CN112538158A - Lactone polymers, polyurethanes, and polyester production methods - Google Patents
Lactone polymers, polyurethanes, and polyester production methods Download PDFInfo
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- CN112538158A CN112538158A CN202010968498.6A CN202010968498A CN112538158A CN 112538158 A CN112538158 A CN 112538158A CN 202010968498 A CN202010968498 A CN 202010968498A CN 112538158 A CN112538158 A CN 112538158A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
Abstract
Provided are a method for producing a lactone polymer, a polyurethane and a polyester, which have a narrow molecular weight distribution and an excellent hue, and which, when used as a resin raw material, provide a resin material (such as a polyurethane or a polyester) having excellent physical properties, viscosity, molding processability and heat resistance. A method for producing a lactone polymer obtained by ring-opening polymerization of a lactone compound represented by the following general formula (1), characterized in thatWherein a non-metal halide or a heteropoly acid is used as a catalyst, a compound containing an active hydrogen atom is used as an initiator in the ring-opening polymerization, the moisture content of the compound containing an active hydrogen atom is adjusted,
in the formula 1, R1～R3Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 6.
Description
Technical Field
The invention relates to a preparation method of a lactone polymer. Further, it relates to a method for producing a polyurethane or polyester using the lactone polymer obtained by the production method.
Background
The lactone polymer having a molecular weight of 500 to 5000 is particularly useful as a raw material for polyurethane resins, polyester resins, artificial leathers, coating materials and the like. The lactone polymer can be obtained by ring-opening polymerization of a lactone such as e-caprolactone or delta-valerolactone. In the conventional method for producing a lactone polymer, a wide molecular weight distribution (weight average molecular weight (M) () is obtained by simultaneously causing side reactions such as transesterification reaction in the case of using an anionic ring-opening polymerization catalyst such as tetrabutyl titanate or the like or in the case of carrying out the reaction at a high temperature of 100 to 200 ℃w) Number average molecular weight (M)n) 1.5 to 3.5) and a large amount of oligomer, and the lactone polymer has a high color number and an insufficient hue.
Although there have been proposed methods for improving the molecular weight distribution of a lactone polymer (patent document 1, patent document 2, and the like), the obtained lactone polymer has MW/MnThe molecular weight distribution is as broad as 1.2 to 1.8, and the color number is high, which is not satisfactory. Lactone polymers having a wide molecular weight distribution and a high color number have problems in that various resins such as polycaprolactone and polyurethane obtained using the compounds have insufficient physical properties (strength, elongation, heat resistance, etc.) and high viscosity, and have many practical problems in molding processability, handling, and the like.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 57-155230
Patent document 2: international publication No. 2015/60192
Disclosure of Invention
The problem to be solved by the present invention is to provide a method for producing a lactone polymer having a narrow molecular weight distribution and an excellent hue. It is another object of the present invention to provide a resin material (such as polyurethane or polyester) having excellent physical properties, viscosity, moldability and heat resistance of various resins by using the lactone polymer obtained by the production method of the present invention as a resin raw material.
In order to solve the above problems, the inventors have made extensive studies on a method for improving the molecular weight distribution and the color number of a lactone polymer, and have found a method for obtaining a lactone polymer having a low color number, an excellent hue, a low acid value and a molecular weight distribution close to monodispersity. That is, the present invention is constituted as follows.
1) A method for producing a lactone polymer obtained by ring-opening polymerization of a lactone compound represented by the following general formula (1), characterized in that a nonmetallic halide or a heteropolyacid is used as a catalyst, a compound containing an active hydrogen atom is used as an initiator in the ring-opening polymerization, and the moisture content of the compound containing an active hydrogen atom is adjusted,
[ chemical formula 1]
In the formula 1, R1～R3Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 6.
2) The method for producing a lactone polymer is characterized in that the compound having an active hydrogen atom is a polyol, and 0.01 to 10mol of a polyol (polyhydroic alcohol) is used relative to 1mol of the lactone compound.
