JP2003128834A - Method for decomposing thermosetting resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for decomposing a thermosetting resin in which downsized and energy-saved equipment can be achieved since the thermosetting resin can be decomposed under atmospheric pressure and in a short time, and a decomposed material of the thermosetting resin to be obtained can be easily recycled as a fuel or a raw material or rendered harmless by biodegradability. SOLUTION: The method for decomposing a thermosetting resin comprises heating the thermosetting resin 2 in a vegetable oil 4 and subjecting to decomposition reaction of the resin to obtain the decomposed material. The heating temperature is preferably higher than 290 deg.C. The heating temperature, reaction time and quantity of the vegetable oil are selected so as to control molecular distribution of the decomposed material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for decomposing a thermosetting resin, and further relates to a method for decomposing a thermosetting resin contained in a fiber reinforced resin represented by unsaturated polyester polymer and the like.

[0002]

2. Description of the Related Art Fiber Reinforced Resin (FRP)
ed Plastics) have excellent characteristics such as light weight, robustness, and high corrosion resistance, and are used for various parts such as automobile parts, boats, and housing equipment. However, most of the matrix resin used for FRP is a thermosetting resin, and since it contains fibers such as glass, it is extremely difficult to recycle and reuse the FRP.
Most of the discarded FRPs are landfilled or incinerated as industrial wastes, which poses a serious environmental burden.

Therefore, as a technique for effectively utilizing the waste FRP, a technique has been developed in which FRP is crushed, then oiled by thermal decomposition, and the obtained oil or the like is reused as fuel. However, in this technology, since the pyrolysis is performed at a high temperature of 500 to 1200 ° C., the operation cost is high, and the equipment cost is high because a large-scale plant is required.
There is also a problem that transportation costs to the plant are also high. On the other hand, a technique has been developed in which, after crushing FRP, it is incinerated to recover waste heat and the incinerated ash is reused as a cement raw material. However, there are problems that the equipment cost of the dedicated incinerator and the plant for recovering the waste heat is high, and the transportation cost to the plant is also high. Also,
A technique has been developed in which FRP is crushed and then heated at 300 ° C., and the obtained plastic is reused as a blast furnace reducing agent in a steelmaking blast furnace. However, generally, heavy oil is used as the blast furnace reducing agent, and cost advantage is low as an alternative to heavy oil. There is also a problem that combustion ash is generated, which needs to be landfilled. Furthermore, a technique has been developed in which FRP is pulverized and then mixed with a resin material for reuse. However, finely pulverizing FRP has a problem that the cost is high and the working environment is inferior due to generation of dust. In addition, the resin material mixed with fine pulverization has a problem that the mechanical strength is lowered and the use is considerably limited.

On the other hand, as a technique for removing glass fibers from FRP, the FRP is heated and melted and then kept at 250 ° C.
Technology for filtering in a low viscosity state has been developed. However, the high temperature solution is actually difficult to handle, and the resin is cooled and solidified after filtration, which makes maintenance of equipment and the like difficult. Furthermore, it is necessary to make the pores of the filter large in order to increase the filtration rate, and there is a problem that the glass fiber is not completely removed.

[0005]

In view of the above problems, the present invention can decompose a thermosetting resin in the atmosphere and in a short time, so that downsizing of equipment and energy saving can be realized. Further, the decomposition product of the thermosetting resin obtained is intended to provide a decomposition method of the thermosetting resin, which can be easily reused as a fuel or a raw material or detoxified by biodegradability. .

[0006]

In order to achieve the above object, the method for decomposing a thermosetting resin of the present invention is such that the thermosetting resin is heated in vegetable oil and fat to cause a decomposition reaction of the resin. Thus, a decomposed product is obtained. Thus, when heating the vegetable oils and fats, radicals necessary for the decomposition reaction of the resin are generated, so that it is possible to accelerate the thermal decomposition of the thermosetting resin, it is possible to perform heating in the atmosphere, It is possible to downsize equipment and save energy. Furthermore, since natural vegetable oils and fats are used, there is little environmental load when regenerating and reusing the obtained decomposition products, and biodegradable treatment is also possible.

