JP4501577B2 - Method for producing recycled polymer molding - Google Patents

Description

The present invention relates to a method for producing a recycled polymer molded product using a processed product of the polymer molded product .

  When treating polymer moldings as waste, in many cases, either a landfill or incineration method has been adopted.

  For example, in the case of landfill, the polymer molded product is usually molded into a shape having an internal space such as a container and occupies a large volume, and the waste and used landfill processing efficiency of the waste after use is poor. there were.

  Therefore, although attempts have been made to reduce the volume by crushing by mechanical force, etc., since there is no crushing device that crushes a large amount of polymer moldings simply and economically, it is not actually pulverized. It was disposed of in landfill with the same size.

  For this reason, when a polymer molded product is disposed of in landfills, problems such as securing landfill sites and environmental destruction are problems to be overcome.

  On the other hand, when incinerated, incineration itself is possible, but there are problems such as the generation of toxic gases such as hydrogen cyanide, which are likely to affect the environment and damage the incinerator.

  For example, when processing a polymer molding made of a thermosetting resin, the thermosetting resin undergoes a chemical reaction when it is heated, so that it does not soften once cured and becomes insoluble in any solvent. ing. For this reason, disposal of a polymer molded product made of a thermosetting resin has various problems such as difficulty in processing, economy, and preservation of the global environment. For this reason, there is no processing method other than landfill or incineration. is the current situation.

  In particular, when a urethane wheel or a rubber wheel is discarded, it is difficult to separate the metal portion and the resin portion, and a method has been adopted in which only the metal portion that has been burned and burned without being separated is reused.

  There is also a treatment method in which a polymer molded product is pyrolyzed under high heat (for example, see Patent Document 1). However, in order to perform this processing method, a large-scale processing facility, a lot of labor and energy are required.

For example, in recent years, the above-described disassembly treatment has been used for plastic bottles that have been enacted by the Containers and Packaging Recycling Law and whose national, local governments, and regions are jointly promoting their recycling business. However, in order to perform the above-described decomposition process, a process of crushing and washing the PET bottle to be processed into a predetermined size is necessary as a previous process, which requires a lot of labor and time.
JP-A-8-188780

  The present invention has been made in view of the above circumstances, and the problems to be solved include problems such as securing landfill sites and environmental destruction that occur when polymer molded products that become waste are disposed of. It is the environmental impact caused by the generation of poisonous gas, the damage of the incinerator, the large-scale processing facilities, many troubles, the trouble of requiring energy, and the difficulty of recycling as a polymer molding resource.

An object of this invention is to provide the manufacturing method of the regenerated polymer molding using the processed material of a polymer molding .

In order to achieve the above object, the present invention is a polymer molded product treated in a pressurized saturated water vapor at 100 ° C. or higher and 0.1 MPa or higher for 1 to 250 minutes , or a crosslinking agent is mixed into the processed product. The mixture is used as a raw material for re-polymerization, and is contained in the treated product. The gist of the present invention is a method for producing a recycled polymer molded product characterized by reacting or reacting the treated product with a crosslinking agent.

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In the present invention, by treating a polymer molded product that has been treated in high-pressure steam at 100 ° C. or higher and 0.1 MPa or higher for 1 to 250 minutes , the polymer molded product is liquid, pasty, or solid ( And can greatly reduce the volume of the polymer molded product before processing, and can greatly contribute to solving problems such as securing land for landfill and environmental destruction.

  Moreover, according to the present invention, the volume of the polymer molded product can be reduced to liquid, paste, or solid (granular), so that the energy cost can be greatly reduced even when incineration is performed.

  Further, according to the present invention, the polymer molding may be treated as it is in a high-pressure steam at 100 ° C. or more and 0.1 MPa or more, and it is not necessary to crush and wash the polymer molding prior to the treatment.

  In addition, the processed polymer molded product obtained by the present invention, that is, a liquid, paste, or solid, can be used as a raw material for regenerated polymerization as it is or by mixing with a crosslinking agent.

  Moreover, according to the present invention, a processed product obtained by treating a used polymer molded product in high-pressure steam, or a mixture obtained by mixing a cross-linking agent with the treated product can be recycled as a new polymer molded product, Compared with a conventionally known recycling method for polymer moldings, a large-scale processing facility is not required, and energy, labor and cost required for the processing can be greatly reduced.

  In addition, according to the present invention, the polymer molded product can be processed and recycled without using a catalyst such as an acid or an alkali, so that the global environment is not adversely affected.

