WO2012132824A1

WO2012132824A1 - Method for producing polyester polyol, method for producing modified polyester, polyester polyol and modified polyester

Info

Publication number: WO2012132824A1
Application number: PCT/JP2012/056019
Authority: WO
Inventors: 大地岡本; 有馬　聖夫
Original assignee: 太陽インキ製造株式会社
Priority date: 2011-03-31
Filing date: 2012-03-08
Publication date: 2012-10-04
Also published as: KR20130117877A; KR101545071B1; CN103459462A; JP5670552B2; TWI455957B; CN103459462B; JPWO2012132824A1; TWI496812B; TW201307435A; TW201422668A

Abstract

Provided is a method by which a polyester polyol can be produced by depolymerizing a starting material polyester within a short time without using a tin-based metal catalyst. A method for producing a polyester polyol, which is characterized by comprising a step wherein a starting material polyester is depolymerized by heating a mixture that contains, as essential ingredients, the starting material polyester, a polyol component, and a non-tin-based metal catalyst or a non-metal basic catalyst. It is preferable that the non-tin-based metal catalyst is a compound that is selected from the group consisting of zinc compounds, manganese compounds, lithium compounds and calcium compounds.

Description

Polyester polyol and method for producing polyester modified product, polyester polyol and polyester modified product

The present invention relates to a method for producing a polyester polyol and a polyester-modified product using polyester as a raw material, and a polyester polyol and a polyester-modified product, and more specifically, a method for producing a polyester polyol that does not use a tin-based metal catalyst and the production method. The present invention relates to a method for producing a polyester-modified product in which a polyester polyol is modified.

Polyester typified by polyethylene terephthalate (PET) is used in various applications such as molded products, films, and fibers. Among them, the amount of PET bottles has been rapidly increasing in recent years because it is lightweight, excellent in transparency and gas barrier properties, and has high strength.

On the other hand, various resins are derived by depolymerizing a polyester with a polyhydric alcohol to produce a polyester polyol, or by modifying the polyester polyol.

For example, Patent Document 1 discloses the production of a coating alkyd resin using a depolymerization reaction with glycols, and Patent Documents 2 and 3 disclose a method for producing a coating polyester resin using recycled polyester. Patent Document 4 discloses that recycled polyester is used as a raw material for a photocurable urethane resin. All of the resins described in the above patent documents are intended for use in coating compositions.

Conventionally, a polyester depolymerization reaction is performed by charging a raw material polyester, a polyhydric alcohol, and a depolymerization catalyst into a reactor and heating them. At this time, a metal catalyst, particularly a tin-based catalyst is used as a depolymerization catalyst.

Japanese Patent No. 3310661 Japanese Patent No. 3443409 Japanese Patent No. 3256537 JP 2004-307779 A

However, some tin compounds, particularly organic tin compounds, have been reported to be toxic to living organisms, and their effects on the environment have been pointed out. Therefore, the development of a catalyst that can replace the tin-based metal catalyst in the depolymerization reaction of polyester has been demanded.

Therefore, an object of the present invention is to provide a method capable of producing a polyester polyol by depolymerizing a raw material polyester in a short time without using a tin-based metal catalyst.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a non-tin-based metal catalyst or a non-metallic basic catalyst, and have completed the present invention. .

That is, the method for producing a polyester polyol of the present invention comprises a step of depolymerizing a raw material polyester by heating a mixture containing the raw material polyester, a polyol component, and a non-tin-based metal catalyst or a non-metallic basic catalyst as essential components. It is characterized by comprising.

In the method for producing a polyester polyol of the present invention, the non-tin metal catalyst is preferably a compound selected from the group consisting of a zinc compound, a manganese compound, a lithium compound, and a calcium compound, and includes a naphthenic acid metal complex and an acetylacetone metal. A compound selected from the group consisting of a complex and a metal octylate soap is more preferable.

Furthermore, in the method for producing a polyester polyol of the present invention, the non-tin metal catalyst is zinc naphthenate, zinc acetylacetone, zinc octylate, calcium naphthenate, calcium acetylacetone, calcium octylate, lithium naphthenate, lithium acetylacetone, A compound selected from the group consisting of lithium octylate, lithium acetate, manganese naphthenate, manganese acetylacetone and manganese octylate is preferred.

In the method for producing a polyester polyol of the present invention, it is preferable that the nonmetallic basic catalyst is a heterocyclic compound having an amidine structure.

In the method for producing a polyester polyol of the present invention, the nonmetallic basic catalyst is preferably at least one selected from the group consisting of diazabicycloundecene, diazabicyclononene and derivatives thereof.

In the method for producing a polyester polyol according to the present invention, the polyol component preferably contains a trifunctional or higher functional polyol.

