JP2002327055A - Polyester macromonomer and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester macromonomer which enables recycling of a waste polyester resin and is applicable industrially. SOLUTION: The polyester macromonomer has a structure represented by chemical formula (1) [wherein n is an integer of 1-50; X is a polymerizable functional group or hydrogen (excluding when the both molecular ends are added with hydrogen simultaneously); and R is a glycol residue].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyester macromonomer and a method for producing the same. Further, the present invention enables the reuse of polyester resin waste,
In particular, the present invention provides a method of chemically treating polyester resin waste to obtain a valuable raw material that can be industrially reused.

[0002]

2. Description of the Related Art A polyester macromonomer is an oligomer or polymer having an ester structure in the molecular main chain, having a molecular weight of hundreds to tens of thousands, and having a polymerizable functional group at its terminal. Here, the polymerizable functional group is a vinyl group, a vinylidene group, a vinylene group, a cyclic olefin, or the like, and a graft copolymer can be obtained by the functional group.

[0003] Conventionally, polyester macromonomers produced are polyester condensates of phthalic acid and glycol, condensates of aliphatic dibasic acids such as adipic acid and glycol, or ring-opening polymers of caprolactone. Was used.

[0004] In the production of aromatic polyesters, phthalic acid has the highest reactivity with glycols, and decreases in the order of isophthalic acid and then terephthalic acid.
Therefore, the production of a polyester of terephthalic acid is most difficult, and therefore, the production of a polyester macromonomer having terephthalic acid in the molecular main chain is also most difficult.

[0005] Conventionally, PET bottles and films are mainly recycled by melting and reshaping the material by heat (RJ Ehring, edited by the Plastic Recycling Research Society, "Plastic Recycling-From Recovery to Recycling"). -", P. 71, Industrial Research Council (1993)). In addition, as a method for recycling PET bottles and films, a technique of recovering monomers by hydrolysis, methanol decomposition, and glycol decomposition and resynthesizing them into PET has been developed (“Waste Plastic Thermal & Chemical Recycling”, p. Chemical Daily (199
4)).

[0006]

A conventional polyester macromonomer has a polyester portion produced from a condensate of phthalic acid and glycol, a condensate of adipic acid and glycol, or a ring-opening polymer of caprolactone.
It has been difficult to produce a polyester macromonomer having a terephthalic acid polyester structure. The regeneration of the saturated polyester resin waste is carried out by a material recycling method which is generally employed for a thermoplastic resin and is remolded after melting. However, in the case of a colored resin or a resin to which dirt is adhered, the recycling method is not used because it has no commercial value. In addition, in this method, hydrolysis occurs due to moisture at the time of remolding, and the molecular weight is reduced, and the physical properties of the product are also reduced.

Further, a technique has been developed in which a monomer is recovered by hydrolysis, methanol decomposition or glycol decomposition for the regeneration of PET bottles and films, and then resynthesized into PET. However, it is difficult to purify the monomer because most oligomers are produced. is there.

Accordingly, the present invention provides a method for chemically decomposing polyethylene terephthalate resin, particularly its waste, with glycol in a relatively short period of time to industrially easily produce a raw material of a polyester macromonomer without purification. It is intended to be reused. That is, the present invention provides a polyester macromonomer obtained from a decomposition product of a polyester resin waste, and a method for producing the same.

[0009]

The present invention is a polyester macromonomer having a structure represented by the following chemical formula (1) or (2).

[0010]

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Here, n is an integer of 1 to 50, X is a polymerizable functional group or hydrogen (except when hydrogen is simultaneously added to both terminals), and R is a glycol residue. is there.

In the present invention, the functional group is preferably a vinylphenylene group, an allyl group, an acryloyl group or a methacryloyl group. Here, the acryloyl group is a term including acrylate, and the methacryloyl group is a term including methacrylate. The present invention further provides a polyester macromonomer having a vinyl phenylene group, an allyl group, an acryloyl group or a methacryloyl group at one end or both ends of a molecular chain, using a decomposition product as a raw material by decomposing a saturated polyester resin with glycol. It is a manufacturing method.
Here, as the saturated polyester resin, its waste can be used.

In the method for producing a polyester macromonomer, a saturated polyester resin is decomposed with glycol, and the decomposed product is reacted with phthalic anhydride, succinic anhydride or maleic anhydride, and then chloromethylstyrene or allyl bromide is converted. By reacting, a polyester macromonomer having a vinyl phenylene group terminal or an allyl group terminal can be produced.

In another method for producing a polyester macromonomer, a saturated polyester resin is decomposed with glycol, and the decomposition product is reacted with methacrylic acid or acrylic acid to form a polyester macromonomer having a methacryloyl group terminal or an acryloyl group terminal. Can be manufactured.

