WO2010041509A1 - ポリヒドロキシポリエステルの製造方法 - Google Patents

ポリヒドロキシポリエステルの製造方法 Download PDF

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Publication number
WO2010041509A1
WO2010041509A1 PCT/JP2009/063719 JP2009063719W WO2010041509A1 WO 2010041509 A1 WO2010041509 A1 WO 2010041509A1 JP 2009063719 W JP2009063719 W JP 2009063719W WO 2010041509 A1 WO2010041509 A1 WO 2010041509A1
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Prior art keywords
polyester
carboxyl group
polyhydroxy
product
polyhydroxypolyester
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PCT/JP2009/063719
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English (en)
French (fr)
Japanese (ja)
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和彦 井上
緑 志村
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日本電気株式会社
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Priority to CN200980139918.1A priority Critical patent/CN102177192B/zh
Priority to JP2010532851A priority patent/JPWO2010041509A1/ja
Publication of WO2010041509A1 publication Critical patent/WO2010041509A1/ja

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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

Definitions

  • the present invention relates to a method for producing a polyhydroxypolyester, and more specifically, eliminates the need to remove a linear polyester as a by-product having a carboxyl group at the terminal, and suppresses the generation of carbon dioxide generated from the terminal carboxyl group.
  • the present invention also relates to a method for producing polyhydroxypolyester which enables efficient production by reducing environmental burden.
  • Polymers having a radial molecular structure are called star polymers and hyperbranched polymers, and are attracting attention because they have different viscosity behavior and physical properties from linear polymers.
  • Polyhydroxypolyester known as a polymer having such a radial molecular structure can be used as a precursor of a three-dimensional crosslinked structure resin, and a thermosetting resin can be obtained by crosslinking with an appropriate linker.
  • Polyhydroxypolyesters can be produced by a polymerization method in which a polyfunctional hydroxy compound is used as a core and a cyclic ester composed of polyoxyacid or a polyoxyacid monomer or dimer is added sequentially, or a linear polyester having a large molecular weight is used as a core.
  • Removal of the linear polyester having a carboxyl group at the terminal is performed by a reprecipitation step after the above-described polyhydroxypolyester production step.
  • the by-product linear polyester has a lower molecular weight and higher solubility than polyhydroxypolyester, so the linear polyester is separated by reprecipitation to purify the polyhydroxypolyester. Since the amount of the solvent is large, the environmental load is large and the cost is high. Moreover, even if the organic solvent is reused by distillation, installation of distillation recovery equipment and a large amount of heat energy are required, so that environmental load and high cost are still problems.
  • Patent Documents 1 and 2 By using carbodiimide as a sealing agent for the carboxyl group of the polyester end group, and by adding an aliphatic polyester resin (Patent Documents 1 and 2) with improved hydrolysis resistance and the like, or adding carbodiimide at the time of polymerization An unsaturated polyester resin (Patent Document 3) and the like that have improved hydrolyzability have been reported.
  • An object of the present invention is to eliminate the need for a by-product removal step for the polyhydroxy polyester that can suppress the occurrence of molding defects due to the generation of carbon dioxide due to the carboxyl group at the end during molding of the molded body. Accordingly, it is an object of the present invention to provide a method for producing a polyhydroxy polyester that can be produced efficiently by eliminating the need for a solvent, a recovery device, etc., reducing the environmental burden. In particular, it is an object of the present invention to provide a method for producing a polyhydroxypolyester with good yield by forming a by-product linear polyester into a polyhydroxypolyester to effectively use the polyester.
  • the present inventors obtained a polyhydroxy polyester by growing a polyester using an oxyacid on a polyhydroxy compound serving as a nucleus, and then added a carboxyl group blocking agent to the reaction system to form a linear product as a by-product.
  • the carboxyl group at the end of the polyester is bonded to a carboxyl group-capping agent.
  • the reaction system does not contain a linear polyester having a carboxyl group at the terminal, and the knowledge that the purification step for removing the linear polyester from the obtained reaction product can be omitted. It was.
