JP2012036261A - Method for manufacturing polybasic acid vinyl monomer copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a polybasic acid vinyl monomer copolymer, in which polybasic acid vinyl monomer copolymers within a desired molecular weight range can be selectively recovered by subcritical water decomposition from a thermosetting resin that contains a polyester and a crosslinked part.SOLUTION: The method of manufacturing the polybasic acid vinyl monomer copolymer includes: a process for setting the molecular weight or molecular weight distribution of the polybasic acid vinyl monomer copolymer obtained by the subcritical water decomposition of the thermosetting resin; a process for selecting raw materials of the thermosetting resin corresponding to the polybasic acid vinyl monomer copolymer of the desired molecular weight or molecular weight distribution; and a process for decomposing the selected raw materials of the thermosetting resin in subcritical water to obtain the polybasic acid vinyl monomer copolymer of the desired the molecular weight or molecular weight distribution.

Description

  The present invention relates to a method for producing a polybasic acid vinyl monomer copolymer by subcritical water decomposition of a thermosetting resin comprising polyester and a cross-linked portion thereof.

  Conventionally, most plastic wastes made of thermosetting resins have been disposed of in landfills. However, there is a problem that it is difficult to secure a land for landfill and that the ground becomes unstable after landfill, and it is desired to recycle plastic waste made from this thermosetting resin.

  As a technique for recycling plastic waste such as FRP using a thermosetting resin as a material, a decomposition method of a thermosetting resin using a subcritical water as a reaction medium has been proposed so far (for example, patents). References 1 and 2).

  Also, by applying this decomposition method, the modified styrene fumaric acid copolymer obtained by esterifying and modifying the styrene fumaric acid copolymer obtained as a decomposition product with alcohol to be reusable as a low shrinkage agent for thermosetting resins. A polymer has been proposed (see, for example, Patent Document 3).

  On the other hand, polybasic acid-vinyl monomer copolymers and esters thereof have been conventionally used as functional polymers for various uses, but their uses are selected according to their molecular weights. For example, a styrene maleic acid copolymer has been proposed for use as a polymer alloy with other polymers as a dispersant when the molecular weight is 20000 or less (see, for example, Patent Document 4) and as a resin when the molecular weight is 100000 or more (for example, patents). Reference 5).

  Therefore, if the styrene fumaric acid copolymer obtained by subcritical water splitting can be recovered for each molecular weight, the use will expand to functional polymers other than low shrinkage agents for thermosetting resins, and FRP subcriticality The water splitting recycling technology can be further improved.

Japanese Patent Laid-Open No. 10-24274 JP 2004-155964 A JP 2008-208186 A JP-A-8-39931 JP 2006-16559 A

  However, in the FRP subcritical water decomposition recycling technology proposed in Patent Documents 1 to 3, since the used FRP (waste FRP) is used as a raw material, the product styrene fumaric acid copolymer Structure control is difficult, and no means for recovering each molecular weight has been proposed yet.

  The present invention has been made in view of the circumstances as described above. From a thermosetting resin containing a raw material, such as waste FRP, and a cross-linked portion thereof, a desired molecular weight range can be obtained by subcritical water decomposition. It is an object of the present invention to provide a method for producing a polybasic vinyl monomer copolymer capable of selectively recovering a vinyl acid vinyl monomer copolymer.

  The method for producing a polybasic acid vinyl monomer copolymer according to the present invention produces a polybasic acid vinyl monomer copolymer by performing subcritical water decomposition using a thermosetting resin containing polyester and a cross-linked portion thereof as a raw material. In the method, a step of setting a molecular weight or molecular weight distribution of a polybasic vinyl monomer copolymer obtained by subcritical water decomposition of a thermosetting resin, and a polybasic vinyl monomer copolymer having a desired molecular weight or molecular weight distribution A step of selecting a thermosetting resin raw material corresponding to the above, and a step of subcritical water decomposition of the selected thermosetting resin raw material to obtain a polybasic acid vinyl monomer copolymer having a desired molecular weight or molecular weight distribution It is characterized by including.

