JP4096000B2 - Recycling method for organic fiber reinforced plastic waste - Google Patents

Description

  The present invention relates to a method for recycling organic fiber reinforced plastic waste containing unsaturated polyester resin, and is particularly industrially valuable by chemically treating unsaturated polyester resin matrix organic fiber reinforced plastic waste. This is a method in which a raw material is obtained and synthesized again to obtain a recycled resin for reuse.

Generally, a thermoplastic resin such as polyethylene that is melted by heat is re-melted and reused after being re-melted by heat, as described in Non-Patent Document 1 below.
Magazine "Science and Industry" (Shitsuo Kubota, 77 (10), 517 (2003))

Further, as in Non-Patent Document 2 below, material recycling, in which a PET bottle or film made of a saturated polyester resin is regenerated by being melted by heat, is mainly performed.
Book “Plastic Recycling-From Recovery to Recycling” (edited by RJEhring, translated by Plastic Recycling Society, p.71, Industrial Research Committee (1993))

By the way, since unsaturated polyester resin is a thermosetting resin, it cannot be remelted by heat. Therefore, as shown in Non-Patent Document 3 below, these wastes are recycled by being finely pulverized and mixed as a filler into new bulk molding material (BMC) or sheet-shaped molding material (SMC). Some material recycling is performed.
Magazine "Science and Industry" (Nobuhiro Fukuda, 68 (2), 60 (1994))

On the other hand, the Ministry of Land, Infrastructure, Transport and Tourism is carrying out a project project that dismantles and crushes FRP (fiber reinforced plastic) abandoned ships and thermally recycles them as raw material for cement kilns (Chemical Industry Daily, October 14, 2003) . In addition, the National Maritime Research Institute conducts this empirical research, and by mixing waste oil when crushing FRP waste ships, it suppresses the generation of dust and increases heat generation, enabling thermal recycling. (Nihon Keizai Shimbun dated February 13, 2004).
Mannequins using organic fiber reinforced FRP can be thermally recycled (Pearl Mannequin website).
Furthermore, as a chemical recycle of unsaturated polyester resin waste generated during button manufacturing, the waste is decomposed with glycol, and the resulting decomposition product is reacted with a dibasic acid as a glycol component to produce unsaturated polyester resin waste. A technique for re-synthesizing is developed and described in Patent Document 1 below.
Patent No. 2701012 (Title of Invention: “Resaturation and Reuse Equipment for Unsaturated Polyester Resin Waste”)

Such chemical recycling of unsaturated polyester resin waste by glycol decomposition is also reported in Non-Patent Documents 4 to 9 below.
Magazine `` Water '' (Shitsuo Kubota, 38 (9), 72 (1996)) Magazine “Industrial Materials” (Shitsuo Kubota, 44 (10), 118 (1996) Magazine "FRP fishing boat" (Shitsuo Kubota, No.196, p.1 (1996) Magazine "Synthetic Resin" (Shitsuo Kubota, 43 (1), 70 (1997) Book “Ecomaterial Encyclopedia” (Shitsuo Kubota, p.517 (1996) Magazine "Network Polymer" (Shitsuo Kubota et al., 45 (10), 453 (2003))

As described above, the unsaturated polyester resin is a thermosetting resin and has a three-dimensional network structure, and therefore does not melt with heat. Therefore, material recycling such as melting with heat and re-molding, as is generally done with thermoplastic resins, is not possible.
In addition, material recycling that pulverizes unsaturated polyester resin waste, mixes it with new BMC and SMC as fillers, and reuses the recycled resin strength as the mixing ratio increases as shown in Non-Patent Document 10 below. Has the disadvantage of lowering.
Book "Heisei 6-8 fiscal year technical development research fund subsidy project extension seminar text (wide area joint research)" (Wakayama Prefectural Industrial Technology Center, Chapter 6 Research on advanced utilization technology of thermosetting resin-based industrial waste, 6 -Page 3 (H9.4)

In addition, FRP waste contains a large amount of glass fiber and filler, so its calorific value is low. Magnesium oxide, a thickener, is not suitable as a raw material for cement, and there are problems in using cement kiln as raw fuel. It has become. Furthermore, thermal recycling is difficult to say as recycling, and is considered inferior in effective use of resources.
The unsaturated polyester resin generally crosslinks an unsaturated portion of a linear unsaturated polyester having a molecular weight of several thousand obtained by condensing ethylene glycol, propylene glycol and maleic anhydride by radical copolymerization with styrene. It is a thermosetting resin obtained. In the degradation of unsaturated polyester resin with glycol, the ester portion is easily glycolyzed at a temperature of about 200 ° C., but as shown in Non-Patent Document 10 above, the styrene crosslinked portion (styrene-fumarate copolymer) is decomposed. Therefore, it is necessary to treat at 290 ° C. for 2 hours because it cannot be decomposed unless it is 230 ° C. or higher. And as shown in the following nonpatent literature 11, fiber reinforced plastic (FRP) usually uses unsaturated polyester resin as a matrix and glass fiber as reinforcing fiber. Naturally, when this FRP is decomposed with glycol, a heterogeneous reaction occurs, and when stirring, the glass fiber is rounded to form a hard ball, or when the glass fiber remains and is removed, a filtration step is required. It is also possible to re-synthesize while containing glass fiber, but it becomes a heterogeneous system, OH value measurement (to measure the OH group of the decomposition product by titration, to obtain a high molecular weight unsaturated polyester, It is necessary to react an equivalent amount of dibasic acid with the existing OH group), acid value measurement (when the acid value is measured at the time of synthesis of unsaturated polyester is 40 or less, the raw dibasic acid is sufficiently reacted and almost remains However, if a high molecular weight polymer is obtained, the reaction end point cannot be accurately determined, and it is difficult to obtain a high molecular weight polymer.
Book "Heisei 12-2014 Regional Manufacturing Measures Subsidy Project (Small and Medium Enterprise Technology Development Industry-Academia-Government Collaboration Promotion Project) Results Dissemination Seminar Text" (Wakayama Prefecture, Chapter 4 "Efficient Utilization of Polymeric Waste by Decomposition Reaction" Technology Development ”, page 4-57 (H14.12))