  • the present invention relates to a polyhydroxy polyester obtained by growing a polyester using a nucleating polyhydroxy compound having two or more hydroxy groups and an oxyacid, and a linear product having a carboxyl group at a terminal as a by-product. After obtaining the polyester, a carboxyl group-capping agent is added to the reaction system, the carboxyl group-capping agent and the carboxyl group at the end of the linear polyester are bonded, and the hydroxyl group equivalent is 50,000 g / mol or less.
  • the present invention relates to a method for producing a polyhydroxypolyester characterized by obtaining a polyhydroxypolyester.
  • the method for producing a polyhydroxypolyester according to the present invention comprises a step of removing a by-product from a polyhydroxypolyester capable of suppressing the occurrence of molding defects due to the generation of carbon dioxide due to carboxyl groups at the end during molding of a molded article.
  • a solvent, a recovery device, and the like are not required, and the environmental load can be reduced, so that efficient production can be achieved.
  • the polyhydroxypolyester can be produced with good yield by making effective use thereof.
  • the method for producing a polyoxypolyester according to the present invention comprises growing a polyester using a nucleating polyhydroxy compound having two or more hydroxy groups and an oxyacid to form a polyhydroxypolyester and a by-product as a carboxyl group at the terminal. After obtaining a linear polyester having a hydroxyl group, a carboxyl group-capping agent is added to the reaction system, and the carboxyl group-capping agent and the carboxyl group at the end of the linear polyester are bonded to each other. 000 g / mol or less of polyhydroxypolyester is obtained.
  • the nucleation polyhydroxy compound used in the method for producing a polyoxypolyester of the present invention may be any compound having two or more hydroxy groups and capable of ester reaction with a carboxyl group of oxyacid.
  • Specific examples of such nucleating polyhydroxy compounds include ethylene glycol, propylene glycol, dipropylene glycol, 1,3- or 1,4-butanediol, dihydric alcohols such as 1,6-hexanediol, glycerin, Trivalent alcohols such as trimethylolpropane, trimethylolethane and hexanetriol, tetrahydric alcohols such as pentaerythritol, methylglycoside and diglycerin, polyglycerins such as triglycerin and tetraglycerin, polypentyl such as dipentaerythritol and tripentaerythritol Examples thereof include cycloalkane polyols such as pentaeryth
  • sugar alcohols such as adonitol, arabitol, xylitol, sorbitol, mannitol, iditol, tallitol, dulcitol
  • sugars such as glucose, mannose glucose, mannose, fructose, sorbose, sucrose, lactose, raffinose, and cellulose
  • a polyoxypolyester with high environmental compatibility will be obtained.
  • the oxyacid may be any one as long as it has one carboxyl group that allows the polyester to grow by reacting with the hydroxy group of the nucleating polyhydroxy compound and one hydroxy group.
  • Specific examples of the oxyacid include aromatic hydroxy acids such as p-hydroxybenzoic acid, glycolic acid which is a biodegradable resin, lactic acid, ⁇ -caprolactone, ⁇ -hydroxybutyric acid, linolenic acid, 12-hydroxystearic acid and the like. Can be mentioned. These can be used alone or in combination of two or more.
  • oxyacid a homocondensation polymer or a condensation copolymer of the oxyacid, a mixture of two or more selected from these polymers, and the like can also be used. Moreover, by using a plant-derived raw material or a biodegradable resin as the oxyacid, the resulting polyoxypolyester itself becomes a material with high environmental compatibility.
  • the production method for growing the polyester using the nucleating polyhydroxy compound and oxyacid is not particularly limited, and examples thereof include a method of polymerizing by heating the polyhydroxy compound and oxyacid together with a catalyst.
  • the catalyst used include tin octylate when lactide is used as the oxyacid.
  • the ratio of the amount of the nucleating polyhydroxy compound and the oxyacid used is such that the hydroxyl group equivalent of the resulting polyhydroxypolyester is 50,000 g / mol or less.
  • the reaction between the nucleating polyhydroxy compound and the oxyacid causes an esterification reaction between the hydroxy group of the nucleating polyhydroxy compound and the carboxyl group of the oxyacid. Thereafter, the esterification reaction of the oxyacid is repeated and the polyester grows. Thereby, the polyhydroxy polyester which has a hydroxyl group at the terminal is formed.
  • a dihydroxy compound is used as the nucleating polyhydroxy compound, a dihydroxy polyester having hydroxy groups at both ends is obtained, and when a polyhydroxy compound having three or more hydroxy groups is used, a radial polyhydroxy polyester is obtained.
  • a linear polyester having a hydroxy group at one end and a carboxyl group at the other end is obtained as a by-product by an esterification reaction of an oxyacid that does not bind to the hydroxy group of the nucleating polyhydroxy compound. It is done.
