JP4694862B2 - Polyester macromonomer and method for producing the same - Google Patents

Description

  The present invention relates to a polyester macromonomer and a method for producing the same. Furthermore, the present invention provides a method for obtaining a valuable raw material that enables the polyester resin waste to be reused, and in particular, chemically treats the polyester resin waste for industrial reuse.

  The polyester macromonomer is an oligomer or polymer having an ester structure in the molecular main chain, a molecular weight of several hundred to several tens of thousands, and having a polymerizable functional group at its terminal. Here, examples of the polymerizable functional group include a vinyl group, a vinylidene group, a vinylene group, a cyclic olefin, and the like, and a graft copolymer can be obtained by the functional group.

  Polyester macromonomers that have been produced in the past are polyester condensates of phthalic acid and glycol, aliphatic dibasic acids such as adipic acid and glycol, or caprolactone ring-opening polymerization polymers. It was.

  In general, in the production of an aromatic polyester, the reactivity with glycol is greatest for phthalic acid, and decreases in the order of isophthalic acid and then terephthalic acid. Therefore, since the polyester of terephthalic acid is most difficult to produce, it is also most difficult to produce a polyester macromonomer having terephthalic acid in the molecular main chain.

  Conventionally, as described in Non-Patent Document 1 below, material recycling in which PET bottles and films are regenerated by melting them with heat and remolding them has been mainly performed. In addition, as a method for recycling PET bottles and films, a technique has been developed in which monomers are recovered by hydrolysis, methanol decomposition, and glycol decomposition and re-synthesized into PET (Non-patent Document 2).

  In the above method, monovalent or divalent alcohols, that is, water, methanol, ethylene glycol, and the like are used for the decomposition. Similarly, examples in which a PET resin is decomposed with a divalent alcohol are disclosed in Patent Documents 1 and 2 below.

  As disclosed in Patent Documents 1 and 2, when a PET resin is decomposed with a divalent alcohol, the oligomer obtained in principle is limited to a bifunctional one. That is, an alcohol derived from a divalent alcohol and an alcohol derived from ethylene glycol in PET are present at both ends of the oligomer.

  However, in recent years, with the diversification of functional materials, various acrylic, epoxy, and isocyanate monomers and oligomers have been developed, and many of them are multifunctional compounds. Such a polyfunctional compound is considered to be obtained basically by synthesis using a trihydric or higher polyhydric alcohol.

However, it has been difficult to obtain such polyfunctional monomers or oligomers by conventional PET decomposition methods.
JP 2002-327055 A JP 2003-277342 A R. J. et al. Ehring, edited by Plastic Recycling Research Group, “Plastic Recycling-From Recovery to Recycling”, p. 71, Industrial Research Committee (1993) “Waste Plastic Thermal & Chemical Recycling”, p. 201, Chemical Industry Daily (1994)

  The present invention has been made to solve the above-mentioned conventional problems, and its purpose is to decompose a saturated polyethylene resin such as polyethylene terephthalate with a polyhydric alcohol and chemically treat the decomposition product. It is to provide a method for producing a multifunctional polyester macromonomer.

  According to one aspect of the present invention, there is provided a polyester macromonomer having a structure represented by the following formula (1) or (2):

Here, m is an integer of 1 to 50, l and n are integers satisfying the following relational expression: 6 ≧ l + n ≧ 3, and R ¹ is a polyhydric alcohol having at least three hydroxyl groups. Polyester macromonomers are provided wherein X is a residue and X is an organic group or hydrogen having an acryloyl or methacryloyl group, except where all X are hydrogen.

Preferably, R ¹ is a residue of an alcohol selected from the group consisting of trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, ditrimethylolpropane, and their alkylene oxide adducts.

Preferably, X is 2 -methacryloyloxyethyl isocyanate (formula (5)) or a compound obtained by the reaction of an acryloyl group or an alcohol having a methacryloyl group with a diisocyanate compound (formula (6)) :

(In Formula (6), Y is a residue except the isocyanate group of diisocyanate, and Z is the following formulas (7) to (9):

It is an alcohol used for reaction with diisocyanate, and shows a residue of hydroxyl group (—OH) excluding H).