The heating temperature is preferably higher than 290 ° C. This makes it possible to dramatically improve the decomposition rate of the thermally decomposable resin. Further, by selecting the heating temperature, the reaction time, and the amount of vegetable oil and fat, it is possible to control the molecular weight distribution of the above decomposition product. This allows the resulting degradation product to be selectively oligomerized,
It is easy to recycle and reuse the decomposed products.

In the method for decomposing a thermosetting resin of the present invention, a fiber reinforced resin (FRP) containing a thermosetting resin and glass fibers is heated in a vegetable oil and fat to decompose the fiber reinforced resin. A decomposition step of obtaining the decomposition product, a cooling step of cooling the decomposition product to room temperature, and a filtration step of separating the decomposition product of the thermosetting resin and the glass fiber by performing filtration after diluting with mineral oil. It is characterized by The glass fiber contained in the FRP decomposed product is an inorganic component different from the organic component. Glass fiber is useless, and FR is due to the presence of glass fiber.
It made it difficult to reuse and process P. According to the invention,
By diluting with mineral oil, the FRP decomposed product can be filtered at room temperature, the glass fiber can be easily removed, and the decomposed product can be reused and treated easily. In addition to mineral oil, an organic solvent such as acetone can be used.

The heating temperature is preferably higher than 290 ° C. This makes it possible to dramatically improve the decomposition rate of the thermally decomposable resin. Further, the filtration rate of the filtration can be controlled by selecting the content of the mineral oil. As a result, the glass fiber can be removed in a short time, so that the decomposition treatment of FRP becomes practical.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. The thermosetting resin to be decomposed in the present invention is, for example, unsaturated polyester resin (UP), phenol resin (PF), urea resin (UF), melamine resin (M
F), epoxy resin (EP), diallyl phthalate resin (DAP), silicone resin (SI), polyimide resin (PI), polyurethane resin (PU) and the like, and unsaturated polyester resin is particularly preferable. Further, the thermosetting resin may be in the form of a fiber reinforced resin (FRP) containing glass fiber.

The vegetable oil is not particularly limited,
For example, drying oil (linseed oil, tung oil, etc.), semi-drying oil (soybean oil, rapeseed oil, etc.), non-drying oil (olive oil, castor oil, etc.), vegetable oil (palm oil, cacao oil, etc.) are preferable. Examples of classification by composition are lauric acid type (coconut oil, palm kernel oil, babassu oil, etc.), oleic acid / linoleic acid type (safflower oil, cottonseed oil, olive oil, sesame oil, palm oil, corn oil, peanuts). Oils, etc., erucic acid type (Mustard oil, traditional rapeseed oil, etc.), Linolenic acid type (soybean oil, rapeseed oil, linseed oil, etc.), Conjugate acid type (Tung oil, Ouch deer oil, etc.), Hydroxy acid type (castor oil) ) Is preferred.

The amount of vegetable oil to be added is not particularly limited. This is because the decomposition rate of the thermosetting resin is not significantly affected by the amount of vegetable oil. However, by adjusting the amount of vegetable oil / fat relative to the thermosetting resin, the physical properties such as the viscosity and molecular weight of the decomposed product can be controlled. Therefore, by selecting the amount of vegetable fats and oils according to the purpose of chemical recycling of decomposed products, the strength of the material,
Control of physical properties such as viscosity or control of biodegradation rate can be performed.

The heating method is not particularly limited, and heating can be performed in the air or in a nitrogen gas atmosphere. The heating temperature is preferably higher than 290 ° C, and more preferably 320 ° C or higher. When the heating temperature is higher than 290 ° C, the decomposition rate of the thermosetting resin can be improved. The reaction time is not particularly limited, and the thermosetting resin can be decomposed in a short time. However, as the reaction time elapses, the distribution of the decomposed product with a molecular weight of 10,000 or more decreases and the distribution with a molecular weight of 1,000 or less increases, so a longer reaction time is preferable.

