TW201422668A - Method for producing polyester polyol, method for producing modified polyester, polyester polyol and modified polyester - Google Patents

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. The method for producing the polyester polyol 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

Method for producing polyester polyol and 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, a polyester polyol and a polyester modified product, and more particularly, a tin-based metal is not used. A method for producing a polyester polyol of a catalyst and a method for producing a polyester modified product obtained by modifying the polyester polyol obtained by the production method.

The polyester represented by polyethylene terephthalate (PET) can be used in various applications such as molded articles, films, and fibers. Among them, PET bottles have been used in recent years due to their light weight, transparency, gas barrier properties, and high strength.

Further, the polyester is subjected to crack polymerization in a polyol to produce a polyester polyol, or a polyester obtained by modifying the polyester polyol to obtain various resins.

For example, Patent Document 1 discloses a production of an alkyd resin for a coating which is reacted with a cracking polyglycol of a glycol, and Patent Documents 2 and 3 disclose a polyester for coating using a recycled polyester. A method for producing a resin, and Patent Document 4 discloses a use of recycled polyester as a light hardening Raw material of urethane resin. Any of the resins described in the above patent documents is intended to be used in a coating composition.

Conventionally, the crack polymerization reaction of polyester is carried out by feeding a raw material polyester, a polyol, and a cracking polymerization catalyst into a reactor and heating. At this time, a metal catalyst, particularly a tin-based catalyst, is used for the cracking polymerization catalyst.

Prior technical literature Patent literature

Patent Document 1: License No. 3310661

Patent Document 2: License No. 3443409

Patent Document 3: License No. 3256537

Patent Document 4: JP-A-2004-307779

Summary of invention

However, tin compounds, especially organic tin compounds, have been reported to be toxic to living organisms, and have also been shown to have an impact on the environment. Therefore, development of a catalyst which can replace tin-based metal catalyst in the crack polymerization of polyester is sought.

Accordingly, an object of the present invention is to provide a process for producing a polyester polyol by polymerizing a raw material polyester in a short time without using a tin-based metal catalyst.

In order to solve the above problems, the inventors of the present invention have found that the above problems can be solved by using a non-tin-based metal catalyst or a non-metal-based basic catalyst, and the present invention has been completed.

That is, the method for producing a polyester polyol of the present invention is characterized in that it comprises heating a mixture containing a raw material polyester, a polyol component, a non-tin-based metal catalyst, or a non-metal-based basic catalyst as essential components. The step of cracking and polymerizing the raw material polyester.

In the method for producing a polyester polyol of the present invention, the non-tin-based 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 more preferably a naphthenic acid. A compound selected from the group consisting of a metal complex, an ethenylacetone metal complex, and a metal octoate.

Further, in the method for producing a polyester polyol of the present invention, the non-tin-based metal catalyst is preferably zinc naphthenate, zinc acetylacetonate, zinc octoate, calcium naphthenate, calcium acetyl ketone or octanoic acid. A compound selected from the group consisting of calcium, lithium naphthenate, lithium acetylacetonate, lithium octoate, lithium acetate, manganese naphthenate, manganese acetylacetonate, and manganese octoate.

In the method for producing a polyester polyol of the present invention, the non-metallic alkaline catalyst is preferably a heterocyclic compound having a fluorene structure.

In the method for producing a polyester polyol of the present invention, it is preferred that the non-metal basic catalyst is composed of diazobicycloundecene, diazobicycloalkenene, and the like. One or more selected from the group.

In the method for producing a polyester polyol of the present invention, the polyol component is preferably a polyol having three or more functional groups.

In the method for producing a polyester polyol of the present invention, the raw material polyester is preferably a recycled polyester.

In the method for producing a polyester polyol of the present invention, it is preferred to further carry out a crack polymerization of the raw material polyester by further adding water to the 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, it is preferred that the crack polymerization is carried out at 200 to 300 °C.

In the method for producing a polyester polyol of the present invention, it is preferred to obtain a mixture of compounds represented by the following formula (1);

(wherein R ¹ represents a group from which an OH group is removed from a (l+m)-valent polyol, R ² represents an alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon atom number of 6 to 20 The aryl group, R ³ represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, 1 is an integer of 0 to 10, m is an integer of 1 to 10, and n is an integer of 1 to 10.