  Furthermore, according to the present invention, when a urethane wheel or the like is subjected to high-pressure steam treatment, the metal portion and the resin portion can be treated as they are without separation, and not only the metal portion but also the resin portion can be reused after the treatment. There is an advantage.

The method for producing a regenerated polymer molded article using the processed polymer molded article of the present invention is characterized in that the polymer molded article is treated in high-pressure steam. The polymer molded product treated by the method of the present invention has a chain structure or a network formed by a homopolymer obtained by polymerizing a single monomer, or a copolymer obtained by copolymerizing a plurality of monomers. Examples thereof include those having a structure and made of a polymer mainly containing any one or two or more selected from the group consisting of urethane, urea, ester, amide, carbonate, ether, imide, and phosgene. .

  The category of the polymer molded product to be treated by the method of the present invention includes, for example, a polymer molded product made of a thermosetting resin such as epoxy, a polymer molded product made of rubber, and a new recycled product by the method of the present invention. Polymer moldings are also included.

  The treatment according to the method of the present invention means that the polymer chain and the network constituting the polymer molded product are all broken and decomposed into monomers as starting materials. This means that a part of the chain or the net is cut and decomposed into a lower molecular weight polymer.

  As the high-pressure steam applied to the method of the present invention, pressurized saturated steam at 100 ° C. or higher and 0.1 MPa or higher is preferably used. If the high-pressure steam used to treat the polymer molding is less than 100 ° C. or less than 0.1 MPa, decomposition of the polymer molding does not proceed effectively, resulting in a longer treatment time and higher energy costs. This is because. More preferably, it is 100-250 degreeC and 1-5 MPa pressurized saturated water vapor | steam. In this case, the decomposition of the polymer molded product proceeds more effectively, the processing time can be shortened, and the energy cost can be reduced. In addition, in order to suppress the oxidation of a polymer molding, for example, inert gas, such as nitrogen, can also be added in water vapor.

  The time for treating the polymer molded product in high-pressure steam is appropriately changed according to the type of polymer molded product, the amount of treatment, the size or shape of the molded product. Specifically, it is preferably 1 to 250 minutes, more preferably 1 to 120 minutes. When the treatment time is less than 1 minute, the polymer molded product is not sufficiently in contact with the high-pressure steam and the treatment becomes insufficient. When the processing time exceeds 250 minutes, even if the processing time increases, the decomposition does not proceed any further, so that the processing itself is wasted.

  Since the treatment method of the present invention is carried out in contact with high-pressure steam at 100 ° C. or higher and 0.1 MPa or higher, the reactor to be used is sufficiently resistant to such temperature and pressure, and charged with a polymer molding and It is desirable to easily discharge the processed material. Specifically, it is desirable that the inner diameter of the tubular steam flow is turbulent so that the high-pressure steam is sufficiently in contact with the polymer molded product charged in the reactor.

  In addition, as a method of supplying high-pressure steam into the reactor, for example, a method using a boiler such as a vertical boiler, a furnace boiler, a natural circulation boiler, a forced circulation boiler, or the like, the water in the reactor is heated to increase the pressure. There is a method like autoclave raising.

  Depending on the type of polymer molded product and the processing conditions (temperature of water vapor, pressure, processing time), the processed product of the polymer molded product that has been subjected to high-pressure steam treatment by the method of the present invention is liquid, pasty, or solid (granular) It becomes a form.

  Moreover, the processed product of the polymer molded product subjected to the high-pressure steam treatment by the method of the present invention can be used as a raw material for regenerated polymerization as it is or by mixing with a crosslinking agent. Examples of the crosslinking agent include one or more selected from the group of dichloric acid derivatives such as dichloric acid chloride, diisocyanate, dicarboxylic acid, dicarbamate, bisurethane, and diamine.

  Reactive groups such as hydroxyl groups and amino groups are present in the processed polymer molded product that has been subjected to high-pressure steam treatment due to the high-pressure steam treatment. These reactive groups react when the treated product is re-reacted as a regenerated polymerization raw material to obtain a new polymer molded product, or a mixture obtained by mixing a cross-linking agent with the treated product is used as a regenerated polymerization raw material to react these treated product and the cross-linking agent. Thus, when a new polymer molding is obtained, it has a function of determining the reaction amount in the re-reaction of the treated product or the reaction of the treated product and the crosslinking agent.