3) The method for producing a lactone polymer is characterized in that 0.0001 to 10mol of the catalyst is used relative to 1mol of the lactone compound.
4) The method for producing a lactone polymer is characterized in that the reaction temperature for the ring-opening polymerization is 60 to 100 ℃.
5) The method for producing a lactone polymer is characterized in that the compound having an active hydrogen atom has a moisture content of 1 to 500 ppm.
6) A method of preparing a polyurethane comprising: and a step for reacting the lactone polymer obtained by the lactone polymer production method with a polyisocyanate compound to produce a polyurethane.
7) A method of making a polyester comprising: and a step of reacting the lactone polymer obtained by the lactone polymer production method with a polyol (polyol) compound to produce a polyester.
According to the production process of the present invention, a lactone polymer having a nearly monodisperse molecular weight distribution, containing no oligomer, having a low color number, a low acid value and a low viscosity can be provided. Further, by using the lactone polymer obtained by the production method of the present invention as a raw material, a polyurethane, a polyester, or the like excellent in resin physical properties, processability, heat resistance, and the like can be produced.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention. The lactone compound represented by the above general formula (1) will be specifically described below, but the present invention is not limited thereto.
In the general formula (1), R1～R3Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and n R' s1And n R2May be the same or different, respectively. n represents an integer of 0 to 6. n is preferably an integer of 0 to 2, 4 or 5, more preferably 4 or 5.
In the general formula (1), as R1～R3The "linear or branched alkyl group having 1 to 4 carbon atoms" may specifically include methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl and tert-butyl. Preferably R1～R3Each independently is a hydrogen atom or a methyl group.
Specific examples of the lactone compound represented by the general formula (1) include β -propiolactone, β -butyrolactone, β -valerolactone, γ -butyrolactone, γ -valerolactone, γ -octalactone (γ -caprolactone), gamma-octalactone (γ -caprylolactone), δ -valerolactone, β -methyl- δ -valerolactone, δ -stearic acid lactone (δ -stearolactone), e-caprolactone, 2-methyl-e-caprolactone, 4-methyl-e-caprolactone, e-caprylolactone and e-palmitolactone.
The present invention relates to a method for producing a lactone polymer obtained by ring-opening polymerization of a lactone compound represented by the general formula (1). The present invention also relates to a method for producing a lactone polymer, which is characterized in that a non-metal halide or a heteropoly acid is used as a catalyst, a compound containing an active hydrogen atom is used as an initiator in the ring-opening polymerization, and the moisture content of the compound containing an active hydrogen atom is adjusted.
The catalyst in the method for producing a lactone polymer of the present invention may be a non-metal halide as a lewis acid or a heteropoly acid as a solid acid. The non-metal halide may, for example, be boron trifluoride (BF)3) Phosphorus Pentafluoride (PF)5) And the like. The heteropoly acid may, for example, be phosphotungstic acid hydrate (H)3(PW12O40)·nH2O (n is approximately equal to 30), abbreviated as PWA, silicotungstic acid hydrate (H)4(SiW12O40)·nH2O (n ≈ 30)), phosphomolybdic acid hydrate (H)3(PMo12O40)·nH2O (n ≈ 30)), sodium phosphomolybdate hydrate (Na)3(PMo12O40)·nH2O (n 1) and phosphotungstomolybdic acid hydrate (H)3(PW12-xMoxO40)·nH2O (x is more than 0 and less than 12, n is approximately equal to 30)), phosphovanadomolybdic acid hydrate (H)15-x(PV12-xMoxO40)·nH2Heteropoly acids such as O (6 < x < 12, n ≈ 30)). Further, as a form in which these catalysts are used, boron trifluoride (BF) may be mentioned3) And complexes with linear and cyclic ethers such as diethyl ether and Tetrahydrofuran (THF) (e.g., boron trifluoride tetrahydrofuran (C)4H8O·BF3Abbreviated as BF3THF), etc.).