According to another aspect of the present invention, a step of decomposing a saturated polyester resin with a polyhydric alcohol having three or more hydroxyl groups , and an acryloyl group or a methacryloyl group are bonded to the molecular ends of the decomposition product decomposed in the step And a process for producing a polyester macromonomer comprising the steps of:

Preferably, the saturated polyester resin, in the step of decomposing by the polyhydric alcohol having a hydroxyl group three or more, with a polyhydric alcohol having three or more hydroxyl groups, using a divalent alcohol together.

Preferably, the polyhydric alcohol having 3 or more hydroxyl groups is selected from the group consisting of trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, ditrimethylolpropane, and alkylene oxide adducts thereof. .

According to another aspect of the present invention, a step of decomposing a saturated polyester resin with a polyhydric alcohol having three or more hydroxyl groups , and a decomposition product decomposed in the step are reacted with methacrylic acid or acrylic acid. And a step of bonding a methacryloyl group or an acryloyl group to a molecular terminal.

According to another aspect of the present invention, a step of decomposing a saturated polyester resin with a polyhydric alcohol having three or more hydroxyl groups, and reacting methacrylic acid chloride or acrylic acid chloride with the decomposition product decomposed in the step. And a step of bonding a methacryloyl group or an acryloyl group to a molecular end, and a method for producing a polyester macromonomer is provided.

According to another aspect of the present invention, a saturated polyester resin is decomposed with a polyhydric alcohol having three or more hydroxyl groups , and a decomposition product decomposed in the step is converted into 2 -methacryloyloxyethyl isocyanate (formula ( 5)) or a compound obtained by reacting an alcohol having an acryloyl group or a methacryloyl group with a diisocyanate compound (formula (6)) :

(In Formula (6), Y is a residue except the isocyanate group of diisocyanate, and Z is the following formulas (7) to (9):

Is an alcohol used for the reaction with diisocyanate, and shows a residue of hydroxyl group (—OH) excluding H), and a methacryloyl group or an acryloyl group is bonded to the molecular end. And a method for producing a polyester macromonomer comprising the steps of:

  Preferably, the saturated polyester resin is polyethylene terephthalate.

  According to another aspect of the present invention, there is provided a polyester macromonomer produced by the above method for producing a polyester macromonomer.

  The polyfunctional acrylate produced by the method for producing a polyester macromonomer of the present invention is a multi-branched compound, and unlike the linear compound obtained by the conventional method, the multi-branched acrylate is cured. In this case, a three-dimensional crosslinked network is formed to give a very strong polyfunctional oligomer of a cured product, so that it is particularly useful for applications such as hard coating.

  The inventors of the present invention crush the saturated polyester resin or its waste and then decompose it with polyhydric alcohol, and bond the acryloyl group or methacryloyl group to the molecular terminal of the decomposition product decomposed in this step. A process for producing a polyester macromonomer comprising This makes it possible to reuse the saturated polyester resin waste, and at the same time, obtain a polyfunctional polyester acrylate or methacrylate.

  Such a polyfunctional polyester acrylate or methacrylate can form a branched structure, unlike a linear macromonomer obtained by a conventional method. When the introduced macromonomer is cured, a three-dimensional crosslinked structure can be formed, resulting in a very strong cured product, and particularly excellent in applications such as hard coating.

(Polyester macromonomer)
In general, a polyester macromonomer is a functional group having an ester structure in the molecular main chain and having a molecular weight in the range of about 100 to 20,000, preferably in the range of about 300 to 10,000, and polymerizable at its terminal. An oligomer or polymer having Here, examples of the polymerizable functional group include a vinyl group, a vinylidene group, a vinylene group, a cyclic olefin, a dicarboxylic acid, a diol, a diamine, and the like, and a graft copolymer can be obtained by this functional group.

  In particular, in the present invention, since the polyhydric alcohol is used in the decomposition of the saturated polyester, two or more hydroxyl groups may be present at the molecular end of the decomposition product, and the hydroxyl group of the polyhydric alcohol may be present. In the case where all contributes to decomposition, a branched decomposition product can be formed around the alcohol, and a polymerizable functional group such as an acryloyl group or a methacryloyl group is bonded to the molecular end of the decomposition product. Thus, a polyfunctional polyester macromonomer and a branched polyester macromonomer can be obtained.

  Specifically, the polyester macromonomer of the present invention is a polyester macromonomer having a structure of the following formula (1) or (2):

Here, m is an integer of 1 to 50, l and n are integers satisfying the following relational expression: 6 ≧ l + n ≧ 3, and R ¹ is a polyhydric alcohol having at least three hydroxyl groups. Polyester macromonomers are provided wherein X is a residue and X is an organic group or hydrogen having an acryloyl or methacryloyl group, except where all X are hydrogen.