The polyester polyol of the present invention is characterized by the method for producing a polyester polyol of any of the above.

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

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

According to the method for producing a polyester polyol of the present invention, the raw material polyester can be easily dissolved in an organic solvent and converted into a polyester polyol which can be variously chemically modified without using a tin-based metal catalyst. Thereby, a polyester polyol which is more reduced in tin content than those manufactured by a method using a known tin-based catalyst can be obtained. Moreover, when a non-metallic alkaline catalyst is used, deterioration of electrical insulation due to the influence of residual metal catalyst of the obtained product can be avoided.

Further, according to the present invention, it is possible to produce a polyester-modified product which imparts photosensitivity with low cost and high production efficiency.

Form for implementing the invention

The method for producing a polyester polyol of the present invention is basically characterized in that a non-tin-based metal catalyst or a non-metal-based basic catalyst is used in the polymerization of a raw material polyester by a polyol component.

[Non-tin metal catalyst]

The non-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, more preferably a metal naphthenate complex, an ethylene acetylacetonate metal complex or a octanoic acid metal. soap. Among them, zinc naphthenate, zinc acetylacetonate, zinc octoate, calcium naphthenate, calcium acetyl ketone, calcium octylate, lithium naphthenate, lithium acetyl acetonate, lithium octoate, lithium acetate, Manganese naphthenate, manganese acetylacetonate and manganese octoate.

The above-mentioned non-tin-based metal catalyst is used in an amount relative to the raw material polyester. The total amount of the polyol component is preferably from 0.005 to 5 parts by mass, more preferably from 0.05 to 3 parts by mass, per 100 parts by mass.

[Non-metal alkaline catalyst]

The non-metallic alkaline catalyst used in the method of the present invention is preferably a cyclic nitrogen-containing compound, more preferably a heterocyclic compound having a fluorene structure. Among them, it is particularly preferably a diazobicycloundecene (1,8-diazocyclo[5.4.0]undecene-7, hereinafter also referred to as "DBU"), a diazo ring Terpene (1,5-diazocyclo[4.3.0]nonene-5, hereinafter also referred to as "DBN") and derivatives thereof. DBU and DBN are both organic strong bases, similar in structure, and can be used as a catalyst for the same reaction as the urethanation reaction, Wittig reaction, and the like.

Examples of the diazobicycloundecene (DBU), the diazobicycloalkenene (DBN), and the like may be, for example, DBU, DBN, DBU carbonate, DBU carboxylate, DBU phenate, DBU thiolate, DBN carbonate, DBN carboxylate, DBN phenate, DBN thiolate.

Commercial products of DBU, DBN and derivatives thereof may, for example, be U-CAT SA1, U-CAT SA102, U-CAT SA 506, U-CAT SA 603, U-CAT SA 810, U-CAT SA 831, U-CAT SA 841, U-CAT SA 851, U-CAT 881, U-CAT 5002 (any trade name, manufactured by San-apro Co., Ltd.).

The amount of the non-metallic alkaline catalyst to be used is preferably from 0.005 to 5 parts by mass, more preferably from 0.05 to 3 parts by mass, per 100 parts by mass of the total of the raw material polyester and the polyol component.

[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 of the polyesters if it can be melted by heating.

Further, the raw material polyester is preferably a repeating unit represented by the following formula (2).

(wherein R ⁴ represents an alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and R ⁵ represents a substituted or unsubstituted carbon atom number of 6 to 20; Extending an aryl group, O is an integer of 1 or more).

In the above formula (2), R ⁴ is an alkylene group having 1 to 10 carbon atoms which can be obtained, and examples thereof include a methylene group, a 1,2-extended ethyl group, a 1,3-propanyl group, and 1,4. - butyl, 1,2-butyl, 1,5-amyl, and the like.

In the above formula (2), R ⁴ is a aryl group having 6 to 20 carbon atoms which can be obtained, and examples thereof include a 1,4-phenylene group and a 2,6-anthranyl group. These aryl groups may also be substituted with an alkyl group, an alkoxy group, a halogen atom or the like.

In the above formula (2), R ⁵ is a aryl group having 6 to 20 carbon atoms which can be obtained, and is, for example, the same as those exemplified in the above R ⁴ .

