibits a very good degree of decomposition properties comparable to cellulose.

As described above, the present invention provides a method for preparing a composite disintegrating agent for polyurethane, which is capable of fully dissolving the polyurethane within a short period of time by exhibiting excellent complex degradability when added to a general-purpose polyurethane having biodegradability and hydrolyzability, and There is a useful effect of providing a polydegradable polyurethane composition containing a complex degradant prepared by the process.

Claims (9)

20-40% by weight of phosphoric acid, 10-30% by weight of phosphorus acid, 5-15% by weight of sodium perchlorate and saturated fatty acid bisamide were added to the reaction vessel to adjust the amount to 100% by weight, and then heated to 120-180 ° C. Method of producing a composite disintegrating agent for polyurethane, characterized in that the reaction by melting and cooling. The method according to claim 1, A method for producing a composite disintegrating agent for polyurethane, characterized in that the reaction vessel by further adding 0.1 to 2% by weight of calcium carbonate to promote ultraviolet collapse. The method according to claim 1 or 2, The saturated fatty acid bisamide is a methylene bis stearamide (methylene bis stearamide) or ethylene bis stearamide (ethylene bis stearamide) characterized in that the manufacturing method of the complex decomposition agent for polyurethane. Composite decomposition agent for polyester urethane characterized in that it is produced by the manufacturing method of claim 3. Polyurethane composition having a complex degradability, characterized in that by adding and mixing the polyurethane composite decomposition agent of claim 4 to the polyurethane. The method according to claim 5, The polyurethane is a polyurethane composition having a complex degradability, characterized in that the ester produced by reacting the aromatic polyester and diisocyanate. The method according to claim 6, The polyurethane-based polyurethane composition is characterized in that the melting point is 120 ~ 220 ℃, number average molecular weight is 1,000 to 150,000, weight average molecular weight is 1,500 to 300,000, surface strength is 50 to 100. The method according to any one of claims 5 to 7, The polyurethane composite decomposer is a polyurethane composition having a complex degradability, characterized in that the mixture in a ratio of 0.5 to 3.5 parts by weight with respect to 100 parts by weight of polyurethane. Polyurethane product, characterized in that prepared by extruding or injection molding the multi-decomposable polyurethane composition of claim 8.

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