  In this method for producing a polybasic acid vinyl monomer copolymer, at least one type of information selected from parameters relating to the molecular structure of the thermosetting resin and molding conditions of the thermosetting resin, and thermosetting corresponding to this information Including the step of creating correspondence data in association with the molecular weight or molecular weight distribution of the polybasic vinyl monomer copolymer obtained by subcritical water decomposition of the functional resin, and selecting the raw material of the thermosetting resin, Based on the correspondence data, a raw material for the thermosetting resin having the molecular structure corresponding to the desired polybasic acid vinyl monomer copolymer having the molecular weight or molecular weight distribution or molded according to the molding conditions is selected. It is preferable that

  In the method for producing a polybasic vinyl monomer copolymer, it is preferable that the information of the corresponding data is an average molecular weight of a polyester constituting the thermosetting resin.

  In the method for producing a polybasic acid vinyl monomer copolymer, the information of the corresponding data is preferably a ratio of the unsaturated dicarboxylic acid in the organic acid of the polyester raw material constituting the thermosetting resin.

  In this method for producing a polybasic vinyl monomer copolymer, the information of the corresponding data is preferably a molding temperature of a thermosetting resin.

  According to the present invention, a polybasic acid vinyl monomer copolymer having a desired molecular weight range is selectively recovered from a thermosetting resin comprising a raw material such as waste FRP and a cross-linked portion thereof by subcritical water decomposition. can do.

It is a figure explaining an example of the manufacturing method of the polybasic acid vinyl monomer copolymer of this invention.

  The present invention is described in detail below.

  In the present invention, the plastic to be decomposed is a thermosetting resin including polyester and a cross-linked portion thereof.

  Here, the “polyester” is a polymer obtained by polycondensation of a polyhydric alcohol component and a polybasic acid component, in which a polyhydric alcohol residue and a polybasic acid residue are linked to each other via an ester bond. Moreover, this polyester may contain the double bond derived, for example from an unsaturated polybasic acid.

  The “crosslinked part” is a part that crosslinks between the polyester molecules. Although this bridge | crosslinking part is a part originating in a crosslinking agent, for example, it is not specifically limited. Further, the cross-linked part may be a part derived from one cross-linking agent, or may be a part derived from an oligomer or polymer obtained by polymerizing a plurality of cross-linking agents. The bonding position and bonding mode between the cross-linking agent molecule and the polyester are not particularly limited.

  Therefore, “a thermosetting resin comprising a polyester and its cross-linked portion” means a reticulated thermosetting resin (a reticulated polyester) in which a polyester obtained from a polyhydric alcohol component and a polybasic acid component is cross-linked via a cross-linked portion. Resin). The structure of such a thermosetting resin and its constituent components, the type and amount of the cross-linking part (cross-linking agent), the degree of cross-linking, the type and amount of additives, etc. are not particularly limited.

  The “thermosetting resin” in the present invention means a resin that has been cured (crosslinked) mainly by heating or the like, but an uncured or partially cured resin that is cured (crosslinked) by heating or the like. Is also included.

  Although it does not specifically limit as said polyhydric alcohol component, For example, glycols, such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, etc. can be used. These may be used alone or in combination of two or more.

  The polybasic acid component is not particularly limited, but examples thereof include unsaturated polybasic acids such as unsaturated dicarboxylic acids such as maleic anhydride, maleic acid, and fumaric acid, saturated polybasic acids such as phthalic anhydride, and the like. Can be used. These may be used alone or in combination of two or more.

  Although it does not specifically limit as said crosslinking agent, For example, polymeric vinyl monomers, such as styrene and methyl methacrylate, etc. can be used. These may be used alone or in combination of two or more.