  Therefore, the object of the present invention is to recycle the organic fiber reinforced plastic waste chemically without any filtration in a relatively short time and with simple equipment to obtain an industrially valuable raw material. To provide a method for synthesizing and easily recycling the unsaturated polyester resin, that is, an economical method for chemically recycling the organic fiber reinforced plastic waste to the unsaturated polyester resin.

In order to solve the above problem, the present inventors crushed organic fiber reinforced plastic waste, then decomposed with glycol at about 150 to 300 ° C., and used this decomposition product as a raw material component and filtered. We have devised a method for reusing organic fiber reinforced plastic waste that is chemically synthesized and re-synthesized from unsaturated polyester without purification.
That is, after crushing the organic fiber reinforced plastic waste, it is reacted with glycol to decompose the unsaturated polyester resin of the matrix and the organic fiber of the reinforcing material to obtain a decomposition product, and the obtained decomposition product is converted to a dibasic acid. And an unsaturated polyester is synthesized by a condensation reaction. In other words, the FRP waste is applied to an organic fiber reinforced plastic containing an unsaturated polyester resin.
Polyesters, polyarylate, nylon-6,6, polycondensation polymers such as aramid, polyaddition polymers such as polyurethane, ring-opening polymerization polymers such as nylon-6, and addition polymerization polymers such as vinylon are used for reinforcing fibers. If so, the fiber will easily break down.

  According to the organic fiber reinforced plastic waste recycling method according to the present invention, the unsaturated polyester resin as the matrix resin and the organic fiber as the reinforced fiber in the organic fiber reinforced plastic waste are The unsaturated polyester resin can be regenerated by decomposing glycol at a low temperature and reacting the decomposition product with a dibasic acid as a resin raw material. In other words, if the organic fiber, which is a reinforcing fiber, can also be decomposed by glycol, the decomposition solution becomes homogeneous, and the OH value is measured (by measuring the OH group of the decomposition product by titration to obtain a high molecular weight unsaturated polyester, It is necessary to react an equivalent dibasic acid with a group), acid value measurement (when the acid value is measured at the time of synthesis of unsaturated polyester is 40 or less, the dibasic acid of the raw material is sufficiently reacted and hardly remains Assuming that a high molecular weight polymer is obtained, the reaction end point can be accurately determined, and a high molecular weight regenerated polymer is easily obtained. And an unsaturated polyester resin can be obtained by making it use as a glycol component as it is, without refine | purifying a decomposition product, and carrying out a dehydration condensation reaction with a dibasic acid.

Next, the best embodiment of the present invention will be described.
The organic fiber reinforced plastic waste applied to the present invention is not particularly limited as long as it is a FRP waste containing an organic fiber as a reinforcing fiber with a cross-linked and unsaturated polyester resin as a matrix, and the organic fiber is polyester. When polycondensation polymers such as polyarylate, nylon-6,6, and aramid, polyaddition polymers such as polyurethane, ring-opening polymerization polymers such as nylon-6, and addition polymerization polymers such as vinylon are used as reinforcing fibers. The fiber also breaks down easily. Examples of the waste material containing the unsaturated polyester resin include fiber reinforced plastic (FRP) containing a filler such as calcium carbonate and composited with organic fibers. Examples of the FRP include those used for applications such as artificial marble, mannequins, display shaped objects (animals and the like), waterproof materials, and the like.

  In the present invention, it is desirable that the organic fiber reinforced plastic waste is crushed prior to decomposition with glycol to facilitate decomposition and to facilitate processing. Further, if necessary, pretreatment such as cleaning treatment and sieving treatment may be performed. Crushing treatment is performed by impact type crusher (hammer type, chain type), shear type crusher, cutting type crusher, compression type crusher (roll type, conveyor type, screw type), stamp mill, ball mill, rod mill crusher, etc. Do. The size of the waste crushed material should be small, but it is desirable that the size of the waste crushed material be 50%. A crushed material that passes through a sieve having an opening of preferably 25 mm, more preferably 3 mm, is advantageously used.

In the present invention, glycols used for decomposition include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butanediol. 1,6-hexanediol, hydrogenated bisphenol A, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, dibromoneopentyl glycol, cyclohexanediol, and the like.
The weight ratio of unsaturated polyester resin and organic fiber contained in the waste to glycol used for decomposition is 1: 0.2 to 3, preferably 1: 0.5 to 1.5. In this case, if the value of the glycol ratio is reduced, the amount of waste in the recycled resin increases, and the organic fiber reinforced FRP waste can be efficiently recycled.