The compound containing active hydrogen atoms in the preparation method of the lactone polymer of the present invention specifically contains hydroxyl (-OH) groups and amino (-NH) groups2Monosubstituted amino, disubstituted amino), mercapto (thiol group, -SH) compounds, which are useful as reaction initiators (or, simply, initiators) in the polymerization reaction of the present invention.
Specific examples of the hydroxyl group-containing compound include: aliphatic alcohols such as methanol, ethanol, propanol, n-butanol, 2-butanol, isobutanol, t-butanol, allyl alcohol and 2-hydroxyethyl methacrylate;
aromatic alcohols such as benzyl alcohol, 2-methylbenzyl alcohol, benzyl alcohol (2-phenyl-2-propanol), 4-hydroxybenzyl alcohol, 4-methoxyphenol and trityl alcohol, and various phenol aldehydes;
alicyclic alcohols such as cyclohexanol, 3, 5-trimethylcyclohexanol and cyclohexane ethanol;
polyhydric alcohols (or polyols) such as ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycerol, trimethylolpropane, 1, 2-cyclohexanediol, 1, 4-cyclohexanediol, m-xylene glycol, p-xylene glycol, and thiodiglycol;
and organic carboxylic acids such as acetic acid, propionic acid, benzoic acid, phthalic acid, oxalic acid, and fumaric acid.
Specific examples of the amino group-containing compound include: alkylamines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, and tert-butylamine, and dialkylamines such as dimethylamine, diethylamine, and dibutylamine;
aromatic, alicyclic and heterocyclic amines such as aniline, o-toluidine, diphenylamine, cyclohexylamine and piperidine;
aliphatic, aromatic, alicyclic and heterocyclic polyamines such as ethylenediamine, propylenediamine, hexamethylenediamine, o-, m-and p-phenylenediamine, 1, 4-cyclohexanediamine, piperazine, diethylenetriamine and 4,4 ', 4 "-methylenetriphenylamine (4, 4', 4" -methylidyne trianine).
Examples of the mercapto group (thiol group) -containing compound include: aliphatic thiols such as methyl mercaptan (methanethiol; ethanethiol), ethyl mercaptan (ethanethiol), Propyl mercaptan (propanethiol), and n-butyl mercaptan (1-butanetiol);
aromatic thiols such as benzyl thiol and trityl thiol;
dithioethylene glycol (ethylene dithioglycol), 1, 4-benzenedimethylmercaptan, xylylene glycol (xylene glycol), 2-mercaptoethanol, bis (2-mercaptoethyl) ether (bis (2-mercaptoethyl) ether), and the like.
The method for producing the lactone polymer of the present invention is specifically described. The lactone compound represented by the general formula (1) and the active hydrogen atom-containing compound are mixed in appropriate amounts, respectively, into a reaction vessel, and an appropriate amount of an appropriate catalyst is added, heated at an appropriate temperature, and reacted for an appropriate time, thereby obtaining a reaction mixture containing the lactone polymer of the present invention. The product of the lactone polymer can be purified by a known method using an appropriate solvent and an appropriate purification apparatus or the like for the reaction mixture thus obtained.
Characterized in that the compound containing an active hydrogen atom used in the present invention has an adjusted moisture content. The active hydrogen atom-containing compound having the adjusted moisture content may be a commercially available product, and is preferably subjected to a dehydration operation on the commercially available product or product before purification, and specifically, a purification operation using a distillation apparatus, a dehydration operation using a molecular sieve or the like, may be mentioned, but is not limited thereto. The compound containing active hydrogen atoms to be purified is preferably a compound whose moisture content is measured by a moisture meter or the like. In addition, when the ring-opening polymerization is carried out, the ring-opening polymerization reaction is preferably carried out under anaerobic conditions, preferably under a nitrogen or inert gas atmosphere, in order to prevent moisture in the outside air from being mixed in. The moisture content of the compound containing an active hydrogen atom preferred in carrying out the present invention is preferably 1ppm to 500ppm, more preferably 1ppm to 200 ppm. When the moisture content is more than 500ppm, M is formed due to the formation of an oligomer componentW/MnIt becomes too large.