The decomposition product of the thermosetting resin thus obtained can be used as a heat energy source such as a fuel for a boiler or an incinerator. In addition, chemical recycling is possible as raw materials, fillers, additives, etc. for general-purpose polymer products such as asphalt materials, general-purpose plastic materials, and general-purpose coating materials. Furthermore, this decomposed product is in a molten state because the thermosetting resin component has a low molecular weight in biodegradable vegetable oil. Therefore, if sprayed on soil, it can be efficiently biodegraded and rendered harmless. In addition, the disassembling method according to the present invention does not require large-scale equipment and can perform disassembling treatment at low cost.

When the resin to be decomposed contains glass fibers, the mineral oil used is not particularly limited, but kerosene, light oil, gasoline, heavy oil, etc. are preferable. The amount of mineral oil to be added is not particularly limited, but when the total amount with the FRP decomposed product is 100 wt%, it is preferably about 40 wt% or more. The filtration rate can be improved by adding 40 wt% or more of mineral oil. Further, by adjusting the mixing ratio of the FRP decomposed product and the mineral oil, it is possible to control the calorific value when the decomposed product is thermally recycled.

The filter used for filtration is not particularly limited, but a non-woven fabric filter, a metal lattice filter, a paper filter and the like are preferable, and a polyester fiber non-woven fabric filter is particularly preferable. As a result, most of the glass fibers can be removed from the FRP decomposed product, and fine dust and the like can be removed almost completely.

The FRP decomposed product from which the glass fiber has been removed is reused as a fuel for a boiler or an incinerator, or recycled as a raw material for a general-purpose polymer product, like the decomposed product of a thermosetting resin described above. In addition, soil reclamation due to biodegradability is possible. In particular, when reused as fuel for boilers and incinerators, if FRP decomposed products remain, glass adheres to the inner surface of the furnace, causing problems such as damage to the furnace and cleaning. Therefore, it can be reused as fuel for boilers and incinerators.

[0018]

EXAMPLES Example 1 (decomposition of thermosetting resin) 1. Experimental method 1-1. Sample preparation Orthophthalic acid-based unsaturated polyester was mixed with styrene as a cross-linking agent and polymerized using methyl ethyl ketone peroxide as an initiator, and a flat plate resin having a thickness of 3 mm (density 1.
22 g / cm ³ ) was produced. This flat plate is 10 × 10m
The test piece was cut into m. Table 1 shows the composition ratio of the unsaturated polyester resin (hereinafter referred to as UP resin). Table 2
Shows the composition ratio of the fatty acids in the vegetable oil.

[0019]

[Table 1]

[0020]

[Table 2]

1-2. Decomposition experiment PID (Proportional Integ) used to decompose UP resin
A heating device (accuracy ± 1.0%) by ral and Differential Gain control is shown in FIG. Explaining the experimental procedure with reference to FIG. 1, first, a test tube 16 in which a predetermined UP resin 2 and vegetable oil 4 (weight ratio 1: 1) are placed in a heating device 10
(Inner diameter 13 × 165 mm) was installed. The test tube 16 was covered with the heat insulating material 14. Then, while maintaining a constant temperature, the decomposition reaction was carried out under open air. The heating temperature is 290 ° C, 320 ° C and 350 ° C by the thermocouple 18 and the temperature controller 20.
The temperature was adjusted to ° C. The reaction was started at the time when the temperature reached a predetermined heating temperature, and heating was performed for a maximum of 360 minutes.

1-3. Analytical evaluation Thermogravimetric change of UP resin and vegetable oil is TG (Thermal Gr
avity, Mac Science TG-DAT202
It was measured in 0). The amount of decomposition of the UP resin over time was determined by the weight change of the solid resin remaining in the vegetable oil. The residual resin was washed with hexane, dried at room temperature for 24 hours or more, and then weighed. The surface of the residual resin is SE
M (Scanning Electron Microscope, sm made by Topcon)
-200). The average molecular weight and the molecular weight distribution of the decomposed product were measured by GPC (Gel Permeation Chromatography, GPC-8010 manufactured by Tosoh Corporation). Tetrahydrofuran was used as an eluent, and the column and detector temperatures were 50 ° C and the flow rate was 0.8 ml / min.
m) is TSKgel-G1000 _XL x1, TSKge
l-G2000 _XL x 2, TSKgel-G3000 _XL x
1 was used. Further, a calibration curve based on standard polystyrene having a molecular weight of 190,000 to 266 was used. The structural change of the decomposed product is FTIR (Fourier Transform Infrared Spe
ctrometry, Perkin Elma Spetrum One) was used for analysis.