By the way, in the decomposition of the unsaturated polyester resin of the matrix with glycol, the ester portion is easily glycosylated at a temperature of about 200 ° C., but the styrene crosslinked portion (styrene-fumarate copolymer) is difficult to decompose. In the case of using a catalyst such as sodium hydroxide, the ester bond is easily glycolyzed by the ionic mechanism, but the styrene-fumarate copolymer of the styrene cross-linked portion is decomposed only at a high temperature of 230 ° C. or more, and is decomposed by the radical mechanism. It is thought that.

  The organic fibers used as the reinforcing fibers include nylon-6,6, nylon-6 (ring-opening polymerization), nylon-11, aramid fibers (para-Kevlar, Twaron, Technora) as polyamide-based synthetic fibers obtained by polycondensation. Polyethylene terephthalate is typical as a polyester-based synthetic fiber such as, for example, meta-conex, etc., but there are polybutylene terephthalate, polyethylene naphthalate, etc., polyarylate fiber (Vectran, etc.), polycarbonate (carbonate ester), etc. . There are also polyurethane fibers obtained by polyaddition reaction. In addition, there are acrylic fiber, vinylon, polyethylene and the like obtained by addition polymerization. There are also natural fibers such as cotton, wool and rayon.

Polyamide synthetic fiber obtained by polycondensation, polyester synthetic fiber, polyurethane fiber obtained by polyaddition reaction, vinylon obtained by addition polymerization, etc. are suitable for recycling organic fiber reinforced plastic by glycol decomposition and resynthesis. Yes.
Nylon-6 is decomposed with ethylene glycol as follows.

Alternatively, these oligomers are formed.
The amino group and hydroxy group at the terminal of the decomposition product undergo dehydration condensation with the carboxy group of the dibasic acid during resynthesis.
Nylon-6,6 is decomposed with ethylene glycol as follows.

Alternatively, these oligomers are formed.
The amino group and hydroxy group at the terminal of the decomposition product undergo dehydration condensation with the carboxy group of the dibasic acid during resynthesis.
In the case of polyethylene terephthalate, it is decomposed with ethylene glycol as follows.

Alternatively, these oligomers are formed.
The terminal hydroxy group of the decomposition product undergoes dehydration condensation with the carboxy group of the dibasic acid during resynthesis.
In the case of polyurethane, it is decomposed by ethylene glycol as follows.

Alternatively, these oligomers are formed.
The amino group and hydroxy group at the terminal of the decomposition product undergo dehydration condensation with the carboxy group of the dibasic acid during resynthesis.
When a phenolic hydroxy group is generated, it may be re-synthesized by adding a transesterification catalyst such as tributyltin methoxide.
In addition polymerization polymers such as vinylon, for example, hydrogen on the tertiary carbon of —CH 2 —CH (—O −) − is extracted, carbon radicals are generated, and decomposition seems to start.

  In the decomposition using glycol, a catalyst is preferably used. Examples of such catalysts include sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, zinc acetate, magnesium acetate, calcium acetate, lithium acetate, sodium acetate, and other metal acetates, antimony oxide, titanium alkoxide, and tributyltin. Methoxide, and mixtures thereof. When an alkali catalyst is used, the decomposition product is neutralized before resynthesis. For such neutralization operation, sulfuric acid, hydrochloric acid or the like is used. The decomposition with glycol can be carried out without using a catalyst.

  At the time of decomposition with glycol, the decomposition temperature needs to be about 150 ° C to 300 ° C. Preferably, the decomposition temperature is convenient at a decomposition temperature of 200 ° C to 300 ° C. The decomposition with glycol can be carried out under atmospheric pressure or under pressure.

Then, an unsaturated polyester is regenerated by using a decomposition product obtained by decomposition with glycol as a glycol component and subjecting it to a condensation reaction with a dibasic acid by a conventional method (Non-patent Document 12). The regenerated unsaturated polyester thus obtained is a vinyl monomer copolymerizable with C = C double bond of unsaturated polyester such as styrene, methyl methacrylate, vinyl toluene, vinyl acetate in the presence of a polymerization initiator. Or a crosslinked unsaturated polyester resin by crosslinking with diallyl phthalate or the like. In the case of BMC and SMC for FRP, glass fiber and organic fiber are added to regenerated unsaturated polyester resin, and filler is added if necessary, and then molded by compression molding or the like.
Book "Experimental Methods for Polymer Synthesis" (Takayuki Otsu and Masaaki Kinoshita, 332-334, 383-384 (Chemical Doujin, S47.3))

  The synthesis of the unsaturated polyester from the decomposition product is carried out by adding the glycol component in the decomposition product and the dibasic anhydride in the reaction temperature range of 140 to 210 ° C., for example, at 150 ° C. for about 1 hour. To do. Then, condensation is performed while distilling off water under nitrogen at 210 ° C. for about 4 hours. Then, after cooling, styrene is added to obtain a recycled resin solution having a styrene content of 30 to 40 wt%, and hydroquinone, t-butylcatechol, etc. are added as a polymerization inhibitor to a total of about 100 ppm.

Dibasic acids used to synthesize unsaturated polyesters include unsaturated dibasic acids and saturated dibasic acids. Unsaturated dibasic acids are essential, but these are usually used to obtain appropriate physical properties. A mixture of both is used.
Among the unsaturated dibasic acids, the maleic acid, chloromaleic acid, fumaric acid, chlorofumaric acid, citraconic acid, mesaconic acid, glutaconic acid, itaconic acid, allylmalonic acid, isopropylidene succinic acid, muconic acid, etc. Is mentioned. Among these, maleic anhydride is preferable from the viewpoint of cost, reactivity, and physical properties.
Among the dibasic acids, the saturated dibasic acids include oxalic acid, malonic acid, succinic acid, chlorosuccinic acid, bromosuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and brassic acid. , Methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, tetramethylsuccinic acid, phthalic acid, chlorophthalic acid, isophthalic acid, terephthalic acid, 5 -Methylisophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, tetrabromophthalic acid, chlorendic acid, phenylsuccinic acid, o-carboxyphenylacetic acid, o-phenylenediacetic acid, etc. Phthalic anhydride is preferred in terms of price, reactivity and physical properties.