In the formula (1), polyethylene terephthalate (PET) is decomposed with a polyhydric alcohol having at least three hydroxyl groups to obtain a decomposition product having a polyhydric alcohol used for decomposition at one end. A polyester macromonomer obtained by introducing an organic group having an acryloyl group or a methacryloyl group into the product, wherein R ¹ is a residue of the polyhydric alcohol used in the decomposition.

Formula (2) is a polyester macromonomer in which the polyhydric alcohol used for decomposition is introduced into both ends of the polyester of the molecular main chain. Depending on the decomposition with the polyhydric alcohol, the polyester skeleton ( It is also possible to obtain a compound in which (excludes (XO) ₁ R ¹ in formula (1)) extends in a branched manner, or a polyester macromonomer having a possibly basic structure having two or more such branched structures in the compound. Is possible. In Formula (1) or Formula (2), m is an integer of 1 to 50, and l and n are integers satisfying the following relational expression: 6 ≧ l + n ≧ 3.

Here, R ¹ is preferably an alcohol residue selected from the group consisting of trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, ditrimethylolpropane, and these alkylene oxide adducts. Such an alcohol has three or more hydroxyl groups in the molecule, so that a multifunctional and / or branched polyester macromonomer can be obtained. The alkylene oxide adduct preferably has 2 to 4 carbon atoms. Moreover, it is preferable that the said adduct is added within the range of 1-30 mol with respect to each hydroxyl group of a polyhydric alcohol.

X is 3-isopropenyl-α, α′-dimethylbenzyl isocyanate (formula (3)) , allyl isocyanate (formula (4)) and 2-methacryloyloxyethyl isocyanate (formula (5)), acryloyl group or methacryloyl group Although the compound (Formula (6)) obtained by reaction of the alcohol which has this, and a diisocyanate compound can be enumerated, the compound of Formula (5) and Formula (6) is used for this invention. :

(In Formula (6), Y is a residue except the isocyanate group of diisocyanate, and Z is the following formulas (7) to (9):

It is an alcohol used for reaction with diisocyanate, and shows a residue of hydroxyl group (—OH) excluding H).

  Thus, since the acryloyl group or the methacryloyl group has couple | bonded with the molecular principal chain through the urethane bond, improvement in flexibility can be expected as a physical property of the cured product.

  In addition, when a decomposition product obtained by decomposing a saturated polyester resin by using an alcohol having two hydroxyl groups together with an alcohol having at least three hydroxyl groups is used, an acryloyl group and / or a methacryloyl group at one molecule end A polyester macromonomer in which two or more are present and one acryloyl group and / or methacryloyl group is present at the other molecular end can be obtained.

(Manufacturing method)
The above polyester macromonomer is produced by the following method. First, if necessary, the saturated polyester resin or its waste is pretreated by crushing, washing, and sieving. If necessary, the pretreated saturated polyester resin or waste is mixed into the polyhydric alcohol to obtain a decomposition product of the saturated polyester resin. Then, this decomposition product is reacted with an organic group having an acryloyl group or a methacryloyl group to produce a polyester macromonomer.

  In the present invention, the saturated polyester resin can be decomposed by adding a new saturated polyester resin to the decomposition product. In addition, the saturated polyester resin can be efficiently recycled by separating excess polyhydric alcohol from the decomposition product.

(Crushing)
In the production of the polyester macromonomer of the present invention, the saturated polyester resin is crushed by impact type crushers (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 grinder, etc. The size of the crushed material is preferably small, and a material that passes through a sieve having an opening of 20 mm is suitable. A crushed material is preferably used which passes through a 10 mm, more preferably 5 mm sieve.

(Conditions for decomposition with polyhydric alcohol)
The temperature at which the saturated polyester resin is decomposed with the polyhydric alcohol is usually in the range of 100 ° C to 300 ° C, preferably in the range of 150 ° C to 280 ° C. In this decomposition temperature range, the decomposition rate of the saturated polyester resin is fast, and a decomposition product can be obtained efficiently. The decomposition reaction is performed in a nitrogen atmosphere and in the presence of an antioxidant, whereby coloring due to the oxidation reaction can be prevented. In the present invention, the decomposition can be carried out under atmospheric pressure or under pressure. When a low boiling point glycol is used for the decomposition reaction and the decomposition reaction is performed at a temperature equal to or higher than the boiling point of the glycol, it is performed under pressure.