2. Results and discussion 2-1. Thermogravimetric change TG curves of UP resin and vegetable oils and fats measured in the atmosphere and in a nitrogen gas atmosphere are shown in FIG. In FIG. 2, a is UP resin under the atmosphere, b is UP resin under nitrogen gas atmosphere, c is vegetable oil and fat under atmosphere, and d is vegetable oil and fat under nitrogen gas atmosphere. UP resin is 320 ° C with or without oxygen
Above the range, a rapid weight loss behavior was observed. After the measurement, several percent of combustion residue was confirmed. In the atmosphere, due to the effect of the exothermic oxidation reaction, the UP resin decomposes faster than under nitrogen,
A two-step decomposition reaction was observed. Further, the vegetable fats and oils started to lose weight at 200 ° C. in the atmosphere, and a sharp weight loss was observed from around 290 ° C., and a three-step decomposition reaction was confirmed.
Under nitrogen, the decrease started at 250 ° C, and a sharp decrease was observed from around 350 ° C.

2-2. Decomposition amount Fig. 3 shows the decomposition amount of the UP resin with respect to the reaction time in the vegetable oil and fat at each temperature. In FIG. 3, a is 290 ° C., b is 320 ° C., and c is 350 ° C. While reaching each of these temperatures, a weight loss of 3 wt%, 5 wt%, and 12 wt% was confirmed, respectively. When the temperature exceeded 300 ° C., it was confirmed that bubbles were generated from the resin surface. At 350 ° C., the amount of decomposition of the UP resin increased rapidly after 5 minutes of heating (decomposition amount of 30 wt%), and the decomposition amount reached 100 wt% in 12 minutes.
The same decomposition behavior was exhibited even at 320 ° C., and the decomposition amount reached 100 wt% after 90 minutes of heating. On the other hand, at 290 ° C., the decomposition amount was at most 11 wt% even after heating for 360 minutes. This reflects the result of FIG. 2 in which a rapid weight loss phenomenon was observed at 320 ° C. or higher. Further, the weight ratio (1: 1 to 1: 3) of the UP resin and the vegetable oil and fat was changed at 350 ° C., but the amount of decomposition of the UP resin with respect to the reaction time was not significantly different. It is considered that the decomposition rate of UP resin in vegetable oil has a large temperature dependency.

Next, U heated in vegetable oil at 320 ° C.
Changes in the P resin surface are shown in SEM photographs of FIGS. Before heating, the resin surface was flat as shown in FIG. 4, but after 10 minutes of heating, fine grooves were observed on the surface as shown in FIG. 5, and after 50 minutes, the surface was as shown in FIG. Unevenness and swelling occurred, and cracks were also confirmed. These observations are shown in Figure 3.
It corresponds to the change in the decomposition amount of the UP resin shown in (4). That is, at the initial stage of heating, only the resin surface layer is decomposed, so the amount of decomposition is small. However, it is considered that the cracking caused by the progress of the reaction facilitated the diffusion and penetration of the vegetable oil and fat, and thus the decomposition reaction was rapidly accelerated. Hojo's FRP in alkaline aqueous solution, boiling water and alcohol
Similar decomposition behavior was observed in the corrosion reaction of UP resin for automobiles (Hojo, Tsuda, Ogasawara: 32nd Special Lecture, Vol. 34, No. 2 (1988), and Hojo,
Ogasawara, Zhang, Tsuda: Journal of Japan Society for Composite Materials, Vol.1
8, No. 2 (1992)).