  On the other hand, styrene is generally used as a crosslinking monomer that crosslinks and cures the C = C double bond of an unsaturated polyester. However, crosslinking with an α, α-2 substituted vinyl monomer is more effective due to steric hindrance. There is a decrease, and it is thought that it is easy to decompose. In fact, the heat of polymerization of α, α-2 substituted vinyl monomers is much lower than other vinyl monomers. This is interpreted because the polymer chain is sterically hindered and unstable. Low polymerization heat means that the difference in energy between the original system (monomer) and the generation system (polymer) is small, which means that the polymer is not stabilized. Incidentally, the polymerization heat of ethylene as an unsubstituted monomer is 21.2 kcal / mol. The polymerization heat of 1-substituted vinyl monomer styrene is 16.7 kcal / mol, the polymerization heat of methyl acrylate is 18.5 kcal / mol, and the polymerization heat of propylene is 19.5 kcal / mol. The heat of polymerization of α-methylstyrene, a disubstituted vinyl monomer, is 8.4 kcal / mol, the heat of polymerization of methyl methacrylate is 13.2 kcal / mol, and the heat of polymerization of isobutylene is 12.9 kcal / mol (reference: edited by Hirotaro Kobe) , "Thermal decomposition and heat resistance of polymers", p.225 (1974)). Accordingly, it is easier to decompose the cured unsaturated polyester resin having a crosslink containing α, α-2 substituted vinyl monomer units by glycol than the styrene cross-linked resin.

The above-described chemical recycling according to the present invention does not require a purification step and can be performed without any trouble even if there is some moisture. Further, colored resin waste, some dirt, and resin waste adhering to a different resin can be re-synthesized into unsaturated polyester and used for resin concrete or the like.
In the case of organic fiber reinforced plastic waste that is hardly decomposed organic fiber, the decomposition product may be subjected to a filtration step to remove organic fiber and filler. When trying to reuse the fiber, the waste is decomposed with 30 to 50 cm square, the fiber is separated, washed and reused, and the decomposition product is condensed with dibasic acid and re-synthesized into unsaturated polyester. May be. Or you may synthesize | combine again, including a fiber etc., and reuse.

As a decomposition apparatus used for the decomposition with glycol and a synthesis apparatus used for the reaction with the dibasic acid, a normal reaction tank can be used. Of course, the decomposition reaction can be performed even under pressure. Some devices can perform decomposition, synthesis, and styrene mixing operations in a single reaction tank. However, if there is an installation site, decomposition, synthesis, and styrene mixing can be performed in three separate reaction vessels. It doesn't matter.
For example, an agitator (motor, stirring blade) for stirring in the container, raw material organic fiber reinforced FRP waste tank, decomposition catalyst, glycol, maleic anhydride, etc. A tank for injecting chemicals, a tank for decomposition liquid, a polymerization injection tank for polymerization inhibitors, styrene, a low shrinkage agent, etc., a nitrogen gas inflow pipe, a partial condenser (water vapor is extracted at the top, and high boiling points such as other glycols) To return the product to the reaction vessel), a condenser, and a receiver. Heating and cooling in the container are usually performed by a heat medium boiler, but electromagnetic induction heating may be used. After decomposition with glycol, the valve at the bottom of the reaction vessel is opened, and unreacted substances and the like are separated from the decomposition solution by a filter. The decomposition solution is stored in the decomposition solution tank by a pump and used for subsequent resynthesis. The re-synthesized unsaturated polyester styrene solution is stored in a dedicated tank.

The stainless steel reaction vessel described above is stronger against alkali than the glass reaction vessel, can be used at a higher temperature, and can be used under pressure. Further, since the stirring torque can be increased, the ratio of the amount of waste to the amount of glycol can be increased, which is preferable in terms of the amount of processing.
Decomposition can also be performed using an extruder. As the extruder used, a single-screw extruder equipped with a vacuum pump, preferably a twin-screw kneading extruder (same direction rotation or reverse direction rotation) can be used. Such an extruder preferably has a large barrel L / D and a long residence time. The temperature of the extruder is preferably about 20 ° C. higher than the decomposition temperature in the decomposition tank. A kneader such as a kneader can also be used for the decomposition.
For molding the recycled unsaturated polyester resin, ordinary centrifugal drum method molding, casting molding, hand lay-up molding, spray-up molding, compression molding, pultrusion molding, injection molding, transfer molding, and the like are used.
The resin of unsaturated polyester regenerated in this way is suitably used for applications such as molding materials, adhesives and paints.