The active hydrogen atom-containing compound used as an initiator in the method for producing a lactone polymer of the present invention is preferably a polyol. In the production method of the present invention, it is preferable to use 0.01 to 10mol of the polyol, and more preferably 0.1 to 1.0mol of the polyol, based on 1mol of the lactone compound. When the amount of the initiator used is more than 10mol per 1mol of the lactone compound, the molecular weight of the product becomes too small, and it becomes difficult to form a polymer having a sufficiently high molecular weight.
The amount of the Lewis acid or solid acid catalyst used in the method for producing a lactone polymer of the present invention is preferably 0.0001 to 10mol, more preferably 0.0001 to 1mol, and particularly preferably 0.0001 to 0.1mol, based on 1mol of the lactone compound. Since the amount of the catalyst used is extremely small relative to the lactone compound, the removal thereof is also facilitated. When the amount of the catalyst used is more than 10 moles, heat generation becomes significant, the molecular weight distribution of the product becomes extremely broad, and moreover, side reactions cause quality deterioration, such as coloration, to be significant. In addition, the cost for removing the catalyst is too high, which is not preferable.
The reaction temperature of the ring-opening polymerization in the method for producing a lactone polymer of the present invention is preferably in the range of 60 to 100 ℃, more preferably 60 to 90 ℃, and the optimum temperature depends on the kind and amount of the initiator, the quality, molecular weight, and the like of the target polymer, and usually more preferably 60 to 80 ℃. The polymerization reaction may also be carried out in an inert organic solvent. In bulk polymerization at a relatively low temperature, crystallization is likely to occur while the polymerization is carried out, and therefore, it is preferable to carry out the polymerization in an inert organic solvent such as benzene, toluene, or xylene. At a temperature higher than 100 ℃, the molecular weight distribution of the product becomes extremely broad, and moreover, side reactions cause quality deterioration, such as coloration, to be remarkable. On the other hand, the polymerization reaction time is dependent on the reaction rate, and can be appropriately adjusted depending on the temperature, the kind of the initiator, the amount of the initiator used, and the like, and the reaction time of 2 hours to 10 hours or more can be selected. In the production method of the present invention, in order to simplify the purification operation of the lactone polymer and improve the quality, it is preferable that the polymerization reaction is carried out until unreacted lactone compound disappears, and in this case, it is recommended to carry out sufficient aging.
The reaction mixture containing a lactone polymer obtained by the production method of the present invention can be purified by a known method to obtain a product of the lactone polymer, and specific examples are described below. Dissolving or dispersing an appropriate amount of an organic solvent such as toluene (specifically, esters such as ethanol, acetone, ethyl acetate, and N-butyl acetate; ethers such as diethyl ether, Propylene Glycol Monomethyl Ether (PGME), and ethylene glycol monoethyl ether (ethyl cellosolve), ether esters such as Propylene Glycol Monomethyl Ether Acetate (PGMEA) (ether ester), ketones such as acetone and cyclohexanone; alcohols such as methanol, ethanol, and 2-propanol; diacetone alcohol (DAA), aromatic hydrocarbons such as benzene, toluene, and xylene; amides such as N, N-Dimethylformamide (DMF), and N-methylpyrrolidone (NMP)), dimethyl sulfoxide (DMSO), and an appropriate amount of an ion exchange resin, etc. and stirring at an appropriate temperature for an appropriate time, filtering the reaction mixture, the solvent is removed by distillation under reduced pressure or the like, whereby the produced lactone polymer can be obtained. The ion exchange resin may be selected as appropriate depending on the raw materials used for the polymerization and the polymerization conditions.
The moisture content of the substance and the product used in the production method of the present invention can be measured by a moisture meter based on Karl Fischer volumetric titration method or the like.
With respect to the molecular weight distribution of the lactone polymer of the present invention, the number average molecular weight (M) can be measured by Gel Permeation Chromatography (GPC)n) Weight average molecular weight (M)W)、MW/Mn. M of the lactone polymers of the inventionW/MnPreferably less than 1.3.