In the process for producing a polyester macromonomer, polyethylene terephthalate is preferably used as the saturated polyester resin.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors crushed a saturated polyester resin or its waste,
It is possible to recycle saturated polyester resin waste by decomposing it with glycol to a certain degree and using this decomposition product as a raw material to produce a polyester macromonomer.

The following method is used to produce a polyester macromonomer. First, the pulverized saturated polyester resin or its waste is mixed with glycol, and a decomposition product of the saturated polyester resin waste is obtained using a catalyst or without a catalyst. Then, a compound having a polymerizable functional group at at least one end of the decomposition product is subjected to a condensation reaction to produce a polyester macromonomer.

In the present invention, polyethylene terephthalate is preferably used as the saturated polyester resin.
Saturated polyester resin is polyethylene terephthalate (PE) used for bottles, films, and molded products.
T), polybutylene terephthalate, polyethylene naphthalate (PEN), etc., or their waste can be used.

In the present invention, the saturated polyester resin is subjected to pretreatment such as crushing, washing if necessary, and sieving.
Crushing 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, etc. It is preferable that the crushed material is small, but it is preferable that the crushed material pass through a sieve having an opening of 20 mm. Preferably 10 mm, more preferably 5 m
A crushed material passing through a sieve of m is used.

The saturated polyester resin (E) and the glycol (G) used to decompose the saturated polyester resin
Has a weight ratio (E / G) of 1 / 0.2 to 1/5, preferably 1 / 0.5 to 1/2. By changing the weight ratio, the molecular weight of the decomposition product can be adjusted. If the amount of the glycol is small, the molecular weight of the decomposition product is large, and if the amount of the glycol is large, the molecular weight of the decomposition product is small.

Then, a saturated polyester resin can be decomposed by further adding a new saturated polyester resin to the above decomposition product. Further, by separating excess glycol from the decomposition product, the saturated polyester resin can be efficiently recycled.

In the present invention, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,4-butane are used as glycols for decomposing the saturated polyester resin. Diol, 1,6-hexanediol, hydrogenated bisphenol A, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, tricyclodecane dimethanol ethylene oxide adduct, dibromoneopentyl glycol, and the like can be used.

In the present invention, the decomposition of the saturated polyester resin can be carried out in the absence of a catalyst, but it is preferable to use a catalyst. Here, as a catalyst, sodium hydroxide,
Metal acetate metal salts such as potassium hydroxide, sodium methylate, sodium ethylate, zinc acetate, magnesium acetate, calcium acetate, lithium acetate, sodium acetate,
Examples include antimony oxide, tributyltin methoxide, titanium alkoxide, and the like, and mixtures thereof. The amount of the catalyst used is usually in the range of 0.1 to 1.0%.

The temperature at which the saturated polyester resin is decomposed is usually in the range of 100 ° C to 300 ° C, preferably 150 ° C to 2 ° C.
It is in the range of 50 ° C. Within this decomposition temperature range, the decomposition rate of the saturated polyester resin is high, and a polyester macromonomer can be efficiently produced. By carrying out the decomposition reaction in a nitrogen atmosphere in the presence of an antioxidant, coloring due to the oxidation reaction can be prevented. In the present invention, the decomposition reaction can be performed under atmospheric pressure or under pressure. When using a glycol having a low boiling point for the decomposition reaction and performing the decomposition reaction at a temperature equal to or higher than the boiling point of the glycol, the reaction is performed under pressure.

The decomposition reaction of the saturated polyester resin by glycol is fast. Decomposition products of glycol usually have OH groups at both ends. A compound having a functional group capable of polymerizing with the OH group of the decomposition product, for example, acrylic acid or methacrylic acid is subjected to an esterification reaction to produce a polyester macromonomer having methacrylate (methacryloyl group) and acrylate (acryloyl group) at the terminal. Is done. In this esterification reaction, an acid catalyst such as p-toluenesulfonic acid can be used.

Next, a polyester macromonomer having a styrene (vinylphenylene group) having the structure of the formula (3) or an allyl group having a structure of the formula (4) at a molecular chain terminal is produced by the following method. First, a dibasic acid such as phthalic anhydride is reacted with a decomposition product of a saturated polyester resin by glycol to introduce a carboxylic acid into a molecular chain terminal of the decomposition product. Then, chloromethylstyrene or allyl bromide is reacted with the carboxylic acid, and a dehydrohalogenation reaction is performed to produce a polyester macromonomer having a polymerizable functional group at a molecular chain terminal and having a structure represented by the formula (3) or (4). . In the dehydrohalogenation reaction, a base catalyst or a phase transfer catalyst can be used.

[0027]

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In the equations (3) and (4), Z represents the following equations (5), (6) and (7).

