Classifications

• • 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
  • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
• • 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
  • C08G63/91—Polymers modified by chemical after-treatment
  • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
• • 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
• • 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
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

• the present invention relates to a method for producing a modified polyester resin.
• Polyhydroxyalkanoic acid is a resin that is biodegradable in freshwater, seawater, compost, soil, etc. Therefore, it is attracting attention as a resin that is friendly to the natural environment, and is widely used and is expected to expand its application areas in the future. ing.
• polyhydroxyalkanoic acid itself is soluble in some halogen-based solvents, it has poor solvent solubility. Therefore, it is difficult to use polyhydroxyalkanoic acid itself for inks, paints, adhesives, and the like. Therefore, in order to improve the solvent solubility of polyhydroxyalkanoic acid, attempts have been made to modify polyhydroxyalkanoic acid by various methods.
• Non-Patent Document 1 a method for modifying polyhydroxybutyric acid has been proposed in which polyhydroxybutyric acid, which is a polyhydroxyalkanoic acid, is subjected to glycolysis (reaction temperature: 170°C) with propylene glycol or diethylene glycol, and then maleic anhydride is added and heated to 240°C.
• Non-Patent Document 2 a method for modifying poly(hydroxybutyrate-co-hydroxyvalerate) is proposed in which poly(hydroxybutyrate-co-hydroxyvalerate), which is a polyhydroxyalkanoic acid, is transesterified with polybutylene adipate in the presence of a solvent.
• the present invention provides a modified polyester resin obtained by modifying a polyhydroxyalkanoic acid and having excellent solvent solubility, which can be produced without requiring purification of the product and by suppressing thermal decomposition. It aims at providing the manufacturing method of resin.
• the present inventors have found that a reactive raw material having a low proportion of aromatic components in the absence of a solvent and at a reaction temperature lower than the decomposition temperature of polyhydroxyalkanoic acid.
• the inventors have found that the above problems can be solved by modifying the polyhydroxyalkanoic acid using the polyhydroxyalkanoic acid, and have completed the present invention.
• a polyhydroxyalkanoic acid and a reactive raw material satisfying at least one of the following conditions (A-1) and (A-2) and the following condition (B) are mixed in the absence of a solvent, and the polyhydroxyalkane
• Condition (A-1) The reactive raw material contains diol and dicarboxylic acid components.
• the monomers constituting the polyhydroxyalkanoic acid are a hydroxyalkanoic acid represented by the following formula (2), a lactone of a hydroxyalkanoic acid represented by the following formula (2), and a lactone of the hydroxyalkanoic acid represented by the following formula (2).
• R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 6.
• a modified polyester resin obtained by modifying a polyhydroxyalkanoic acid and having excellent solvent solubility can be produced without requiring purification of the product and with suppressed thermal decomposition.
• the method for producing the modified polyester resin of the present invention includes at least a reaction step and, if necessary, other steps.
• reaction step the polyhydroxyalkanoic acid and the reactive raw material are reacted.
• the reaction is carried out in the absence of solvent and at a reaction temperature below the decomposition temperature of polyhydroxyalkanoic acid.
• thermal decomposition of the polyhydroxyalkanoic acid can be suppressed by conducting the reaction at a reaction temperature lower than the decomposition temperature of the polyhydroxyalkanoic acid. By doing so, it is possible to suppress the formation of by-products and the reduction in the molecular weight of the modified polyester resin, which is a reactive product, and the like. This leads to easier control of the molecular weight.
• the decomposition temperature of polyhydroxyalkanoic acid can be evaluated, for example, by GPC (gel permeation chromatography) based on the method described in Non-Patent Document (Macromolecules, 23, (1990), 1933-1936).
• GPC gel permeation chromatography
• the average degree of polymerization of a sample when heat-treated at a certain temperature is measured by GPC, and the thermal decomposition constant at each temperature can be calculated from the time dependence of the reciprocal thereof.
• the temperature at which the thermal decomposition constant was 1 ⁇ 10 ⁇ 5 min ⁇ 1 or more was defined as the decomposition temperature of the polymer.
• the polyhydroxyalkanoic acid may be a single polymer (homopolymer) consisting of one type of monomer, or may be a copolymer (copolymer) consisting of two or more types of monomers.
• the polyhydroxyalkanoic acid is a copolymer, it may be either a random copolymer or a block copolymer.