The acid value of the lactone polymer of the present invention can be determined by the Japanese Industrial Standard (JIS K0070-. The acid value is preferably from 0.1mgKOH/g to 1.5mgKOH/g, more preferably from 0.1mgKOH/g to 1.0 mgKOH/g.
The color number in the present invention can be determined by the Japanese Industrial Standard (JIS K4101-. The color number is preferably 10 to 40, more preferably 10 to 20.
A polyurethane resin or a polyester resin or the like can be prepared by using the lactone polymer obtained in the present invention. The method for producing these resins is not particularly limited, and they can be produced by a known method. For example, in the case of a method for producing a polyurethane, the polyisocyanate component may be added together to the lactone polymer, the polyol, the chain extender, and the organic metal catalyst to carry out the reaction, or the polyol and the polyisocyanate component may be reacted to obtain an isocyanate group-terminated prepolymer, and then the chain extender may be added to carry out the elongation reaction. In the case of a method for producing a polyester, the polyester can be synthesized by a known method such as dehydration condensation of a lactone polymer and a polyhydric alcohol.
Examples of the polyisocyanate compound include aromatic, alicyclic and aliphatic polyisocyanates having 2 or more isocyanate groups. Specific examples thereof include polyisocyanates such as Tolylene Diisocyanate (TDI), 4' -diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (MDI), Xylylene Diisocyanate (XDI), isophorone diisocyanate (IPDI), and hexamethylene diisocyanate (HMDI). Among them, MDI is preferable in terms of easy availability and control of the reaction with hydroxyl groups.
Examples of the chain extender include low molecular weight glycols such as 1, 3-propanediol, 1, 4-butanediol, and 1, 5-pentanediol.
The organometallic catalyst is not particularly limited, and specific examples thereof include: organotin catalysts such as dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride and dioctyltin dilaurate; nickel octoate, nickel naphthenate; cobalt octoate, cobalt naphthenate; bismuth octoate, bismuth naphthenate, and the like. Among these organometallic catalysts, an organotin catalyst is preferred, and dibutyltin dilaurate (dibutyl tin dilaurate) is more preferred.
The amount of the organometallic catalyst used in the method for producing a polyurethane of the present invention is preferably 0.0001 to 5 parts by weight, and more preferably 0.001 to 3 parts by weight, based on 100 parts by weight of the polyol.
Physical properties, thermal properties, electrical properties, and chemical properties of the polyurethane obtained by the method for producing a polyurethane of the present invention can be evaluated. In the present invention, as physical properties using a tensile tester, the breaking strength (breaking stress) (MPa) and the breaking elongation (%) at the breaking point are measured and evaluated. In addition, as the thermal/chemical properties, it can be evaluated by the thermal decomposition temperature (. degree. C.) based on thermogravimetric-differential thermal analysis (TG-DTA).
[ examples ]
The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In the examples, the moisture (ppm) of the initiator (ethylene glycol, etc.) was measured by the Karl Fischer volumetric titration method using the following moisture meter.
Device name: volumetric automatic moisture measuring device
The model is as follows: KF-31 (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) detector: RI (Ri)
GPC measurement was carried out using a high-speed GPC apparatus (model: HLC-8320GPC, manufactured by Nippon Kabushiki Kaisha) and a column (model: TSK gelG4000H + G2500H, manufactured by Nippon Kabushiki Kaisha) under the following conditions.