[0029]

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The polyester macromonomer of the present invention comprises
In the presence of a polymerization initiator, if necessary, a predetermined amount of a polyfunctional monomer is added for polymerization. Polyester macromonomer usually has a molecular weight in the range of 300 to 20,000,
It is homogeneous and has reactivity close to ordinary polymerized monomers.

The polyester macromonomer of the present invention comprises
It can also be used as a crosslinking agent for unsaturated polyester. The polymerizable carbon-carbon double bond of the unsaturated polyester usually has a fumarate group since it isomerizes into a trans form. Although the ester portion of this fumarate group has a long chain, its polymerizability is considered to be almost the same as that of diisopropyl fumarate. Here, the monomer reactivity ratio in radical copolymerization of the vinyl monomer (M1) and diisopropyl fumarate (M2) is shown.

[0032]

[Table 1]

T.Otsu, A.Matsumoto, K.Shiraishi, N.Amay
a, Y.Koinuma, J.Polym.Sci.: PartA: Polym.Chem., 30 (8), 1
559 (1992) From Table 1, it can be seen that the radical copolymerization monomer reactivity ratios (r ₁ , r ₂ ) of vinyl monomer (M1) such as methyl acrylate and methyl methacrylate and diisopropyl fumarate (M2) are greatly different. Therefore, when a polyester macromonomer having a methacrylate terminal is used for crosslinking an unsaturated polyester,
It is preferable to use styrene or a polyester macromonomer having styrene at the terminal. In the case of a polyester macromonomer having an acrylate terminal, it can be used alone, but it is better to use styrene or a polyester macromonomer having a styrene terminal. The styrene-terminated polyester macromonomer can be used alone.

Next, the monomer reactivity ratio of the radical copolymerization of fumarate (M1) and diallyl phthalate (M2) will be shown.

[0035]

[Table 2]

According to Table 2, the product (r ₁ × r ₂ ) of the reactivity ratio of the radical copolymerization monomer of fumarate (M1) and diallyl phthalate (M2) is close to 0, so that the copolymerizability is poor.
Allyl-terminated polyester macromonomers can also be used for crosslinking unsaturated polyesters.

These polyester macromonomers are used as coating agents, UV curable inks, coating agents for optical disks, adhesives, paints, photoresists, resists for printed circuit boards, photosensitive resin relief plates, photopolymerized dental materials, and the like.

[0038]

The polyester macromonomer according to the invention forms a hard coating. A decomposition product is obtained by glycol decomposition of the saturated polyester resin, and this is reacted as a raw material,
High value-added polyester macromonomers can be produced.

[0039]

The present invention will be described below in detail with reference to examples.

In the following examples, a drinking water bottle made of a polyester resin was cut with scissors, and a sample crushed by a rotary cutter mill, Granulaters U-140 manufactured by Horai Co., Ltd. to a particle size of 5 mm was used.

Example 1 A waste PET bottle was pulverized, 15.22 kg of propylene glycol (molar ratio 1: 2) was added to 19.22 kg of PET, and the bottle was decomposed at 240 ° C. for 2 hours. PET is decomposed by 100%, and the acid value of the decomposed product is 19.93 mgKOH / g, and the OH value (mol number of OH groups per 1 kg of sample) is 9.0 mol.
/ Kg, number average molecular weight = 332, weight average molecular weight = 41
It was 8.

Phthalic anhydride 1 was added to 10 g of the obtained decomposition product.
3.12 g and 50 ml of pyridine were added and reacted at 60 ° C. for 1 hour. The product was dissolved in THF, precipitated in hexane and purified twice. 12.6 g of phthalic acid adduct was obtained, acid value = 4.9 mol / kg (mol number of carboxyl group), OH value was not detected, and number average molecular weight of the product = 3
90, weight-average molecular weight = 438.

To 10 g of the phthalic acid adduct, 22.00 g of chloromethylstyrene, 50 ml of DMF, 50% NaOH
2.6 ml of an aqueous solution was added, and the mixture was stirred and reacted at room temperature under nitrogen for 24 hours. After completion of the reaction, o-dichlorobenzene and hydroquinone 0.1% in twice the amount of DMF were added, and the mixture was added under reduced pressure.
DMF was distilled off. An o-dichlorobenzene solution of the product was poured into a large amount of hexane to obtain a precipitate. This precipitate is
It was dissolved in HF, poured into hexane, purified twice, and dried under reduced pressure. 8.30 g of product are obtained, acid value = 0.4 mo
1 / kg, number average molecular weight = 416, weight average molecular weight = 7
86.

¹ H-NMR (400 MHz, C
(DCl ₃ solvent), and the NMR measurement results are shown in Table 4.