In the method for producing a polyester polyol of the present invention, it is preferable that the raw material polyester is a regenerated polyester.

Further, in the method for producing a polyester polyol of the present invention, it is preferable to depolymerize the raw material polyester by further adding water to a mixture containing the raw material polyester, the polyol component, and the non-tin metal catalyst as essential components.

In the method for producing a polyester polyol of the present invention, the depolymerization is preferably performed at 200 to 300 ° C.

Moreover, in the manufacturing method of the polyester polyol of this invention, it is preferable that the mixture of the compound represented by following General formula (1) is obtained.

(Wherein R ¹ represents a group obtained by removing an OH group from a (l + m) -valent polyhydric alcohol, and R ² represents an alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted carbon atom having 6 to 6 carbon atoms. 20 represents an arylene group, R ³ represents a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, l is an integer of 0 to 10, m is an integer of 1 to 10, and n is 1 Represents an integer of ~ 10)

The polyester polyol of the present invention is obtained by any one of the above-described methods for producing a polyester polyol.

The method for producing a polyester-modified product of the present invention is characterized in that a polyester polyol obtained by the above-described polyester polyol production method is reacted with a compound having a group capable of reacting with a hydroxyl group and an ethylenically unsaturated group. It is.

The polyester-modified product of the present invention is obtained by the above-described method for producing a polyester-modified product.

According to the method for producing a polyester polyol of the present invention, it is possible to easily convert a raw material polyester into a polyester polyol that can be dissolved in an organic solvent and can be chemically modified without using a tin-based metal catalyst. Thereby, the polyester polyol with which content of tin was reduced rather than what was manufactured by the method using the existing tin type catalyst can be obtained. In addition, when a nonmetallic basic catalyst is used, it is possible to avoid deterioration of electrical insulation due to the influence of the residual metal catalyst of the obtained product.
Furthermore, according to the present invention, a polyester-modified product imparted with photosensitivity can be produced at a relatively low cost with high production efficiency.

The basic characteristic of the method for producing a polyester polyol of the present invention is that a non-tin metal catalyst or a non-metal basic catalyst is used when depolymerizing the raw material polyester with a polyol component.

[Non-tin metal catalyst]
The tin-based metal catalyst used in the method of the present invention is preferably a zinc compound, a manganese compound, a lithium compound, or a calcium compound, and more preferably a naphthenic acid metal complex, an acetylacetone metal complex, or an octylic acid metal soap. Among these, zinc naphthenate, zinc acetylacetone, zinc octylate, calcium naphthenate, calcium acetylacetone, calcium octylate, lithium naphthenate, lithium acetylacetone, lithium octylate, lithium acetate, manganese naphthenate, manganese acetylacetone and manganese octylate are particularly preferred. preferable.

The amount of the above-mentioned non-tin metal catalyst used is preferably 0.005 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the raw material polyester and the polyol component. is there.

[Non-metallic basic catalyst]
As the nonmetallic basic catalyst used in the method of the present invention, a cyclic nitrogen-containing compound is preferable, and a heterocyclic compound having an amidine structure is more preferable. Among them, diazabicycloundecene (1,8-diazabicyclo [5.4.0] undecene-7, hereinafter also referred to as “DBU”), diazabicyclononene (1,5-diazabicyclo [4.3.0] nonene- 5, hereinafter also referred to as “DBN”) and their derivatives are particularly preferred. DBU and DBN are both strong organic bases, have similar structures, and are compounds used as catalysts for similar reactions such as urethanization and Wittig reactions.

Examples of diazabicycloundecene (DBU), diazabicyclononene (DBN) and derivatives thereof include DBU, DBN, DBU carbonate, DBU carboxylate, DBU phenol salt, DBU thiol salt, DBN carbonate, Examples thereof include DBN carboxylate, DBN phenol salt, and DBN thiol salt.

Commercially available products of DBU, DBN and their derivatives include, for example, U-CAT SA1, U-CAT SA102, U-CAT SA506, U-CAT SA603, U-CAT SA810, U-CAT SA831, U-CAT SA841, U-CAT SA851, U-CAT 881, U-CAT 5002 (all are trade names, manufactured by Sun Apro).

The amount of the nonmetallic basic catalyst used is preferably 0.005 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the raw material polyester and polyol component. It is.

[Raw material polyester]
The raw material polyester used in the method of the present invention is not particularly limited as long as it is a known polyester. The method of the present invention can be applied to any polyester as long as it can be melted by heating.

Moreover, as raw material polyester, what has a repeating unit represented by following General formula (2) is preferable.