Eluent: tetrahydrofuran, standard substance: polytetramethylene ether glycol
Injection amount: 100 μ L, flow rate: 1.0 mL/min, measurement temperature: 40 ℃, detector: RI (Ri)
EXAMPLE 1 Synthesis of polycaprolactone
114.0g (1.00mol, manufactured by K.K., Douguenza chemical Co., Ltd.) of ε -caprolactone (abbreviated as CL) and 3.2g (0.05mol, water content 200ppm, manufactured by Nippon Tanskian chemical Co., Ltd.) were added to a 500mL reaction vessel purged with nitrogen, and 1.0g (0.0003 mol, manufactured by Nippon Kaisha) of phosphotungstic acid hydrate (PWA) was added thereto and stirred at 70 ℃ for 5 hours. 100mL of toluene and 50g of ion exchange resin IRA-96SB (manufactured by Organo corporation, Japan) were added to the reaction mixture, and the mixture was stirred at room temperature for 2 hours. After stirring, the reaction mixture was filteredThe solvent was removed from the filtrate by distillation under the reduced pressure, whereby a polymer (107g, yield 94%) was obtained as a colorless solid (ordinary temperature). GPC measurement results (Mn, M) of the obtained lactone polymer (polycaprolactone)W/Mn) The results of analysis of the acid value (mgKOH/g) and the color number (APHA) are shown in Table 1.
EXAMPLE 2 Synthesis of polycaprolactone
A colorless solid (room temperature) lactone polymer (108g, yield 95%) was obtained in the same manner as in example 1, except that ethylene glycol of example 1 was replaced with 2-methyl-1, 3-propanediol (MPD)5.0g (0.06mol, moisture content 200ppm, manufactured by Nippon Takeda chemical Co., Ltd.). The analysis results of the polymer obtained by the measurement in the same manner as in example 1 are summarized in table 1.
EXAMPLE 3 Synthesis of polycaprolactone
A colorless solid (room temperature) lactone polymer (107g, yield 94%) was obtained in the same manner as in example 1, except that ethylene glycol in example 1 was replaced with 10.0g (0.07mol, water content 200ppm, manufactured by Nippon Takeda chemical Co., Ltd.) of Trimethylolpropane (TMP). The analysis results of the polymer obtained by the measurement in the same manner as in example 1 are summarized in table 1.
EXAMPLE 4 Synthesis of polycaprolactone
A colorless solid (room temperature) lactone polymer (104g, yield 91%) was obtained in the same manner as in example 1, except that the ethylene glycol in example 1 was replaced with 13.6g (0.10mol, moisture content 200ppm, manufactured by Nippon Takeda chemical Co., Ltd.) of Pentaerythritol (PEN). The analysis results of the polymer obtained by the measurement in the same manner as in example 1 are summarized in table 1.
EXAMPLE 5 Synthesis of polycaprolactone
Except that phosphotungstic acid hydrate of example 1 was replaced with boron trifluoride tetrahydrofuran (BF)3THF)4.0g (0.03mol, manufactured by Sigma Aldrich Japan) of a colorless solid (room temperature) like lactone polymer (109g, yield 96%) was obtained in the same manner as in example 1. Analysis of the obtained Polymer to be determined by the same manner as in example 1The results are summarized in table 1.
EXAMPLE 6 Synthesis of polyurethane
To a 200mL reaction vessel, 100.0g (0.04mol) of the lactone polymer (polycaprolactone, PCL) synthesized in example 1 was added, heated to 70 ℃, and 34.6g (0.14mol, manufactured by Tosoh Corp., Japan) of 4, 4' -diphenylmethane diisocyanate (MDI) was added, and stirred at 80 ℃ for 3 hours. After defoaming the reaction solution by depressurizing the vessel, 8.2g (0.09mol, manufactured by Nihon Kagaku K.K.) of 1, 4-butanediol was added thereto, and the mixture was stirred at 85 to 90 ℃ for 3 minutes. Thereafter, it was cast into a glass plate mold and aged at 110 ℃ for 3 hours in a drier to obtain a polyurethane sheet (thickness 2mm) after cooling.
EXAMPLE 7 Synthesis of polyurethane
To a 200mL reaction vessel, 100.0g (0.04mol) of the lactone polymer (polycaprolactone, PCL) synthesized in example 2 was added, heated to 70 ℃, and 35.3g (0.14mol, manufactured by Tosoh Corp., Japan) of 4, 4' -diphenylmethane diisocyanate (MDI) was added, and stirred at 80 ℃ for 3 hours. After defoaming the reaction solution by depressurizing the vessel, 8.2g (0.09mol, manufactured by Nihon Kagaku K.K.) of 1, 4-butanediol was added thereto, and the mixture was stirred at 85 to 90 ℃ for 3 minutes. Thereafter, it was cast into a glass plate mold and aged at 110 ℃ for 3 hours in a drier to obtain a polyurethane sheet (thickness 2mm) after cooling.
