JP2003268098A - Method and apparatus for reusing polyester resin waste - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a raw material for regeneration, having industrial value by chemically treating a polyester resin waste by a simple installation at a comparatively short time, and to easily regenerate an unsaturated polyester by directly using the raw material. <P>SOLUTION: The polyester resin waste is decomposed by using a glycol adduct of maleic anhydride and/or itaconic anhydride in the presence or absence of a catalyst to provide a resin raw material for resynthesis. The unsaturated polyester is synthesized by condensing the resin raw material. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recycling polyester resin waste and an apparatus therefor, and more particularly to chemically treating polyester resin waste to obtain industrially valuable raw materials. The present invention relates to a method and an apparatus for attempting reuse by using the method.

[0002]

2. Description of the Related Art Recycling of PET bottles and films of saturated polyester resin is mainly carried out by material recycling by melting and reforming with heat (RJEhri
ng, Translated by Plastic Recycling Study Group, "Plastic Recycling-From Collection to Recycling-", p.
71, Industrial Research Council (1993)).

On the other hand, a technique for recovering monomers by hydrolysis, methanol decomposition, and glycol decomposition has also been developed for recycling PET bottles and films (“waste plastic thermal & chemical recycling”,
p. 201, Chemical Daily Co., Ltd. (1994)).

As a method of regenerating PET bottles and films, a method of decomposing glycol and reacting the decomposed product with an unsaturated dibasic acid to regenerate an unsaturated polyester resin has been studied (JP-A-8-151438, URVaid
ya, VMNadkarni, Ind.Eng.Chem.Res., 26 , 194 (198
7), United States Patent 3,951,886 (1976), JBSchn
eider, RJEhring, GLBrownell, DAKosmack, Proc
eedings 48th Annual Technical Conference of the So
ciety of Plastics Engineers (ANTEC'90), 1462 (199
0), KSRebeiz, DWFowler, DRPaul, Plastics Eng
inering, 47 (2), 33 (1991)).

On the other hand, the unsaturated polyester resin waste is partially pulverized and mixed into new BMC and SMC as a filler, and the material is reused in part (Nobuhiro Fukuda, Science and Industry, 68 ( 2), 60
(1994)). For chemical recycling, a technology has been developed that decomposes with glycol, reacts the decomposed product with a dibasic acid as a glycol component, and re-synthesizes unsaturated polyester (“Recycling method and waste of unsaturated polyester resin waste”). Utilization device ", Japanese Patent No. 2701012 (H9.10.3)).

[0006]

Saturated polyester resin waste is generally subjected to material recycling such as melting and re-molding, which is a common method for thermoplastic resins.

However, the colored resin and the resin with stains are not used because they lose their commercial value at the time of recycling. Further, when water is present, hydrolysis occurs during remolding, which lowers the molecular weight and thus the physical properties.

Further, as a technique for recovering a PET bottle or a film, a technique for recovering a monomer by hydrolysis, methanol decomposition, or glycol decomposition has been developed, but it is difficult to purify the monomer.

When the saturated polyester resin is decomposed with glycol to be resynthesized into an unsaturated polyester, the hydroxyl group (OH group) of the glycol decomposition product is quantified, and the decomposition product is accurately equimolar to the dibasic acid. If the condensation reaction is not carried out, a high molecular weight unsaturated polyester cannot be obtained. However, accurate quantification of hydroxyl groups has been extremely difficult due to coloration during decomposition and the presence of carboxyl groups. Therefore, the quantification of hydroxyl groups is likely to be inaccurate, and due to the error in the quantification, resynthesis of high molecular weight unsaturated polyesters by this method was technically extremely difficult.

Furthermore, since the amount of glycol used for the above decomposition is such that the waste is soaked, the same amount of glycol as the waste resin is required, and this glycol is reacted with an equimolar amount of dibasic acid. After obtaining the regenerated unsaturated polyester, this is further used as a 30-40% styrene solution. Therefore, it is supposed that a regenerated unsaturated polyester resin having about 5 times the mass of the waste saturated polyester resin will be obtained in the end. It was Therefore, the ratio of the amount of waste resin to the recycled unsaturated polyester resin was small, and the recycling efficiency was extremely low.

On the other hand, the material recycling in which unsaturated polyester resin waste is pulverized and mixed into new BMC and SMC as a filler and reused has a drawback that the strength decreases as the mixing ratio increases (Wakayama Prefectural Industrial Technology Center). , 1994-1994 Technology Development Research Expenses Subsidy Project Results Dissemination Workshop Text (Wide Area Joint Research), Chapter 6 Study on Advanced Utilization Technology of Thermosetting Resin Industrial Waste, 6-3
Page (H9.4)).

Further, in the chemical recycling in which the unsaturated polyester resin waste is decomposed with glycol and the obtained decomposed product is subsequently reacted with a dibasic acid as a glycol component to re-synthesize the unsaturated polyester, the glycol decomposed product is the same as above. It was difficult to quantify the OH group of and to react it with equimolar amount of dibasic acid.

Also in this case, since the amount of glycol used for decomposition is such that the waste is soaked, almost the same amount of glycol as that of the waste resin is required, and equimolar dibasic acid is added to this glycol. After the reaction to obtain the regenerated unsaturated polyester, the regenerated unsaturated polyester resin is made to be a 30-40% styrene solution, and thus the regenerated unsaturated polyester resin of about 5 times the mass of the waste unsaturated polyester resin is obtained in the same manner as above. It was. Therefore, according to this method, the recycling efficiency was extremely low.

Therefore, an object of the present invention is to chemically process polyester resin waste in a relatively short time with simple equipment to obtain industrially valuable raw material for regeneration, and to use this raw material. An object of the present invention is to provide a method for easily regenerating an unsaturated polyester directly without purification, that is, an economically excellent method for chemically recycling polyester resin waste to unsaturated polyester.

[0015]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies in order to solve the above problems. As a result, after crushing polyester resin waste (saturated polyester resin, unsaturated polyester resin, etc.), Polyester resin waste that is decomposed by a glycol adduct such as maleic anhydride at about 150 to 300 ° C, is used as a raw material for resynthesis without purification, and is resynthesized unsaturated unsaturated polyester resin and chemically recycled We came to complete the method of reusing things.

That is, the present invention provides a resin for resynthesis by decomposing polyester resin waste with a glycol adduct of maleic anhydride and / or itaconic anhydride in the presence or absence of a catalyst. The present invention provides a method for reusing polyester resin waste, which comprises a step of obtaining a raw material and a step of synthesizing an unsaturated polyester by subjecting the resin raw material obtained above to a condensation reaction.

The present invention also provides the use of a glycol adduct of a mixture of maleic anhydride and / or itaconic anhydride, and phthalic anhydride to decompose polyester resin waste in the presence or absence of a catalyst. And a step of synthesizing an unsaturated polyester by subjecting the resin raw material obtained above to a condensation reaction to obtain a resin raw material for resynthesis. providing.

Further, the method for recycling the polyester resin waste of the present invention comprises a step of decomposing the polyester resin waste to obtain a resin raw material for resynthesis, and a condensation reaction of the resin raw material obtained above. Both steps of synthesizing the unsaturated polyester can be performed using an extruder.

The present invention also includes a method of recycling polyester resin waste, which comprises a step of producing a curable unsaturated polyester by further adding a reactive monomer to the synthesized unsaturated polyester. Is also provided.

The polyester resin waste in the method for recycling polyester resin waste of the present invention may be a saturated polyester resin, an unsaturated polyester resin, or a fiber reinforced plastic (FRP) waste thereof.

In the apparatus used in the present invention, the reaction tank has a stirrer, a heater, a cooler, a partial condenser,
It may be equipped with a condenser, a raw material tank, a chemical injection tank, a filter and a pump.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION <Process of Decomposing Polyester Resin Waste to Obtain Resin Raw Material for Resynthesis> In the method for recycling polyester resin waste of the present invention, the polyester resin waste is first crushed and if necessary. For example, it is preferable to carry out a pretreatment of washing and sieving. Crushing is performed with an 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. be able to.

The size of the crushed material of the waste is preferably small, but any material that passes through a sieve with 20 mm openings can be used. However, crushed material that passes through a 5 mm sieve, and more preferably 1 mm, is preferable.