(Wherein R ⁴ represents an alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and R ⁵ represents a substituted or unsubstituted carbon atom having 6 to 20 carbon atoms. An arylene group, O represents an integer of 1 or more.)

Examples of the alkylene group having 1 to 10 carbon atoms that R ⁴ can take in the general formula (2) include a methylene group, 1,2-ethylene group, 1,3-propylene group, 1,4-butylene group, 1,2 -Butylene group, 1,5-pentylene group and the like.

Examples of the arylene group having 6 to 20 carbon atoms that R ⁴ can take in the general formula (2) include a 1,4-phenylene group and a 2,6-naphthylene group. These arylene groups may be substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

Examples of the arylene group having 6 to 20 carbon atoms that R ⁵ can take in the general formula (2) include the same groups as those exemplified for R ⁴ above.

Specific examples of preferable raw material polyester include polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycondensate of ethylene terephthalate and parahydroxybenzoic acid, 4,4- Examples thereof include liquid crystal polymers such as polycondensates of dihydroxybiphenol, terephthalic acid and parahydroxybenzoic acid, and polycondensates of 2,6-hydroxynaphthoic acid and parahydroxybenzoic acid. Among these, polyethylene terephthalate is particularly preferable.

Also, from the viewpoint of environmental protection, recycled PET and recycled PET collected from waste such as PET bottle waste are more preferable as the raw material polyester. The collected PET can be crushed and washed, and the recycled PET can be obtained from the market after being washed and pelletized.

[Polyol component]
As the polyol component, a bifunctional polyol or a trifunctional or higher functional polyol can be used without particular limitation. The said polyol component may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of the bifunctional polyol include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, 1,3-butanediol, Neopentyl glycol, spiro glycol, dioxane glycol, adamantanediol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methylpropanediol 1, Bifunctional phenols such as 3,3-methylpentanediol 1,5, hexamethylene glycol, octylene glycol, 9-nonanediol, 2,4-diethyl-1,5-pentanediol, bisphenol A Ethylene oxide modified compound of bisphenol, propylene oxide modified compound of bifunctional phenol such as bisphenol A, ethylene oxide of bisphenol A, propylene oxide copolymer modified compound, polyether polyol of ethylene oxide and propylene oxide, polycarbonate diol , Polyether diol, polyester diol, polycaprolactone diol, 1,4-polyisoprene diol, 1,4-polybutadiene diol, 1,2-polybutadiene diol, 1,4- or 1,2-polybutadiene diol hydrogenated product, etc. Examples include hydroxyl group-terminated polyalkanediene diols.

Examples of commercially available products of the above polycaprolactone diol include, for example, Plaxel 205, Plaxel L205AL, Plaxel 205U, Plaxel 208, Plaxel L208AL, Plaxel 210, Plaxel 210N, Plaxel 212, Plaxel L212AL, Plaxel 220, Plaxel 220N, Plaxel 220NP1, Plaxel L220AL, Plaxel 230, Plaxel 240, Plaxel 220EB, Plaxel 220EC (all are manufactured by Daicel Chemical Industries, Ltd.).

Examples of commercially available products of the hydroxyl group-terminated polyalkanediene diol include, for example, Epol (registered trademark; hydrogenated polyisoprene diol, molecular weight 1,860, average polymerization degree 26, manufactured by Idemitsu Kosan Co., Ltd.), PIP (poly Isoprene diol, molecular weight 2,200, average polymerization degree 34, manufactured by Idemitsu Kosan Co., Ltd.), polytail H (hydrogenated polybutadiene diol, molecular weight 2,200, average polymerization degree 39, manufactured by Mitsubishi Chemical Corporation), R-45HT (Polybutanediol, molecular weight 2,270, average polymerization degree 42, manufactured by Idemitsu Kosan Co., Ltd.).

Examples of the tri- or higher functional polyol include glycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, adamantanetriol, polycaprolactone triol, and the like. Examples of the trifunctional or higher functional polyol having an aromatic ring include ethylene oxide and propylene oxide modified products of a trifunctional or higher functional phenol compound. The trifunctional or higher functional polyol having a heterocyclic ring is manufactured by Shikoku Kasei Kogyo Co., Ltd. Sake etc. are mentioned.

Examples of commercially available products of the above polycaprolactone triol include, for example, Plaxel 303, Plaxel 305, Plaxel 308, Plaxel 312, Plaxel L312AL, Plaxel 320ML, Plaxel L320AL; Can be mentioned.