Specific examples of preferred raw material polyesters include, for example, polyethylene terephthalate (PET), poly(p-propyl phthalate), polybutylene terephthalate, polyethylene naphthalate, and polynaphthalene. Butic acid diester, polyethylene terephthalate and para-hydroxyl a polycondensate of acid, a polycondensate of 4,4-dihydroxybiphenol and p-hydroxyacetic acid, a liquid condensate of a polycondensate of 2,6-hydroxynaphthoic acid and p-hydroxybenzoic acid, etc. . Among the above, polyethylene terephthalate is also particularly preferred.

Further, from the viewpoint of environmental protection, it is more preferable to form a raw material polyester from recycled PET and recycled PET recovered from waste such as PET bottle waste materials. The recovered PET is pulverized and washed, and the recycled PET is washed and granulated by the market.

[Polyol content]

The polyol component is not particularly limited, and may be a bifunctional polyol or a trifunctional or higher polyhydric alcohol. The above-mentioned polyol component may be used alone or in combination of two or more.

Examples of the bifunctional polyols include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, and dipropylene glycol. 1,3-butanediol, neopentyl glycol, spirodiol, dioxanediol, adamantanediol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6 -hexanediol, 1,4-cyclohexanedimethanol, 2-methylpropanediol 1,3, 3-methylpentanediol 1,5, hexanediol, octanediol, 9-anthracene Ethylene oxide modified compound of diol, 2,4-diethyl-1,5-pentanediol, difunctional phenol such as bisphenol A, propylene oxide modification of difunctional phenol such as bisphenol A Compound, ethylene oxide of bisphenol A, propylene oxide copolymerization modified compound, copolymerized polyether polyol of ethylene oxide and propylene oxide, polycarbonate diol, polyether diol, polyester Glycol, polycaprolactone diol, 1,4-polyisoprene diol, 1,4-polybutadiene diol, 1,2-polybutadiene diol, 1,4- or 1 , 2-polybutadiene diol Hydroxyl terminated polyalkylene diene glycols.

Examples of commercially available polycaprolactone diols include, for example, Placcel 205, Placcel L205AL, Placcel 205U, Placcel 208, Placcel L208AL, Placcel 210, Placcel 210N, Placcel 212, Placcel L212 AL, Placcel 220, Placcel 220N, Placcel. 220NP1, Placcel L220AL, Placcel 230, Placcel 240, Placcel 220EB, Placcel 220EC (all of which are manufactured by Daicel Chemical Industry Co., Ltd.).

For example, Epol (registered trademark; hydrogenated polyisoprene diol, molecular weight 1860, average degree of polymerization 26, manufactured by Idemitsu Kosan Co., Ltd.) is exemplified as a commercially available product of the above-mentioned hydroxy terminal polyalkylene diene glycol. , PIP (polyisoprene diol, molecular weight 2200, average polymerization degree 34, manufactured by Idemitsu Kosan Co., Ltd.), polyether H (hydrogenated polybutadiene diol, molecular weight 2200, average polymerization degree 39, Mitsubishi Chemical (manufactured by the company), R-45HT (polybutanediol, molecular weight 2270, average degree of polymerization 42, manufactured by Idemitsu Kosan Co., Ltd.).

The trifunctional or higher polyhydric alcohol may, for example, be glycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, trimethylolpropane, dipentaerythritol, tripentaerythritol, adamantanetriol, poly Caprolactone triol and the like. In addition, examples of the polyhydric alcohol having a trifunctional or higher functional group of the aromatic ring include, for example, an ethylene oxide or a propylene oxide modified product of a trifunctional or higher phenol compound, and a polyvalent alcohol having a trifunctional or higher functional group of a heterocyclic ring. For example, Theic, a company of the Shikoku Chemical Industry Co., Ltd., may be mentioned.

An example of a commercially available product of the above polycaprolactone triol is, for example, Placcel. 303, Placcel 305, Placcel 308, Placcel 312, Placcel L312 AL, Placcel 320 ML, Placcel L320AL; any of the above is manufactured by Daicel Chemical Industry Co., Ltd.; trade name).

As the polyol component, a plant-derived alcohol component (derived from a plant polyol) can also be used. The plant-derived alcohol component is preferably a castor oil-based component. Commercial products include, 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,POL CASTOR # 10. POLYCASTOR #30, URIC SE-2003 (any one is manufactured by Ito Oil Co., Ltd.).