  And this invention selects the property of raw materials, such as waste FRP by a thermosetting resin as mentioned above, and subcritical water-decompositions, The polybasic acid vinyl monomer copolymer as a decomposition product is the molecular weight distribution. It is characterized by controlled production.

  That is, in order to achieve control of this molecular weight distribution and obtain a polybasic acid vinyl monomer copolymer having a desired molecular weight, an optimum thermosetting resin is selected as a raw material and subcritical water decomposition is performed.

  In the present invention, as the first step, the molecular weight or molecular weight distribution of the polybasic vinyl monomer copolymer obtained by subcritical water decomposition of the thermosetting resin is set. This can be set according to the use of a polybasic acid vinyl monomer copolymer as described later.

  In this invention, the raw material of the thermosetting resin corresponding to the polybasic acid vinyl monomer copolymer of desired molecular weight or molecular weight distribution is selected as a next process. Selection of the optimal raw material for obtaining a polybasic vinyl monomer copolymer having a desired molecular weight or molecular weight distribution can be performed by various methods. For example, the molecular weight or molecular weight distribution of the polybasic vinyl monomer copolymer after subcritical water decomposition is known in advance for each type of product, model number, application, etc., collected as waste FRP, or Prediction based on the product, model number, application, etc., analogy, etc. can also be performed.

  The raw material of the thermosetting resin for performing subcritical water decomposition may be one kind, and two or more kinds as long as the molecular weight or molecular weight distribution of the target polybasic acid vinyl monomer copolymer is obtained. There may be.

  In one preferred embodiment, the present invention relates to at least one type of information selected from parameters related to the molecular structure related to the thermosetting resin and molding conditions of the thermosetting resin, and thermosetting corresponding to this information. Creating correspondence data in association with the molecular weight or molecular weight distribution of the polybasic vinyl monomer copolymer obtained by subcritical water decomposition of the resin. The step of selecting the raw material of the thermosetting resin has a molecular structure corresponding to the polybasic vinyl monomer copolymer having a desired molecular weight or molecular weight distribution based on the correspondence data, or is molded according to molding conditions. The raw material of the thermosetting resin selected is selected.

  Here, the parameters related to the molecular structure relating to the thermosetting resin include the average molecular weight of the polyester constituting the thermosetting resin, and the unsaturated dicarboxylic acid in the organic acid of the polyester raw material constituting the thermosetting resin. A percentage is included.

  The molding conditions of the thermosetting resin include the molding temperature of the thermosetting resin, that is, the molding temperature at the time of manufacturing a molded product such as waste FRP.

  The molecular weight distribution of the polybasic vinyl monomer copolymer is not particularly limited, and includes a wide range of distribution information relating to molecular weight, such as those based on weight average molecular weight and number average molecular weight, other statistical numerical values, and measured values.

  The correspondence data can be created as follows.

  For example, when creating the corresponding data based on the average molecular weight of the polyester constituting the thermosetting resin, the polybasic acid obtained by the average molecular weight and subcritical water decomposition of various thermosetting resins having different average molecular weights. The correlation with the molecular weight or molecular weight distribution of the vinyl monomer copolymer is measured in advance. According to the knowledge of the present inventors, for example, when a thermosetting resin having a weight average molecular weight of about 20,000 is used, a styrene fumaric acid copolymer (hereinafter referred to as “SFC”) having a molecular weight of about 35,000 is obtained. be able to. Further, there is a certain correlation between the average molecular weight of the polyester constituting the thermosetting resin and the molecular weight distribution of SFC. For example, the molecular weight of the SFC obtained tends to be smaller as the average molecular weight of the polyester constituting the thermosetting resin comprising polyester and its cross-linked portion is larger.

  Based on the above matters, the average molecular weight of the polyester constituting the thermosetting resin, and the molecular weight or molecular weight of the polybasic vinyl monomer copolymer obtained by subcritical water decomposition of the thermosetting resin corresponding to this Create correspondence data that correlates with the distribution. Such correspondence data can be stored in the database in, for example, two-dimensional plot data, regression equations, and other various formats.