• a repeating unit in polyhydroxyalkanoic acid is represented by, for example, the following formula (1).
• R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
• n represents an integer of 0 to 6. *1 and *2 represent a bond.
• Monomers constituting polyhydroxyalkanoic acid include, for example, hydroxyalkanoic acid represented by the following formula (2), lactone of hydroxyalkanoic acid represented by the following formula (2), and the following formula (2).
• Examples include lactide of hydroxyalkanoic acid.
• R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 6.
• monomers constituting polyhydroxyalkanoic acid include lactic acid, glycolic acid, 3-hydroxybutyric acid (3-hydroxybutanoic acid), 4-hydroxybutanoic acid, 3-hydroxyvaleric acid (3-hydroxypentanoic acid ), 3-hydroxyhexanoic acid, 6-hydroxyhexanoic acid, lactide of lactic acid, ⁇ -caprolactone, and the like.
• the monomer constituting the polyhydroxyalkanoic acid is an optical isomer
• the monomer may be either L-isomer or D-isomer, and in some cases D-isomer and L-isomer may be mixed in the polymer ( DL form), and from the viewpoint of excellent physical properties such as mechanical strength, it is preferable to consist only of the D form or the L form.
• Polyhydroxyalkanoic acids include, for example, polylactic acid, polyglycolic acid, poly-3-hydroxybutanoic acid (P3HB), poly-4-hydroxybutanoic acid, poly(3-hydroxybutyrate-co-3-hydroxyvalerate ) (PHBV), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), poly- ⁇ -caprolactone and the like.
• P3HB poly-3-hydroxybutanoic acid
• PHBV poly(3-hydroxybutyrate-co-3-hydroxyvalerate )
• PHBH poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)
• a repeating unit derived from 3-hydroxyhexanoic acid lowers the crystallinity and melting point of polyhydroxyalkanoic acid and improves the solubility of polyhydroxyalkanoic acid in reactive raw materials. As a result, the reactivity in the reaction step is improved.
• thermal decomposition of the polyhydroxyalkanoic acid can be suppressed by conducting the reaction at a reaction temperature lower than the decomposition temperature of the polyhydroxyalkanoic acid.
• An example of thermal decomposition of a polyhydroxyalkanoic acid is thermal decomposition via a pseudo six-membered ring structure, such as shown below.
• thermal decomposition of polyhydroxyalkanoic acid is thermal decomposition caused by backbiting of polymer chain ends as shown below.
• the polyhydroxyalkanoic acid used may be synthesized or commercially available.
• the polyhydroxyalkanoic acid used refers to those having an average degree of polymerization of 10 or more of the constituent monomers.
• Synthesis of polyhydroxyalkanoic acid can be carried out, for example, using a general method for synthesizing polyester resins.
• the reactive raw material satisfies at least one of the following conditions (A-1) and (A-2) and the following condition (B).
• Condition (A-1) The reactive raw material contains diol and dicarboxylic acid components.
• Condition (A-2) The reactive raw material contains a polyester resin other than polyhydroxyalkanoic acid.
• the aromatic monomers constituting the reactive raw material include the aromatic monomers constituting the polyester resin.
• the reactive raw material consists of only a polyester resin, and the polyester resin has a non-aromatic diol, a non-aromatic dicarboxylic acid, and an aromatic carboxylic acid as constituent monomers in a molar ratio (non-aromatic diol: non-aromatic dicarboxylic acid When the ratio of acid:aromatic carboxylic acid is 2:1:1, the proportion of the aromatic monomer constituting the reactive raw material in the reactive raw material is 25 mol %.
• the reactive raw material is composed of only the non-aromatic diol (A), the aromatic dicarboxylic acid component (B), and the polyester resin (C), and the polyester resin (C) is used as a constituent monomer of the non-aromatic diol.
• non-aromatic diol non-aromatic dicarboxylic acid: aromatic carboxylic acid
• polyester resin in the reaction raw material
• Condition (A-1) is that the reactive feedstock contains diol and dicarboxylic acid components.
• diols contained in the reactive raw material under condition (A-1) include non-aromatic diols and aromatic diols.
• non-aromatic diols examples include aliphatic diols and alicyclic diols.
• the number of carbon atoms in the non-aromatic diol includes, for example, 1 to 15 carbon atoms.
• aliphatic diols examples include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol, and cyclohexanedimethanol. , 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, diethylene glycol, propylene glycol, tripropylene glycol and the like.