As the polyol component, a plant-derived alcohol component (plant-derived polyol) may be used. As the plant-derived alcohol component, a castor oil alcohol component is preferable. As commercial products, for example, URIC H-30, URIC H-31, URIC H-52, URIC H-56, URIC H-57, URIC H-62, URIC H-73X, URIC H-92, URIC H-420 , URIC H-854, URIC Y-202, URIC Y-403, URIC Y-406, URIC Y-563, URIC AC-005, URIC AC-006, URIC PH-5001, URIC PH-5002, URIC PH-6000 , URIC F-15, URIC F-25, URIC F-29, URIC F-40, URIC SE-2010, URIC SE-3510, URIC SE-2606, URIC SE-3506, URIC SE-2003, POLYCAS OR # 10, POLYCASTOR # 30, URIC SE-2003 (all manufactured by Itoh Oil Co., Ltd.).

The polyol component used in the present invention preferably contains a tri- or higher functional polyol, particularly preferably trimethylolpropane.

The amount of the polyol component used is preferably 0.5 mol to 7.0 mol of the hydroxyl group of the polyol component, and 1.0 mol to 5.0 mol per mol of the ester bond of the raw material polyester. Is more preferable.

[Reaction conditions]
In the method of the present invention, the raw material polyester is depolymerized by putting a mixture containing the above-described components into a reactor and heating the mixture. A conventionally known method can be used as the heating method. The above components may be mixed and then heated as a mixture, or each component may be sequentially introduced into the reactor while heating. The heating temperature is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. Moreover, when using an organic solvent, although a conventionally well-known solvent can be used, it is preferable to react without using an organic solvent from a viewpoint of the influence on an environment.

In the method of the present invention, it is preferable to depolymerize the raw material polyester by further adding water to a mixture containing the raw material polyester, polyol component, and non-tin metal catalyst as essential components. By adding water, the raw material polyester and polyol become slurry, which is preferable because the stirring efficiency is improved.

In the manufacturing method of the polyester polyol of this invention, it is preferable that the mixture of the compound represented by following General formula (1) is obtained.

R ¹ in the general formula (1) represents a group obtained by removing an OH group from a (l + m) -valent polyhydric alcohol, and the polyhydric alcohol is exemplified by the above bifunctional polyol, trifunctional or higher polyol. Things can be mentioned. In addition, examples of the alkylene group, arylene group, and R ³ that R ² can take include the same groups as those described above.

The compound represented by the general formula (1) is a suitable raw material for the method for producing a polyester-modified product of the present invention.

[Method for producing polyester-modified product]
The method for producing a polyester-modified product of the present invention is characterized in that a polyester polyol obtained by the above-described polyester polyol production method is reacted with a compound having a group capable of reacting with a hydroxyl group and an ethylenically unsaturated group. It is. This modification can impart photosensitivity to the polyester. The modification reaction of the polyester polyol is the same as the conventionally well-known esterification reaction. In the presence or absence of an organic solvent, an acid catalyst or a polymerization inhibitor is usually added, and preferably at 80 ° C. to 130 ° C. Under a temperature range, it is performed in the range of 2 hours to 10 hours. The synthesis can be carried out at normal pressure or under pressure, and the reaction temperature can be lowered under pressure. Even if unreacted hydroxyl groups derived from the depolymerized product are present in the obtained polyester-modified product, there is no problem in properties.

[Compound having a group capable of reacting with a hydroxyl group and an ethylenically unsaturated group]
The compound used for modification | denaturation of the polyester polyol obtained by said manufacturing method is a compound which has the group and ethylenically unsaturated group which can react with a hydroxyl group in 1 molecule. It is preferable to have one group capable of reacting with a hydroxyl group in the molecule and one or more ethylenically unsaturated groups in the molecule. Examples of the group capable of reacting with a hydroxyl group include a cyclic ether group such as a carboxyl group, an isocyanate group, and an epoxy group, and a hydroxyl group.
Any compound having a group capable of reacting with a hydroxyl group and an ethylenically unsaturated group in one molecule can be used for modification of the polyester polyol obtained by the above production method. From the standpoint of reactivity, a compound having an acryloyl group or a methacryloyl group is particularly preferable.

Compounds having one carboxyl group and one or more ethylenically unsaturated groups include acrylic acid, dimer of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, crotonic acid, α -Cyanocinnamic acid, cinnamic acid, (meth) acrylic acid caprolactone adduct, and half ester compounds of saturated or unsaturated dibasic acid anhydrides and (meth) acrylates having one hydroxyl group in one molecule, etc. Can be mentioned. Examples of (meth) acrylates having a hydroxyl group for producing a half ester compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, Examples include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and phenylglycidyl (meth) acrylate. Examples of the dibasic acid anhydride for producing the half ester compound include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenetetrahydro And phthalic anhydride. These compounds may be used individually by 1 type, and may be used in combination of 2 or more types.
In the present specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