  • the polyhydroxypolyester can also be obtained by previously forming a linear polyester by an esterification reaction of an oxyacid and then performing an ester exchange reaction with the nucleating hydroxy compound. Since the linear polyester has a hydroxy group at one end and a carboxyl group at the other end, the resulting polyhydroxypolyester has a hydroxy group at the end. In this reaction system, linear polyester that is a by-product of the transesterification reaction and linear polyester that does not undergo reaction with the nucleating hydroxy compound remain.
  • the carboxyl group-capping agent added to the reaction system containing the main product of the polyhydroxy polyester and the linear polyester having a carboxyl group at one end as a by-product is bonded to the terminal carboxyl group of the linear polyester. Any one can be used. Furthermore, it is preferable to have a plurality of functional groups that bind to a carboxyl group, because a linear polyester can be formed into a radial polyester.
  • Such carboxyl group-capping agents include monocarbodiimide compounds having one functional group bonded to the carboxyl group at the end of the linear polyester, polycarbodiimide compounds having two or more functional groups, oxazoline compounds, oxazine compounds, epoxy A compound etc. can be mentioned. Of these, carbodiimide compounds and epoxy compounds are preferable, and these can be used in combination.
  • the monocarbodiimide compound has one carbodiimide group in one molecule, and specifically includes diphenylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, di-2,6-diethylphenylcarbodiimide, di-2, 6-diisopropylphenylcarbodiimide, di-2,6-ditert-butylphenylcarbodiimide, di-o-tolylcarbodiimide, di-p-tolylcarbodiimide, di-2,4,6-trimethylphenylcarbodiimide, di-2,4 , 6-triisopropylphenylcarbodiimide, di-2,4,6-triisobutylphenylcarbodiimide and other aromatic monocarbodiimides; di-cyclohexylcarbodiimide and other alicyclic monocarbodiimides; di-isopropylcarbodiimide, di-octadecyl
  • aromatic monocarbodiimide is preferable from the viewpoint of showing good reactivity with a carboxyl group, and di-2,6-diisopropylphenylcarbodiimide and di-2,6-dimethylphenylcarbodiimide are more preferable.
  • a polycarbodiimide compound is a compound having two or more carbodiimide groups in one molecule, and is obtained by subjecting diisocyanate to a condensation reaction using a catalyst such as 3-methyl-1-phenyl-2-phospholene-1-oxide. It is done.
  • the diisocyanate used as a raw material include aromatic diisocyanate compounds, aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and mixtures thereof.
  • polycarbodiimide compounds include Carbodilite LA-1 (Nisshinbo, Aliphatic), Carbodilite V-05 (Nisshinbo, Aromatic), Carbodilite V-02B (Nisshinbo, isocyanate-blocked) ), Stabaxol P (manufactured by Rhein Chemie, aromatic) and the like.
  • epoxy compound as the carboxyl group-capping agent examples include epoxy-modified acrylic resins (ARUFON UG4040: manufactured by Toa Gosei Co., Ltd., Jongkrill ADR-4368: manufactured by BASF Japan Ltd., Mar. Proof G-0150M: manufactured by NOF Corporation, Modiper A4300: manufactured by NOF Corporation, Bond Fast 7M: manufactured by Sumitomo Chemical Co., Ltd.), and epoxy-modified natural oil (Newsizer 510R: NOF ( And the like). Moreover, these can be utilized industrially and are preferable.
  • a polyhydroxy compound such as a nucleation polyhydroxy compound can also be applied.
  • the amount of the carboxyl group-capping agent added can be appropriately selected depending on the amount of carboxyl groups produced in the by-product.
  • the molar ratio of the functional group of the carboxyl group sealing agent to the carboxyl group is preferably 0.9 or more from the viewpoint that the functional group can be generally bonded to the carboxyl group, more preferably 1.0 or more, and still more preferably. Is 1.1 or more.
  • the amount of carboxyl groups contained in the by-product can be determined by dissolving these products in chloroform and methanol solution, adding an indicator such as phenol red, and titrating with an aqueous sodium hydroxide solution. .
  • the mass ratio of the polycarbodiimide compound to be added is 20% by mass or less based on the by-product, and the polyester is hydrolyzed by the excess polycarbodiimide compound. It is preferable because it is possible to suppress the deterioration of the mechanical properties of a molded article obtained using the same. More preferably, it is 10 mass% or less, More preferably, it is 5 weight% or less.
  • the excess polycarbodiimide compound causes gelation, and therefore, it is preferable to use a compound in which the terminal isocyanate group of the polycarbodiimide compound is blocked.
  • the terminal isocyanate group of the polycarbodiimide compound can be blocked beforehand by, for example, a urethane reaction with a hydroxy compound.