The polyol component used in the present invention is preferably a trifunctional or higher polyhydric alcohol, and particularly preferably contains trimethylolpropane.

The polyol component is used in an amount of from 0.5 mol to 7.0 mol, more preferably from 1.0 mol to 5.0 mol, based on the hydroxyl group of the ester bond of the starting polyester.

[Reaction conditions]

In the method of the present invention, a mixture containing the above components is placed in a reactor, and by heating, crack polymerization of the raw material polyester is carried out. Heating side The method can use a conventionally known method. Each of the above components is mixed to form a mixture, and then heated, and each component may be introduced into the reactor in order while heating. The heating temperature is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. Further, when an organic solvent is used, a conventionally known solvent can be used, but from the viewpoint of environmental influence, it is preferred to carry out the reaction without using an organic solvent.

In the method of the present invention, a mixture containing a raw material polyester, a polyol component, and a non-tin-based metal catalyst as an essential component is further added with water to carry out a crack polymerization of the raw material polyester. By adding water, the polyester or polyol of the raw material becomes a slurry, which is preferable because the stirring efficiency is improved.

In the method for producing a polyester polyol of the present invention, it is preferred to obtain a mixture of compounds represented by the following formula (1);

(wherein R ¹ represents a group from which an OH group is removed from a (l+m)-valent polyol, R ² represents an alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon atom number of 6 to 20 The aryl group, R ³ represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, 1 is an integer of 0 to 10, m is an integer of 1 to 10, and n is an integer of 1 to 10.

In the above formula (1), R ¹ represents a group from which an OH group is removed from a (l+m)-valent polyol, but the polyvalent alcohol may, for example, be a bifunctional polyol or a trifunctional or higher polyhydric alcohol. The exemplified. Further, R ² is an alkylene group or an aryl group which can be obtained, and R ³ is an exocyclic group which can be obtained, for example, the same as the above.

The compound represented by the above formula (1) is a preferred 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 method for producing a polyester polyol is reacted with a compound having a group reactive with a hydroxyl group and an ethylenically unsaturated group. . By this modification, sensitivity can be imparted to the polyester. The modification reaction of the polyester polyol is the same as the conventional esterification reaction. In the presence or absence of an organic solvent, an acid catalyst or a polymerization inhibitor is generally added, preferably at a temperature of from 80 ° C to 130 ° C. The range is from 2 hours to 10 hours. It can be synthesized under normal pressure or under pressure, and under reduced pressure, the temperature of the reaction can be lowered. Further, even if the obtained polyester modified product has an unreacted hydroxyl group derived from the cracked polymer, there is no problem in properties.

[Compound having a group reactive with a hydroxyl group and an ethylenically unsaturated group]

The polyester polyol-modified compound obtained by the above production method can be a compound having a group reactive with a hydroxyl group and an ethylenically unsaturated group in one molecule. The group which can react with a hydroxyl group is preferably one in the molecule, and the ethylenically unsaturated group has one or more in the molecule. Examples of the group reactive with a hydroxyl group include a cyclic ether group such as a carboxyl group, an isocyanate group or an epoxy group, and a hydroxyl group.

If it is a compound having a group reactive with a hydroxyl group and an ethylenically unsaturated group in one molecule, since the polyester obtained by the above production method can be used more The modification of the primary alcohol is not particularly limited, but a compound having an acrylonitrile group or a methacryl group is particularly preferable from the viewpoint of reactivity with the polyester polyol or the like.

Examples of the compound having one hydroxyl group and one or more ethylenically unsaturated groups include acrylic acid, acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furyl methacrylic acid, crotonic acid, and α- a cyano cinnamic acid, a cinnamic acid, a (meth)acrylic acid caprolactone adduct, a saturated or unsaturated dibasic acid anhydride, a half ester compound having one hydroxyl group in one molecule, and the like. . The (meth) acrylate having a hydroxyl group for producing a half ester compound may, for example, be hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate or hydroxybutyl (meth) acrylate. And trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, phenylglycidyl (meth)acrylate, and the like. The dibasic acid anhydride used for the production of the half ester compound may, for example, be succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride or methyl endomethylenetetrahydroanthracene. Anhydride, etc. These compounds may be used alone or in combination of two or more.