EXAMPLE 8 Synthesis of polyurethane
To a 200mL reaction vessel, 100.0g (0.08mol) of the lactone polymer (polycaprolactone, PCL) synthesized in example 4 was added, heated to 70 ℃, and 45.8g (0.18mol, manufactured by Tosoh Corp., Japan) of 4, 4' -diphenylmethane diisocyanate (MDI) was added and stirred at 80 ℃ for 3 hours. After defoaming the reaction solution by depressurizing the vessel, 8.9g (0.10mol, manufactured by Nihon Kagaku K.K.) of 1, 4-butanediol was added thereto, and the mixture was stirred at 85 to 90 ℃ for 3 minutes. Thereafter, it was cast into a glass plate mold and aged at 110 ℃ for 3 hours in a drier to obtain a polyurethane sheet (thickness 2mm) after cooling.
[ measurement of breaking Strength and elongation at Break of polyurethane ]
The polyurethane sheet having a thickness of 2mm prepared as above was cut into a dumbbell No. 3 and cured at 23 ℃ and a humidity of 50% RH for 5 days to be used as an evaluation sample for a tensile test. The tensile strength, breaking strength (MPa) and breaking elongation (%) of the sample were determined at 23 ℃ and 50% RH using a Tensilon tensile tester (model AG-1, manufactured by Shimadzu corporation, Japan) under conditions of a chuck pitch of 20mm and a tensile rate of 500 mm/min. The measurement was performed 3 times, and the average value was calculated. The measurement results of the physical properties of the obtained polyurethane are shown in table 2.
[ measurement of thermal decomposition temperature of polyurethane ]
The following apparatus was used to measure the thermal decomposition temperature of polyurethane.
Device name: thermogravimetric-differential thermal analysis apparatus (TG-DTA) (model: DSC 3100S, manufactured by Mac Scienc, Japan K.K.)
Sample amount: 10mg of
Temperature rising conditions are as follows: 20-500 ℃, heating rate: 20 ℃ per minute
As the thermal decomposition temperature, the temperature at 1% weight change was measured. The measurement results of the thermal decomposition temperature (. degree. C.) of the obtained polyurethane are summarized in Table 2.
[ comparative example 1 ]: synthesis of polycaprolactone
A polymer (106g, yield 93%) was obtained as a colorless solid (room temperature) by the same operation and under the same conditions as in example 1, except that ethylene glycol of example 1 was replaced with 5.0g (0.05mol, water content 600ppm) of 2-methyl-1, 3-propanediol. The analysis results of the polymer obtained by the measurement in the same manner as in example 1 are summarized in table 1.
Comparative example 2 Synthesis of polycaprolactone
A colorless solid (room temperature) like lactone polymer (108g, yield 95%) was obtained by the same method as example 1 except that the ethylene glycol of example 1 was replaced with ethylene glycol having a water content of 800 ppm. The analysis results of the polymer obtained by the measurement in the same manner as in example 1 are summarized in table 1.
Comparative example 3 Synthesis of polycaprolactone
A brown solid (room temperature) polymer (112g, yield 98%) was obtained in the same manner as in example 1, except that the reaction temperature in example 1 was changed to 120 ℃. The analysis results of the polymer obtained by the measurement in the same manner as in example 1 are summarized in table 1.
Comparative example 4 Synthesis of polyurethane
To a 200mL reaction vessel, 100.0g (0.05mol) of polycaprolactone synthesized in comparative example 2 was added and heated to 70 ℃, 36.6g (0.15mol) of 4, 4' -diphenylmethane diisocyanate (MDI) was added and stirred at 80 ℃ for 3 hours. After defoaming by depressurizing the vessel, 8.3g (0.09mol) of 1, 4-butanediol was added and stirred at 85 ℃ to 90 ℃ for 3 minutes. Thereafter, a polyurethane sheet (thickness 2mm) was obtained by casting on a glass plate and aging at 110 ℃ for 3 hours in a dryer and cooling. The measurement results of the physical properties of the obtained polyurethane measured in the same manner as in example 6 are summarized in table 2.