Examples of the compound having one isocyanate group and one or more ethylenically unsaturated groups in one molecule include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxyethoxyethyl isocyanate, and bis (acryloxymethyl) ethyl. Examples thereof include isocyanates and modified products thereof. Further, a half urethane compound of a compound having one hydroxyl group and one or more ethylenically unsaturated groups in one molecule and a diisocyanate such as isophorone diisocyanate, toluylene diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate is also used. be able to. These compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

Commercially available compounds having one isocyanate group and one or more ethylenically unsaturated groups in one molecule include “Karenz MOI” (methacryloyloxyethyl isocyanate), “Karenz AOI” (acryloyloxyethoxyethyl isocyanate). ), “Karenz MOI-EG” (methacryloyloxyethoxyethyl isocyanate), “Karenz MOI IBM” (is an isocyanate block of Karenz MOI), “Karenz MOI-BP” (isocyanate block of Karenz MOI), “Karenz BEI” (1,1-bis (acryloxymethyl) ethyl isocyanate) is commercially available from Showa Denko K.K. These trade names are registered trademarks.

Compounds having one cyclic ether group and one or more ethylenically unsaturated groups in one molecule include 2-hydroxyethyl (meth) acrylate glycidyl ether, 2-hydroxypropyl (meth) acrylate glycidyl ether, 3-hydroxy Propyl (meth) acrylate glycidyl ether, 2-hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxypentyl (meth) acrylate glycidyl ether, 6-hydroxyhexyl (meth) acrylate glycidyl Examples include ether or glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl acrylate, and the like. These compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

The compound having a hydroxyl group and an ethylenically unsaturated group is not particularly limited as long as it is a compound having one hydroxyl group and one or more ethylenically unsaturated groups in one molecule. Specific examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta ( And hydroxyalkyl (meth) acrylates such as (meth) acrylate. These compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

The polyester-modified product produced by the production method of the present invention is photosensitive by reacting the polyester polyol with a compound having a group capable of reacting with a hydroxyl group and one or more ethylenically unsaturated groups to chemically modify the polyester polyol. Therefore, it is useful as a photosensitive component of a photocurable resin composition or a photocurable thermosetting resin composition. For example, oxime ester photopolymerization initiator, α-aminoacetophenone photopolymerization initiator, acylphosphine oxide photopolymerization initiator, benzoin compound, acetophenone compound, anthraquinone compound, thioxanthone compound, ketal compound , A benzophenone compound, a xanthone compound, a tertiary amine compound, and other conventionally known and commonly used photopolymerization initiators, photoinitiator assistants, and sensitizers can be blended to form a photocurable resin composition.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following, “parts” and “%” are based on mass unless otherwise specified.

[Example 1]
In a 500 ml four-necked round bottom separable flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, 192 parts of PET flakes (Mitsubishi Chemical Corporation: Novavex (trade name)), 67 parts of trimethylolpropane, zinc octylate After charging 52 parts and making the inside of the flask a nitrogen atmosphere, the flask was immersed in an oil bath heated to 220 ° C., and the reaction was continued until the inside of the flask became transparent to obtain a polyester oligomer.

[Example 2]
A polyester oligomer was obtained using the same amount of zinc acetylacetone instead of the zinc octylate of Example 1.

[Example 3]
A polyester oligomer was obtained using the same amount of calcium acetylacetone instead of the zinc octylate of Example 1.

[Example 4]
A polyester oligomer was obtained using the same amount of lithium acetylacetone instead of the zinc octylate of Example 1.

[Example 5]
A polyester oligomer was obtained using the same amount of zinc naphthenate in place of the zinc octylate of Example 1.

[Example 6]
A polyester oligomer was obtained using the same amount of calcium naphthenate in place of the zinc octylate of Example 1.

[Example 7]
A polyester oligomer was obtained using the same amount of calcium octylate in place of the zinc octylate of Example 1.

[Example 8]
A polyester oligomer was obtained using the same amount of lithium naphthenate in place of the zinc octylate of Example 1.

[Example 9]
A polyester oligomer was obtained using the same amount of lithium octylate instead of the zinc octylate of Example 1.

[Example 10]
A polyester oligomer was obtained using the same amount of manganese naphthenate in place of the zinc octylate of Example 1.

[Example 11]
A polyester oligomer was obtained using the same amount of acetylacetone manganese in place of the zinc octylate of Example 1.

[Example 12]
A polyester oligomer was obtained using the same amount of manganese octylate instead of the zinc octylate of Example 1.

[Example 13]
A polyester oligomer was obtained using the same amount of lithium acetate in place of the zinc octylate of Example 1.