Among the polyester resin wastes used in the present invention, saturated polyester resin wastes include polyethylene terephthalate (PET), polybutylene terephthalate, used for bottles, films, molded products, etc.
Examples thereof include polyethylene naphthalate (PEN) as a constituent resin.

On the other hand, examples of the unsaturated polyester resin wastes include button punching scraps, shavings, FRP product wastes, and the like, and the constituent resins thereof include normal unsaturated polyester resin wastes.

Further, as the fiber reinforced plastic (FRP) waste, the above-mentioned saturated polyester or unsaturated polyester is used as a constituent resin, and various reinforcing fibers are added thereto.
Examples of such waste products include glass fibers, carbon fibers, heat-resistant fibers such as Kevlar, organic fibers such as vinylon, and the like.

As the glycol constituting the glycol adduct of the present invention, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,3- Examples thereof include butanediol, 1,6-hexanediol, hydrogenated bisphenol A, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, dibromoneopentyl glycol and cyclohexane diol.

Examples of the acid anhydrides that form an adduct with these glycols include maleic anhydride and itaconic anhydride, and these can be used alone or in combination to form a glycol adduct. .

Further, a glycolic acid adduct can be obtained by using phthalic anhydride in combination with the above acid anhydride.

The method for producing the glycol adduct according to the present invention can be produced by a conventional method and is not particularly limited.

The composition ratio of the acid anhydride and glycol is not particularly limited, but usually the former is 1 mol and the latter is 0.
It is suitable to set the latter in the range of 1.00 to 1.10 mol relative to 90 to 1.20 mol, preferably 1 mol of the former.

Depending on conditions such as reaction temperature and time,
This adduct may be obtained as a mixture of monomers, dimers and polymers. Further, a mixture of structural isomers of a compound which is added with a primary alcohol such as an addition product of 1,2-propanediol and a compound which is added with a secondary alcohol, E and Z.
-May be obtained as a mixture of isomers (cis, trans-isomers).

In the present invention, when the polyester resin waste is decomposed, the mass ratio of the polyester resin waste and the glycol adduct such as maleic anhydride used to decompose the polyester resin waste is 1: 0.2 to 5 , Preferably 1:
It is 0.5 to 1.5. By changing this ratio, the degree of unsaturation, that is, C = occupied in the oligomer molecule before curing,
The proportion of C double bonds can be varied. When this ratio is decreased, the ratio of C = C double bonds is decreased, and when this ratio is increased, the ratio of C = C double bonds is increased. When the proportion of C = C double bonds is large, the cured product obtained by crosslinking with a reactive monomer such as styrene has a high curing density and generally becomes hard.

If this ratio is reduced, the amount of waste resin in the recycled resin is large, and the waste resin can be efficiently recycled.

The catalyst used for the above decomposition is
Sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, zinc acetate, magnesium acetate, calcium acetate, lithium acetate, acetate metal salts such as sodium acetate, antimony oxide, titanium alkoxide, tributyltin methoxide and mixtures thereof. Can be mentioned.

When an alkali catalyst is used, sulfuric acid, hydrochloric acid or the like is used to neutralize it. On the other hand, the above decomposition can be carried out without a catalyst, that is, without using the above catalyst.

The decomposition temperature of the polyester resin waste in the present invention is required to be about 150 ° C. to 300 ° C., and more preferably 200 ° C. to 300 ° C., because the decomposition rate is fast, which is preferable.

On the other hand, the decomposition in the present invention is preferably carried out under nitrogen because the coloration due to the oxidation reaction can be prevented.
In this respect, it is preferable to use a small amount of an antioxidant or a polymerization inhibitor.

Further, such decomposition can be carried out under atmospheric pressure or under pressure. <Step of synthesizing unsaturated polyester> In the present invention, the decomposed product obtained above is used as a resin raw material, and the unsaturated polyester is regenerated by directly condensing it without purification. For the regeneration of unsaturated polyester, the reaction temperature is 140 ° C to 230 ° C.
Can be carried out by condensation, for example, at 210 ° C. for 1 to 4 hours under nitrogen while distilling off water.

During the above regeneration, a transesterification catalyst such as calcium acetate or antimony trioxide may be added.

This chemical recycling can be carried out without any need for the refining step as described above and even if there is some water. Further, a colored resin or a resin having stains can be regenerated into unsaturated polyester and used for resin concrete or the like. Further, even when different resins such as PP and PE are mixed, they can be easily removed by using a filtering device or the like.

The regenerated unsaturated polyester obtained as described above is usually cooled and then charged with 30% to 40% of a reactive monomer such as styrene, and hydroquinone is added as a polymerization inhibitor in an amount of about 100 ppm. It may be an unsaturated polyester resin for curing.

As the above-mentioned reactive monomer, styrene copolymerizable with C = C double bond of unsaturated polyester,
Examples thereof include vinyl monomers such as methyl methacrylate, vinyltoluene and vinyl acetate, diallyl phthalates and the like.

The regenerated unsaturated polyester resin is crosslinked by the action of these reactive monomers in the presence of a polymerization initiator to obtain a cured unsaturated polyester resin with or without a filler. be able to.

As the above-mentioned filler, any conventionally known filler may be arbitrarily selected according to the use of the recycled resin and is not particularly limited.

<Decomposition and Synthesis Device> On the other hand, as the decomposition and synthesis device used in the present invention, the device shown in FIG. 1 is used. Of course, the reaction can be carried out under pressure. The apparatus shown in FIG. 1 is an apparatus for decomposing, synthesizing, and mixing reactive monomers such as styrene in one reaction tank. However, if there is a place to install, decomposition and synthesis and mixing of reactive monomers such as styrene can be performed. It may be carried out in another reaction tank.

The apparatus shown in FIG. 1 comprises a reaction vessel 1 made of stainless steel, a third tank 4 for waste resin on top, a decomposition catalyst,
A first tank 2, a second tank 3 for injecting a chemical such as maleic anhydride and glycol, and a fourth tank 1 for a decomposing solution.
3. Inhibitor, reactive monomer such as styrene, fifth tank 14 for injecting chemicals such as low shrinkage agent, sixth tank 1
5, a seventh tank 16, a nitrogen inflow pipe 18, a partial condenser 9, a condenser 7, a receiver 8, a stirring blade 6, and a stirrer motor 20. Heating and cooling are performed by the heat medium boiler 5. After the decomposition, the valve 11 of the outlet 10 at the bottom of the reaction vessel is opened, and the unreacted substances and the like are separated by the filter 12. Decomposition liquid is pumped to the fourth tank 1
Sent to 3 and used for re-synthesis. Alternatively, it may be directly returned to the reaction vessel after filtration. If filtration is not necessary, the product is resynthesized as it is in the reaction vessel. The resynthesized resin is stored in the recycled unsaturated polyester resin tank 19.

The stainless steel reaction container of the present invention is more resistant to alkalis than the glass reaction container and can be used at higher temperatures. And it can be used under pressure. Further, the stirring torque is large, and the ratio of the glycol adduct such as maleic anhydride to the waste can be increased.

As the extruder of the present invention, a single-screw extruder equipped with a vacuum pump, preferably a twin-screw kneading extruder (in the same direction or in the opposite direction) can be used. It is better that the L / D value is large and the residence time is long. Further, it is preferable to perform the treatment at a temperature higher by about 20 ° C. than in the case of a reaction vessel, and a kneader such as a kneader can be used.

<Function> Conventionally, when the polyester resin waste is decomposed by glycol, the saturated polyester resin is 240 ° C. and the unsaturated polyester resin is 290 ° C.
Each required 2 hours, and the decomposition was performed twice a day. On the other hand, 150 ℃ for the synthesis of unsaturated polyester resin
After heating for 1 hour at 210 ° C., further heating at 210 ° C. for 4 to 7 hours was required, and the synthesis could only be performed once a day.

On the other hand, according to the method of the present invention, a glycol adduct such as maleic anhydride is synthesized at 110 ° C.
0 minutes, followed by resin decomposition at 240 ° C for saturated polyester resin and 290 ° C for unsaturated polyester resin
It takes 1-2 hours each, and then 210 for resynthesis.
Since it takes 2 hours at a temperature of 0 ° C., the required time can be greatly shortened as compared with the conventional method, and the whole process can be sufficiently performed in one day. Moreover, it is very economical because it can be decomposed and re-synthesized in one pot.