  • the bond between the carboxyl group-capping agent and the carboxyl group at the end of the linear polyester is such that the required amount of carboxyl group is sealed in the reaction system containing the main product radial polyester and the by-product linear polyester in the molten state. It can be performed by adding a stop agent and mixing with heating.
  • the heating and mixing time is affected by the heating temperature, the concentration of the carboxyl group, and the like. For example, when the reaction is performed at 150 ° C. or higher, the heating time is preferably 1 minute or more, more preferably 10 minutes or more, More preferably, it is 1 hour or more. Since the polyester group may be hydrolyzed during the heating reaction due to moisture in the air or may be oxidatively deteriorated by oxygen, the reaction is preferably performed in a nitrogen atmosphere.
  • the terminal carboxyl group of the linear polyester is bonded to the carboxyl group-capping agent, and a linear polyester having no carboxyl group at the terminal is obtained.
  • a carboxyl group sealant having multiple functional groups that bind to carboxyl groups is used, multiple linear polyesters bind to the carboxyl group sealant to form a radial polyester and remove by-products. This eliminates the need for a purification step, reduces the environmental burden, and can efficiently obtain a radial polyester having only a hydroxy group at the terminal.
  • the hydroxyl equivalent of the polyhydroxypolyester and linear polyester thus obtained is 50,000 g / mol or less, preferably 20,000 g / mol or less.
  • a polymer having a low viscosity having excellent moldability as a hyperbranched polymer can be obtained.
  • the obtained polyhydroxypolyester is used as a thermosetting resin raw material, the hydroxyl equivalent is 10,000 g / mol or less to obtain a thermosetting resin excellent in heat resistance, strength, elastic modulus and the like. From the above, more preferably 5,000 g / mol or less, still more preferably 3,000 g / mol or less.
  • Example 1 7 g of sorbitol was added to 200 g of polylactic acid (Unitika Ltd. TE-4000), and the mixture was heated and melted and mixed in a nitrogen atmosphere at 200 ° C. for 4 hours to obtain a crude polyhydroxypolyester (P) (Comparative Example 1). .
  • FIG. 1 shows changes with time in the molecular weight and carboxyl group concentration of the polyhydroxypolyester in this reaction. As the reaction progressed, the carboxyl group increased to 88 ⁇ mol / g.
  • the molecular weight was measured by GPC (10A-VP: manufactured by Shimadzu Corporation).
  • the carboxyl group concentration was determined by dissolving a sample (100 mg) in a mixed solvent of chloroform (20 ml) and methanol (20 ml), and titrating with 0.01 N aqueous sodium hydroxide solution using phenol red as an indicator.
  • Example 2 P (10 g) was melted at 200 ° C., and polycarbodiimide B (V-02B: Nisshinbo Co., Ltd., carbodiimide equivalent 603 g / mol) was added by 5.0 mass%, followed by heating and mixing for 1 hour. In the same manner as in Example 1, the molecular weight and carboxyl group concentration of the obtained polyhydroxypolyester were measured. The results are shown in Table 1.
  • Example 3 P (10 g) was melted at 200 ° C., and 2.1% by mass of polycarbodiimide C (LA-1: Nisshinbo Co., Ltd., carbodiimide equivalent 247 g / mol) was added thereto, followed by heating and mixing for 1 hour. In the same manner as in Example 1, the molecular weight and carboxyl group concentration of the obtained polyhydroxypolyester were measured. The results are shown in Table 1.
  • Example 4 P (10 g) was melted at 200 ° C., and 3.1% by mass of polycarbodiimide D (Rheinheme Co., Ltd .: stavaxol P, carbodiimide equivalent 360 g / mol) was added thereto, followed by heating and mixing for 1 hour. In the same manner as in Example 1, the molecular weight and carboxyl group concentration of the obtained polyhydroxypolyester were measured. The results are shown in Table 1.
  • Example 5 After melting P (10 g) at 200 ° C. and adding 4.1% by mass of epoxy-modified acrylic resin E (ARUFON UG4040: manufactured by Toagosei Co., Ltd., epoxy equivalent: 480 g / mol), heat for 1 hour. Mixed. In the same manner as in Example 1, the molecular weight and carboxy group concentration of the obtained polyhydroxypolyester were measured. The results are shown in Table 1.
  • the method for producing a polyhydroxypolyester of the present invention can efficiently produce a polyhydroxypolyester having a significantly reduced content of by-products at a low cost. Foaming is suppressed, and it is particularly useful as a thermosetting resin having a radial molecular structure.
  • the present invention includes all contents described in the claims, specification, or drawings of Japanese Patent Application No. 2008-263997 (filed on October 10, 2008) on which the priority of the present invention is based. Is included.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
PCT/JP2009/063719 2008-10-10 2009-08-03 ポリヒドロキシポリエステルの製造方法 WO2010041509A1 (ja)