Example 2 After a waste PET bottle was pulverized, 11.41 kg of propylene glycol was added to 19.22 kg of PET (molar ratio 1: 1.5).
And decomposed at 240 ° C. for 2 hours. 100% decomposed,
Acid value of decomposed product = 18.83 mgKOH / g, OH value (O
Number of moles of H group) = 8.2 mol / kg, number average molecular weight =
363, weight average molecular weight = 489.

To 10 g of the obtained decomposed product, phthalic anhydride 1
2.00 g and 50 ml of pyridine were added and reacted at 60 ° C. for 1 hour. The product was dissolved in THF, precipitated in hexane and purified twice. 14.3 g of phthalic acid adduct was obtained, acid value = 4.6 mol / kg (mol number of carboxyl group), OH value was not detected, and number average molecular weight of the product = 4
19. The weight average molecular weight was 526.

To 10 g of the phthalic acid adduct, 20.65 g of chloromethylstyrene, 50 ml of DMF, 50% NaOH
An aqueous solution (2.4 ml) was added, and the mixture was stirred and reacted at room temperature under nitrogen for 24 hours. After completion of the reaction, o-dichlorobenzene and hydroquinone 0.1% in twice the amount of DMF were added, and the mixture was added under reduced pressure.
DMF was distilled off. An o-dichlorobenzene solution of the product was poured into a large amount of hexane to obtain a precipitate. This precipitate is
It was dissolved in HF, poured into hexane, purified twice, and dried under reduced pressure. 7.28 g of product are obtained, acid value = 0.2 mo
1 / kg, number average molecular weight = 530, weight average molecular weight = 6
67.

¹ H-NMR (400 MHz, C
DCL ₃ solvent), and the NMR measurement results are shown in Table 4.

Example 3 A waste PET bottle was pulverized, and 15.22 kg of diethylene glycol was added to 19.22 kg of PET (at a molar ratio of 1: 1.5).
Was added and decomposed at 240 ° C. for 1 hour. 100% decomposed,
Acid value of decomposition product = 10.60 mg KOH / g, OH value (O
(Mol number of H group) = 7.5 mol / kg, number average molecular weight =
396, weight average molecular weight = 538.

10 g of phthalic anhydride was added to 10 g of the obtained decomposition product.
1.06 g and 50 ml of pyridine were added and reacted at 60 ° C. for 1 hour. The product was dissolved in THF, precipitated in hexane and purified twice. 13.8 g of phthalic acid adduct was obtained, acid value = 4.5 mol / kg (mole number of carboxyl group), OH value was not detected, and number average molecular weight of the product = 4
38, weight average molecular weight = 549.

To 10 g of the phthalic acid adduct, 20.20 g of chloromethylstyrene, 50 ml of DMF, 50% NaOH
An aqueous solution (2.4 ml) was added, and the mixture was stirred and reacted at room temperature under nitrogen for 24 hours. After completion of the reaction, o-dichlorobenzene and hydroquinone 0.1% in twice the amount of DMF were added, and the mixture was added under reduced pressure.
DMF was distilled off. An o-dichlorobenzene solution of the product was poured into a large amount of hexane to obtain a precipitate. This precipitate is
It was dissolved in HF, poured into hexane, purified twice, and dried under reduced pressure. 7.62 g of product are obtained, acid value = 0.5 mo
1 / kg, number average molecular weight = 601, weight average molecular weight = 7
It was 11.

¹ H-NMR (400 MHz, D
MSO-d ₆ solvent) and the NMR measurement results are shown in Table 4.

Example 4 After a waste PET bottle was pulverized, 19.13 kg of PET was added to 20.13 kg of dipropylene glycol (molar ratio: 1: 1.
5) was added and the mixture was decomposed at 240 ° C. for 2 hours. The product was decomposed by 100%, and the acid value of the decomposed product was 9.16 mgKOH / g, the OH value (mol number of OH group) was 6.6 mol / kg, the number average molecular weight was 539, and the weight average molecular weight was 744.

To 10 g of the obtained decomposed product, phthalic anhydride 9.
76 g and 50 ml of pyridine were added and reacted at 60 ° C. for 1 hour. The product was dissolved in THF, precipitated in hexane and purified twice. 14.0 g of phthalic acid adduct was obtained, acid value = 3.9 mol / kg (mol number of carboxyl group), OH value was not detected, and number average molecular weight of the product = 5
47, weight average molecular weight = 720.

To 10 g of the phthalic acid adduct, 17.51 g of chloromethylstyrene, 50 ml of DMF, 50% NaOH
2.0 ml of an aqueous solution was added, and the mixture was stirred and reacted at room temperature under nitrogen for 24 hours. After completion of the reaction, o-dichlorobenzene and hydroquinone 0.1% in twice the amount of DMF were added, and the mixture was added under reduced pressure.
DMF was distilled off. An o-dichlorobenzene solution of the product was poured into a large amount of hexane to obtain a precipitate. This precipitate is
It was dissolved in HF, poured into hexane, purified twice, and dried under reduced pressure. 9.23 g of product are obtained, acid value = 0.2 mo
1 / kg, number average molecular weight = 799, weight average molecular weight = 9
78.