  When creating the corresponding data based on the proportion of the unsaturated dicarboxylic acid in the organic acid of the polyester raw material constituting the thermosetting resin, it can be performed as follows. First, for various thermosetting resins having different ratios, the correlation between the ratio and the molecular weight or molecular weight distribution of the polybasic acid vinyl monomer copolymer obtained by subcritical water decomposition is measured. According to the knowledge of the present inventors, for example, when an unsaturated dicarboxylic acid occupying 80% to 100% of the total organic acid is selected and used, an SFC having a molecular weight of about 5000 to 25000 can be obtained. it can. On the other hand, when an unsaturated dicarboxylic acid occupying ratio of 0 to 40% of the total organic acid is selected and used, SFC having a molecular weight of about 35,000 to 75,000 can be obtained.

  A specific example of such a measurement will be shown. 4 g of FRP crushed material as a thermosetting resin and 16.5 g of 0.8 mol / l NaOH aqueous solution were taken and charged into a reaction tube. Next, the reaction tube was immersed in a constant temperature bath at 230 ° C., the NaOH aqueous solution in the reaction tube was brought into a subcritical state, and the thermosetting resin was decomposed for 2 hours by leaving it immersed. Thereafter, the reaction tube was taken out of the thermostatic bath and immersed in a cooling bath, and the reaction tube was rapidly cooled to room temperature. The contents of the reaction tube after the decomposition treatment were water-soluble components, unreacted resin residues, and inorganic components such as calcium carbonate and glass fibers. By filtering this content, the solid content was separated and the water-soluble component was recovered from the reaction tube. Next, the unreacted resin residue was analyzed and the decomposition rate was calculated.

  Next, the precipitate produced by neutralizing the water-soluble component with sulfuric acid was collected and dried to obtain SFC. For SFC, we measured the mass and compared and calculated the mass with the thermosetting resin charged in the reaction tube. The SFC production rate was determined by gel permeation chromatography (GPC), the weight average molecular weight, and the nuclear magnetic resonance. The styrene / fumaric acid ratio (S / F ratio) was analyzed by spectroscopic analysis (NMR analysis).

  The ratio of alkali to resin, reaction temperature, reaction time, etc. for each of FRP crushed material (tank) with an unsaturated dicarboxylic acid ratio of 40% or less and FRP crushed material with a 100% unsaturated dicarboxylic acid ratio (tub) The above test was conducted in a unified manner.

  As a result, the FRP crushed material (tank) having an unsaturated dicarboxylic acid ratio of 40% or less had a decomposition rate of 97.9%, an SFC generation rate of 98.0%, and a weight average molecular weight of 62,000. The FRP crushed material (bathtub) having an unsaturated dicarboxylic acid ratio of 100% had a decomposition rate of 83.4%, an SFC generation rate of 90.3%, and a weight average molecular weight of 35,000.

  Based on the above matters, the proportion of the unsaturated dicarboxylic acid in the organic acid of the polyester raw material constituting the thermosetting resin, and the number obtained by subcritical water decomposition of the corresponding thermosetting resin. Corresponding data is created in association with the molecular weight or molecular weight distribution of the vinyl acid monomer copolymer. Such correspondence data can be stored in the database in, for example, two-dimensional plot data, regression equations, and other various formats.

  When the correspondence data is created based on the molding temperature of the thermosetting resin, it can be performed as follows. First, for various thermosetting resins having different molding temperatures, the correlation between the molding temperature and the molecular weight or molecular weight distribution of the polybasic vinyl monomer copolymer obtained by subcritical water decomposition is measured. According to the knowledge of the present inventors, for example, when a polymer molded at about 140 ° C. is selected and used, a polybasic vinyl monomer copolymer having a molecular weight of about 20,000 can be obtained. On the other hand, when a polymer molded at room temperature is selected and used, a polybasic acid vinyl monomer copolymer having a molecular weight of about 60000 can be obtained.