  In the present invention, the saturated polyester resin can be decomposed in the presence or absence of a catalyst, but it is preferably performed in the presence of a catalyst. Here, as the catalyst, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, zinc acetate, nickel acetate, cobalt acetate, magnesium acetate, calcium acetate, lithium acetate, sodium acetate, and other metal acetates, oxidation And antimony, tributyltin methoxide, titanium alkoxide, and mixtures thereof.

(Saturated polyester resin)
As the saturated polyester resin that can be used in the present invention, polyethylene terephthalate is preferably used, and polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate (PEN) used in bottles, films, and molded articles are used. It is also possible to use other wastes. Furthermore, these virgin pellets can also be used.

(Polyhydric alcohol)
In the present invention, the polyhydric alcohol is used for decomposing a saturated polyester resin or its waste and obtaining a decomposition product. Examples of the polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, mannitol, ditrimethylolpropane, dipentaerythritol, 1,3,5-cyclohexanetriol, and alkylene oxide adducts thereof. . Here, the alkylene oxide preferably has 2 to 4 carbon atoms, and is preferably used within a range of 1 to 30 mol with respect to each hydroxyl group of the polyhydric alcohol. In the present invention, the polyhydric alcohol is an alcohol having three or more hydroxyl groups in the molecule.

(Ratio of saturated polyester resin to polyhydric alcohol )
The molecular weight of the decomposition product can be adjusted by changing the mass ratio of the saturated polyester resin and the polyhydric alcohol used to decompose the saturated polyester. The ratio of the number of moles of ester bonds (E ′) of saturated polyester resin to the number of moles of polyhydric alcohol (G ′) is 1
: 0.2-5, preferably 1: 0.2-2. When the mixing amount of the polyhydric alcohol is small, the average molecular weight of the decomposition product becomes large. On the other hand, when the mixing amount of the polyhydric alcohol is large, the molecular weight of the decomposition product becomes small.

(Introduction of acryloyl group or methacryloyl group)
In the present invention, the step of bonding an acryloyl group or a methacryloyl group to a decomposition product of a saturated polyester resin with a polyhydric alcohol can be performed by a condensation reaction with acrylic acid or methacrylic acid.

  In the condensation reaction, an organic acid catalyst such as p-toluenesulfonic acid, benzenesulfonic acid and camphorsulfonic acid or an inorganic acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid can be used. The reaction can be carried out in an organic solvent, and usable organic solvents include aromatic organic compounds such as toluene, benzene and xylene, ethers such as tetrahydrofuran and diethyl ether, and halogen solvents such as chloroform and dichloromethane. However, a system capable of azeotropic dehydration of water such as toluene and benzene is desirable. The reaction temperature is preferably in the range of 0 ° C to 200 ° C, more preferably 80 ° C to 150 ° C. Although the number of moles of acrylic acid or methacrylic acid can be about 1 to 10 moles relative to the number of moles of hydroxyl groups in the polyhydric alcohol decomposition product, it is preferably 1.0 to 2.0 moles.

  In the present invention, the introduction of acryloyl group or methacryloyl group into the decomposition product of saturated polyester resin by polyhydric alcohol is carried out by reacting this decomposition product with methacrylic acid chloride or acrylic acid chloride in the presence of a base. You can also.

  The (meth) acrylic acid chloride which can be used is mixed in the range of 0.5 to 10 equivalents, preferably in the range of 1.0 to 2.0 equivalents, relative to the hydroxyl group of the polyhydric alcohol decomposition product. Usable bases include tertiary amines such as triethylamine and diisopropylethylamine, or pyridine. These bases can be used in an equivalent amount or more with respect to the carboxylic acid chloride used, and preferably 1.0 to 2.0 equivalents with respect to the carboxylic acid chloride. The reaction can be carried out in an organic solvent, and usable organic solvents include aromatic organic compounds such as toluene, benzene and xylene, ethers such as tetrahydrofuran and diethyl ether, and halogen solvents such as chloroform and dichloromethane. It is done. Although the reaction can be carried out under heating, it is more preferably carried out at about 0 ° C. to 30 ° C. in view of the problem of reaction heat. Although carboxylic acid chloride can be used about 1-10 mol with respect to the number of moles of the hydroxyl group of a polyhydric alcohol decomposition product, Preferably it is 1.0-2.0 mol.