¹ H-NMR (400 MHz, C
DCL ₃ solvent), and the NMR measurement results are shown in Table 4.

Example 5 After a waste PET bottle was pulverized, 28.84 kg of tripropylene glycol was added to 19.22 kg of PET (molar ratio: 1: 1.
5) was added, and the mixture was decomposed at 240 ° C. for 2 hours. The product was decomposed by 100%, and the acid value of the decomposed product was 7.79 mgKOH / g, the OH value (mol number of OH group) was 5.7 mol / kg, the number average molecular weight was 698, and the weight average molecular weight was 898.

The phthalic anhydride was added to 10 g of the obtained decomposition product.
37 g and 50 ml of pyridine were added and reacted at 60 ° C. for 1 hour. The product was dissolved in THF, precipitated in hexane and purified twice. 10.8 g of phthalic acid adduct was obtained, acid value = 3.4 mol / kg (mol number of carboxyl group), OH value was not detected, and number average molecular weight of the product = 6
30, weight average molecular weight = 839.

To 10 g of the phthalic acid adduct, 15.26 g of chloromethylstyrene, 50 ml of DMF, 50% NaOH
1.7 ml of an aqueous solution was added, and the mixture was stirred and reacted at room temperature under nitrogen for 24 hours. After completion of the reaction, o-dichlorobenzene and hydroquinone 0.1% in twice the amount of DMF were added, and
DMF was distilled off. An o-dichlorobenzene solution of the product was poured into a large amount of hexane to obtain a precipitate. This precipitate is
It was dissolved in HF, poured into hexane, purified twice, and dried under reduced pressure. 7.08 g of product are obtained, acid value = 0.9 mo
1 / kg, number average molecular weight = 900, weight average molecular weight = 1
188. ¹ H-NMR of the product (400 MH
z, CDCl ₃ solvent), and the NMR measurement results are shown in Table 4.

Example 6 After a waste PET bottle was pulverized, 19.13 kg of PET was added to 20.13 kg of dipropylene glycol (molar ratio: 1: 1.
5) was added, and the mixture was decomposed at 240 ° C. for 2 hours. The product was decomposed by 100%, and the acid value of the decomposed product was 9.16 mgKOH / g, the OH value (mol number of OH group) was 6.6 mol / kg, the number average molecular weight was 539, and the weight average molecular weight was 744.

To 10 g of the obtained decomposition product, phthalic anhydride 9.
76 g and 50 ml of pyridine were added and reacted at 60 ° C. for 1 hour. The product was dissolved in THF, precipitated in hexane and purified twice. 14.0 g of phthalic acid adduct was obtained, acid value = 3.9 mol / kg (mol number of carboxyl group), OH value was not detected, and number average molecular weight of the product = 5
47, weight average molecular weight = 720.

To 10 g of the phthalic acid adduct, 8.76 g of chloromethylstyrene, 50 ml of DMF and 0.85 ml of a 50% aqueous NaOH solution were added, and the mixture was stirred and reacted at room temperature under nitrogen for 24 hours. After completion of the reaction, o-dichlorobenzene and hydroquinone 0.1% in twice the amount of DMF were added, and the mixture was added under reduced pressure.
DMF was distilled off. An o-dichlorobenzene solution of the product was poured into a large amount of hexane to obtain a precipitate. This precipitate is
It was dissolved in HF, poured into hexane, purified twice, and dried under reduced pressure. 6.65 g of product are obtained, acid value = 1.4 mo
1 / kg, number average molecular weight = 682, weight average molecular weight = 8
It was 18.

¹ H-NMR (400 MHz, C
DCL ₃ solvent), and the NMR measurement results are shown in Table 4.

Example 7 After a waste PET bottle was pulverized, 19.13 kg of PET was added to 20.13 kg of dipropylene glycol (molar ratio: 1: 1.
5) was added, and the mixture was decomposed at 240 ° C. for 2 hours. The product was decomposed by 100%, and the acid value of the decomposed product was 9.16 mgKOH / g, the OH value (mol number of OH group) was 6.6 mol / kg, the number average molecular weight was 539, and the weight average molecular weight was 744.

The phthalic anhydride was added to 10 g of the obtained decomposition product.
76 g and 50 ml of pyridine were added and reacted at 60 ° C. for 1 hour. The product was dissolved in THF, precipitated in hexane and purified twice. 14.0 g of phthalic acid adduct was obtained, acid value = 3.9 mol / kg (mol number of carboxyl group), OH value was not detected, and number average molecular weight of the product = 5
47, weight average molecular weight = 720.