In the present invention, the decomposition product of the polyester resin waste due to the glycol adduct such as maleic anhydride is a compound having a hydroxy group at one end of the molecule and a carboxy group at the other end. It can be used as a resin raw material without purification.

Further, since each molecule has one hydroxy group and one carboxy group, it is not necessary to match the molar ratio as in the case of the reaction between glycol and dibasic acid. Therefore, it is not necessary to quantify the hydroxy group of the decomposed product with a glycol adduct such as maleic anhydride, and it has become possible to regenerate the unsaturated polyester, which has been conventionally difficult.

As described above, according to the method for recycling the waste polyester resin and the apparatus therefor according to the present invention, the waste resin is decomposed at a relatively low temperature of about 150 to 300 ° C. and purified as a resin raw material for resynthesis. The unsaturated polyester resin can be regenerated by directly conducting the condensation reaction without performing the reaction.

That is, a glycol adduct of maleic anhydride (maleic acid or fumaric acid-glycol condensate), a glycol adduct of itaconic anhydride (itaconic acid-glycol condensate) or a glycol adduct of these with phthalic anhydride. Polyester resin waste (saturated polyester resin,
Unsaturated polyester resin) is decomposed, and the decomposed product is directly subjected to dehydration and condensation reaction without purification to obtain unsaturated polyester resin.

Therefore, according to the present invention, the decomposition is carried out with an adduct having a boiling point higher than that of glycol, and the pressure at the time of decomposition is lower than that of the conventional method. Thus, the decomposition of polyester resin waste and the synthesis of unsaturated polyester resin are carried out in one device (one pot ) And can be carried out in a short time, it can be said that its industrial utility is extremely high in that it provides a very economical recycling method.

Further, according to the method of the present invention, it is possible to omit the work of quantifying the OH group after the decomposition with glycol, which has been carried out by the conventional method, and the step of condensing the equimolar dibasic acid. Also has.

Further, according to the method of the present invention, since the ratio of the amount of waste in the recycled resin is higher than that in the conventional method, the recycling efficiency is very high, and the recycled resin having a high molecular weight and high quality is used. It also has the advantage that

Below, the conventional method by glycol decomposition (hereinafter simply referred to as the conventional method) and the reusing method of the present invention (hereinafter simply referred to as the present method) will be specifically compared to further clarify the action of the present invention. To do.

<Case 1> First, a case where the polyester resin waste is a saturated polyester resin waste (hereinafter, simply referred to as PET waste) will be exemplified.

In the conventional method, for example, 192 g of P
Decomposition of ET waste (1 gram equivalent) with 192 g of propylene glycol (2.52 mol) will give 384 g of decomposition product.

Subsequently, with respect to 384 g of the decomposition product, an acid anhydride equivalent to the above-mentioned propylene glycol, that is, 224 g of phthalic anhydride (1.51 mol) and 99 g of maleic anhydride (1.01 mol). 262 g of unsaturated polyester resin is regenerated and 45 g of water (2.52 mol) is produced by dehydration condensation with.

Then, using 662 g of this unsaturated polyester resin as a 30% styrene solution (using 284 g of styrene), a total of 946 g of recycled resin was obtained, which was 4. It is 93 times the mass.

On the other hand, in this method, for example, the amount of the propylene glycol adduct of maleic anhydride is 0.67 mol (111 g) per 192 g of PET waste (1 gram equivalent) in the same amount as above. Sufficiently, if this is decomposed and then dehydrated and condensed, 291 g of unsaturated polyester resin is regenerated and 12 g of water (0.67 mol) is produced.

Then, when 291 g of this unsaturated polyester resin was used as a 30% styrene solution (125 g of styrene was used), a total of 416 g of recycled resin was finally obtained, which was 2. The mass is only 17 times.

Therefore, this method has remarkably improved recycle efficiency as compared with the conventional method.

<Case 2> Next, the polyester resin waste is an unsaturated polyester resin waste ((propylene glycol unit) 0.25- (phthalic acid unit) 0.30- (ethylene glycol unit) 0.25- ( A unit of fumaric acid having two styrene molecules added) Waste of unsaturated polyester resin having a composition of 0.20, hereinafter simply referred to as UPES waste)
The case will be exemplified.

In the conventional method, for example, 131 g of U
Decomposition of PES waste (0.25 gram equivalent) with 131 g of ethylene glycol (2.11 mol) gives 262 g.
The decomposition product of is obtained.

Subsequently, with respect to 262 g of this decomposition product, an acid anhydride equivalent to the above ethylene glycol, ie, 1
When dehydration-condensation was performed using 88 g of phthalic anhydride (1.27 mol) and 83 g of maleic anhydride (0.84 mol), 495 g of the unsaturated polyester resin was regenerated and 38 g of water (2.11 mol) was recovered. Occurs.

Then, when 495 g of this unsaturated polyester resin was used as a 30% styrene solution (using 212 g of styrene), a total of 707 g of recycled resin was finally obtained, which was 5. 5% based on the mass of the original UPES waste. 40 times the mass.

On the other hand, in this method, for example, the same amount of 131 g of UPES waste (0.25 gram equivalent) as described above, the amount of maleic anhydride and phthalic anhydride ethylene glycol adduct is 133 g ( 0.50 mol of maleic anhydride, 0.25 mol of phthalic anhydride and 0.75 mol of ethylene glycol are sufficient, and when this is decomposed and dehydrated and condensed, 250 g of the unsaturated polyester resin is regenerated and 14 g of water (0 0.75 mol) is produced.

Then, if 250 g of this unsaturated polyester resin was used as a 30% styrene solution (107 g of styrene was used), a total of 357 g of recycled resin was finally obtained, which was 2. Only 73 times the mass.

Therefore, even in the case of UPES waste, this method has remarkably improved recycling efficiency as compared with the conventional method.

In the above, phthalic acid: maleic acid = 6: 4 is usually used.
Mol + 0.25 mol added to the decomposition, 0.55 mol in total):
Maleic acid = 0.55: 0.50.

The PET waste is the theoretical amount, and the amount of recycled resin cannot be reduced any more. However, since the styrene cross-linking portion is present in the UPES waste, the recycled resin amount is slightly larger than the theoretical amount. By devising the treatment method such as decomposing the ester portion at 230 ° C. or lower and then decomposing the styrene crosslinked portion at 230 ° C. or higher, the amount of UPES waste in the recycled resin can be further increased.

C = of the glycol adduct of maleic anhydride
If a polymerization inhibitor such as hydroquinone is added, the C double bond will be present without being broken despite the high temperature treatment.

The reason why PET waste is decomposed with a propylene glycol adduct of maleic anhydride is that the introduction of the propylene glycol component makes the regenerated resin easily dissolved in styrene. The terephthalic acid unit of PET waste is regarded as a phthalic acid unit, and it is not necessary to add a new phthalic acid component.

In UPES waste, the propylene glycol component is in the waste, so ethylene glycol adducts may be used. Although the phthalic acid component is also present in the waste, a small amount is added to adjust the proportion of C = C double bonds in the recycled resin.

In the glycol decomposition of the PET waste of the conventional method, the pressure became 0.6 MPa or more at 240 ° C. for 2 hours. And the synthesis to unsaturated polyester is 210 ℃, 4
It took ~ 7 hours. On the other hand, in the decomposition of maleic anhydride by the propylene glycol adduct of this method,
The pressure was 0.2 MPa at 1 ° C. for 1 hour. And 2
Since the unsaturated polyester can be regenerated at 10 ° C. for 2 hours, the unsaturated polyester having a higher molecular weight than the conventional method can be obtained in one pot.

These regenerated unsaturated polyester resins are used as molding materials, adhesives, paints and the like.

For the molding of the recycled resin, the usual hand lay-up molding, centrifugal drum molding, compression molding, cast molding, injection molding, transfer molding and the like are used.

[0082]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

In the following examples, polyester resin waste was removed by a rotary cutter mill, unless otherwise specified.
A sample crushed to a particle size of 5 mm by Granulaters U-140 manufactured by Horai Co., Ltd. was used.

Example 1 In this example, propylene glycol (1,2-propanediol) maleic anhydride was used.
Decomposition of PET waste by adducts and resynthesis of unsaturated polyesters.