  As a specific example, an FRP crushed material having a molding temperature of 140 ° C. (motor sealing material) and an FRP crushed material molded at room temperature in the same manner as the measurement of the FRP crushed material in which the ratio of the unsaturated dicarboxylic acid is changed. (Tank) was tested. As a result, the FRP crushed material (motor sealing material) having a molding temperature of 140 ° C. had a decomposition rate of 93.3%, an SFC generation rate of 93.3%, and a weight average molecular weight of 21,000. On the other hand, the FRP crushed material (tank) molded at room temperature had a decomposition rate of 97.9%, an SFC generation rate of 98.0%, and a weight average molecular weight of 62,000.

  Based on the above matters, the thermosetting resin molding temperature is associated with the molecular weight or molecular weight distribution of the polybasic vinyl monomer copolymer obtained by subcritical water decomposition of the thermosetting resin. Create the corresponding data. Such correspondence data can be stored in the database in, for example, two-dimensional plot data, regression equations, and other various formats.

  As illustrated above, the molecular weight or molecular weight distribution of the polybasic acid vinyl monomer copolymer and a certain amount of information are selected based on one type of information selected from the parameters related to the molecular structure of the thermosetting resin and the molding conditions of the thermosetting resin. Corresponding data with correlation can be created. For example, polybasic acid vinyl monomer co-polymerization can be performed according to any of the following information: average molecular weight of polyester constituting thermosetting resin, proportion of unsaturated dicarboxylic acid in organic acid of polyester raw material, molding temperature of thermosetting resin Corresponding data having a certain degree of correlation with the molecular weight or molecular weight distribution of the coalesced can be created.

  However, the present invention is not limited to this, and the molecular weight or molecular weight distribution of the polybasic vinyl monomer copolymer is correlated with two or more kinds of information selected from parameters related to the molecular structure of the thermosetting resin and molding conditions of the thermosetting resin. Corresponding data can be created. For example, the polybasic acid can be obtained by combining two or more of the average molecular weight of the polyester constituting the thermosetting resin, the proportion of the unsaturated dicarboxylic acid in the organic acid of the polyester raw material, and the molding temperature of the thermosetting resin. The accuracy of the correlation with the molecular weight or molecular weight distribution of the vinyl monomer copolymer can be increased.

  Next, based on this correspondence data, a raw material of a thermosetting resin having the molecular structure corresponding to the polybasic acid vinyl monomer copolymer having a desired molecular weight or molecular weight distribution or molded according to the molding conditions is selected. To do.

  This selection can be performed, for example, by measuring parameters related to the molecular structure of various waste FRP molded products, or investigating and grasping the molding conditions of the thermosetting resin. In addition, for each type of molded product recovered as waste FRP, for each type of product, model number, usage, etc., the parameters related to the molecular structure and the molding conditions of the thermosetting resin are grasped in advance. When the waste FRP such as the model number and the usage is collected, it can be collated with the data grasped in advance.

  The raw material of the thermosetting resin for performing subcritical water decomposition may be one kind, and two or more kinds as long as the molecular weight or molecular weight distribution of the target polybasic acid vinyl monomer copolymer is obtained. There may be.

  In the present invention, a polybasic vinyl monomer copolymer is then produced by subcritical water decomposition of the selected thermosetting resin material.

  The raw material of the thermosetting resin is treated with subcritical water (subcritical water) having a temperature lower than the decomposition temperature of the thermosetting resin. That is, water is added to a thermosetting resin (mainly waste FRP), and the temperature and pressure are increased to bring the water into a subcritical state, thereby decomposing the thermosetting resin. Thus, for example, a polybasic such as SFC comprising a polyester-derived monomer (polyhydric alcohol and polybasic acid), a polyester-derived acid residue (fumaric acid), and a residue derived from a cross-linking portion (styrene polymer) The acid vinyl monomer copolymer can be recovered.