[Example 14]
225 parts of the polyester oligomer obtained in Example 2, 187 parts of acrylic acid, 1.87 parts of paratoluenesulfonic acid, paramethoxy, in a 500 ml four-necked round bottom separable flask equipped with a stirrer, a nitrogen inlet tube, and a condenser tube After adding 1.50 parts of phenol and stirring to dissolve it uniformly, it was immersed in an oil bath heated to 118 ° C., and the reaction was continued for 16.5 hours. After completion of the reaction, the acid value of the reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask for neutralization. Then, brine (20 wt%) was added and stirred. Thereafter, the solution was transferred to a separatory funnel, 1.4 times as much methyl isobutyl ketone as the reaction solution was added, and the aqueous phase was discarded. The oil phase was washed again with brine (5 wt%) and the aqueous phase was discarded. Thereafter, the oil phase was reprecipitated in hexane, dissolved in methyl ethyl ketone, and impurities were removed by suction filtration. After reprecipitation of the filtrate with tap water, the supernatant is discarded, the reprecipitate is further stirred and washed with tap water, and finally diluted with carbitol acetate to a solid content of 70%. Obtained.

[Comparative Example 1]
A polyester oligomer was obtained using the same amount of dibutyltin oxide instead of the zinc octylate of Example 1.

[Comparative Example 2]
A polyester oligomer was obtained using the same amount of dibutyltin dilaurate instead of the zinc octylate of Example 1.

<Depolymerization time>
The time required for depolymerization in Examples 1 to 13 and Comparative Examples 1 and 2 is shown in Table 1 below. Even if the reaction is carried out for 10 hours or longer, “x” is used for those in which raw materials remain.

<Tin free>
The concentration (ppm) of tin contained in the depolymerized products of Examples 1 to 13 and Comparative Examples 1 and 2 was measured. The description method of evaluation is as follows.
○: Tin concentration is less than 10 ppm Δ: Tin concentration is 10 to 500 ppm
×: Tin concentration exceeds 500 ppm

<Molecular weight>
The molecular weights of the depolymerized products of Examples 1 to 13 and Comparative Example 1 were measured by GPC (gel permeation chromatography). Measurement conditions were as follows. Shodex GPC KF-806L × 3 manufactured by Showa Denko Co., Ltd. was used for the column, and the column temperature was 40 ° C. Standard polystyrene was used as a reference material, and tetrahydrofuran was used as an eluent at a flow rate of 1 mL / min. The measurement results are shown in Table 1 below.

<Solvent solubility test>
The solvent solubility of the depolymerized products of Examples 1 to 13 and Comparative Examples 1 and 2 was confirmed.
As a confirmation method, 50 parts of various solvents were added to 50 parts of the depolymerized product and stirred to prepare a 50 wt% solution of the depolymerized product, and the transparency of the solution was evaluated. The description method of the evaluation is completely transparent as follows:
Slightly cloudy: △
There is turbidity: ×

From the above, in the solvent solubility, Comparative Example 2 is completely transparent to each solvent as in Comparative Example 1 which is not tin-free, as compared to Comparative Example 2 which is turbid with respect to each solvent. It was confirmed that there was.

[Reference Example 1]
100 parts of the acrylate resin varnish obtained in Example 14 was mixed with 5 parts of a photopolymerization initiator (Irgacure 184; manufactured by BASF Japan Ltd.), and then applied to a glass plate with a thickness of 20 μm using an applicator. did. After coating, the film was dried for 20 minutes in a hot air circulation drying oven at 80 ° C., and exposed using an exposure apparatus equipped with a high-pressure mercury lamp at an exposure amount of 1 J / cm ² to obtain an evaluation coating film.

<Rubbing test>
When the evaluation coating film was rubbed 50 times with a waste cloth containing acetone, it was confirmed that there was no surface dissolution and the film was sufficiently cured.

<Pencil hardness test>
A pencil of B to 9H sharpened so that the tip of the pencil core was flattened against the evaluation coating film was pressed against the coating film at an angle of 45 ° C. with a load of 1 kg. As a result of scratching the coating film by about 1 cm with this load applied and measuring the hardness of the pencil on which the coating film was not peeled off, it was 6H.

<Heat resistance test>
The said evaluation coating film was put into a 200 degreeC hot-air circulation type drying furnace, and was heated for 3 minutes. The sample was taken out after heating and visually observed for melting to conduct a heat resistance test. As a result, it was confirmed that the sample had heat resistance at 200 ° C. for 3 minutes.

As described above, according to the method of the present invention, by using a non-tin metal catalyst, it is possible to easily convert the polyester into a polyester polyol that can be dissolved in an organic solvent and can be variously modified.