Hereinafter, the present invention will be described more specifically with reference to examples. In addition, the Example described below is only the example which actualized this invention, and does not limit the technical scope of this invention.
In Examples 1 to 5 and Comparative Example 1, organic fiber reinforced plastic waste and glass fiber reinforced plastic waste are decomposed with glycol, the decomposition product is reacted with dibasic acid, and a method for regenerating unsaturated polyester resin is studied. It is a thing.
In each of the following examples, unless otherwise specified, organic fiber reinforced plastic waste is FRP waste for mannequins (hand layup molding), particle size of 3 mm or less by rotary cutter mill (Granulators U-140 manufactured by Horai Co., Ltd.). The crushed sample was used. Or what crushed organic fiber reinforcement FRP to about 25 mm with scissors etc. was used.
The organic fiber reinforced FRP is a desktop hot press (Techno) at 150 ° C. for 10 minutes by adding 1% of t-butyl perbenzoate as an initiator to an unsaturated polyester styrene solution and impregnating the resin with organic fiber. Supply Co., Ltd.) was compression-molded and cured, measured for physical properties, and used for glycol decomposition and resynthesis.
Regenerated unsaturated polyester resin is 1% each of methyl ethyl ketone peroxide and cobalt naphthenate as an initiator for unsaturated polyester, and is cured by casting at 30 ° C for 2 hours and 100 ° C for 2 hours after curing. The physical properties were measured. A commercially available resin used as a reference was Polylite BS210M (a styrene solution of an unsaturated polyester resin containing 30 to 40 wt% of styrene) manufactured by Dainippon Ink and Chemicals, Inc.
The dynamic viscoelasticity of the organic fiber reinforced FRP waste for mannequins, the compression-molded organic fiber reinforced FRP, and the unsaturated polyester resin molded and cured by casting is measured by Seiko Instruments DMS210, and the glass transition point (Tg) Was obtained from the peak temperature of tan δ (10 Hz). The average molecular weight (Mc) between cross-linking points was calculated from the storage elastic modulus (E ') at (Tg + 40) ° C using the theoretical formula of rubber elasticity shown in the following formula (1) (reference: Hasegawa Kiichi, Journal of the Adhesion Society of Japan, 29 , 75 (1993)).
E ′ = 3φdRT / Mc (1)
Here, φ: front coefficient, d: density, R: gas constant, T: absolute temperature.

"Decomposition of polyester fiber reinforced plastic mannequin with ethylene glycol, resynthesis to unsaturated polyester"
A mannequin made of polyester fiber reinforced plastic (manufactured by Kyoya Co., Ltd.) was impregnated with an unsaturated polyester resin regenerated from PET on two polyester fiber fabrics, and hand laid up. Bending strength is 623 MPa (displacement 0.5 mm), Barcoal hardness (Method A) is 26, Charpy impact strength is flatwise (perpendicular to the surface) 21.17 KJ / m ² , etchwise (thickness direction) 37.53 KJ / m ² .
The glass transition point (Tg) determined from the tan δ peak of dynamic viscoelasticity (10 Hz) was 121.9 ° C.
The average molecular weight (Mc) between cross-linking points determined from the value of the storage elastic modulus (E ') at (Tg + 40) ° C of dynamic viscoelasticity (10Hz) was 97.
Pressure resistant glass industry TAS-095 reactor (material SUS316, capacity 950ml, maximum operating temperature 300 ° C, maximum operating pressure 20MPa), ethylene glycol 155.2g (2.5mol), then polyester fiber reinforced plastic mannequin (Kyoya Co., Ltd.) Made) 130g (propylene glycol unit) 0.25- (phthalic acid unit) 0.30- (ethylene glycol unit) 0.25- (unit of maleic acid plus two molecules of styrene) 0.20 unsaturated polyester resin (matrix resin) 0.5 + polyester Fiber 0.5) was added and stirred at 290 ° C. for 2 hours at 600 rpm for decomposition. The pressure at the end of the decomposition was 3.0 MPa. The decomposition product was a brown liquid. When the decomposition product was subjected to GPC analysis (THF solvent, 40 ° C., polystyrene standard), the number average molecular weight (Mn) = 276, the weight average molecular weight (Mw) = 3,067, the weight average molecular weight / number average molecular weight (D) = 11.13, The peak top molecular weight (P) was 146.
Next, 141.2 g (1.44 mol) of maleic anhydride and 142.2 g (0.96 mol) of phthalic anhydride were added to the decomposition product, 100 ppm of hydroquinone was added, and while blowing nitrogen, 200 rpm, 150 ° C., 1 hour, 210 Dehydration condensation was carried out at 2 ° C. for 2 hours. After the reaction for 2 hours, the stirring rotation speed was increased to 800 rpm, and the nitrogen flow rate was increased. The reaction product was a brown solid. When the reaction product was subjected to GPC analysis (THF solvent, 40 ° C., polystyrene standard), the number average molecular weight (Mn) = 1,500, the weight average molecular weight (Mw) = 7,100, the weight average molecular weight / number average molecular weight (D) = 4.73, Peak top molecular weight (P) = 1,635 (commercially available number average molecular weight = 1,646, weight average molecular weight = 5,366, weight average molecular weight / number average molecular weight = 3.26).
Styrene was added to this reaction product, and 100 ppm of t-butylcatechol was added to obtain a recycled resin solution containing 30 wt% styrene with respect to the unsaturated polyester resin content in the reaction product. 1% each of methyl ethyl ketone peroxide and cobalt naphthenate was added to this styrene solution, and cast molding was performed at 30 ° C for precuring for 2 hours and 100 ° C for postcuring for 2 hours. The bending strength of the obtained molded product is 72.8 MPa (commercial product 92.1 MPa), flexural modulus 3.47 GPa (commercial product 3.68 GPa), glass transition temperature 119.0 ° C. (commercial product 138.0 ° C.), average molecular weight between bridges 297 ( It was a commercial product 241).