<Synthesis of Glycol Adduct> First, TAS-095 type reactor manufactured by Pressure Resistant Glass Industry Co., Ltd. (material SUS)
316, capacity 950 ml, maximum operating temperature 300 ° C., maximum operating pressure 20 MPa), propylene glycol 38.
05 g (0.5 mol), maleic anhydride 49.03 g
(0.5 mol), hydroquinone 0.02 g (100 p
pm) was added and reacted at 150 ° C. for 30 minutes while stirring at 40 rpm to obtain a colorless solid product.

This product was analyzed by GPC (THF solvent, 4
0 ° C, polystyrene standard), peak 1, number average molecular weight = 280, weight average molecular weight = 287, weight average molecular weight / number average molecular weight = 1.03, peak 2, number average molecular weight = 590, weight average molecular weight = 650 , Weight average molecular weight / number average molecular weight = 1.10, overall peak, number average molecular weight = 418, weight average molecular weight = 511, weight average molecular weight / number average molecular weight = 1.22.

Further, when FT-IR measurement was carried out, 2
982.62 cm^-1(Methyl group), 1721.61 cm
^-1(Ester group), 1643.51 cm^-1(C = C double
Combined), 1454.24 cm^-1(Methyl, methylene
Base), 1386.74 cm^-1(Methyl group), 1266.
82 cm^-1, 1166.68 cm^-1, 1074.83c
m ^-1, 982.56cm^-1, 830.16 cm^-1, 77
8.79 cm^-1There was absorption such as.

From the above results, it was confirmed that a propylene glycol adduct of maleic anhydride was obtained.

<Decomposition of PET waste> Next, 96.11 g of crushed PET bottle (0.5 gram equivalent of ethylene terephthalate unit) was placed in the above reaction apparatus, the air was replaced with nitrogen, and the temperature was 240 ° C. for 1 hour at 600 rpm. It reacted with stirring. The pressure was 0.2 MPa.

The product thus obtained is a pale yellow,
It was a solid. This product was analyzed by GPC (THF solvent,
At 40 ° C., polystyrene standard), the number average molecular weight = 928, the weight average molecular weight = 1622, and the weight average molecular weight / number average molecular weight = 1.75.

Further, when FT-IR measurement was performed, it was 3
077.83 cm ^-1 (phenyl group), 2963.41c
m ^-1 (methyl group), 1725.88 cm ^-1 (ester group), 1646.41 cm ^-1 (C = C double bond), 15
78.12 cm ^-1 (phenyl group), 1506.65 cm
^-1 (phenyl group), 1452.50 cm ^-1 (phenyl,
(Methyl, methylene group), 1406.10 cm ^-1 , 126
9.75 cm ^-1 , 1161.00 cm ^-1 , 1109.5
7cm ^-1, 1021.70cm ^-1, 980.69c
m ^-1 , 876.97 cm ^-1 , 778.65 cm ^-1 , 72
There was an absorption such as 9.50 cm ^-1 .

From the above results, it was confirmed that PET (polyethylene terephthalate) was decomposed.

<Regeneration of Unsaturated Polyester> Next, 0.02 g (100 pp) of hydroquinone was added to the above reactor.
m) was added, and dehydration condensation was performed at 210 ° C. for 2 hours with stirring at 200 rpm while blowing nitrogen. After the reaction for 1 hour, the stirring rotation speed was increased to 800 rpm and the nitrogen flow rate was increased.

The product thus obtained is a pale yellow colour,
It was a solid. This product was analyzed by GPC (THF solvent,
At 40 ° C., polystyrene standard), the number average molecular weight was 3148, the weight average molecular weight was 8797, and the weight average molecular weight / number average molecular weight was 2.79. (By the way, the commercially available product number average molecular weight = 1646, the weight average molecular weight = 5366, Weight average molecular weight / number average molecular weight = 3.26).

Further, when FT-IR measurement was performed, it was 3
079.60 cm ^-1 (phenyl group), 2982.28c
m ^-1 (methyl group), 2892.13 cm ^-1 (methyl group), 1723.65 cm ^-1 (ester group), 164
7.14 cm ^-1 (C = C double bond), 1577.41c
m ⁻¹ (phenyl group), 1506.35 cm ⁻¹ (phenyl group), 1455.04 cm ⁻¹ (phenyl, methyl, methylene group), 1407.98 cm ⁻¹ , 1254.65 cm
^-1 , 1156.23 cm ^-1 , 1101.96 cm ^-1 , 9
77.51 cm ^-1 , 873.38 cm ^-1 , 774.56
cm ^-1, there were absorption such as 728.26cm ^-1.

From the above results, it was confirmed that the unsaturated polyester was regenerated. Then, the regenerated product was added to 74.7 g of styrene and BHT (2,6-di-t-
Butylparacresol) 0.03 g (100 ppm) was added to obtain 248 g of a 30% styrene solution.

As a result, a recycled resin having a mass of 2.59 times that of 96.11 g of waste PET was obtained. To this recycled resin, methyl ethyl ketone peroxide and cobalt naphthenate were added at 1% each, and Precurer 30
Cast molding was carried out under conditions of 2 hours at 100 ° C. and 2 hours at 100 ° C. for post cure. The bending strength of the obtained molded product is 140.5M.
It was Pa (commercial item 92.1 MPa). Impact strength,
The hydrolysis resistance was also large.

Comparative Example 1 This comparative example relates to the decomposition of PET waste with propylene glycol and the resynthesis of unsaturated polyester resin.

150 kg of crushed PET bottles (780.4 g equivalent of ethylene terephthalate unit), 135 kg (1774 mol) of propylene glycol and 15 kg (141.3 mol) of diethylene glycol were placed in a 500 liter reaction vessel (with a stirrer, pressure resistance 0.7 MPa). Get in,
It processed at 240 degreeC for 2 hours. The decomposition rate was 100%. The OH group value was 5.441 glycol mol / kg and the pressure was 0.6 MPa.

295.53 kg (160
81.9 mol), maleic anhydride 141.9 kg
(1447.2 mol) and phthalic anhydride 23.82 kg
(160.8 mol), and at 150 ° C under nitrogen flow 1
After reacting for 2 hours, the temperature was further raised to 210 ° C. and reacted for 2 hours.

The initial acid value was 66.40 KOHmg / g, but after the reaction at 210 ° C. for 4 hours, the acid value was 5
The acid value was 8.74 KOHmg / g and the acid value was 52.49 KOHmg / g after 6 hours at 210 ° C.

After reacting for 7 hours, 432.31 kg of unsaturated polyester was obtained. GPC analysis of this product revealed that the unsaturated polyester obtained had a number average molecular weight of 1,622 and a weight average molecular weight of 474.
9, weight average molecular weight / number average molecular weight = 2.93.

Then, the above product was added with styrene 185.3 k.
g, 30% styrene unsaturated polyester resin 6
17.6 kg was obtained. In addition, since the above-mentioned weight is an actually measured value, some loss was recognized from the theoretical amount.

As a result of the above, a recycled resin having a mass 4.12 times that of 150 kg of PET waste was obtained. Methyl ethyl ketone peroxide and cobalt naphthenate were added to the regenerated resin in an amount of 1%, and the mixture was cast under the conditions of pre-cure 30 ° C. for 2 hours and post-cure 100 ° C. for 2 hours. The bending strength of the obtained molded product is 90.5.
It was MPa (commercial item 92.1 MPa).

Comparing the above results with the results of Example 1, it can be seen that the recycling efficiency is lowered and the strength of the molded product of recycled resin is also inferior.

(Example 2) This example relates to decomposition of unsaturated polyester resin waste by ethylene glycol adduct of maleic anhydride and phthalic anhydride and resynthesis of unsaturated polyester.

<Synthesis of Glycol Adduct> First, TAS-095 type reactor manufactured by Pressure Resistant Glass Industry Co., Ltd. (material SUS)
316, capacity 950 ml, maximum operating temperature 300 ° C., maximum operating pressure 20 MPa), ethylene glycol 46.5
5 g (0.75 mol), maleic anhydride 49.03 g
(0.5 mol), phthalic anhydride 37.05 g (0.25
Mol) was added and reacted at 120 ° C. for 30 minutes with stirring at 80 rpm to obtain a colorless solid product.