2-3. Degradation mechanism The molecular weight distribution curve by the GPC measurement of the degradation product of UP resin which changed reaction time in vegetable fats and oils of 350 degreeC is shown in FIG. In FIG. 7, a is 30 minutes, b is 60 minutes, c is 120 minutes,
d is 240 minutes. In addition, in oils and fats, temperature and UP
FIG. 8 shows a molecular weight distribution curve of a decomposed product of UP resin reacted by changing the amount of the resin. In FIG. 8, a is 32
The weight ratio of UP resin to vegetable oil is 1: 1 at 0 ° C, and b is 35.
The same weight ratio is 1: 1 at 0 ° C, c is 350 ° C and the same weight ratio is 1: 2, and d is 320 ° C and the same weight ratio is 1: 3. Figure 7
As shown in, at 350 ° C., the molecular weight decreased and the molecular weight distribution decreased with the reaction time. That is, the distribution with a molecular weight of 10,000 or more decreases, and the molecular weight of 1,000
The following distributions have increased. Further, as shown in FIG. 8, when the heating temperature was low, the molecular weight increased, and the decomposed product obtained at 320 ° C. for 180 minutes had many distributions with a molecular weight of 10,000 or more, but at 350 ° C. for 180 minutes. Then, the degradation product had a molecular weight distribution of 10,000 or less. In addition, the distribution of molecular weights of 1,000 or less increased as the amount of oil and fat decreased. The molecular weight distribution of these degradation products is clearly different from that of vegetable oils and fats heated under the same conditions. That is, it is considered that the difference in the molecular weight distribution is due to the difference in the UP resin decomposition reaction. Degradation of UP resin in vegetable oils and fats depends on heating temperature, reaction time, and amount of oils and fats.

In a study by Kubota et al., It was reported that UP resin was hydrolyzed by glycol, styrene-fumarate copolymer remained at 200 ° C., and styrene cross-linking portion was decomposed at 245 ° C. (Kubota) Shizuo: Industrial Materials, Vol.44, No. 10 (1996)). From this, it is expected that the decomposition of UP resin in vegetable oils and fats will occur due to the cleavage of the ester bond part and the styrene cross-linking part in the main chain. FIG. 9 shows the FTIR spectrum of the UP decomposition product heated in vegetable oil at 350 ° C. In FIG. 9, a is 30 minutes, b is 60 minutes, c is 120 minutes, and d is 2
40 minutes. At 350 ℃, 126 with the reaction time
The absorption due to the CO stretching vibration of the aromatic ester found at 0 cm ^-1 was reduced. This is because phthalic acid diester is selectively decomposed by hydrolysis in UP resin (Ogasawara, Rejar, Hojo: Journal of Japan Society for Materials Science,
Vol. 22, No. 5, p. 280 (1986)), the decomposition of UP resin in high temperature fats and oils is considered to have cleaved the C—O part of the phthalic acid diester in the main chain. Further, although it could not be confirmed from the absorption spectrum, a styrene-fumarate copolymer obtained by completely hydrolyzing the UP resin (fumarate component: ~
30 mol%) has a molecular weight of 10,000 to 15,000.
(Eiichiro Takigawa: Polyester Resin Handbook, Nikkan Kogyo Shimbun, p.156 (19)
88)), and from the result of GPC measurement in FIG. 7, it is presumed that the styrene cross-linking portion is cut.