To 10 g of the phthalic acid adduct, 11.85 g of allyl bromide, 50 ml of DMF and 1.7 ml of a 50% aqueous NaOH solution were added, and the mixture was stirred at room temperature under nitrogen for 24 hours.
Reacted. After completion of the reaction, o-dichlorobenzene and hydroquinone 0.1% in twice the amount of DMF were added, and DM was added under reduced pressure.
F was distilled off. An o-dichlorobenzene solution of the product was poured into a large amount of hexane to obtain a precipitate. This precipitate is washed with THF
, Poured into hexane, purified twice, and dried under reduced pressure. 8.20 g of product are obtained, acid value = 1.1 mol /
kg, number average molecular weight = 890, weight average molecular weight = 103
It was 8.

¹ H-NMR (400 MHz, D
MSO-d ₆ solvent) were measured, the results thereof NMR measurements in Table 4.

Example 8 113.6 g of pulverized PET waste was added to 287.0 g of a 4-mol adduct of bisphenol A ethylene oxide (a molar ratio of PET ester group to glycol = 1: 1.2), 0.2 gN
Decomposed for 2 hours at 240 ° C under nitrogen in addition to aOH.
Thereafter, the mixture was neutralized with dilute sulfuric acid. OH value of decomposition product = 3.42
Mol / kg, OH equivalent = 292.1 g / mol, acid value =
1.9 mgKOH / g, number average molecular weight by GPC = 9
53, weight average molecular weight = 1,502.

To 203.1 g (0.69 OH gram equivalent) of the decomposed product, 61.9 g (0.72 mol, molar ratio 1: 1.04) of methacrylic acid, 800 ml of toluene, 20 g of p-toluenesulfonic acid, and 0.1 g of hydroquinone were added. 4 g was added, and the mixture was heated, refluxed, and dehydrated with stirring, and an esterification reaction was performed for 5 hours. After the completion of the reaction, the resultant was washed with a 10% aqueous NaOH solution to remove the catalyst and hydroquinone, and then washed with water until neutral. Then add sodium sulfate, dry overnight,
The toluene was distilled off under reduced pressure. Yield: 88.9%, acid value = 4.0 mg KOH / g, refractive index (n _D ²⁵ ) = 1.54
7, viscosity (mPa · s / 25 ° C) = 27000, GPC
Number average molecular weight = 936, weight average molecular weight = 154
It was 6.

F of the obtained polyester macromonomer
The T-IR was measured, and the FT-IR measurement results are shown in Table 5.

The obtained macromonomer was tested for UV curing properties using a UV initiator Irgacure907 (manufactured by Ciba-Geigy). Table 3 shows the results.

[0072]

[Table 3]

From Table 3, it can be seen that the synthesized polyester macromonomer having a methacrylate terminal has a relatively low UV curing rate, and particularly has a slow surface curing in air and is sticky, but was completely cured by irradiation five times. When a multifunctional urethane acrylate U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.) was added, the curing speed was increased.

Example 9 187.4 g of pulverized PET waste was added to 224.9 g of tripropylene glycol (the molar ratio of PET ester group to glycol = 1: 1.2), and the mixture was heated at 240 ° C. under nitrogen.
Degraded for 2 hours. OH value of decomposition product = 5.37 mol / k
g, OH equivalent = 186.1 g / mol, acid value = 2.7 m
gKOH / g, number average molecular weight by GPC = 662, and weight average molecular weight = 1006.

176.0 g (0.946 OH gram equivalent) of the decomposed product was added to 86.0 g (1.00 mol,
Molar ratio 1: 1.06), 800 ml of toluene, 20 g of p-toluenesulfonic acid, and 0.5 g of hydroquinone.
While stirring, the mixture was heated, refluxed and dehydrated, and an esterification reaction was carried out for 8 hours. After the completion of the reaction, the resultant was washed with a 10% aqueous NaOH solution to remove the catalyst and hydroquinone, and then washed with water until neutral. Then, sodium sulfate was added, dried overnight, and toluene was distilled off under reduced pressure. The yield is 81.5%,
The acid value was 3.4 mgKOH / g, the number average molecular weight by GPC was 655, and the weight average molecular weight was 1022.

F of the obtained polyester macromonomer
The T-IR was measured, and the FT-IR measurement results are shown in Table 5.

Example 10 182.0 g of ground PET waste was added to 220.7 g of tetraethylene glycol (the molar ratio of ester group of PET: glycol = 1: 1.2).
Degraded for 2 hours. OH value of decomposed product = 5.35 mol / k
g, OH equivalent = 186.7 g / mol, acid value = 2.0 m
gKOH / g, number average molecular weight by GPC = 640, and weight average molecular weight = 1060.