This product was analyzed by GPC (THF solvent, 4
0 ° C., polystyrene standard), peak 1, number average molecular weight = 223, weight average molecular weight = 228, weight average molecular weight / number average molecular weight = 1.02, peak 2, number average molecular weight = 404, weight average molecular weight = 422 , Weight average molecular weight / number average molecular weight = 1.05, overall peak, number average molecular weight = 288, weight average molecular weight = 324, weight average molecular weight / number average molecular weight = 1.13.

Further, when FT-IR measurement was performed, it was 3
059.67 cm^-1(Phenyl group), 2958.95c
m^-1(Methyl group), 1723.07 cm^-1(ester
Base), 1642.81 cm^-1(C = C double bond), 14
86.75 cm^-1(Methylene group), 1446.88 cm
^-1(Methyl group), 1408.69 cm^-1, 1285.0
0 cm^-11,170.11 cm^-11075.43 cm
^-11037.76 cm ^-1, 979.10 cm^-1, 88
2.95 cm^-1, 822.21 cm^-1, 747.24c
m^-1, 709.33 cm^-1There was absorption such as.

From the above results, it was confirmed that ethylene glycol adducts of maleic anhydride and phthalic anhydride were obtained.

<Decomposition of unsaturated polyester resin waste>
Then, 131.25 g of button punch scraps (particle size of about 1 mm), which is unsaturated polyester resin waste
((Propylene glycol unit) 0.25- (Phthalic acid unit) 0.30- (Ethylene glycol unit) 0.25
-(Fumaric acid is a unit of two molecules of styrene added) 0.20
Unsaturated polyester resin unit of composition 0.25 g equivalent), hydroquinone 0.26 g (1000 ppm),
0.8 g (0.02 mol) of sodium hydroxide was placed in each of the above devices, the air was replaced with nitrogen, and 270 ° C. to 29 ° C.
It decomposed | disassembled at 0 degreeC for 1 hour, stirring at 800 rpm.
The pressure was 4.8 MPa.

The product thus obtained is brown,
It was a solid. This product was analyzed by GPC (THF solvent,
At 40 ° C., polystyrene standard), the number average molecular weight was 787, the weight average molecular weight was 10475, and the weight average molecular weight / number average molecular weight was 13.3.

Further, when FT-IR measurement was performed, 2
933.58 cm ^-1 (methylene group), 2881.64c
m ^-1 (methyl group), 1727.72 cm ^-1 (ester group), 1646.00 cm ^-1 (C = C double bond), 16
01.11 cm ^-1 (phenyl group), 1583.47 cm
^-1 (phenyl group), 1554.22 cm ^-1 (phenyl group), 1491.37 cm ^-1 (phenyl group), 145
1.00 cm ^-1 (phenyl, methyl, methylene group), 1
375.56 cm ^-1 , 1281.61 cm ^-1 , 112
6.63 cm ^-1 , 1073.61 cm ^-1 , 885.66
cm ^-1, 748.38cm ^-1, there were absorption such as 712.67cm ^-1.

From the above results, it was confirmed that the unsaturated polyester resin was decomposed.

<Regeneration of Unsaturated Polyester> Next, it was neutralized with 0.98 g (0.01 mol) of sulfuric acid, and dehydrated and condensed at 210 ° C. for 1.5 hours while stirring at 200 rpm while blowing nitrogen. After the reaction for 1 hour, the stirring speed was changed to 10
It was increased to 00 rpm and the nitrogen flow rate was increased.

The product thus obtained is brown,
It was a solid. This product was analyzed by GPC (THF solvent,
At 40 ° C., polystyrene standard), the number average molecular weight was 1090, the weight average molecular weight was 94482, and the weight average molecular weight / number average molecular weight was 86.69 (by comparison, the commercially available product number average molecular weight = 1646, weight average molecular weight = 536).
6, weight average molecular weight / number average molecular weight = 3.26).

Further, when FT-IR measurement was performed, it was 3
062.69 cm ^-1 (phenyl group), 3027.71c
m ^-1 (phenyl group), 2929.71 cm ^-1 (methyl group), 1727.87 cm ^-1 (ester group), 164
6.00 cm ^-1 (C = C double bond), 1600.63c
m ^-1 (phenyl group), 1583.51 cm ^-1 (phenyl group), 1491.23 cm ^-1 (phenyl group), 145
0.71 cm ^-1 (phenyl, methyl, methylene groups), 1
374.36 cm ^-1 , 1281.00 cm ^-1 , 112
4.65 cm ^-1 , 1072.75 cm ^-1 , 904.00
cm ^-1, 748.13cm ^-1, there were absorption such as 711.74cm ^-1.

From the above results, it was confirmed that the unsaturated polyester was regenerated. Then 107.6 g of styrene and 0.04 g of BHT (10
0 ppm) was added to obtain 358 g of a 30% styrene solution.

As a result of the above, 2.73 times the mass of the recycled resin was obtained with respect to 131.25 g of the unsaturated polyester resin waste. Methyl ethyl ketone peroxide and 1% cobalt naphthenate were added to this recycled resin.
Add and pre-cure 2 hours at 30 ℃, post cure 1
Cast molding was performed at 00 ° C. for 2 hours. The bending strength of the obtained molded product is 135.5 MPa (commercial product 92.1MP
It was a). The impact resistance and hydrolysis resistance were also large.

Example 3 This example relates to the decomposition of unsaturated polyester resin (FRP) waste by the addition of maleic anhydride and phthalic anhydride to ethylene glycol and propylene glycol and the resynthesis of unsaturated polyester.

<Synthesis of Glycol Adduct> First, TAS-095 type reactor manufactured by Pressure Resistant Glass Industry Co., Ltd. (material SUS)
316, capacity 950 ml, maximum operating temperature 300 ° C., maximum operating pressure 20 MPa), ethylene glycol 23.2
8 g (0.375 mol), propylene glycol 28.
54 g (0.375 mol), maleic anhydride 49.03
g (0.5 mol), phthalic anhydride 37.05 g (0.2
(5 mol) was added and reacted at 130 ° C. for 20 minutes while stirring at 40 rpm to obtain a colorless solid product.

The product was analyzed by GPC (THF solvent, 4
Number average molecular weight = 0 ° C, polystyrene standard)
309, weight average molecular weight = 349, and weight average molecular weight / number average molecular weight = 1.13.

Further, when FT-IR measurement was performed, it was 30
60.62 cm ^-1 (phenyl group), 2977.65 cm
^-1 (methyl group), 1726.41 cm ^-1 (ester group), 1643.37 cm ^-1 (C = C double bond), 16
01.68 cm ^-1 (phenyl group), 1582.21 cm
^-1 (phenyl group), 149.013 cm ^-1 (phenyl group), 1450.35 cm ^-1 (phenyl, methyl, methylene group), 1407.24 cm ^-1 , 1288.23 cm
^-1 , 1169.29 cm ^-1 , 1074.30 cm ^-1 , 1
041.89 cm ^-1 , 981.68 cm ^-1 , 921.0
^{8cm -1, 884.59cm -1, 823.96cm -1} ,
793.21 cm ^-1 , 746.39 cm ^-1 , 706.8
There was absorption such as 4 cm ^-1 .

From the above results, it was confirmed that ethylene glycol and propylene glycol adducts of maleic anhydride and phthalic anhydride were obtained.

<Decomposition of FRP waste> Next, 131 g of waste FRP (40% resin, 30% glass fiber, 30% calcium carbonate) for septic tank (5-10 mm square)
((Propylene glycol unit) 0.25- (Phthalic acid unit) 0.30- (Ethylene glycol unit) 0.25
-(Fumaric acid is a unit obtained by adding two molecules of styrene) 0.20
(0.10 gram equivalent of unsaturated polyester resin unit of composition) and 0.13 g (500 ppm) of hydroquinone were put thereinto, nitrogen was replaced with air, and the mixture was decomposed while stirring at 200 rpm for 2 hours at 270 ° C to 280 ° C. Pressure is 6.0
It was MPa.

The product thus obtained was brown and solid, with the glass fibers falling apart. GPC analysis (THF solvent, 40 ° C., polystyrene standard) of this product (soluble matter) revealed that the number average molecular weight = 476, the weight average molecular weight = 1551, and the weight average molecular weight / number average molecular weight = 3.26. .