• Alicyclic diols include, for example, alicyclic diols having 6 to 15 carbon atoms.
• Alicyclic diols include, for example, 1,3-bis(2-hydroxypropyl)cyclopentane, 1,3-bis(2-hydroxybutyl)cyclopentane, 1,4-bis(hydroxymethyl)cyclohexane, 1, 4-bis(2-hydroxypropyl)cyclohexane, 1,4-bis(2-hydroxybutyl)cyclohexane and the like.
• aromatic diols examples include aromatic diols having 6 to 20 carbon atoms.
• aromatic diols having 6 to 20 carbon atoms include 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,4-bis(2-hydroxyethoxy)benzene and the like. is mentioned.
• diols may be used singly or in combination of two or more.
• dicarboxylic acid component examples include dicarboxylic acids, their anhydrides, their halides, and their esters. Examples of dicarboxylic acids include non-aromatic dicarboxylic acids and aromatic dicarboxylic acids.
• non-aromatic dicarboxylic acids examples include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, unsaturated bond-containing non-aromatic dicarboxylic acids, and the like.
• the number of carbon atoms in the non-aromatic dicarboxylic acid includes, for example, 3 to 15 carbon atoms.
• aliphatic dicarboxylic acids examples include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid and the like.
• Alicyclic dicarboxylic acids include, for example, alicyclic dicarboxylic acids having 8 to 15 carbon atoms.
• Alicyclic dicarboxylic acids include, for example, 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid.
• unsaturated bond-containing non-aromatic dicarboxylic acids examples include maleic acid and fumaric acid.
• aromatic dicarboxylic acids include aromatic dicarboxylic acids having 6 to 20 carbon atoms.
• aromatic dicarboxylic acids include orthophthalic acid, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1 , 2-bis(phenoxy)ethane-p,p'-dicarboxylic acid.
• the molar ratio of the reactive raw material diol and dicarboxylic acid component is preferably 1.0 to 2.0, particularly preferably 1.05 to 1.40.
• Condition (A-2) is that the reactive raw material contains a polyester resin other than polyhydroxyalkanoic acid.
• polyester resins include polycondensates of polyhydric alcohols such as diols and polycarboxylic acid components such as dicarboxylic acid components.
• the polyester resin may have, for example, urethane bonds, urea bonds, etc., in addition to the ester bonds.
• a polyester resin is, for example, a polyester polyol.
• a polyester polyol can be synthesized, for example, by using a polyhydric alcohol and a polyvalent carboxylic acid component when synthesizing a polyester resin such that the hydroxyl groups are in excess of the carboxyl groups.
• the molecular weight of the polyester resin is not particularly limited.
• the viscosity of the polyester resin at the reaction temperature is not particularly limited, but is preferably 4 Pa ⁇ s or less, more preferably 1.0 Pa ⁇ s or less, and particularly preferably 0.5 Pa ⁇ s or less.
• Viscosity can be measured by the following method. [Method for measuring viscosity] The viscosity of the polyester resin can be measured using a rotational rheometer.
• the measurement temperature is the same as the reaction temperature, and a parallel plate jig with a diameter of 25 mm is used as a measurement jig, with a gap of 1 mm and a shear rate of 10 s. 1 can be measured.
• the polyester resin used may be synthesized or commercially available. Synthesis of the polyester resin can be carried out using a general method for synthesizing a polyester resin.
• Condition (B) is a condition that the ratio of the aromatic monomer constituting the reactive raw material in the reactive raw material is 0 mol % or more and less than 50 mol %. Modification of the polyhydroxyalkanoic acid increases the solvent solubility of the resulting modified polyester resin. However, when a polyhydroxyalkanoic acid is modified to produce a modified polyester resin, if the reactive raw material used for modification contains a large amount of aromatic components, the degree of improvement in the solvent solubility of the obtained modified polyester resin is reduced. descend. In this respect, the method for producing a modified polyester resin of the present invention requires condition (B).
• the ratio of the aromatic monomer constituting the reactive raw material in the reactive raw material is preferably 40 mol% or less, more preferably 30 mol% or less, from the viewpoint of the solvent solubility of the modified polyester resin. mol % or less is particularly preferred. The smaller the ratio of the aromatic monomer constituting the reactive raw material in the reactive raw material, the more excellent the solvent solubility of the modified polyester resin can be obtained even if the ratio of polyhydroxyalkanoic acid in the modified polyester resin is increased.