  The blending ratio of the thermosetting resin and water is not particularly limited, but the amount of water added is preferably in the range of 100 to 500 parts by mass with respect to 100 parts by mass of the thermosetting resin.

  In the present invention, “subcritical water” means that the temperature and pressure of water are below the critical point of water (critical temperature 374.4 ° C., critical pressure 22.1 MPa) and the temperature is 140 ° C. or higher (in this case, Since the ionic product is about 100 times the normal temperature and the dielectric constant of water is reduced to about 50% of the normal temperature, hydrolysis is accelerated and the thermosetting resin can be decomposed into monomers and the like). Water in a state where the pressure is in the range of 0.36 MPa (saturated vapor pressure of 140 ° C.) or higher.

  The temperature of subcritical water in the present invention is lower than the thermal decomposition temperature of the thermosetting resin, and is preferably in the range of 180 to 270 ° C. If the temperature during the decomposition reaction is less than 180 ° C., the decomposition process takes a lot of time and the processing cost may increase. On the other hand, if the temperature during the decomposition reaction exceeds 270 ° C., the polyester and the crosslinked part may be decomposed, making it difficult to recover the SFC.

  The treatment time with subcritical water varies depending on the reaction temperature and other conditions, but is preferably about 1 to 4 hours. This processing time is preferably shorter because processing costs are reduced. Furthermore, the pressure of the decomposition reaction (during treatment with subcritical water) varies depending on conditions such as the reaction temperature, but is preferably in the range of about 2 to 15 MPa.

  The subcritical water preferably contains an alkali salt. Since the hydrolysis reaction of the thermosetting resin is promoted by the alkali salt, the treatment time can be shortened and the treatment cost can be reduced. Here, the “alkali salt” means an alkali metal or alkaline earth metal salt that reacts with an acid and exhibits basic properties. For example, alkali metal hydroxides such as potassium hydroxide (KOH) and sodium hydroxide (NaOH), calcium carbonate, barium carbonate, calcium hydroxide, magnesium carbonate, and the like can be used. Of these, alkali metal hydroxides are preferred.

  The content of the alkali salt in the subcritical water is not particularly limited, but when obtaining SFC as a polybasic acid vinyl monomer copolymer, it is based on the theoretical number of moles of acid residues contained in SFC. It is preferable that it is 2 molar equivalents or more. If the content of the alkali salt is less than 2 molar equivalents, it may be difficult to recover SFC. In addition, although the upper limit of content of the alkali salt in subcritical water is not specifically limited, It is preferable from a cost surface etc. that it is 10 molar equivalent or less.

  After the decomposition treatment, the decomposition product is cooled and then solid-liquid separated by a method such as filtration. Here, the inorganic fillers such as glass fiber and calcium carbonate contained in the thermosetting resin are obtained as a solid content. Moreover, water and the water-soluble component melt | dissolved in this are obtained as a liquid component. In addition, when the unreacted residue etc. of a thermosetting resin are contained in solid content, solid content is mixed with solvents, such as chloroform, as needed. Thereby, the component soluble in the solvent (unreacted residue of the thermosetting resin) and the inorganic filler insoluble in the solvent can be separated. As a result, the inorganic filler can be recovered with high purity.

  On the other hand, an acid solution such as hydrochloric acid is added to the liquid obtained by solid-liquid separation for neutralization or acidification, thereby causing precipitation. Next, it is separated into an aqueous phase and a precipitate by a method such as filtration. By recovering the precipitate, a polybasic acid vinyl monomer copolymer such as SFC having a controlled molecular weight can be obtained.

  Polybasic acid vinyl monomer copolymers such as SFC thus obtained are, for example, polymeric surfactants, photoresist inks, powder coating matting agents, emulsion waxes, chelating agents, coating agents, detergents. It can be used as a builder, a polymer raw material, a compatibilizer for polymer alloys, and the like. Each of these uses has a molecular weight range suitable for each, but a polybasic acid vinyl monomer copolymer having a desired molecular weight or molecular weight distribution can be obtained according to the present invention. Can do.