(Introduction of (meth) acryloyl group via urethane bond)
In the present invention, the degradation product of the saturated polyester resin with a polyhydric alcohol usually has an OH group at the terminal. When a polymerizable group is introduced into this decomposition product via a urethane bond, it can be synthesized by subjecting an isocyanate compound to an addition reaction of a polyhydric alcohol decomposition product. As shown in the following chemical formulas (3) to (6), the isocyanate compound is commercially available 3-isopropenyl-α, α′-dimethylbenzyl isocyanate (3), allyl isocyanate (4) and 2-methacryloyloxy. Ethyl isocyanate (5) can be used, and a compound (6) obtained by reaction of an alcohol having an acryloyl group or a methacryloyl group with a diisocyanate compound as a synthetic product can also be used. This synthetic isocyanate compound can be obtained by reacting an alcohol having an acryloyl group or a methacryloyl group with a diisocyanate in a molar ratio of 1: 1. Diisocyanates that can be used in the production of this synthetic isocyanate compound include toluene diisocyanate, m-xylene diisocyanate, 2,4-tolylene isocyanate, norbornane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4-phenylmethane diisocyanate, dicyclohexylmethane. Diisocyanate etc. are mentioned. Examples of alcohols that can be used in the production of this synthetic isocyanate include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, pentaerythritol triacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, and the like.

In the allylamide group represented by the above formula (4), an unsaturated hydrocarbon is used as the allyl group, and propylene is typically preferably used. In Formula (6), Y is the residue except the isocyanate group of diisocyanate, and Z is shown by the following formulas (7) to (9). Formulas (7) to (9) are alcohols used for the reaction with the diisocyanate, and represent residues obtained by removing H of the hydroxyl group (—OH). Where R ′ is H or Me and R ″ is —CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) —, —CH ₂ CH ₂ CH ₂ CH ₂ — and mixtures thereof. Selected from the group consisting of m is an integer of 1 to 23, preferably an integer of 1 to 8.

  The reaction between the polyhydric alcohol decomposition product and the isocyanate can be carried out in an organic solvent. Usable organic solvents include aromatic organic compounds such as toluene, benzene and xylene, ethers such as tetrahydrofuran and diethyl ether, halogen solvents such as chloroform and dichloromethane, and the like, one or more of these. Can be used. Furthermore, depending on the reactivity of the isocyanate compound, the reaction may be carried out in the presence of a urethanization catalyst, or the reaction may be carried out under heating. As the urethanization catalyst, those used in ordinary urethanation reactions can be used, for example, tin compounds such as dibutyltin dilaurate and dibutyltin di- (2-ethylhexoate), amines such as triethylenediamine and the like. The thing etc. which combined 2 or more types can be mentioned. When using a urethanization catalyst, the required addition amount is usually in the range of 0.01 to 1.0 equivalent, preferably in the range of 0.05 to 0.5 equivalent, relative to the hydroxyl group. The addition amount of the isocyanate compound is in the range of 0.5 to 10 mol, preferably in the range of 1.0 to 2.0 mol, with respect to the hydroxyl group of the polyhydric alcohol decomposition product.

(Use)
The synthesized polyester macromonomer can be polymerized in the presence of a polymerization initiator by adding a dilution monomer if necessary. Macromonomers are said to be homogeneous and have the same reactivity as the monomers with a molecular weight of 3,000 or less.

  The synthesized multifunctional oligomer can be used as a coating agent, a UV curable ink, a paint, a resist for printed circuit boards, a photosensitive resin relief plate, a photopolymerized dental material, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not intending to be limited to this.

Example 1
To 250 g of PET pellets, 250 g of trimethylolpropane (1.5 mol based on the ester bond of PET) and 2.5 g of zinc acetate dihydrate were added as polyhydric alcohol and reacted for 27 hours at 190 ° C. in a nitrogen atmosphere in an autoclave. I let you. The decomposition product was dissolved in chloroform and taken out from the reaction vessel, and then concentrated under reduced pressure. Further, 505 g of a decomposed product was obtained by drying under reduced pressure at 60 ° C. for 6 hours. The acid value of the decomposition product was 0.03 mmol / g, the OH value (number of moles of OH groups) was 8.3 mol / kg, the number average molecular weight was 953, and the weight average molecular weight was 1680.