• aromatic monomers include polyhydric alcohols having aromatic groups such as aromatic diols, and polycarboxylic acid components having aromatic groups such as aromatic dicarboxylic acid components.
• the reactive raw material may contain reactive raw materials other than diols, dicarboxylic acid components, and polyester resins.
• reactive raw materials include trihydric or higher polyhydric alcohols and trihydric or higher polycarboxylic acid components.
• the total content of the diol, dicarboxylic acid component, and polyester resin in the reactive raw material is not particularly limited, but is preferably 80% by mass or more and 100% by mass or less of the reactive raw material.
• the mass ratio between the polyhydroxyalkanoic acid (PHA) and the reactive raw material (PHA: reactive raw material) during the reaction is not particularly limited, and may be, for example, 1:99 to 99:1. , 5:95 to 95:5, or 10:90 to 90:10.
• the mass ratio of the polyhydroxyalkanoic acid (PHA) and the sum of the diol and dicarboxylic acid components during the reaction [PHA: (total of diol and dicarboxylic acid components)]
• the ratio is preferably from 1:99 to 50:50, more preferably from 3:97 to 40:60, and particularly preferably from 5:95 to 20:80, from the viewpoint that the modified polyester resin to be obtained has better dissolving solvent properties.
• the mass ratio (PHA:PE) between the polyhydroxyalkanoic acid (PHA) and the polyester resin (PE) during the reaction is 10:90 to 90:10 is preferred, 10:90 to 70:30 is more preferred, and 15:85 to 70:30 is particularly preferred.
• the reaction may be carried out without a catalyst or in the presence of a catalyst.
• Catalysts used for the reaction include, for example, acid catalysts.
• the acid catalyst include tin-based catalysts such as monobutyl tin oxide and dibutyl tin oxide; titanium-based catalysts such as titanium tetraisopropoxide and titanyl acetylacetonate; and zirconia-based catalysts such as tetra-butyl-zirconate.
• the amount of the catalyst used in the reaction is not particularly limited, but is preferably 1 to 1000 ppm by mass, more preferably 10 to 100 ppm by mass, based on the reactive raw material used.
• the reaction temperature is not particularly limited as long as it is lower than the decomposition temperature of the polyhydroxyalkanoic acid, but is preferably 100° C. or higher, more preferably 120° C. or higher, and particularly preferably 130° C. or higher.
• the reaction temperature is preferably 15° C. lower than the decomposition temperature (Td) of the polyhydroxyalkanoic acid (Td ⁇ 15° C.) or less in order to further suppress the thermal decomposition of the polyhydroxyalkanoic acid. More preferably, the temperature is 20° C. lower than the decomposition temperature (Td) of the hydroxyalkanoic acid (Td ⁇ 20° C.).
• the reaction temperature is preferably 50° C.
• Td decomposition temperature of the polyhydroxyalkanoic acid
• Td ⁇ 50° C. decomposition temperature of the polyhydroxyalkanoic acid
• the order in which the polyhydroxyalkanoic acid and the two reactive raw materials are reacted in the reaction step is not particularly limited.
• the reaction step may be carried out, for example, by any one of the following methods (i) to (iii), or a combination of two or more thereof.
• (i) or (ii) is preferable because the solvent solubility of the resulting modified polyester resin tends to be more excellent.
• R represents, for example, a hydrogen atom or an alkyl group.
• R 1 represents, for example, an alkylene group.
• k represents a positive integer.
• l represents a positive integer.
• m represents a positive integer.
• p represents a positive integer.
• n represents a positive integer.
• R 1 represents, for example, an alkylene group.
• R 2 represents, for example, an alkylene group.
• b represents a positive integer.
• R 1 represents, for example, an alkylene group.
• R represents, for example, a hydrogen atom or an alkyl group.
• p represents a positive integer.
• R represents, for example, a hydrogen atom or an alkyl group.
• R 1 represents, for example, an alkylene group.
• R 2 represents, for example, an alkylene group.
• k represents a positive integer.
• a represents a positive integer.
• R represents, for example, a hydrogen atom or an alkyl group.
• R 1 represents, for example, an alkylene group.
• R 2 represents, for example, an alkylene group.
• b represents a positive integer.
• c represents a positive integer.