Further, when FT-IR measurement was performed, it was 30
63.14 cm ^-1 (phenyl group), 3027.07 cm
^-1 (phenyl group), 2959.72 cm ^-1 (methyl group), 2932.10 cm ^-1 (methylene group), 172
6.88 cm ^-1 (ester group), 1627.36 cm ^-1
(C = C double bond), 1599.72 cm ^-1 (phenyl group), 1579.90 cm ^-1 (phenyl group), 153
4.14 cm ^-1 (phenyl group), 149.047 cm ^-1
(Phenyl group), 1450.85 cm ^-1 (Phenyl, methyl, methylene group), 1408.59 cm ^-1 , 137
6.49 cm ^-1 , 1282.56 cm ^-1 , 1129.0
1cm ^-1, 1074.19cm ^-1, 958.87c
m ^-1 , 870.20 cm ^-1 , 839.85 cm ^-1 , 75
There were absorptions such as 2.14 cm ^-1 , 703.74 cm ^-1 .

From the above results, it was confirmed that the unsaturated polyester resin was decomposed.

<Regeneration of Unsaturated Polyester> Next, while blowing nitrogen into the reaction apparatus, a dehydration condensation reaction was carried out at 190 ° C. for 0.5 hours under stirring at 400 rpm to obtain a brown solid product.

GPC analysis (THF solvent, 40 ° C., polystyrene standard) of the product thus obtained revealed that the number average molecular weight = 661 and the weight average molecular weight = 557.
3, weight average molecular weight / number average molecular weight = 8.43 (commercial number average molecular weight = 1646, weight average molecular weight = 5366,
Weight average molecular weight / number average molecular weight = 3.26).

Further, when FT-IR measurement was performed, it was 30
63.69 cm ^-1 (phenyl group), 3027.15 cm
^-1 (phenyl group), 2928.49 cm ^-1 (methylene group), 1727.48 cm ^-1 (ester group), 162
7.36 cm ^-1 (C = C double bond), 1598.28c
m ⁻¹ (phenyl group), 1574.93 cm ⁻¹ (phenyl group), 1535.30 cm ⁻¹ (phenyl group), 149
0.35 cm ^-1 (phenyl group), 1450.90 cm ^-1
(Phenyl, methyl, methylene group), 1430.47c
m ^-1 , 1411.40 cm ^-1 , 1371.40 cm ^-1 ,
1282.20 cm ^-1 , 1134.24 cm ^-1 , 107
4.43 cm ^-1 , 957.88 cm ^-1 , 869.47c
m ^-1 , 838.00 cm ^-1 , 794.72 cm ^-1 , 75
There were absorptions such as 4.74 cm ^-1 , 704.14 cm ^-1 .

From the above results, it was confirmed that the unsaturated polyester was regenerated. Then, 118.3 g of styrene and 0.05 g of BHT (20 g
0 ppm) was added to obtain 374 g of 40% (based on resin content) styrene solution.

As a result, a recycled resin having a mass of 2.86 times that of 131 g of FRP resin waste was obtained.

Example 4 This example relates to the decomposition of PET waste and the re-synthesis of unsaturated polyester by a compound obtained by adding a 4 mol adduct of bisphenol A ethylene oxide to maleic anhydride as a glycol adduct.

<Synthesis of Glycol Adduct> First, TAS-095 type reactor manufactured by Pressure Resistant Glass Industry Co., Ltd. (material SUS)
316, capacity 950 ml, maximum operating temperature 300 ° C., maximum operating pressure 20 MPa), 126.4 g of bisphenol A ethylene oxide 4 mol adduct (high viscosity liquid).
4 mol), maleic anhydride 39.22 g (0.4 mol)
Was added thereto and reacted at 120 ° C. for 30 minutes while stirring at 40 rpm to obtain a colorless solid product.

This product was analyzed by GPC (THF solvent, 4
Number average molecular weight = 0 ° C, polystyrene standard)
747, weight average molecular weight = 849, and weight average molecular weight / number average molecular weight = 1.13.

When FT-IR measurement was performed, it was 3
044.55cm ^-1 (phenyl group), 2963.59c
m ^-1 (methyl group), 2933.76 cm ^-1 (methylene group), 2878.14 cm ^-1 (methyl group), 1731.
17cm ^-1 (ester group), 1639.04cm ^-1 (C
= C double bond), 1610.49 cm ^-1 (phenyl group), 1509.60 cm ^-1 (phenyl group), 145
6.38 cm ^-1 (phenyl, methyl, methylene groups), 1
413.51 cm ^-1 , 1360.34 cm ^-1 , 129
0.97 cm ^-1 , 1247.20 cm ^-1 , 1180.0
6cm ^-1, 1132.61cm ^-1, 1062.51cm
^-1 , 973.80 cm ^-1 , 929.44 cm ^-1 , 88
9.45 cm ^-1 , 831.61 cm ^-1 , 756.28c
There was absorption such as m ^-1 , 732.96 cm ^-1 .

From the above results, it was confirmed that a compound in which 4 mol of bisphenol A ethylene oxide adduct was added to maleic anhydride was obtained.

<Decomposition of PET waste> Next, 115.33 g of crushed PET bottles (ethylene terephthalate unit: 0.6 g equivalent), 0.03 g of hydroquinone (10
(0 ppm), replace the air with nitrogen, and
The reaction was carried out for 0 minutes with stirring at 600 rpm. The pressure was 0.2 MPa.

The product thus obtained is a pale yellow colour,
It was a solid. This product was analyzed by GPC (THF solvent,
At 40 ° C., polystyrene standard), number average molecular weight = 2195, weight average molecular weight = 4846, weight average molecular weight / number average molecular weight = 2.21.

Further, when FT-IR measurement was performed, it was 3
061.64 cm ^-1 (phenyl group), 2962.96c
m ^-1 (methyl group), 1721.08 cm ^-1 (ester group), 1647.07 cm ^-1 (C = C double bond), 16
09.85 cm ^-1 (phenyl group), 1580.67 cm
^-1 (phenyl group), 1510.65 cm ^-1 (phenyl group), 1456.93 cm ^-1 (phenyl, methyl, methylene group), 1410.52 cm ^-1 , 1373.03 cm
^-1 , 1250.51 cm ^-1 , 1100.88 cm ^-1 , 9
77.81 cm ^-1 , 847.91 cm ^-1 , 776.34
cm ^-1, there were absorption such as 729.86cm ^-1.

From the above results, it was confirmed that PET (polyethylene terephthalate) was decomposed.

<Regeneration of Unsaturated Polyester> Next, dehydration condensation was carried out at 210 ° C. for 1 hour under stirring at 400 rpm while blowing nitrogen into the reaction apparatus. After the reaction for half an hour, the stirring rotation speed was increased to 1000 rpm and the nitrogen flow rate was increased.

The product thus obtained is a pale yellow,
It was a solid. This product was analyzed by GPC (THF solvent,
At 40 ° C., polystyrene standard), number average molecular weight = 3385, weight average molecular weight = 7917, weight average molecular weight / number average molecular weight = 2.34 (commercial number average molecular weight = 1)
646, weight average molecular weight = 5366, weight average molecular weight /
The number average molecular weight was 3.26).

When FT-IR measurement was performed, it was 3
061.24 cm^-1(Phenyl group) 2963.00c
m^-1(Methyl group), 2879.31 cm^-1(Methyl
Basis), 172.35 cm^-1(Ester group), 164
9.23 cm^-1(C = C double bond), 1609.60c
m^-1(Phenyl group) 1581.66 cm^-1(Phenyl
Basis), 1510.39 cm^-1(Phenyl group), 145
5.41 cm^-1(Phenyl, methyl, methylene group), 1
407.70 cm^-1, 1373.13 cm^-1, 125
4.56 cm^-11103.49 cm^-1, 978.20
cm^-1, 874.16 cm ^-1, 831.10 cm^-1, 7
28.74 cm^-1There was absorption such as.

From the above results, it was confirmed that the unsaturated polyester was regenerated. Then 117.32 g of styrene and 0.04 g of BHT (1
(00 ppm) was added to obtain 391 g of a 30% styrene solution.

As a result of the above, a regenerated resin having a mass of 3.39 times that of 115.33 g of waste PET was obtained. To this recycled resin, methyl ethyl ketone peroxide and cobalt naphthenate were added at 1% each, and Precurer 30
Cast molding was carried out under conditions of 2 hours at 100 ° C. and 2 hours at 100 ° C. for post cure. The bending strength of the obtained molded product is 143.5M.
It was Pa (commercial item 92.1 MPa). Impact strength,
The hydrolysis resistance was also large.