  Further, the SFC obtained by the present invention can be esterified and used as a styrene-fumaric acid ester copolymer as a low shrinkage agent for thermosetting resins, particularly unsaturated polyester resins. In this case, it is preferable to produce and use SFC having a molecular weight of about 20,000 to 35,000 by the method of the present invention.

  On the other hand, by distilling the aqueous phase obtained as described above, water, polyhydric alcohol such as glycol, and organic acid can be separately collected. These can be reused as plastic production raw materials (monomers) and the like. In addition, the water obtained by distillation can be utilized again as water for producing subcritical water.

  FIG. 1 is a diagram for explaining an example of a method for producing a polybasic acid vinyl monomer copolymer of the present invention. In this example, a raw material of thermosetting resin that undergoes subcritical water decomposition is selected from various waste FRP molded products A, B, C, D, E, F, G,..., And an SFC having a desired molecular weight distribution is selected. To manufacture.

  In order to achieve control of this molecular weight distribution, an optimal resin is selected from the molded products A, B, C, D, E, F, G.

  First, for example, in the case where the correspondence data is created as described above, parameters related to the molecular structure as described above for the molded products A, B, C, D, E, F, G. Measurement is performed, and the molding conditions of the thermosetting resin are investigated to grasp these pieces of information (S1). At this time, any of the molded products A, B, C, D, E, F, G... Of the waste FRP is the same as the product, model number, application, etc. of the molded product that was previously subject to subcritical water decomposition. In this case, it is possible to collate with parameters related to the molecular structure already known for the molded article and data of molding conditions of the thermosetting resin.

  Next, the target molecular weight or molecular weight distribution of the SFC to be obtained by subcritical water decomposition is set (S2). For example, the molecular weight or molecular weight distribution is set in consideration of the above-mentioned various reuse applications.

  Next, the raw material of the thermosetting resin corresponding to the polybasic acid vinyl monomer copolymer having a desired molecular weight or molecular weight distribution is selected (S3). In this selection of raw materials, for example, parameters related to the molecular structure previously known for the molded products A, B, C, D, E, F, G, etc. of waste FRP, or thermosetting resins The raw material of the thermosetting resin corresponding to the SFC having the desired molecular weight or molecular weight distribution can be selected by comparing the molding conditions with the corresponding data stored in advance in the database (S3-1). Here, the molded products A and C of waste FRP are selected as corresponding to the SFC having a desired molecular weight or molecular weight distribution.

  Next, the selected waste FRP molded products A and C are subjected to subcritical water decomposition in a closed decomposition tank equipped with a stirring blade and the like (S4), and the resulting decomposition product is filtered from the decomposition tank. Are sent to a solid-liquid separation apparatus equipped with a solid-liquid separator (S5). Thereby, an SFC having a target molecular weight or molecular weight distribution can be produced.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
<Example 1>
The proportion of unsaturated dicarboxylic acid in the organic acid of the raw material of the polyester constituting the thermosetting resin (FRP molded product) comprising the polyester and its crosslinked part, and the subcritical water of the corresponding thermosetting resin Corresponding data in association with the weight average molecular weight of SFC obtained by decomposition was created as two-dimensional data and stored in a database.

  In creating the corresponding data, as described above, the ratio of the unsaturated dicarboxylic acid occupying the total organic acid is measured for various FRP molded products, and the SFC obtained by subcritical water decomposition of the FRP molded product. The weight average molecular weight of was measured by gel permeation chromatography (GPC). Subcritical water decomposition of the FRP molded product was performed under normal conditions.

  A part of the corresponding data will be described. The weight average molecular weight of SFC of 5000 to 25000 corresponds to the ratio of 80 to 100% of the unsaturated dicarboxylic acid to the total organic acid. On the other hand, the weight average molecular weight 35000-75000 of SFC corresponds to the ratio 0-40% of the unsaturated dicarboxylic acid with respect to all the organic acids.