TABLE 1
TABLE 2
As above, the molecular weight distribution M of the polyurethane polymer of the examples of the present inventionw/Mn1.08 to 1.23, nearly monodisperse, low in color number and acid value, and superior to the polyurethane polymer of the comparative example. In addition, the polyurethanes prepared using the lactone polymers of the examples of the present invention are high and excellent in breaking strength, elongation at break, and thermal decomposition temperature, as compared to the comparative examples. Thus, problems of conventional lactone polymers, such as physical properties, processability, workability, and heat resistance, can be improved as a raw material for polyurethane, polyester, or the like.
[ Industrial availability ]
The method for producing a lactone polymer of the present invention can provide a lactone polymer having a nearly monodisperse molecular weight distribution, a low color number, and a low acid value. Further, by using the lactone polymer obtained by the production method of the present invention as a raw material, a polyurethane or polyester excellent in resin physical properties, processability, heat resistance and the like can be produced.
Claims (7)
1. A method for producing a lactone polymer obtained by ring-opening polymerization of a lactone compound represented by the following general formula (1),
non-metal halides or heteropolyacids are used as catalysts,
an active hydrogen atom-containing compound is used as an initiator in the ring-opening polymerization,
adjusting the moisture content of the active hydrogen atom-containing compound,
[ chemical formula 1]
In the formula 1, R1～R3Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 6.
2. The method for producing a lactone polymer according to claim 1,
the compound containing active hydrogen atoms is a polyhydric alcohol,
0.01 to 10mol of a polyol is used with respect to 1mol of the lactone compound.
3. The method for producing a lactone polymer according to claim 1 or 2,
0.0001 to 10mol of the catalyst is used relative to 1mol of the lactone compound.
4. The method for producing a lactone polymer according to any one of claims 1 to 3,
the reaction temperature for the ring-opening polymerization is 60 ℃ to 100 ℃.
5. The method for producing a lactone polymer according to any one of claims 1 to 4,
the water content of the active hydrogen atom-containing compound is 1ppm to 500 ppm.
6. A method of preparing a polyurethane comprising:
a step of reacting the lactone polymer obtained by the method for producing a lactone polymer according to any one of claims 1 to 5 with a polyisocyanate compound to produce a polyurethane.
7. A method of making a polyester comprising:
a step of reacting the lactone polymer obtained by the method for producing a lactone polymer according to any one of claims 1 to 5 with a polyol compound to produce a polyester.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63196623A (en) * | 1987-02-12 | 1988-08-15 | Hodogaya Chem Co Ltd | Production of lactone polymer |
| TW200530290A (en) * | 2003-12-24 | 2005-09-16 | Daicel Chem | Novel lactone polymer and the preparing method thereof |
| CN104245774A (en) * | 2012-05-30 | 2014-12-24 | 日本曹达株式会社 | Polyurethane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS57155230A (en) | 1981-02-27 | 1982-09-25 | Daicel Chem Ind Ltd | Lactone polymer having narrow molecular weight distribution and its preparation |
| JP6421127B2 (en) | 2013-10-23 | 2018-11-07 | 株式会社ダイセル | Method for producing lactone polymer |
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- 2020-08-26 TW TW109129158A patent/TW202116859A/en unknown
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63196623A (en) * | 1987-02-12 | 1988-08-15 | Hodogaya Chem Co Ltd | Production of lactone polymer |
| TW200530290A (en) * | 2003-12-24 | 2005-09-16 | Daicel Chem | Novel lactone polymer and the preparing method thereof |
| CN104245774A (en) * | 2012-05-30 | 2014-12-24 | 日本曹达株式会社 | Polyurethane |
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