  To 50 g of the decomposition product, 84 g of methacrylic acid, 180 ml of toluene, 5 g of p-toluenesulfonic acid and 0.5 g of hydroquinone were added, and the mixture was heated, refluxed and dehydrated with stirring, and the esterification reaction was carried out for 7 hours. After completion of the reaction, the mixture was washed with a 15% NaOH aqueous solution to remove the catalyst and hydroquinone, and washed with water until neutrality. Then, sodium sulfate was added and dried overnight, and when toluene was distilled off under reduced pressure, 58 g of product was obtained.

When the ¹ HNMR spectrum (400 MHz, CDCl ₃ ) of the obtained synthetic macromonomer was measured, signals derived from a methacryloyl group were present in the vicinity of 1.9, 5.6, and 6.1 ppm. The methacrylation rate estimated from the integrated value of NMR was 99% or more.

  Moreover, it was number average molecular weight = 935 by GPC (polystyrene conversion), and weight average molecular weight = 1442. The 5% weight loss temperature of the compound obtained by thermosetting the synthetic macromonomer was 369 ° C.

(Example 2)
To 50 g of the polyhydric alcohol decomposition product described in Example 1, 42 g of methacrylic acid, 180 ml of toluene, 5 g of p-toluenesulfonic acid and 0.5 g of hydroquinone are added, and while stirring, heating, refluxing, dehydrating, and esterification reaction are performed. It went for 7 hours. After completion of the reaction, the mixture was washed with a 15% NaOH aqueous solution to remove the catalyst and hydroquinone, and washed with water until neutrality. Then, sodium sulfate was added and dried overnight, and when toluene was distilled off under reduced pressure, 42 g of product was obtained.

When the ¹ HNMR spectrum (400 MHz, CDCl ₃ ) of the obtained synthetic macromonomer was measured, signals derived from a methacryloyl group were present in the vicinity of 1.9, 5.6, and 6.1 ppm. Further, the methacrylation rate estimated from the integral value of NMR was 66%. The number average molecular weight by GPC (polystyrene conversion) was 1080, and the weight average molecular weight was 1302.

(Example 3)
To 50 g of the polyhydric alcohol decomposition product described in Example 1, 77 g of acrylic acid, 180 ml of toluene, 5 g of p-toluenesulfonic acid, and 0.5 g of hydroquinone are added, and the mixture is heated, refluxed and dehydrated with stirring to perform esterification reaction 7 Went for hours. After completion of the reaction, the mixture was washed with a 15% NaOH aqueous solution to remove the catalyst and hydroquinone, and washed with water until neutrality. Then, sodium sulfate was added and dried overnight, and when toluene was distilled off under reduced pressure, 42 g of product was obtained.

When the ¹ HNMR spectrum (400 MHz, CDCl ₃ ) of the obtained synthetic macromonomer was measured, an acryloyl group-derived signal was present in the vicinity of 5.8, 6.1, and 6.4 ppm. The acrylation rate estimated from the integrated value of NMR was 95% or more. Number average molecular weight by GPC (polystyrene conversion) = 1035, weight average molecular weight = 2019. The 5% weight loss temperature of the compound obtained by thermosetting the synthetic macromonomer was 369 ° C. From this 5% weight loss temperature, it can be seen that a three-dimensional network is formed and the heat resistance is excellent.

Example 4
To 10.0 g of the polyhydric alcohol decomposition product described in Example 1, 4.9 ml of methacrylic acid chloride, 8.9 ml of triethylamine and 50 ml of THF were added and reacted at room temperature for 3 hours. After completion of the reaction, it was washed with 1N NaOH aqueous solution, and further washed with water until the organic layer became neutral. The organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 12.97 g of a macromonomer.

When the ¹ HNMR spectrum (400 MHz, CDCl ₃ ) of the obtained synthetic macromonomer was measured, signals derived from a methacryloyl group were present in the vicinity of 1.9, 5.6, and 6.1 ppm. The methacrylation rate estimated from the integral value of NMR was 36%. Number average molecular weight by GPC (polystyrene conversion) = 425, weight average molecular weight = 849.