  In other words, when a new polymer molded product is produced using a treated product or a mixture obtained by mixing a crosslinking agent in the treated product as a raw material for regenerated polymerization, the treated product is re-reacted or treated by the amount of reactive groups contained in the treated product. The smaller the amount, the shorter the reaction time required to obtain a new polymer molding and the smaller the amount of the crosslinking agent. Conversely, the greater the amount of reactive groups, the longer the reaction time required to obtain a new polymer molding, and the greater the amount of crosslinking agent.

  The reactive group having such an effect is generated by cutting the polymer chain or part of the network constituting the polymer molded product and reducing the molecular weight by high-pressure steam treatment. By appropriately changing, the amount of reactive groups in the treated product can be controlled.

  That is, when the temperature and pressure of water vapor used for the high-pressure steam treatment are low and the treatment time is short, the polymer constituting the polymer molded product does not decrease in molecular weight, and the amount of reactive groups in the treated product decreases. On the other hand, when the temperature and pressure of the water vapor used for the high-pressure steam treatment is high and the treatment time is long, the lowering of the polymer constituting the polymer molded product will effectively proceed, and the amount of reactive groups in the treated product will also increase. become.

  For example, when a polymer molded product made of polyurethane is subjected to high-pressure steam treatment, it is expressed as a hydroxyl value and an amine value present in the treated product, and the amount of the crosslinking agent, that is, the diisocyanate is appropriately increased or decreased according to the size of the hydroxyl value and the amine value. A raw material for regenerative polymerization is obtained by mixing in the treated product, and these are reacted and molded to obtain a polymer molded product made of a new polyurethane.

  In addition, this invention is not limited to the following Example, It can implement freely by changing in the range described in the "Claims".

Example 1
Preparation of Sample A 100-part liquid urethane prepolymer having isocyanate groups at both ends is cast with a blend of a curing agent component comprising 12 parts by weight of a diamine, heated at 110 ° C., and 20 cm × 20 cm. A polymer molded product made of thermosetting polyurethane having a size of × 0.2 cm was obtained. Table 1 shows the static physical property values of the obtained polymer molding.

Steam treatment and properties of the treated product The above sample is placed in a reactor made by Nisaka Manufacturing Co., Ltd. having a diameter of 50 cm in a high pressure steam at 200 ° C. and 1.6 MPa for 30 minutes (b) and 60 minutes (c). , 120 minutes (d) and 240 minutes (e), respectively, and the water vapor treatment was performed while changing the treatment time. The viscosity (cps) at each temperature of the processed product is shown in FIG. In FIG. 1, for comparison, the viscosity of the raw material urethane prepolymer is shown as a graph in FIG.

  Moreover, the hydroxyl value and amine value of the processed material for every processing time are shown in FIG. 2, and the IR analysis result of the processed material for each processing time is shown in FIG. The hydroxyl value of the treated product at each treatment time was measured according to JIS K 0070, and the amine value was measured according to JIS K 7237.

  From FIG. 1, it was confirmed that as the treatment time increased, the viscosity (cps) of the treated product decreased, and the viscosity decreased to the same level as the raw material urethane prepolymer. This is thought to be due to the progress of decomposition (decreasing the molecular weight) of the polymer molded product as the steam treatment time becomes longer, and accordingly the viscosity (cps) of the treated product is lowered.

  Moreover, it was confirmed from FIG. 2 that the hydroxyl value and the amine value in the treated product are increased by increasing the time of the steam treatment. This is because the decomposition of the polymer molded product progresses due to the longer treatment time of the steam treatment, and the polymer chain and part of the network in the polymer molded product are broken, resulting in a high hydroxyl value and amine value in these processed products. It is thought that it became.

  This was also confirmed from the IR analysis results shown in FIG. That is, as the processing time increases to 30 minutes, 60 minutes, 120 minutes, and 240 minutes, the expansion and contraction of “C═O” (the peak appearing in the frequency range shown in (1) in FIG. 3), “−CO—NH— ”(The peak appearing in the frequency range shown in (2) in FIG. 3) was confirmed to decrease.

New Polymer Molded Product Using Processed Polymer Molded Product Next, 65 parts by weight of the polymer molded product obtained by the above steam treatment (treated for 120 minutes) was used with diisocyanate (NCO amount of 8). .59%) is blended at a ratio of 100 parts by weight into a mold, and is poured into a mold and heated at 110 ° C. to obtain a new polymer molded article mainly composed of urethane and urea. It was. The static physical property values of the obtained polymer molding are shown in Table 2 below.