"Decomposition of vinylon fiber reinforced plastic mannequin with ethylene glycol, resynthesis to unsaturated polyester"
A vinylon fiber reinforced plastic mannequin (manufactured by Kyoya Co., Ltd.) was impregnated with unsaturated polyester resin regenerated from PET on two vinylon fiber fabrics, and then hand laid up. Bending strength is 734 MPa (displacement 0.5 mm), Barcol hardness (Method A) is 46, Charpy impact strength is flatwise (perpendicular to the surface) 12.94 KJ / m ² , etchwise (thickness direction) 18.47 KJ / m There were ^two .
The glass transition point (Tg) obtained from the tan δ peak of dynamic viscoelasticity (10 Hz) was 99.9 ° C.
The average molecular weight (Mc) between cross-linking points determined from the value of storage elastic modulus (E ') at (Tg + 40) ° C for dynamic viscoelasticity (10Hz) was 153.
Pressure-resistant glass industry TAS-095 type reactor (material SUS316, capacity 950ml, maximum operating temperature 300 ° C, maximum operating pressure 20MPa), ethylene glycol 155.2g (2.5mol), then vinylon fiber reinforced plastic mannequin (Kyoya Co., Ltd.) Made of 25mm square crushed 130g ((propylene glycol unit) 0.25- (phthalic acid unit) 0.30- (ethylene glycol unit) 0.25- (unit of maleic acid plus two styrene molecules) 0.20 unsaturated polyester Resin (matrix resin) 0.5 + vinylon fiber 0.5) was added, 0.4 g of sodium hydroxide was added, and the mixture was stirred at 290 ° C. for 2 hours at 600 rpm for decomposition. The pressure at the end of the decomposition was 2.1 MPa. The vinylon fiber was decomposed and no fiber remained. The decomposition product was a brown liquid. When the decomposition product was subjected to GPC analysis (THF solvent, 40 ° C., polystyrene standard), the number average molecular weight was 452, the weight average molecular weight was 15,432, the weight average molecular weight / number average molecular weight was 34.13, and the peak top molecular weight was 148. .
Next, neutralized with 1.0 g of 36% hydrochloric acid, 141.2 g (1.44 mol) of maleic anhydride and 142.2 g (0.96 mol) of phthalic anhydride were added to the decomposition product, 100 ppm of hydroquinone was added, and 200 rpm was added while blowing nitrogen. The mixture was subjected to dehydration condensation at 150 ° C for 1 hour and at 210 ° C for 2 hours. After the reaction for 2 hours, the stirring rotation speed was increased to 800 rpm, and the nitrogen flow rate was increased. The reaction product was brown and solid. The reaction product was subjected to GPC analysis (THF solvent, 40 ° C., polystyrene standard). As a result, the number average molecular weight was 1,600, the weight average molecular weight was 8,237, the weight average molecular weight / number average molecular weight was 5.15, and the peak top molecular weight was 1,722. (Number average molecular weight of commercial product = 1,646, weight average molecular weight = 5,366, weight average molecular weight / number average molecular weight = 3.26).
Styrene was added to this reaction product, and 100 ppm of t-butylcatechol was added to obtain a regenerated unsaturated polyester resin styrene solution containing 30 wt% styrene.

"Decomposition of nylon-6 fiber reinforced plastic with propylene glycol, resynthesis to unsaturated polyester"
Nylon-6 fiber reinforced FRP is made by adding 1% t-butyl perbenzoate as an initiator to an unsaturated polyester styrene solution, and impregnating three nylon-6 jerseys (201.8 g / m ² per unit area) with the resin. At 150 ° C. for 10 minutes, a tabletop hot press (manufactured by Techno Supply Co., Ltd.) was used for compression molding and curing, and the physical properties were measured. The fiber content was 36.7% and the resin content was 63.3%. The bending strength was 30.1 MPa (displacement 5.9 mm) and the flexural modulus was 1.42 GPa.
The glass transition point (Tg) determined from the tan δ peak of dynamic viscoelasticity (10 Hz) was 178.9 ° C.
The average molecular weight (Mc) between cross-linking points obtained from the value of the storage elastic modulus (E ') at (Tg + 40) ° C of dynamic viscoelasticity (10Hz) was 204.
Pressure-resistant glass industry TAS-095 reactor (material SUS316, capacity 950ml, maximum operating temperature 300 ° C, maximum operating pressure 20MPa), propylene glycol 190.2g (2.5mol), then nylon-6 fiber reinforced plastic 130g ((propylene Glycol unit) 0.25- (phthalic acid unit) 0.30- (ethylene glycol unit) 0.25- (unit of styrene bimolecular addition to maleic acid) 0.20 composition unsaturated polyester resin (matrix resin) 0.63 + nylon fiber 0.37) The mixture was stirred at 600 rpm for 2 hours at 290 ° C. for decomposition. The pressure at the end of the decomposition was 3.0 MPa. The decomposition product was a brown liquid. When the decomposition product was subjected to GPC analysis (THF solvent, 40 ° C., polystyrene standard), the number average molecular weight was 280, the weight average molecular weight was 3,100, the weight average molecular weight / number average molecular weight was 11.07, and the peak top molecular weight was 150. .
Next, 141.2 g (1.44 mol) of maleic anhydride and 142.2 g (0.96 mol) of phthalic anhydride were added to the decomposition product, 100 ppm of hydroquinone was added, and while blowing nitrogen, at 200 rpm, 150 ° C., 1 hour, 210 ° C. It was dehydrated and condensed for 2 hours. After the reaction for 2 hours, the stirring rotation speed was increased to 800 rpm, and the nitrogen flow rate was increased. The reaction product was a brown solid. The reaction product was subjected to GPC analysis (THF solvent, 40 ° C., polystyrene standard). The number average molecular weight was 1,550, the weight average molecular weight was 7,560, the weight average molecular weight / number average molecular weight was 4.88, and the peak top molecular weight was 1,650. (Number average molecular weight of commercial product = 1,646, weight average molecular weight = 5,366, weight average molecular weight / number average molecular weight = 3.26).
Styrene was added to this reaction product, and 100 ppm of t-butylcatechol was added to obtain a regenerated unsaturated polyester resin styrene solution containing 30 wt% styrene. Methyl ethyl ketone peroxide and cobalt naphthenate were added in an amount of 1 wt% to the unsaturated polyester resin, respectively, and cast and molded at 30 ° C. for 2 hours and 100 ° C. for 2 hours. The bending strength of the obtained molded product was 77.0 MPa (commercial product 92.1 MPa), flexural modulus 3.60 GPa (commercial product 3.68 GPa), glass transition temperature 122.7 ° C. (commercial product 138.0 ° C.), average molecular weight between bridge points 233 ( It was a commercial product 241).