[Example 15]
A 500 ml four-necked round bottom separable flask equipped with a stirrer, a nitrogen inlet tube, and a condenser tube was charged with 192 parts of recycled PET flakes having an IV value (intrinsic viscosity value) of 0.6 to 0.7, 67 parts of trimethylolpropane, DBU0 .52 parts was charged and the flask was filled with a nitrogen atmosphere, and then immersed in an oil bath heated to 220 ° C., and the reaction was continued until the inside of the flask became transparent to obtain a polyester oligomer.

[Example 16]
192 parts of PET flakes (Mitsubishi Chemical Corporation: Novavex (trade name)), 67 parts of trimethylolpropane, 0.52 parts of DBU in a 500 ml four-necked round bottom separable flask equipped with a stirrer, nitrogen introduction tube, and cooling tube After making the inside of the flask a nitrogen atmosphere, it was immersed in an oil bath heated to 220 ° C., and the reaction was continued until the inside of the flask became transparent to obtain a polyester oligomer.

[Example 17]
192 parts of recycled PET flakes having an IV value of 0.6 to 0.7, 67 parts of trimethylolpropane, 0.52 parts of DBU, in a 500 ml four-necked round bottom separable flask equipped with a stirrer, nitrogen introduction tube, and cooling tube, After charging 30 parts of water and setting the inside of the flask to a nitrogen atmosphere, the flask was immersed in an oil bath heated to 180 ° C., the temperature of the oil bath was raised to 220 ° C. while gradually removing water, and the flask became transparent. The reaction was continued until a polyester oligomer was obtained.

[Example 18]
In a 500 ml four-necked round bottom separable flask equipped with a stirrer, nitrogen inlet tube, and cooling tube, 192 parts of recycled PET flakes having an IV value of 0.6 to 0.7, 67 parts of trimethylolpropane, 68 parts of pentaerythritol, DBU0 .52 parts and 30 parts of water were charged, the inside of the flask was made into a nitrogen atmosphere, then immersed in an oil bath heated to 180 ° C., and the oil bath was heated to 220 ° C. while gradually removing water, and the flask The reaction was continued until the inside became transparent to obtain a polyester oligomer.

[Example 19]
A polyester oligomer was obtained using the same amount of DBN in place of the DBU of Example 17.

[Example 20]
225 parts of the polyester oligomer obtained in Example 15, 187 parts of acrylic acid, 1.87 parts of paratoluenesulfonic acid, paramethoxy, in a 500 ml four-necked round bottom separable flask equipped with a stirrer, a nitrogen inlet tube, and a condenser tube After adding 1.50 parts of phenol and stirring to dissolve it uniformly, it was immersed in an oil bath heated to 118 ° C., and the reaction was continued for 16.5 hours. After completion of the reaction, the acid value of the reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask for neutralization. Then, brine (20 wt%) was added and stirred. Thereafter, the solution was transferred to a separatory funnel, 1.4 times as much methyl isobutyl ketone as the reaction solution was added, and the aqueous phase was discarded. The oil phase was washed again with brine (5 wt%) and the aqueous phase was discarded. Thereafter, the oil phase was reprecipitated in hexane, dissolved in methyl ethyl ketone, and impurities were removed by suction filtration. After reprecipitation of the filtrate with tap water, the supernatant is discarded, the reprecipitate is further stirred and washed with tap water, and finally diluted with carbitol acetate to a solid content of 70%. Obtained.

[Comparative Example 3]
A polyester oligomer was obtained using the same amount of dibutyltin oxide instead of the DBU of Example 17.

[Comparative Example 4]
A polyester oligomer was obtained using the same amount of dibutyltin dilaurate instead of the DBU of Example 17.

[Comparative Example 5]
A 500 ml four-necked round bottom separable flask equipped with a stirrer, nitrogen introducing tube, and cooling tube was charged with 192 parts of recycled PET flakes having an IV value of 0.6 to 0.7, 67 parts of trimethylolpropane, and 30 parts of water. After making the inside of a flask a nitrogen atmosphere, it was immersed in an oil bath heated to 180 ° C., and the reaction was carried out by heating the oil bath to 220 ° C. while gradually removing water.

<Depolymerization time>
The time required for depolymerization in Examples 15 to 19 and Comparative Examples 3 to 5 is shown in Table 2 below. Even if the reaction is carried out for 10 hours or longer, “x” is used for those in which the raw material remains.