(Example 5) In this example, PET using a 1,4-cyclohexanediol adduct of maleic anhydride was used.
It concerns the decomposition of waste as well as the resynthesis of unsaturated polyesters.

<Synthesis of Glycol Adduct> First, TAS-095 type reactor manufactured by Pressure Resistant Glass Industry Co., Ltd. (material SUS)
316, capacity 950 ml, maximum operating temperature 300 ° C., maximum operating pressure 20 MPa), 58.08 g (0.5 mol) of 1,4-cyclohexanediol, maleic anhydride 4
9.03 g (0.5 mol), hydroquinone 0.04 g
(200ppm) put, 105 ℃ for 1 hour, 40rp
The reaction was carried out with stirring at m to obtain a colorless solid product.

The product was analyzed by GPC (THF solvent, 4
Number average molecular weight = 0 ° C, polystyrene standard)
402, weight average molecular weight = 468, weight average molecular weight / number average molecular weight = 1.16.

Further, when FT-IR measurement was performed, it was 3
056.35 cm ^-1 (= CH-group), 2945.40c
m ^-1 (methylene group), 2869.23 cm ^-1 (methylene group), 172.07 cm ^-1 (ester group), 163
9.47 cm ^-1 (C = C double bond), 1449.72c
m ^-1 (methylene group), 1408.53 cm ^-1 , 137
1.67 cm ^-1 , 1259.73 cm ^-1 , 1219.3
1cm ^-1, 1170.66cm ^-1, 1119.99cm
^-1 , 1061.73 cm ^-1 , 1037.40 cm ^-1 , 9
66.70 cm ^-1 , 913.94 cm ^-1 , 821.37
cm ^-1, there were absorption such as 734.52cm ^-1.

From the above results, maleic anhydride 1,
It was confirmed that a 4-cyclohexanediol adduct was obtained.

<Decomposition of PET waste> Next, 96.11 g of a PET bottle crushed product (0.5 gram equivalent of ethylene terephthalate unit) was put, and air was replaced with nitrogen, and 24
Decomposition was carried out at 0 ° C. for 1 hour and 20 minutes while stirring at 200 rpm. The pressure was 0.4 MPa.

The product thus obtained is a pale yellow,
It was a solid. This product was analyzed by GPC (THF solvent,
At 40 ° C., polystyrene standard), the number average molecular weight was 817, the weight average molecular weight was 1617, and the weight average molecular weight / number average molecular weight was 2.00.

When FT-IR measurement was carried out, it was found to be 29
49.56 cm ^-1 (methylene group), 2873.51 cm
^-1 (methylene group), 1719.03 cm ^-1 (ester group), 1646.97 cm ^-1 (C = C double bond), 15
77.21 cm ^-1 (phenyl group), 1506.65 cm
^-1 (phenyl group), 1450.65 cm ^-1 (phenyl,
(Methyl, methylene group), 1410.99 cm ^-1 , 137
2.85cm ^-1, 1273.86cm ^-1, 1158.8
7cm ^-1, 1103.83cm ^-1, 1037.88cm
^-1 , 1017.50 cm ^-1 , 978.45 cm ^-1 , 91
8.10 cm ^-1 , 876.97 cm ^-1 , 777.10c
There was absorption such as m ⁻¹ , 730.93 cm ⁻¹ .

From the above results, it was confirmed that PET (polyethylene terephthalate) was decomposed.

<Regeneration of Unsaturated Polyester> Then, while blowing nitrogen into the above reactor, dehydration condensation was carried out at 210 ° C. for 1 hour while stirring at 200 rpm. After the reaction for 0.5 hours, the nitrogen flow rate was increased.

The product thus obtained is a pale yellow,
It was a solid. This product was analyzed by GPC (THF solvent,
At 40 ° C., polystyrene standard), number average molecular weight = 2052, weight average molecular weight = 5054, weight average molecular weight / number average molecular weight = 2.46 (commercial number average molecular weight = 1)
646, weight average molecular weight = 5366, weight average molecular weight /
The number average molecular weight was 3.26).

Further, when FT-IR measurement was performed, it was 3
079.60 cm^-1(Phenyl group), 2952.87c
m^-1(Methylene group), 2873.34 cm^-1(Methylene
Basis), 1724.49 cm^-1(Ester group), 164
6.84 cm^-1(C = C double bond), 1576.80c
m^-1(Phenyl group), 1506.63 cm^-1(Phenyl
Base), 1450.10 cm^-1(Phenyl, methyl, methyl
Ren group), 141.72 cm^-1, 137.60 cm
^-11271.35 cm^-1, 1156.34 cm ^-11
101.27 cm^-1, 1016.91 cm^-1, 977.
75 cm^-1, 919.27 cm^-1, 875.16c
m^-1, 775.82 cm^-1, 729.95 cm ^-1Such as
There was absorption.

From the above results, it was confirmed that the unsaturated polyester was regenerated. Then, add 8
3.2 g of styrene and 0.03 g (100 ppm) of BHT (2,6-di-t-butylparacresol) were added to obtain 277 g of a 30% styrene solution.

In this way, a recycled resin having a mass of 2.89 times that of 96.11 g of waste PET was obtained. To this recycled resin, methyl ethyl ketone peroxide and cobalt naphthenate were added at 1% each, and Precurer 30
Cast molding was carried out under conditions of 2 hours at 100 ° C. and 2 hours at 100 ° C. for post cure. The bending strength of the obtained molded product is 135.5M.
It was Pa (commercial item 92.1 MPa). Impact strength,
The hydrolysis resistance was also large.

Example 6 This example relates to the decomposition of PET waste by the propylene glycol adduct of itaconic anhydride and the resynthesis of unsaturated polyester.

<Synthesis of Glycol Adduct> First, TAS-095 type reactor manufactured by Pressure Resistant Glass Industry Co., Ltd. (material SUS)
316, capacity 950 ml, maximum operating temperature 300 ° C., maximum operating pressure 20 MPa), propylene glycol 30.
44 g (0.4 mol), itaconic anhydride 44.83 g
(0.4 mol), hydroquinone 0.04 g (200 p
pm) was added and reacted at 110 ° C. for 30 minutes while stirring at 40 rpm to obtain a pale yellow solid product.

This product was analyzed by GPC (THF solvent, 4
Number average molecular weight = 0 ° C, polystyrene standard)
298, weight average molecular weight = 322, and weight average molecular weight / number average molecular weight = 1.08.

Further, when FT-IR measurement was carried out, 2
977.49 cm^-1(Methyl group), 2938.18 cm
^-1(Methylene group), 1723.02 cm^-1(ester
Base), 164.16 cm^-1(C = C double bond), 14
47.28 cm^-1(Methyl group), 1388.18 cm^-1
(Methyl group), 1332.67 cm^-1, 1276.66
cm^-1, 1222.86 cm^-1, 1197.54c
m^-1, 1149.36 cm^-1, 1073.77 cm^-1,
1043.80 cm^-1, 1003.92 cm^-1, 96
8.69 cm^-1, 930.60 cm^-1, 897.18c
m^-1, 835.73 cm ^-1, 779.86 cm^-1, 73
6.20 cm^-1There was absorption such as.

From the above results, it was confirmed that a propylene glycol adduct of itaconic anhydride was obtained.

<Decomposition of PET waste> Next, 115.33 g of PET bottle crushed product (ethylene terephthalate unit 0.6 g equivalent) and hydroquinone 0.02 g
(100ppm), and replace the air with nitrogen, 240
Decomposition was carried out at 400C for 1 hour with stirring at 400 rpm. The pressure was 0.3 MPa.

The product thus obtained is a pale yellow colour,
It was a solid. This product was analyzed by GPC (THF solvent,
At 40 ° C., polystyrene standard), the number average molecular weight was 1042, the weight average molecular weight was 2210, and the weight average molecular weight / number average molecular weight was 2.12.

When FT-IR measurement was performed, it was 3
059.37 cm ^-1 (phenyl group), 2959.95c
m ^-1 (methyl group), 172.83 cm ^-1 (ester group), 1647.39 cm ^-1 (C = C double bond), 15
77.63 cm ^-1 (phenyl group), 1505.51 cm
^-1 (phenyl group), 1450.69 cm ^-1 (phenyl,
(Methyl, methylene group), 1409.48 cm ^-1 , 126
5.01 cm ^-1 , 1119.99 cm ^-1 , 1020.2
^{0cm -1, 978.27cm -1, 877.35cm -1} ,
818.48 cm ^-1 , 781.45 cm ^-1 , 730.5
There was absorption such as 4 cm ^-1 .