FIG. 10 shows FTIR spectra of UP resin decomposition products heated in oils and fats at different temperatures. In FIG.
a is 320 ° C. and b is 350 ° C. Decomposition product obtained by reaction for 180 minutes in oil and fat at 320 ° C 1260 cm ^-1
Was greater than that at the same time at 350 ° C. This is due to the thermal decomposition reaction of polystyrene in vegetable oil (Dong D, Tasaka S, Inagaki N, Polym. Degrad. St.
ab., Vol.72, p.345 (2001)), it is considered that the number of molecular breaks depends on temperature. Next, FIG. 11 shows FTIR spectra of vegetable oils and fats heated at different temperatures. In FIG. 11, a is unheated, b is 320 ° C. and c
Is 350 ° C. At 350 ° C, compared to unheated vegetable oils and fats, C of the aliphatic ester found at 1740 cm ^-1
= O The absorption by stretching vibration is small, and the tran of 966 cm ^-1
The C-H out-of-plane bending vibration of s-olefin became large. 1
C = O stretching vibration of aliphatic carboxylic acid at 709 cm ⁻¹ , 3
New absorption due to stretching vibration of O—H hydrogen-bonded at 500 to 2500 cm ⁻¹ appeared. Drying oil, which is an unsaturated aliphatic acid compound, is known to absorb oxygen in the atmosphere and cause a coupling reaction with radicals (Igwe, IO, and Og
bobe, O., J. Appl. Polym. Sci., Vol.75, p.1441 (200
See (0)). Furthermore, it has been reported that ester of glyceride at high temperature produces carboxylic acid and olefin by β-cis elimination, and radicals are considerably generated from unsaturated compounds (Aikawa, S., Tasaka, S., Inagak
i, N., Asano, T., Koubunishi Ronbunshu, Vol.55, N
o.8, p465 (1998)). That is, the decomposition of UP resin in vegetable fats and oils is caused by radicals generated from vegetable oils and fats, the cleavage of the phthalic acid diester portion of the UP resin and the styrene cross-linking portion, and then the bond with the radicals in the resin produced by the cleavage, It is considered that the process proceeds while contributing to the stabilization of the resin. Further, it is considered that the decomposed product of the UP resin heated in the vegetable oil and fat at a high temperature has a structure incorporating the oil and fat. Therefore, by selecting the heating temperature, reaction time, and the amount of fats and oils which are the decomposition conditions, it is possible to easily make U in the fats and oils.
It is possible to selectively decompose P resin, that is, to control oligomerization.

3. Conclusion The following results were obtained by the thermal decomposition of orthophthalic acid type UP resin in vegetable oils and fats in the atmosphere and high temperature. (1) The decomposition rate of UP resin depends on the heating temperature. (2) Decomposition of UP resin is caused by cleavage of phthalic acid diester portion and styrene crosslinked portion. (3) Radicals generated from vegetable oil contribute to the decomposition reaction of the UP resin and the stabilization of the decomposed product. (4) The structure of the decomposed product depends on the heating temperature, the reaction time, and the amount of fats and oils. Therefore, selective oligomerization can be expected. The decomposition products of UP resin heated in vegetable oil can be reused as fuels (boilers, incinerators), fillers, raw materials, and land reclamation treatment by biodegradability can be expected. In addition, this thermal decomposition method does not require large-scale equipment and can realize low-cost processing.

Example 2 (Removal of Glass Fiber) 1. FRP Decomposition Experiment The experiment procedure will be described with reference to FIG. 1. First, the test tube 16 in the heating device 10 is provided with the FRP test piece 2 and the vegetable oil 4 in which the weight ratio of the UP resin and the glass fiber is 7: 3. , With a weight ratio of 1: 2. And from room temperature to 350
It was heated to 0 ° C. and kept at that temperature for 30 minutes for thermal decomposition. The generated FRP decomposition product is at room temperature (about 2
It was cooled to 5 ° C.

2. Filtration Experiment The obtained FRP decomposition product was diluted by adding each predetermined amount of kerosene. At this time, the total amount of FRP decomposition products and kerosene is 100 wt.
%, The amount of kerosene added is 20, 40, 60, 80 wt.
A diluted sample of each% FRP digest was made. Then, each diluted sample and an undiluted FRP decomposition product were filtered. The outline of the filtration device used for filtration is shown in FIG. As shown in FIG. 12, the diluted sample 6 of the FRP decomposition product containing kerosene was
It was introduced into a polyester fiber nonwoven fabric filter 34 installed in a filter holder 32 having a diameter of 35 mm through a funnel 30 having a tube having a diameter of 4.5 mm. As the filter 34, 3.3 dtex × 51 mm and 6.6 dtex ×
50% by volume of each 51 mm polyester fiber was blended, and a filter having a basis weight of 150 g / m ² was used.
Most of the glass fibers 7 contained in the diluted sample 6 were trapped by the filter 34. And the filter 34
The purified filtrate 8 was recovered by passing through.

3. Results FIG. 13 shows the relationship between the content of kerosene and the viscosity of the diluted sample and the filtration rate. As shown in FIG. 13, it was found that as the content of kerosene increased, the viscosity of the decomposed product decreased remarkably and the filtration rate increased remarkably. The content of kerosene is 2
At 0 wt%, the filtration rate is 2.2 ml / min / cm ²
Was low. However, when the content of kerosene exceeds 40 wt%, the filtration rate becomes 11.1 ml / min / cm ² or more, which is a level that can be sufficiently put to practical use. From this result, it was confirmed that the dilution of kerosene is a very effective method for removing the glass of the FRP decomposed product.