尚、静的物性値の測定については、硬さがJIS K 6253、引張強度がJIS K 6251、伸びがJIS K 6251、引裂強さがJIS K 6252、反発弾性がJIS K 6255、圧縮永久歪がJIS K 6262の各規格に準拠して行った。

Regarding the measurement of static physical properties, hardness is JIS K 6253, tensile strength is JIS K 6251, elongation is JIS K 6251, tear strength is JIS K 6252, impact resilience is JIS K 6255, compression set is This was performed in accordance with each standard of JIS K 6262.

表２から、表１と比較したとき、処理物から得られた新たなポリマー成形物は、再生合成物ではあるものの高圧水蒸気処理前のポリマー成形物よりも硬く、かつ低反発性に優れることが確認された。また、圧縮永久歪の改善も確認された。

From Table 2, when compared with Table 1, the new polymer molded product obtained from the treated product is harder than the polymer molded product before the high-pressure steam treatment, although it is a regenerated synthetic product, and excellent in low resilience. confirmed. In addition, improvement in compression set was also confirmed.

Example 2
A polymer molded product of polyester (20 cm × 20 cm × 0.2 cm) which is a thermoplastic resin was used, and this was subjected to high-pressure steam treatment for 30 minutes in 200 ° C. and 1.6 Mpa high-pressure steam. After treatment, the polymer molding in the reactor was easily pulverized without using a catalyst.

In the present invention, the polymer molded product becomes liquid, paste, or solid (granular) by treatment in pressurized saturated steam at 100 ° C. or higher and 0.1 MPa or higher for 1 to 250 minutes. The volume of the previous polymer molded product can be greatly reduced, which can greatly contribute to solving problems such as securing landfill sites and environmental destruction.

Moreover, according to the present invention, the volume of the polymer molded product can be reduced to liquid, paste, or solid (granular), so that the energy cost can be greatly reduced even when incineration is performed.

  Further, according to the present invention, the polymer molding may be treated as it is in a high-pressure steam at 100 ° C. or more and 0.1 MPa or more, and it is not necessary to crush and wash the polymer molding prior to the treatment.

In addition, the processed polymer molded product obtained by the present invention, that is, a liquid, paste, or solid, can be used as a raw material for regenerated polymerization as it is or by mixing with a crosslinking agent.

  Furthermore, according to the present invention, a processed product obtained by treating a used polymer molded product in high-pressure steam, or a mixture obtained by mixing a cross-linking agent with the treated product can be recycled as a new polymer molded product, Compared with a conventionally known recycling method for polymer moldings, a large-scale processing facility is not required, and energy, labor and cost required for the processing can be greatly reduced.

  In addition, according to the present invention, the polymer molded product can be processed and recycled without using a catalyst such as an acid or an alkali, so that the global environment is not adversely affected.

  Further, according to the present invention, when a urethane wheel or the like is subjected to high-pressure steam treatment, the metal portion and the resin portion can be treated as they are without being separated, and not only the metal portion but also the resin portion can be reused after the treatment. There is an advantage.

About the sample of Example 1, the viscosity in each temperature of the processed material which changed the processing time into 30 minutes, 60 minutes, 120 minutes, and 240 minutes, respectively, and the raw material urethane prepolymer in high pressure steam The graph which showed (cps). About the sample of Example 1, the hydroxyl value and amine value of each processed material which performed the high-pressure steam treatment for 30 minutes, 60 minutes, 120 minutes, 240 minutes, and 360 minutes in the high-pressure steam for different treatment times are shown. Graph. The graph which showed the IR analysis result of each processed material which changed the processing time about 30 minutes, 60 minutes, 120 minutes, and 240 minutes in the high pressure steam about the sample of Example 1, respectively.

Claims (2)

100 ° C. or higher, processed polymer molded product processed for 1 to 250 minutes in pressurized saturated steam of 0.1 MPa or higher, or a mixture obtained by mixing a cross-linking agent with the processed product as a regenerated polymerization raw material, The reaction product is re-reacted using a reactive group that determines the reaction amount in the re-reaction of the treatment product or the reaction between the treatment product and the crosslinking agent, or the treatment product and the crosslinking agent A process for producing a regenerated polymer molded product characterized in that   The cross-linking agent is one or more selected from the group consisting of dichloric acid derivatives such as dichloric acid chloride, diisocyanate, dicarboxylic acid, dicarbamate, bisurethane, diamine, and phosgene. 2. A method for producing a recycled polymer molded article according to 1.

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