<Metal free>
The concentration (ppm) of metal contained in the depolymerized products of Examples 15 to 19 and Comparative Examples 3 to 5 was measured. The description method of evaluation is as follows.
○: Metal concentration is less than 10 ppm △: Metal concentration is 10 to 500 ppm
×: Metal concentration exceeds 500 ppm

<Molecular weight>
The molecular weights of the depolymerized products of Examples 15 to 19 and Comparative Examples 3 to 5 were measured by GPC (gel permeation chromatography). Measurement conditions were as follows. Shodex GPC KF-806L × 3 manufactured by Showa Denko Co., Ltd. was used for the column, and the column temperature was 40 ° C. Standard polystyrene was used as a reference material, and tetrahydrofuran was used as an eluent at a flow rate of 1 mL / min. The measurement results are shown in Table 2.

<Solvent solubility test>
The solvent solubility of the depolymerized products of Examples 15 to 19 and Comparative Examples 3 to 5 was confirmed.
As a confirmation method, 50 parts of various solvents were added to 50 parts of the depolymerized product and stirred to prepare a 50 wt% solution of the depolymerized product, and the transparency of the solution was evaluated. The description method of evaluation is as follows.
Fully transparent: ○
Slightly cloudy: △
There is turbidity: ×

From the above, in the solvent solubility, the comparative examples 4 and 5 are completely turbid with respect to each solvent as in the comparative example 3 which is not metal-free compared to the turbidity with respect to each solvent. It was confirmed to be transparent.

[Reference Example 2]
100 parts of the acrylate resin varnish obtained in Example 20 was mixed with 5 parts of a photopolymerization initiator (Irgacure 184; manufactured by BASF Japan Ltd.), and then applied to a glass plate with a film thickness of 20 μm using an applicator. did. After coating, the film was dried for 20 minutes in a hot air circulation drying oven at 80 ° C., and exposed using an exposure apparatus equipped with a high-pressure mercury lamp at an exposure amount of 1 J / cm ² to obtain an evaluation coating film.

As described above, according to the method of the present invention, by using a non-metal basic catalyst, it is possible to easily convert the polyester into a polyester polyol that can be dissolved in an organic solvent and that can be chemically modified.

Claims

A method for producing a polyester polyol, comprising a step of depolymerizing a raw material polyester by heating a raw material polyester, a polyol component, and a mixture containing a non-tin-based metal catalyst or a non-metallic basic catalyst as essential components.
The method for producing a polyester polyol according to claim 1, wherein the non-tin-based metal catalyst is a compound selected from the group consisting of a zinc compound, a manganese compound, a lithium compound and a calcium compound.
The method for producing a polyester polyol according to claim 1 or 2, wherein the non-tin metal catalyst is a compound selected from the group consisting of a naphthenic acid metal complex, an acetylacetone metal complex, and an octylic acid metal soap.
The non-tin metal catalyst is zinc naphthenate, zinc acetylacetone, zinc octylate, calcium naphthenate, calcium acetylacetone, calcium octylate, lithium naphthenate, lithium acetylacetone, lithium octylate, lithium acetate, manganese naphthenate, manganese acetylacetone manganese The method for producing a polyester polyol according to any one of claims 1 to 3, wherein the polyester polyol is a compound selected from the group consisting of manganese and octylate.
The method for producing a polyester polyol according to claim 1, wherein the non-metallic basic catalyst is a heterocyclic compound having an amidine structure.
The method for producing a polyester polyol according to claim 5, wherein the non-metallic basic catalyst is at least one selected from the group consisting of diazabicycloundecene, diazabicyclononene and derivatives thereof.
The method for producing a polyester polyol according to any one of claims 1 to 6, wherein the polyol component contains a trifunctional or higher functional polyol.
The method for producing a polyester polyol according to any one of claims 1 to 7, wherein the raw material polyester is a recycled polyester.
The method for producing a polyester polyol according to any one of claims 1 to 8, wherein water is further added to a mixture containing the raw material polyester, the polyol component, and the non-tin metal catalyst as essential components to depolymerize the raw material polyester.
The method for producing a polyester polyol according to any one of claims 1 to 9, wherein the depolymerization is performed at 150 to 350 ° C.
The method for producing a polyester polyol according to any one of claims 1 to 10, wherein a mixture of compounds represented by the following general formula (1) is obtained.

(Wherein R 1 represents a group obtained by removing an OH group from a (l + m) -valent polyhydric alcohol, and R 2 represents an alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted carbon atom having 6 to 6 carbon atoms. 20 represents an arylene group, R 3 represents a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, l is an integer of 0 to 10, m is an integer of 1 to 10, and n is 1 Represents an integer of ~ 10)
A polyester polyol obtained by the method for producing a polyester polyol according to any one of claims 1 to 11.
A method for producing a polyester-modified product, wherein the polyester polyol according to claim 12 is reacted with a compound having a group capable of reacting with a hydroxyl group and an ethylenically unsaturated group.
A polyester modified product obtained by the method for producing a polyester modified product according to claim 13.