"Degradation of Kevlar fiber reinforced plastic with ethylene glycol, resynthesis to unsaturated polyester"
Kevlar fiber reinforced FRP was added 1% t-butyl perbenzoate as an initiator to styrene solution of unsaturated polyester, impregnated with 6 pieces of Kevlar woven fabric (weight per unit: 180.3 g / m ² ) at 150 ° C Then, using a desktop hot press (manufactured by Techno Supply Co., Ltd.) for 10 minutes, it was compression-molded and cured, and the physical properties were measured. The fiber content was 55.6% and the resin content was 44.4%. The bending strength was 76.0 MPa (displacement 5.1 mm) and the flexural modulus was 8.50 GPa.
The glass transition point (Tg) determined from the tan δ peak of dynamic viscoelasticity (10 Hz) was 194.6 ° C.
Pressure-resistant glass industry TAS-095 reactor (material SUS316, capacity 950ml, maximum operating temperature 300 ° C, maximum operating pressure 20MPa), ethylene glycol 155.2g (2.5mol), then Kevlar fiber reinforced plastic 130g ((propylene glycol unit) ) 0.2- (phthalic acid unit) 0.30- (ethylene glycol unit) 0.25- (maleic acid added to styrene bimolecular unit) 0.20 unsaturated polyester resin (matrix resin) 0.44 + Kevlar fiber 0.56) Potassium oxide 0.56g was added and it decomposed | disassembled by stirring at 600 rpm for 2 hours at 290 degreeC. The pressure at the end of the decomposition was 3.9 MPa. The decomposition product was a brown liquid. The decomposition product was subjected to GPC analysis (THF solvent, 40 ° C., polystyrene standard). As a result, the number average molecular weight was 450, the weight average molecular weight was 4,200, the weight average molecular weight / number average molecular weight was 9.33, and the peak top molecular weight was 245. .
Then, neutralized with 36% hydrochloric acid 1.0g, maleic anhydride 141.2g (1.44mol) and phthalic anhydride 142.2g (0.96mol) were added to the decomposition product, hydroquinone 100ppm was added, while blowing nitrogen, 200rpm The mixture was subjected to dehydration condensation at 150 ° C. for 1 hour and at 210 ° C. for 2 hours. After the reaction for 2 hours, the stirring rotation speed was increased to 800 rpm, and the nitrogen flow rate was increased. The reaction product was a brown solid. The reaction product was subjected to GPC analysis (THF solvent, 40 ° C., polystyrene standard). The number average molecular weight was 1,650, the weight average molecular weight was 8,200, the weight average molecular weight / number average molecular weight was 4.96, and the peak top molecular weight was 1,750. (Number average molecular weight of commercial product = 1,646, weight average molecular weight = 5,366, weight average molecular weight / number average molecular weight = 3.26).
Styrene was added to this reaction product, and 100 ppm of t-butylcatechol was added to obtain a regenerated unsaturated polyester resin styrene solution containing 30 wt% styrene.