(Example 5)
To 10.0 g of the polyhydric alcohol decomposition product described in Example 1, 9 ml of methacrylic acid chloride and 9 ml of pyridine were added and reacted at room temperature all day and night. After completion of the reaction, it was washed with 1N NaOH aqueous solution, and further washed with water until the organic layer became neutral. The organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 6.8 g of product.

When the ¹ HNMR spectrum (400 MHz, CDCl ₃ ) of the obtained synthetic macromonomer was measured, signals derived from a methacryloyl group were present in the vicinity of 1.9, 5.9, and 6.1 ppm. Further, the methacrylation rate estimated from the integrated value of NMR was 53%. Number average molecular weight by GPC (polystyrene conversion) = 1141 and weight average molecular weight = 1998.

(Example 6)
To 100 g of PET pellets, 100 g of trimethylolethane (1.5 mol relative to the ester bond of PET) and 3.0 g of zinc acetate dihydrate as polyhydric alcohol and zinc acetate dihydrate were added and reacted at 190 ° C. in a nitrogen atmosphere for 26 hours. I let you. The decomposition product was dissolved in chloroform and taken out from the reaction vessel, and then concentrated under reduced pressure. Further, 210 g of a decomposed product was obtained by drying under reduced pressure at 60 ° C. for 6 hours. The acid value of the decomposition product was 0.08 mmol / g, the OH value (number of moles of OH groups) was 7.7 mol / kg, the number average molecular weight was 913, and the weight average molecular weight was 1320.

To 10.0 g of the decomposed product, 4.1 ml of acrylic acid chloride, 8.2 ml of triethylamine, and 50 ml of THF were added and reacted at room temperature for a whole day and night. After completion of the reaction, it was washed with 1N NaOH aqueous solution, and further washed with water until the organic layer became neutral. The organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give 5.82 g of product. When a ¹ H NMR spectrum (400 MHz, CDCl ₃ ) of the synthetic macromonomer was measured, a signal derived from a methacryloyl group was present in the vicinity of 1.9, 5.6, and 6.1 ppm. The acrylation rate estimated from the integral value of NMR was 52%. Number average molecular weight by GPC (polystyrene conversion) = 1068, weight average molecular weight = 1825.

(Example 7)
To 100 g of PET pellets, 100 g of pentaerythritol as polyhydric alcohol (1.5 mol with respect to the ester bond of PET) and 5.0 g of zinc acetate dihydrate are added and reacted in an autoclave at 190 ° C. for 37 hours in a nitrogen atmosphere. It was. The obtained decomposition product was dissolved in chloroform and taken out from the reaction vessel, and then concentrated under reduced pressure. Further, 195 g of a decomposed product was obtained by drying under reduced pressure at 60 ° C. for 6 hours. The acid value of the decomposition product was 0.19 mmol / g, the OH value (number of moles of OH groups) was 7.9 mol / kg, the number average molecular weight was 761, and the weight average molecular weight was 1092.

To 5.5 g of the decomposed product, 4.1 ml of acrylic acid chloride, 8.2 ml of triethylamine, and 50 ml of THF were added and reacted at room temperature all day and night. After completion of the reaction, it was washed with 1N NaOH aqueous solution, and further washed with water until the organic layer became neutral. The organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 5.2 g of product. When a 1H NMR spectrum (400 MHz, CDCl ₃ ) of the synthetic macromonomer was measured, a signal derived from a methacryloyl group was present in the vicinity of 1.9, 5.6, and 6.1 ppm. The acrylation rate estimated from the integral value of NMR was 52%. The number average molecular weight was 1004 and the weight average molecular weight was 1759 in GPC (polystyrene conversion).

(Example 8)
To 100 g of PET pellets, 50 g of trimethylolpropane, 39 g of neopentyl glycol, and 1.0 g of zinc acetate dihydrate were added and reacted in an autoclave at 190 ° C. in a nitrogen atmosphere for 13 hours. The decomposition product was dissolved in chloroform and taken out from the reaction vessel, and then concentrated under reduced pressure. Further, 178 g of a decomposed product was obtained by drying under reduced pressure at 60 ° C. for 6 hours. Acid value of decomposition product = 0.03 mmol / g, OH value (number of moles of OH group) = 8.1 mol / kg. Number average molecular weight by GPC (polystyrene conversion) = 835, weight average molecular weight = 1132.