From the above results, it was confirmed that PET (polyethylene terephthalate) was decomposed.

<Regeneration of Unsaturated Polyester> Next, while blowing nitrogen into the above reactor, dehydration condensation was carried out at 210 ° C. for 50 minutes under stirring at 400 rpm. After the reaction for half an hour, the stirring rotation speed was increased to 800 rpm and the nitrogen flow rate was increased.

The product thus obtained is a pale yellow,
It was a solid. This product was analyzed by GPC (THF solvent,
At 40 ° C., polystyrene standard), number average molecular weight = 2527, weight average molecular weight = 6801, weight average molecular weight / number average molecular weight = 2.64 (commercial number average molecular weight = 1)
646, weight average molecular weight = 5366, weight average molecular weight /
The number average molecular weight was 3.26).

When FT-IR measurement was performed, it was 3
059.25 cm ^-1 (phenyl group), 2960.47c
m ^-1 (methyl group), 2888.69 cm ^-1 (methyl group), 1725.81 cm ^-1 (ester group), 164
8.10 cm ^-1 (C = C double bond), 1577.86c
m ^-1 (phenyl group), 1505.96 cm ^-1 (phenyl group), 1453.83 cm ^-1 (phenyl, methyl, methylene group), 141.77 cm ^-1 , 1376.09 cm
^-1 , 1265.82 cm ^-1 , 1100.34 cm ^-1 , 1
016.46 cm ^-1 , 874.34 cm ^-1 , 790.5
0cm ^-1, there were absorption such as 728.83cm ^-1.

From the above results, it was confirmed that the unsaturated polyester was regenerated. Then, 78.6 g of styrene was added to the above regenerated product to prepare a 30% styrene solution 26
2 g was obtained.

Thus, a recycled resin having a mass of 2.28 times that of 115.33 g of waste PET was obtained. Methyl ethyl ketone peroxide and cobalt naphthenate 1% were added to the regenerated resin, and Pre-cure 3
Cast molding was performed under the conditions of 0 ° C. for 2 hours and post cure 100 ° C. for 2 hours. The bending strength of the obtained molded product is 133.5.
It was MPa (commercial item 92.1 MPa). The impact resistance and hydrolysis resistance were also large.

Example 7 In this example, maleic anhydride propylene glycol (1,2) was prepared using a twin-screw kneading extruder.
Decomposition of PET waste by 2-propanediol) adduct and resynthesis of unsaturated polyester.

Maleic anhydride adduct of propylene glycol obtained in Example 1 (propylene glycol 76.
1g (1mol), maleic anhydride 98.06g (1mol), hydroquinone 0.04g (100ppm) were added and reacted while stirring at 150 ° C for 30 minutes at 40 rpm) 174.16g and PET bottle crushed Thing 1
92.22 g (1 gram equivalent of ethylene terephthalate unit) was mixed, and a twin-screw kneading extruder KZ manufactured by Techno Bell Co., Ltd.
W15-60MG-WK (L / D = 60, screw diameter φ
Extrusion was carried out at 15 mm, rotation in the same direction, two vacuum vents, cylinder (4 blocks) temperature C1 to C8 = 260 ° C., head die D1 = 240 ° C., screw rotation speed 400 rpm.

The product thus obtained is a pale yellow,
It was a solid. This product was analyzed by GPC (THF solvent,
At 40 ° C., polystyrene standard), number average molecular weight = 3100, weight average molecular weight = 8700, weight average molecular weight / number average molecular weight = 2.81 (commercial number average molecular weight = 1)
646, weight average molecular weight = 5366, weight average molecular weight /
The number average molecular weight was 3.26).

(Embodiment 8) This embodiment relates to decomposition and resynthesis in a stainless steel apparatus.

First, a 100 L reaction vessel 1 made of stainless steel.
Then, from the chemical injection tanks 2 and 3, 9.52 kg (125 mol) of propylene glycol and maleic anhydride 12.2 were added.
5 kg (125 mol) is charged and the stirring blade 6 is rotated to start stirring (24 rpm). The temperature is raised to 110 ° C. by the heating medium boiler 5 and the reaction is performed for 30 minutes. Then tank 4
More polyethylene terephthalate bottle waste 24.03k
g (ethylene terephthalate unit 125 gram equivalent). Then, 4.4 g (100 ppm) of hydroquinone was added from the chemical injection tank 14, heated to 240 ° C., and treated for 1 hour.

Nitrogen was allowed to flow from the nitrogen inflow pipe 18 at 60 L / hour, heated with stirring (84 rpm), water was distilled off, and 210
The mixture was reacted at ℃ for 2 hours, then cooled and 6.2 g (1
(00 ppm) and 18.68 kg of styrene were added from the chemical injection tank 15 to obtain 62.23 kg of regenerated unsaturated polyester resin.

The embodiments and examples disclosed this time are to be considered as illustrative in all points and not restrictive. The scope of the present invention is shown not by the above description but by the claims, and is intended to include meanings equivalent to the claims and all modifications within the scope.

[0183]

INDUSTRIAL APPLICABILITY According to the present invention, industrially useful resin raw materials can be obtained from polyester resin (saturated polyester resin, unsaturated polyester resin, etc.) waste and can be recycled into unsaturated polyester resins. it can. Also,
In this way, decomposition takes place at a relatively low temperature for a relatively short time,
Moreover, since it is possible to perform a relatively simple operation, it is possible to reuse the polyester resin waste with a simple facility.

[Brief description of drawings]

FIG. 1 is a diagram showing a schematic configuration of an example of a polyester resin waste recycling apparatus according to the present invention.

[Explanation of symbols]

1 reaction vessel, 2 first tank, 3 second tank,
4 3rd tank, 5 heat medium boiler (heater, cooler), 6 stirring blades, 7 condenser, 8 receiver, 9
Partial condenser (steam is drained to the upper part and other high-boiling substances are returned to the reaction vessel) 10 outlet, 11 valve, 12 filter, 13 4th tank, 14 5th tank, 15 6th tank, 16 7th tank, 1
7 pump, 18 nitrogen inflow pipe, 19 recycled unsaturated polyester resin tank, 20 stirrer motor.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takuya Maeda             293-5 Mitsuya, Wakayama City, Wakayama Prefecture F-term (reference) 4F301 AA25 CA10 CA23 CA72                 4J029 AA07 AB07 AE01 GA13 KG00                       KG02 KG03 LA10

Claims (6)

[Claims] 1. A process for obtaining a resin raw material for resynthesis by decomposing a polyester resin waste by using a maleic anhydride and / or an itaconic anhydride glycol adduct in the presence or absence of a catalyst. And a step of synthesizing an unsaturated polyester by subjecting the resin raw material obtained above to a condensation reaction, to thereby reuse the waste polyester resin. 2. Resynthesis by degrading polyester resin wastes in the presence or absence of a catalyst, using a glycol adduct of a mixture of maleic anhydride and / or itaconic anhydride and phthalic anhydride. A method for reusing a polyester resin waste, comprising: a step of obtaining a resin raw material for use in the production; and a step of synthesizing an unsaturated polyester by subjecting the resin raw material obtained above to a condensation reaction. 3. A process of obtaining a resin raw material for resynthesis by decomposing polyester resin waste and a process of synthesizing an unsaturated polyester by subjecting the resin raw material obtained above to a condensation reaction. The method for recycling polyester resin waste according to claim 1 or 2, wherein the method is carried out using an extruder. 4. The polyester resin according to claim 1, which further comprises a step of producing a curable unsaturated polyester by further adding a reactive monomer to the synthesized unsaturated polyester. How to reuse waste. 5. The recycled polyester resin waste according to claim 1, 2, 3 or 4, wherein the polyester resin waste is a saturated polyester resin, an unsaturated polyester resin, or a waste of a fiber reinforced plastic (FRP) thereof. How to Use. 6. A reactor, a stirrer, a heater, a cooler, a partial condenser, a condenser, a raw material tank,
The apparatus used in the method for recycling polyester resin waste according to claim 1, comprising a chemical injection tank, a filter and a pump.