Further, in the present specification, the term "(meth)acrylate" is generally referred to as a mixture of acrylate, methacrylate, and the like, and the other similar expressions are also the same.

The compound having one isocyanate group and one or more ethylenically unsaturated groups in one molecule may, for example, be (meth)acryloyloxyethyl isocyanate or (meth)acryloxyethoxyethyl isocyanate. ,double (Propylene oxymethyl) ethyl isocyanate or a modified product thereof. Further, it is also possible to use a compound having one hydroxyl group and one or more ethylenically unsaturated groups in one molecule, isophorone diisocyanate, tolyl diisocyanate, tetramethyl xylylene diisocyanate, and hexa A semi-carbamate compound of a diisocyanate such as methyl diisocyanate. These compounds may be used alone or in combination of two or more.

The commercially available product having one isocyanate group and one or more ethylenically unsaturated groups in one molecule, and the like, may be, for example, "Karenz MOI" (methacryloyloxyethyl isocyanate) or "Karenz AOI". (Acryloxyethoxyethyl isocyanate), "Karenz MOI-EG" (methacrylomethoxyethoxyethyl isocyanate), "Karenz MOI-BM" (Karenz MOI isocyanate block), "Karenz MOI-BP" (isocyanate block of Karenz MOI) and "Karenz BEI" (1,1-bis(acryloxymethyl)ethyl isocyanate) have been sold by Showa Denko. Also, any of these product names are registered trademarks.

Examples of the compound having one cyclic ether group and one or more ethylenically unsaturated groups in one molecule include 2-hydroxyethyl (meth) acrylate glycidyl ether and 2-hydroxypropyl group ( Methyl) acrylate glycidyl ether, 3-hydroxypropyl (meth) acrylate glycidyl ether, 2-hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (methyl) Acrylate glycidyl ether, 2-hydroxypentyl (meth) acrylate glycidyl ether, 6-hydroxyhexyl (meth) acrylate glycidyl ether or glycidyl (meth) acrylate, 3 , 4-epoxycyclohexyl methacrylate Wait. These compounds may be used alone or in combination of two or more.

The compound having a hydroxyl group and an ethylenically unsaturated group is not particularly limited as long as it has one hydroxyl group and one or more ethylenically unsaturated groups in one molecule. Specific examples thereof include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, and pentaerythritol. A hydroxyalkyl (meth) acrylate such as tris(meth)acrylate or dipentaerythritol penta(meth)acrylate. These compounds may be used alone or in combination of two or more.

The polyester modified product produced by the production method of the present invention is chemically modified by reacting the above polyester polyol with a compound having a group reactive with a hydroxyl group and one or more ethylenically unsaturated groups. Since the photosensitive compound is provided with a photosensitive property, it can be used as a photosensitive component of a photocurable resin composition or a photocurable thermosetting resin composition. For example, the above-mentioned polyester modified product may be blended with an oxime ester photopolymerization initiator, an α-aminoethyl benzene photopolymerization initiator, a ruthenium oxyphosphide photopolymerization initiator, a benzophenone. A conventionally known photopolymerization initiator, such as a compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a xanthone compound, or a tertiary amine compound, Or a photoinitiator and a sensitizer, and a photocurable resin composition can be formed.

Example

The present invention will be specifically described below by showing examples and comparative examples, but the present invention is not limited to the following examples. In addition, in the following, "parts" and "%" are all based on quality unless otherwise stated.

[Example 1]

192 parts of PET chips (manufactured by Mitsubishi Chemical Corporation; Novapex (trade name)) and 67 parts of trimethylolpropane were fed into a 500-ml four-neck round bottom flask equipped with a stirrer, a nitrogen gas introduction tube, and a cooling tube. 0.52 parts of zinc octoate was placed in a nitrogen atmosphere in the flask, and then immersed in an oil bath heated to 220 ° C, and the reaction was continued until it was transparent to obtain a polyester oligomer.

[Embodiment 2]

The zinc octoate of Example 1 was replaced with the same amount of zinc acetophenone to obtain a polyester oligomer.

[Example 3]

The same amount of calcium acetylacetonate was used in place of the zinc octoate of Example 1, to obtain a polyester oligomer.