Example 9
To 5.3 ml of isophorone diisocyanate, 3.6 ml of 2-hydroxyethyl methacrylate, 631 mg of dibutyltin dilaurate, 50 mg of hydroquinone and 30 ml of toluene were added and reacted at 50 to 60 ° C. for 1 hour. To the reaction mixture, 3.0 g of the decomposition product described in Example 1 was added, and the mixture was further stirred at 50 to 60 ° C. for 4 hours. The product was poured into excess hexane to produce a precipitate. The precipitate was dried under reduced pressure to obtain 8.7 g of product. As a result of measuring the infrared absorption spectrum of the product, no absorption derived from an isocyanate group was observed at 2200 to 2300 cm ⁻¹ . The number average molecular weight by GPC (polystyrene conversion) was 1052, and the weight average molecular weight was 1573.

(Example 10)
0.3 g of photoinitiator Irgacure 907 was added to 10 g of the macromonomer obtained in Examples 1 and 3 and applied on a glass plate. The obtained thin film was irradiated with UV (210 mJ) to obtain a cured product. When the pencil hardness of the cured film was measured in accordance with JIS K5400 8.4.2, it was 2H, and the macromonomer having methacryloyl group and acryloyl group obtained in Examples 1 and 3 was a very strong cured product. You can see that

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. 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.

Claims (9)

A polyester macromonomer having the structure of the following formula (1) or (2),

Here, m is an integer of 1 to 50, l and n are following relationships: 6 is an integer satisfying ≧ l + n ≧ 3, R 1 is a polyhydric alcohol having three or more hydroxyl groups remaining A polyester macromonomer, wherein X is an organic group or hydrogen having an acryloyl group or a methacryloyl group (except when all X are hydrogen). R ¹ is a residue of an alcohol selected from the group consisting of trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, ditrimethylolpropane, and their alkylene oxide adducts. The polyester macromonomer according to claim 1. X is a compound obtained by reacting 2 -methacryloyloxyethyl isocyanate (formula (5)) or an alcohol having an acryloyl group or a methacryloyl group with a diisocyanate compound (formula (6)) :

(In Formula (6), Y is a residue except the isocyanate group of diisocyanate, and Z is the following formulas (7) to (9):

This is an alcohol used for reaction with diisocyanate, and shows the residue of hydroxyl group (—OH) excluding H)
Polyester macromonomer according to claim 1 or 2, characterized in that Polyethylene terephthalate, and decomposing at a polyhydric alcohol having a hydroxyl group three or more,
A step of binding an acryloyl group or a methacryloyl group to a molecular terminal of the decomposition product decomposed in the step;
The manufacturing method of the polyester macromonomer containing this . The polyethylene terephthalate, the step of decomposing by the polyhydric alcohol having a hydroxyl group three or more, with a polyhydric alcohol having a hydroxyl group three or more, characterized by using a divalent alcohol together, claim 4. A method for producing a polyester macromonomer according to 4. The polyhydric alcohol having three or more hydroxyl groups is selected from the group consisting of trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, ditrimethylolpropane, and alkylene oxide adducts thereof. Item 6. A method for producing a polyester macromonomer according to Item 4 or 5. Polyethylene terephthalate, and decomposing at a polyhydric alcohol having a hydroxyl group three or more,
A step of reacting methacrylic acid or acrylic acid with the decomposition product decomposed in the above step to bond a methacryloyl group or an acryloyl group to a molecular end;
The manufacturing method of the polyester macromonomer containing this . The polybutyl terephthalate, and decomposing at a polyhydric alcohol having a hydroxyl group three or more,
Reacting the decomposition product decomposed in the step with methacrylic acid chloride or acrylic acid chloride to bond a methacryloyl group or an acryloyl group to a molecular terminal;
The manufacturing method of the polyester macromonomer containing this . Polyethylene terephthalate, and decomposing at a polyhydric alcohol having a hydroxyl group three or more,
Compound obtained by reaction of 2 -methacryloyloxyethyl isocyanate (formula (5)) or alcohol having acryloyl group or methacryloyl group with a diisocyanate compound into the decomposed product decomposed in the step (formula (6)) :

(In Formula (6), Y is a residue except the isocyanate group of diisocyanate, and Z is the following formulas (7) to (9):

This is an alcohol used for reaction with diisocyanate, and shows the residue of hydroxyl group (—OH) excluding H)
And bonding a methacryloyl group or an acryloyl group to the molecular end;
The manufacturing method of the polyester macromonomer containing this .