"Degradation of Kevlar fiber reinforced plastic with ethylene glycol, resynthesis to unsaturated polyester"
Kevlar fiber reinforced FRP was added 1% t-butyl perbenzoate as an initiator to styrene solution of unsaturated polyester, and impregnated 9 sheets of Kevlar woven fabric (weight per unit area: 180.3 g / m ² ) at 150 ° C. Then, using a desktop hot press (manufactured by Techno Supply Co., Ltd.) for 10 minutes, it was compression-molded and cured, and the physical properties were measured. The fiber content was 56.1% and the resin content was 43.9%. The bending strength was 299.2 MPa (displacement 6.1 mm) and the flexural modulus was 44.90 GPa.
The glass transition point (Tg) obtained from the tan δ peak of dynamic viscoelasticity (10 Hz) was 200.9 ° C.
Pressure-resistant glass industry TAS-095 reactor (material SUS316, capacity 950ml, maximum operating temperature 300 ° C, maximum operating pressure 20MPa), ethylene glycol 155.2g (2.5mol), then Kevlar fiber reinforced FRP 130g ((propylene glycol unit) 0.25-(phthalic acid unit) 0.30-(ethylene glycol unit) 0.25-(unit of styrene bimolecular addition to maleic acid) 0.20 composition unsaturated polyester resin (matrix resin) 0.44 + Kevlar fiber 0.56), 290 ° C And stirred for 2 hours at 600 rpm for decomposition. The pressure at the end of the decomposition was 3.8 MPa. The decomposition product was a brown liquid. When the decomposition product was subjected to GPC analysis (THF solvent, 40 ° C., polystyrene standard), the number average molecular weight was 493, the weight average molecular weight was 9,819, the weight average molecular weight / number average molecular weight was 19.9, and the peak top molecular weight was 286. .
Next, 141.2 g (1.44 mol) of maleic anhydride and 142.2 g (0.96 mol) of phthalic anhydride were added to the decomposition product, 100 ppm of hydroquinone was added, and while blowing nitrogen, at 200 rpm, 150 ° C., 1 hour, 210 ° C. It was dehydrated and condensed for 2 hours. After the reaction for 2 hours, the stirring rotation speed was increased to 800 rpm, and the nitrogen flow rate was increased. The reaction product was a brown solid. The reaction product was subjected to GPC analysis (THF solvent, 40 ° C., polystyrene standard). The number average molecular weight was 846, the weight average molecular weight was 7,468, the weight average molecular weight / number average molecular weight was 8.82, and the peak top molecular weight was 1,210. (Number average molecular weight of commercial product = 1,646, weight average molecular weight = 5,366, weight average molecular weight / number average molecular weight = 3.26).
Styrene was added and 100 ppm of t-butylcatechol was added to obtain an unsaturated polyester resin solution of 30 wt% styrene.

(Comparative example)
"Decomposition and resynthesis of glass fiber reinforced FRP with ethylene glycol"
Pressure-resistant glass industry TAS-095 reactor (material SUS316, capacity 950ml, maximum operating temperature 300 ° C, maximum operating pressure 20MPa), ethylene glycol 155.2g (2.5mol), then waste FRP 131g (resin content 40) %, Glass fiber 30%, calcium carbonate 30%, (propylene glycol units) 0.25- (phthalic acid units) 0.30- (ethylene glycol units) 0.25- (units of maleic acid plus two styrene molecules) 0.20 Polyester resin (matrix resin) unit 0.1 gram equivalent) was added and stirred at 290 ° C. for 3 hours at 600 rpm for decomposition. The pressure at the end of the decomposition was 1.8 MPa. The decomposition product was a brown viscous liquid (glass fibers and calcium carbonate were separated and remained as they were). When the decomposition product was subjected to GPC analysis (THF solvent, 40 ° C., polystyrene standard), the number average molecular weight was 342, the weight average molecular weight was 11,148, the weight average molecular weight / number average molecular weight was 32.60, and the peak top molecular weight was 237. .
Next, without separating the glass fiber and calcium carbonate, maleic anhydride 122.6 g (1.25 mol) and phthalic anhydride 185.2 g (1.25 mol) were added to the above decomposition product, hydroquinone 100 ppm was added, and nitrogen was blown in , 200 rpm, 150 ° C., 1 hour, and 210 ° C. for 2 hours. After the reaction for 2 hours, the stirring rotation speed was increased to 800 rpm, and the nitrogen flow rate was increased. The reaction product was a brown solid. The reaction product was subjected to GPC analysis (THF solvent, 40 ° C., polystyrene standard). As a result, number average molecular weight = 638, weight average molecular weight = 1,695, weight average molecular weight / number average molecular weight = 2.65, and peak top molecular weight = 962. .
Styrene was added to this reaction product, and 100 ppm of t-butylcatechol was added to obtain a styrene solution of regenerated unsaturated polyester resin containing 40 wt% styrene.

According to the present invention, an industrially useful resin raw material can be obtained from organic fiber reinforced plastic waste, and can be regenerated into an unsaturated polyester resin. In addition, the decomposition can be performed at a relatively low temperature or in a relatively short time and can be carried out with a relatively simple operation, so that it is possible to reuse the organic fiber-reinforced plastic waste economically with simple equipment. it can. That is, according to the present invention, mannequins made of organic fiber reinforced plastic, display shaped objects, wastes produced during the production of building materials, and wastes of those products can be effectively reused.

Claims (3)

Polyester fiber (polyethylene terephthalate, polybutylene terephthalate, polyarylate etc.), polyamide fiber (nylon 6, nylon 6,6 etc.), aramid fiber (Kevlar, Conex etc.), polyurethane fiber, vinylon fiber with unsaturated polyester resin as matrix After pulverizing the fiber-reinforced plastic waste containing organic fibers consisting of at least one member of the group consisting of glycols in the presence or absence of a catalyst, the unsaturated polyester and the reinforcing fibers as the matrix A method for recycling organic fiber-reinforced plastic waste, comprising: simultaneously decomposing certain organic fibers; and synthesizing an unsaturated polyester by subjecting the obtained decomposition product to a condensation reaction with a dibasic acid. 2. The method for recycling organic fiber-reinforced plastic waste according to claim 1, wherein the catalyst is either sodium hydroxide or potassium hydroxide. The organic fiber reinforced plastic waste according to claim 1 or 2, wherein the waste is a mannequin made of organic fiber reinforced plastic, a shaped article for display, a waste generated when manufacturing a building material, and a waste of those products. How to play.