[Example 4]

The zinc octylate of Example 1 was replaced with the same amount of lithium acetylacetonate to obtain a polyester oligomer.

[Example 5]

The zinc octoate of Example 1 was replaced with the same amount of zinc naphthenate to obtain a polyester oligomer.

[Embodiment 6]

The same amount of calcium naphthenate was used in place of the zinc octoate of Example 1 to obtain a polyester oligomer.

[Embodiment 7]

The same amount of calcium octylate was used in place of the zinc octoate of Example 1, to obtain a polyester oligomer.

[Embodiment 8]

The zinc octoate of Example 1 was replaced with the same amount of lithium naphthenate to obtain a polyester oligomer.

[Embodiment 9]

The zinc octoate of Example 1 was replaced with the same amount of lithium octoate to obtain a polyester oligomer.

[Embodiment 10]

The zinc octoate of Example 1 was replaced with the same amount of manganese naphthenate to obtain a polyester oligomer.

[Example 11]

The zinc octoate of Example 1 was replaced with the same amount of acetyl acetonyl acetonide to obtain a polyester oligo.

[Embodiment 12]

The zinc octoate of Example 1 was replaced with the same amount of manganese octoate to obtain a polyester oligomer.

[Example 13]

The zinc octoate of Example 1 was replaced with the same amount of lithium acetate to obtain a polyester oligomer.

[Embodiment 14]

225 parts of the polyester oligomer obtained in Example 2, 187 parts of acrylic acid, and 1.87 parts of p-toluenesulfonic acid were fed into a 500-ml four-neck round bottom flask equipped with a stirrer, a nitrogen gas introduction tube, and a cooling tube. 1.50 parts of p-methoxyphenol was stirred and uniformly dissolved, and then immersed in an oil bath which had been heated to 118 ° C for 16.5 hours. After the reaction was terminated, the acid value of the reaction liquid was measured, and an acid equivalent aqueous base solution was added to the flask to neutralize. Then, brine (20% by weight) was added and stirred. Thereafter, the solution was transferred to a separatory funnel, 1.4 times of methyl isobutyl ketone of the reaction liquid was added, and the aqueous phase was discarded. The oil phase was washed again with saline (5 wt%) and the aqueous phase was discarded. Thereafter, the oil phase was allowed to settle in hexane, and then dissolved in methyl ethyl ketone, and the impurities were removed by suction filtration. After re-precipitating the filtrate with tap water, discard the supernatant and proceed The reprecipitate was stirred in tap water in one step, washed, and finally diluted with carbitol acetate to a solid form to be 70% to obtain an acrylate resin varnish.

[Comparative Example 1]

The zinc octoate of Example 1 was replaced with the same amount of dibutyltin oxide to obtain a polyester oligomer.

[Comparative Example 2]

The zinc octoate of Example 1 was replaced with the same amount of dibutyltin dilaurate to obtain a polyester oligomer.

<Cracking polymerization time>

The time required for the crack polymerization of 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 more, the residue of the raw material is marked as "X".

<Wuxi>

The concentration (ppm) of tin contained in the cracked polymers of Examples 1 to 13 and Comparative Examples 1 and 2 was measured. The method of recording the evaluation is as follows.

○: The concentration of tin is less than 10 ppm

△: The concentration of tin is 10~500ppm

×: The concentration of tin exceeds 500ppm

<Molecular weight>

The molecular weights of the cleavage polymers of Examples 1 to 13 and Comparative Example 1 were measured by GPC (gel permeation chromatography). The measurement conditions were based on Shodex GPC KF-806 L×3 manufactured by Showa Denko Co., Ltd., and used at a column temperature of 40 °C. Standard polystyrene was used as the reference material, and tetrahydrofuran was used 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 cracked polymers of Examples 1 to 13 and Comparative Examples 1 and 2 was confirmed. The confirmation method was carried out by adding 50 parts of various solvents to 50 parts of the cracked polymer, stirring, and preparing a 50 wt% solution of the cracked polymer, and evaluating the transparency of the solution. The method of recording the evaluation is as follows.

Fully transparent: ○

Slightly turbid: △

There is turbidity: ×

From the above, in the solvent solubility, Comparative Example 2 was turbid with respect to each solvent, but in any of the examples, it was confirmed that it was completely transparent to each solvent as in Comparative Example 1 of the tin-free.