177.1 g (0.947 OH gram equivalent) of the decomposed product was added to 86.0 g (1.00 mol,
Molar ratio 1: 1.06), 800 ml of toluene, 20 g of p-toluenesulfonic acid, and 0.5 g of hydroquinone.
While stirring, heating, reflux and dehydration were performed, and an esterification reaction was performed for 6 hours. After the completion of the reaction, the resultant was washed with a 10% aqueous NaOH solution to remove the catalyst and hydroquinone, and then washed with water until neutral. Then, sodium sulfate was added, dried overnight, and toluene was distilled off under reduced pressure. The yield is 86.4%,
Acid value = 3.2 mg KOH / g, refractive index (n _D ²⁵ ) = 1.
503, viscosity (mPa · s / 25 ° C.) = 350, GPC
Number average molecular weight = 638, weight average molecular weight = 108
It was 0.

The obtained polyester macromonomer F
The T-IR was measured, and the FT-IR measurement results are shown in Table 5.

Example 11 114.2 g of pulverized PET waste was added to 285.6 g of polyethylene glycol # 400 (molar ratio of ester group of PET: glycol = 1: 1.2) and 2 g of nitrogen was added under nitrogen.
Decomposed for 2 hours at 40 ° C. OH value of decomposition product = 3.41 mol / kg, OH equivalent = 293.3 g / mol, acid value =
1.9 mgKOH / g, number average molecular weight by GPC = 1
036, weight average molecular weight = 1656.

The decomposition product (196.1 g, 0.669 OH gram equivalent) was added to 60.2 g (0.699 mol, molar ratio 1: 1.04) of methacrylic acid, 800 ml of toluene, p-
Toluenesulfonic acid (20 g) and hydroquinone (0.5 g) were added, and the mixture was heated, refluxed and dehydrated with stirring, and an esterification reaction was carried out for 7 hours. After the completion of the reaction, the resultant was washed with a 10% aqueous NaOH solution to remove the catalyst and hydroquinone, and then washed with water until neutral. Then, sodium sulfate was added, dried overnight, and toluene was distilled off under reduced pressure. The yield is 86.5.
%, Acid value = 1.2 mg KOH / g, refractive index (n _D ²⁵ ) =
1.495, viscosity (mPa · s / 25 ° C.) = 470, G
Number average molecular weight by PC = 1117, weight average molecular weight =
1675.

F of the obtained polyester macromonomer
The T-IR was measured, and the FT-IR measurement results are shown in Table 5.

Example 12 121.2 g of pulverized PET waste was added to 282.3 g of a 4 mol adduct of tricyclodecane dimethanol ethylene oxide (P
ET ester: glycol molar ratio = 1: 1.2)
And decomposed under nitrogen at 240 ° C. for 2 hours. OH value of decomposition product = 3.61 mol / kg, OH equivalent = 274.0
g / mol, acid value = 1.8 mgKOH / g, and weight average molecular weight by GPC = 1039.

To 200.0 g (0.722 OH gram equivalent) of the decomposed product, 64.5 g (0.749 mol, molar ratio 1: 1.04) of methacrylic acid, 800 ml of toluene, p-
Toluenesulfonic acid (20 g) and hydroquinone (0.5 g) were added, and the mixture was heated, refluxed and dehydrated with stirring, and an esterification reaction was performed for 6 hours. After the completion of the reaction, the resultant was washed with a 10% aqueous NaOH solution to remove the catalyst and hydroquinone, and then washed with water until neutral. Then, sodium sulfate was added, dried overnight, and toluene was distilled off under reduced pressure. The yield is 89.2
%, Acid value = 1.0 mgKOH / g, refractive index (n _D ²⁵ ) =
1.515, viscosity (mPa · s / 25 ° C.) = 3700,
The weight average molecular weight by GPC was 1079.

F of the obtained polyester macromonomer
The T-IR was measured, and the FT-IR measurement results are shown in Table 5.

Example 13 121.2 g of pulverized PET waste was converted to 282.3 g of a 4 mol adduct of tricyclodecane dimethanol ethylene oxide (P
ET ester: glycol molar ratio = 1: 1.2)
And decomposed under nitrogen at 240 ° C. for 2 hours. OH value of decomposition product = 3.61 mol / kg, OH equivalent = 274.0
g / mol, acid value = 1.8 mgKOH / g, and weight average molecular weight by GPC = 1039.

200.0 g (0.722 OH gram equivalent) of the decomposed product was added to 54.0 g (0.749 mol,
(Molar ratio 1: 1.04), 800 ml of toluene, 20 g of p-toluenesulfonic acid, and 0.5 g of hydroquinone.
While stirring, heating, reflux and dehydration were performed, and an esterification reaction was performed for 6 hours. After the completion of the reaction, the resultant was washed with a 10% aqueous NaOH solution to remove the catalyst and hydroquinone, and then washed with water until neutral. Then, sodium sulfate was added, dried overnight, and toluene was distilled off under reduced pressure. The yield is 85.0%,
Acid value = 1.5 mg KOH / g, refractive index (n _D ²⁵ ) = 1.
500, viscosity (mPa · s / 25 ° C.) = 3600, GP
Weight average molecular weight by C = 1020.