  Next, the FRP crushed material (tank) having an unsaturated dicarboxylic acid ratio of 40% or less and the FRP crushed material (bathtub) having an unsaturated dicarboxylic acid ratio of 100% are collated with the corresponding data described above for the purpose. The weight average molecular weight of SFC was estimated, subcritical water decomposition was performed, and solid-liquid separation was performed to obtain SFC.

When the weight average molecular weight of the SFC was measured for each of the tank and the bathtub of the FRP crushed material, an SFC having a weight average molecular weight in the target range could be obtained.
<Example 2>
Corresponding data that correlates the molding temperature of a thermosetting resin (FRP molded product) comprising polyester and its cross-linked part and the weight average molecular weight of SFC obtained by subcritical water decomposition of the thermosetting resin corresponding to this. Was created as two-dimensional data and stored in a database.

  When creating the correspondence data, as described above, ascertain the molding temperature of various FRP molded products having different molding temperatures of the thermosetting resin, and the weight average of SFC obtained by subcritical water decomposition of the FRP molded product. Molecular weight was measured by gel permeation chromatography (GPC). Subcritical water decomposition of the FRP molded product was performed under normal conditions.

  A part of the corresponding data will be explained. The weight average molecular weight of SFC corresponds to 20000 to 60000 with respect to the molding temperature of 140 ° C. to room temperature of the thermosetting resin.

  Next, for each of a plurality of FRP crushed motor sealing materials, tanks, bathtubs, etc., in which the thermosetting resin molding temperature is in the range of 140 ° C. to room temperature, the target SFC is collated with the corresponding data described above. The weight average molecular weight was estimated, subcritical water decomposition was performed, and solid-liquid separation was performed to obtain SFC.

  When the weight average molecular weight of the SFC was measured for each of the FRP crushed motor sealant, tank, bathtub, and the like, an SFC having a weight average molecular weight in the target range could be obtained.

Claims (5)

  In a method for producing a polybasic acid vinyl monomer copolymer by performing subcritical water decomposition using a thermosetting resin comprising a polyester and a cross-linked portion thereof as a raw material, a polymer obtained by subcritical water decomposition of the thermosetting resin is used. A step of setting the molecular weight or molecular weight distribution of the vinyl acetate monomer copolymer, a step of selecting a thermosetting resin raw material corresponding to the polybasic vinyl monomer copolymer having the desired molecular weight or molecular weight distribution, A polybasic acid vinyl monomer copolymer comprising a step of subcritical water decomposition of the selected thermosetting resin raw material to obtain a polybasic acid vinyl monomer copolymer having a desired molecular weight or molecular weight distribution. Manufacturing method.   Polybasic vinyl acid obtained by subcritical water decomposition of thermosetting resin corresponding to this information, and at least one type of information selected from parameters related to molecular structure and thermosetting resin molding conditions for thermosetting resin Creating a corresponding data in association with the molecular weight or molecular weight distribution of the monomer copolymer, and selecting the thermosetting resin raw material based on the corresponding data, the desired molecular weight or molecular weight distribution 2. The material according to claim 1, wherein the raw material of the thermosetting resin having the molecular structure corresponding to the polybasic acid vinyl monomer copolymer or molded according to the molding conditions is selected. A method for producing a vinyl acid basic monomer copolymer.   The method for producing a polybasic vinyl monomer copolymer according to claim 2, wherein the information of the correspondence data is an average molecular weight of a polyester constituting the thermosetting resin.   3. The polybasic acid vinyl monomer copolymer according to claim 2, wherein the information of the correspondence data is a ratio of unsaturated dicarboxylic acid in an organic acid of a polyester raw material constituting a thermosetting resin. Manufacturing method of coalescence.   The method for producing a polybasic vinyl monomer copolymer according to claim 2, wherein the information of the correspondence data is a molding temperature of a thermosetting resin.

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