[Reference Example 1]

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

<friction test>

After the evaluation of the coating film was rubbed 50 times with a rag containing acetone, it was confirmed that the surface was not dissolved and sufficiently cured.

<Pencil hardness test>

The pencil of B to 9H which was flattened by the evaluation of the coating film to the tip of the pencil which was ground into a pencil was applied to the coating film by applying a load of 1 kg at an angle of 45 °C. The coating film was scribed at a pressure of about 1 cm in a state where the load was applied, and the hardness of the pencil which was not peeled off from the coating film was measured and found to be 6H.

<heat resistance test>

The evaluation coating film described above was placed in a hot air circulating drying oven at 200 ° C and heated for 3 minutes. After the heat was taken out, the heat resistance test was carried out by visually observing the trace of the melt, and it was confirmed that the heat resistance was 200 ° C for 3 minutes.

As described above, according to the method of the present invention, by using a non-tin-based metal catalyst, the polyester can be easily dissolved in an organic solvent to be converted into various chemically modified polyester polyols.

[Example 15]

The IV value (inherent viscosity value) 0.6~0.7 was fed into a 500 ml four-neck round bottom flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. 192 parts of PET chips, 67 parts of trimethylolpropane and 0.52 parts of DBU were collected. After forming a nitrogen atmosphere in the flask, the mixture 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 16]

PET chips (Mitsubishi Chemical Co., Ltd.; Novapex (trade name)) 192 parts, and trimethylolpropane 67 parts were fed into a 500-ml four-neck round bottom flask equipped with a stirrer, a nitrogen gas introduction tube, and a cooling tube. 0.52 parts of DBU was placed in a nitrogen atmosphere in the flask, 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 17]

Include 192 parts of recovered PET chips with an IV value of 0.6-0.7, 67 parts of trimethylolpropane, 0.52 parts of DBU, and water in a 500-ml four-neck round bottom flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. After 30 parts of the flask were placed in a nitrogen atmosphere, the mixture was immersed in an oil bath heated to 180 ° C, and the oil bath was heated to 220 ° C while slowly removing the water, and the reaction was continued until the inside of the flask became transparent to obtain polyester oligomerization. Things.

[Embodiment 18]

246 parts of recovered PET chips with an IV value of 0.6-0.7, 67 parts of trimethylolpropane, 68 parts of pentaerythritol, DBU were fed into a 500-ml four-neck round bottom flask equipped with a stirrer, a nitrogen gas introduction tube, and a cooling tube. After 0.52 parts of water and 30 parts of water, a nitrogen atmosphere was formed in the flask, and the mixture was immersed in an oil bath heated to 180 ° C, and the oil bath was heated to 220 ° C while slowly removing the water, and the reaction was continued until the inside of the flask became transparent. Polyester oligomer.

[Embodiment 19]

The DBU of Example 17 was replaced with the same amount of DBN to obtain a polyester oligomer.

[Example 20]

245 parts of the polyester oligomer obtained in Example 15, 187 parts of acrylic acid, and 1.87 parts of p-toluenesulfonic acid were fed into a 500 ml four-neck round bottom flask equipped with a stirrer, a nitrogen gas introduction tube, and a cooling tube. 1.50 parts of p-methoxyphenol was stirred and uniformly dissolved, and then immersed in an oil bath which had been heated to 118 ° C for 16.5 hours. After the reaction was terminated, the acid value of the reaction liquid was measured, and an acid equivalent aqueous base solution was added to the flask to neutralize. Then, brine (20% by weight) was added and stirred. Thereafter, the solution was transferred to a separatory funnel, 1.4 times of methyl isobutyl ketone of the reaction liquid was added, and the aqueous phase was discarded. The oil phase was washed again with saline (5 wt%) and the aqueous phase was discarded. Thereafter, the oil phase was allowed to settle in hexane, and then dissolved in methyl ethyl ketone, and the impurities were removed by suction filtration. After the filtrate was reprecipitated with tap water, the supernatant was discarded, and the reprecipitate was further stirred with tap water, washed, and finally diluted with carbitol acetate to a solid content of 70% to obtain an acrylate resin varnish.

[Comparative Example 3]

The DBU of Example 17 was replaced with the same amount of dibutyltin oxide to obtain a polyester oligomer.