Example 14 121.2 g of pulverized PET waste was converted to 282.3 g of a 4-mol adduct of tricyclodecane dimethanol ethylene oxide (P
ET ester: glycol molar ratio = 1: 1.2)
And decomposed under nitrogen at 240 ° C. for 2 hours. OH value of decomposition product = 3.61 mol / kg, OH equivalent = 274.0
g / mol, acid value = 1.8 mgKOH / g, and weight average molecular weight by GPC = 1039.

To 200.0 g (0.722 OH gram equivalent) of the decomposition product, 27.0 g (0.375 mol,
(Molar ratio 1: 0.52), 800 ml of toluene, 20 g of p-toluenesulfonic acid, and 0.5 g of hydroquinone were added,
While stirring, the mixture was heated, refluxed and dehydrated, and an esterification reaction was carried out for 6 hours. After the completion of the reaction, the resultant was washed with a 10% aqueous NaOH solution to remove the catalyst and hydroquinone, and washed with water until the solution became neutral. Then, sodium sulfate was added, dried overnight, and toluene was distilled off under reduced pressure. The yield is 84.0%,
Acid value = 1.4 mg KOH / g, refractive index (n _D ²⁵ ) = 1.
500, viscosity (mPa · s / 25 ° C.) = 3650, GP
The weight average molecular weight by C was 1,015.

[0090]

[Table 4]

[0091]

[Table 5]

The results obtained by measuring the constituent components of the products of the examples by NMR measurement are summarized in Table 4 and FIGS. FIG. 1 shows the amounts of the constituent components of the products based on Examples 1, 2, 4, 5, and 6. FIG. 2 shows the amounts of the constituent components of the product based on Example 7. FIG. 3 shows the component amounts of the constituent components of the product based on Example 3.

The embodiments and examples disclosed this time are to be considered in all respects as illustrative and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

[0094]

According to the present invention, a polyester macromonomer can be easily produced, and an industrially useful raw material can be obtained from a saturated polyester resin or its waste. The polyester macromonomer synthesized from the glycol decomposition product of the waste can be used as a high value-added monomer.

[Brief description of the drawings]

FIG. 1 is a diagram showing component amounts of constituent components of a product based on Examples 1, 2, 4, 5 and 6.

FIG. 2 is a diagram showing component amounts of constituent components of a product based on Example 7.

FIG. 3 is a diagram showing component amounts of constituent components of a product based on Example 3.

Continued on the front page (72) Inventor Michiichi Mori 279 Ogura, Ogura, Wakayama-shi, Wakayama 207 Green full Ogura 207 (72) Inventor Takuya Maeda 293-5 Mitsuya, Wakayama-shi, Wakayama Address: Shin Nakamura Kagaku Kogyo Co., Ltd. BA02 BA03 BA05 BA08 BA10 BD10 BF09 BF10 BF18 BF24 BF25 CA04 CB04 GA13 GA42 GA43 KG02 KH01

Claims (7)

[Claims] 1. The following chemical formula (1) or (2)
A polyester macromonomer having the structure: Embedded image Here, n is an integer of 1 to 50, X is a polymerizable functional group or hydrogen (except when hydrogen is simultaneously added to both terminals), and R is a glycol residue. 2. The polyester macromonomer according to claim 1, wherein the polymerizable functional group is a vinylphenylene group, an allyl group, an acryloyl group or a methacryloyl group. 3. Production of a polyester macromonomer having a vinylphenylene group, an allyl group, an acryloyl group or a methacryloyl group at one or both ends of a molecular chain by decomposing a saturated polyester resin with glycol and using the decomposition product as a raw material. Method. 4. The method for producing a polyester macromonomer according to claim 3, wherein the saturated polyester resin is waste. 5. A saturated polyester resin is decomposed with glycol, and the decomposed product is reacted with phthalic anhydride, succinic anhydride or maleic anhydride, and then is reacted with chloromethylstyrene or allyl bromide to obtain vinylphenylene. The method for producing a polyester macromonomer according to claim 3, wherein a polyester macromonomer having a group end or an allyl group end is produced. 6. A polyester macromonomer having a methacryloyl group terminal or an acryloyl group terminal by decomposing a saturated polyester resin with glycol and reacting the decomposition product with methacrylic acid or acrylic acid. 5. The method for producing a polyester macromonomer according to 3 or 4. 7. The method for producing a polyester macromonomer according to claim 3, wherein the saturated polyester resin is polyethylene terephthalate.