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CN200980139918.1A CN102177192B (zh) 2008-10-10 2009-08-03 多羟基聚酯的制造方法
JP2010532851A JPWO2010041509A1 (ja) 2008-10-10 2009-08-03 ポリヒドロキシポリエステルの製造方法

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JP2008-263997 2008-10-10

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08100057A (ja) * 1994-09-29 1996-04-16 Dainippon Ink & Chem Inc 乳酸系共重合体の製造方法
JP2007126653A (ja) * 2005-10-31 2007-05-24 Kureha Corp 脂肪族ポリエステル組成物の製造方法
JP2008094887A (ja) * 2006-10-06 2008-04-24 Mitsubishi Chemicals Corp バイオマス資源由来ポリエステル製シート及びその製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1546549A (zh) * 2003-12-04 2004-11-17 中国科学院上海有机化学研究所 一种生物降解性聚酯嵌段高分子共聚物、制备方法及用途

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08100057A (ja) * 1994-09-29 1996-04-16 Dainippon Ink & Chem Inc 乳酸系共重合体の製造方法
JP2007126653A (ja) * 2005-10-31 2007-05-24 Kureha Corp 脂肪族ポリエステル組成物の製造方法
JP2008094887A (ja) * 2006-10-06 2008-04-24 Mitsubishi Chemicals Corp バイオマス資源由来ポリエステル製シート及びその製造方法

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CN102177192B (zh) 2013-06-12
CN102177192A (zh) 2011-09-07

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