[Comparative Example 4]

The DBU of Example 17 was replaced with the same amount of dibutyltin dilaurate to obtain a polyester oligomer.

[Comparative Example 5]

Include 192 parts of recovered PET chips with an IV value of 0.6-0.7, 67 parts of trimethylolpropane, and 30 parts of water in a 500-ml four-neck round bottom flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. After forming a nitrogen atmosphere in the flask, the mixture was immersed in an oil bath heated to 180 ° C, and the oil bath was heated to 220 ° C while slowly removing water, and the reaction was carried out.

<Cracking polymerization time>

The time required for the crack polymerization of 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 more, the residue of the raw material is marked as "X".

<No metal>

The concentrations (ppm) of the metals contained in the cracked polymers of Examples 15 to 19 and Comparative Examples 3 to 5 were measured. The method of recording the evaluation is as follows.

○: The concentration of metal is less than 10ppm

△: The concentration of metal is 10~500ppm

×: The concentration of metal exceeds 500ppm

<Molecular weight>

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

<Solvent solubility test>

The solvent solubility of the cracked polymers of Examples 15 to 19 and Comparative Examples 3 to 5 was confirmed. The confirmation method was carried out by adding 50 parts of various solvents to 50 parts of the cracked polymer, stirring, and preparing a 50 wt% solution of the cracked polymer, and evaluating the transparency of the solution. The method of recording the evaluation is as follows.

Fully transparent: ○

Slightly turbid: △

There is turbidity: ×

From the above, in the solvent solubility, Comparative Examples 4 and 5 were turbid with respect to each solvent, but in any of the examples, it was confirmed that the solvent was completely transparent to each solvent as in Comparative Example 3 which was not metal-free.

[Reference Example 2]

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

<friction test>

After the evaluation of the coating film was rubbed 50 times with a rag containing acetone, it was confirmed that the surface was not dissolved and sufficiently cured.

<Pencil hardness test>

The pencil of B to 9H which was flattened by the evaluation of the coating film to the tip of the pencil which was ground into a pencil was applied to the coating film by applying a load of 1 kg at an angle of 45 °C. The coating film was scribed at a pressure of about 1 cm in a state where the load was applied, and the hardness of the pencil which was not peeled off from the coating film was measured and found to be 6H.

<heat resistance test>

The evaluation coating film described above was placed in a hot air circulating drying oven at 200 ° C and heated for 3 minutes. After the heat was taken out, the heat resistance test was carried out by visually observing the trace of the melt, and it was confirmed that the heat resistance was 200 ° C for 3 minutes.

As described above, according to the method of the present invention, by using a non-metallic alkaline catalyst, the polyester can be easily dissolved in an organic solvent to be converted into various chemically modified polyester polyols.

Claims (10)

A method for producing a polyester polyol, comprising the step of heating a mixture of a raw material polyester, a polyol component, and a non-metal basic catalyst as essential components to depolymerize the raw material polyester. The method for producing a polyester polyol according to claim 1, wherein the non-metallic alkaline catalyst is a heterocyclic compound having a fluorene structure. The method for producing a polyester polyol according to claim 2, wherein the non-metal basic catalyst is diazobicycloundecene, diazobicyclononene, and the like One or more selected from the group consisting of. The method for producing a polyester polyol according to claim 1 or 2, wherein the polyol component is a polyol having three or more functional groups. The method for producing a polyester polyol according to claim 1 or 2, wherein the raw material polyester is a recycled polyester. The method for producing a polyester polyol according to claim 1 or 2, wherein the crack polymerization is carried out at 150 to 350 °C. A method for producing a polyester polyol according to claim 1 or 2, wherein a mixture of compounds represented by the following formula (1) is obtained; (wherein R ¹ represents a group from which an OH group is removed from a (l+m)-valent polyol, R ² represents an alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon atom number of 6 to 20 The aryl group, R ³ represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, 1 is an integer of 0 to 10, m is an integer of 1 to 10, and n is an integer of 1 to 10. A polyester polyol obtained by the method for producing a polyester polyol according to any one of claims 1 to 7. A method for producing a modified polyester, characterized in that the polyester polyol of claim 8 is reacted with a compound having a group reactive 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 9 of the patent application.