[0033]

As is clear from the above, according to the present invention, the thermosetting resin can be decomposed in the air and in a short time, so that downsizing of equipment and energy saving can be realized. Further, the obtained decomposition product of the thermosetting resin can be reused as a fuel or a raw material and can be provided with a method for decomposing the thermosetting resin, which can be easily subjected to detoxification treatment by biodegradability. .

[Brief description of drawings]

FIG. 1 is a schematic view showing a thermosetting resin heating device according to the present invention.

FIG. 2 is a graph showing a TG curve of UP resin or vegetable oil and fat measured in the air or under a nitrogen gas atmosphere.

FIG. 3 is a graph showing the amount of UP resin decomposed in vegetable oils and fats with respect to the reaction time at each temperature.

FIG. 4 is an SEM photograph showing the UP resin surface before heating in vegetable oil.

FIG. 5 is an SEM photograph showing the UP resin surface heated in vegetable oil for 10 minutes.

FIG. 6 is an SEM photograph showing the UP resin surface heated in vegetable oil for 50 minutes.

FIG. 7 is a graph showing a molecular weight distribution curve by GPC measurement of a decomposition product of an UP resin with a reaction time changed in a vegetable oil at 350 ° C.

FIG. 8 is a graph showing a molecular weight distribution curve of a UP decomposition product obtained by reacting oils and fats by changing the amount of the oil and the amount of UP.

FIG. 9 is a graph showing an FTIR spectrum of a UP degradation product heated in a vegetable oil at 350 ° C.

FIG. 10 is a graph showing FTIR spectra of UP decomposition products heated in oils and fats at different temperatures.

FIG. 11 is a graph showing FTIR spectra of vegetable oils and fats heated at different temperatures.

FIG. 12 is a schematic view showing a filtration device used for filtration of an FRP decomposed product according to the present invention.

FIG. 13 is a graph showing the relationship between the content of kerosene and the viscosity of the diluted sample and the filtration rate.

[Explanation of symbols]

2 Unsaturated polyester resin (UP resin) 4 vegetable oil 6 Diluted sample of FRP decomposition product with kerosene 7 glass fiber 8 filtrate 10 heating device 12 heater 14 Insulation 16 test tubes 18 thermocouple 20 Temperature controller 30 funnel 32 filter holder 34 Filter

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor ▲ Yoshi ▼ Masaaki Mura             300, Takatsuka-cho, Hamamatsu City, Shizuoka Prefecture Suzuki shares             In the company (72) Inventor Yasuhiko Yokomori             300, Takatsuka-cho, Hamamatsu City, Shizuoka Prefecture Suzuki shares             In the company F-term (reference) 4F301 AA22 AA24 AA25 AA27 AA29                       AB02 CA09 CA26 CA43 CA65                       CA72

Claims (5)

[Claims] 1. A thermosetting resin is heated in vegetable oil or fat,
A method for decomposing a thermosetting resin, characterized in that a decomposition product is obtained by carrying out a decomposition reaction of the resin. 2. The method for decomposing a thermosetting resin according to claim 1, wherein the heating temperature, the reaction time, and the amount of vegetable fats and oils are selected to control the molecular weight distribution of the decomposition product. 3. A decomposition step of heating a fiber reinforced resin containing a thermosetting resin and glass fibers in a vegetable oil to obtain a decomposed product of the fiber reinforced resin, and a cooling step of cooling the decomposed product to room temperature. And a filtration step of separating the decomposition product of the thermosetting resin and the glass fiber by diluting with mineral oil and then performing filtration, and a method for decomposing the thermosetting resin. 4. The method for decomposing a thermosetting resin according to claim 1, wherein the heating temperature is higher than 290 ° C. 5. By selecting the content of the mineral oil,
The method for decomposing a thermosetting resin according to claim 3 or 4, wherein the filtration rate of the filtration is controlled.