• l represents a positive integer.
• n represents a positive integer.
• a polyester resin is synthesized from a diol and a dicarboxylic acid in a reaction vessel, and then a polyhydroxyalkanoic acid is added to the reaction vessel to perform the transesterification of ⁇ 5>. reactions may be carried out.
• the polyhydroxyalkanoic acid may be dissolved in the reactive raw material at a temperature lower than the reaction temperature.
• reaction includes an esterification reaction, which is a condensation reaction, water, lower alcohols, etc. are generated as by-products. They facilitate the condensation reaction by being removed from the reaction system during the reaction process.
• polyhydroxyalkanoic acid does not dissolve in other components (e.g., diol, dicarboxylic acid component, polyester polyol) even under heating (heterogeneous state), and dissolves as the reaction progresses.
• the reaction is preferably carried out in a batch reactor rather than a continuous reactor.
• the reaction is preferably carried out until no monomer (eg, diol, dicarboxylic acid component) in the reactive raw material remains in the reaction system.
• the progress of the reaction can be determined, for example, by measuring the molecular weight by GPC (gel permeation chromatograph) and judging the change in the molecular weight. For example, whether or not the monomer in the reactive raw material no longer remains in the reaction system is determined by taking out the product in the reaction system at regular time intervals and measuring the molecular weight by GPC. can be confirmed by
• the progress of the reaction can be carried out, for example, by following the decrease of the dicarboxylic acid component by measuring the acid value.
• the hydroxyl value of the obtained modified polyester resin is preferably 5.0 mgKOH/g or more. If it is 5.0 mgKOH/g or more, the solvent solubility of the modified polyester resin is further improved. This is because the relationship between the hydroxyl group and the molecular weight is inversely proportional, and the molecular weight can be appropriately kept low at 5.0 mgKOH/g or more.
• the resulting modified polyester resin preferably has a number average molecular weight (Mn) within the range of 1000 to 35000 g/mol.
• the resulting modified polyester resin preferably has a weight average molecular weight (Mw) within the range of 2000 to 50000 g/mol.
• the Mw/Mn ratio of the resulting modified polyester resin is preferably 1-6, more preferably 2-4.
• the obtained modified polyester resin can be used, for example, as a resin component for inks, paints, adhesives, adhesives, and the like.
• thermal decomposition rate of the synthesized product was determined using nuclear magnetic resonance (NMR) based on the method described in Non-Patent Document (Eur. Polym. J., 90, (2017), 92-104).
• the acid value of the synthesized product is the value measured by the acid value measurement method described in JIS-K0070.
• the hydroxyl value of the synthesized product is the value measured by the hydroxyl value measurement method by the phthalation method described in JIS-K1157.
• the viscosity of the polyester resin was measured using a rotational rheometer "MCR-102" manufactured by Anton-Paar, and the measurement temperature was the same as the reaction temperature. , under conditions of a gap of 1 mm and a shear rate of 10 s ⁇ 1 .
• Example 1 100 parts of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and 3-methyl-1 are added to a batch-type polyester reaction vessel equipped with a stirrer, nitrogen gas inlet tube, rectifying tube, moisture separator, etc. , 5-pentanediol and 0.074 parts of titanyl acetylacetonate were charged, and the internal temperature was maintained at 145° C. under a nitrogen stream.
• GPC the molecular weight had not changed
• 367 parts of sebacic acid was added, and the internal temperature was maintained at 145°C under a nitrogen stream.
• the reaction was terminated when the acid value became 2 mgKOH/g or less to obtain a polyester polyol (PHA-modified polyester).
• PHA-modified polyester As a result of GC measurement, residual monomer was not confirmed.
• the evaluation result of the thermal decomposition rate by the NMR method was A.
• solvent solubility was A.
• Example 2 The same procedure as in Example 1 was repeated except that poly(3-hydroxybutyrate), 3-methyl-1,5-pentanediol, sebacic acid and titanyl acetylacetonate were used in the formulations shown in Table 1 as raw materials to obtain a polyester. A polyol was obtained. As a result of GC measurement, residual monomer was not confirmed. The evaluation result of the thermal decomposition rate by the NMR method was A. The evaluation result of solvent solubility was A.
• Example 3 Example 1 except that poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), 1,6-hexanediol, adipic acid and titanyl acetylacetonate were used as raw materials in the formulations shown in Table 1.
• a polyester polyol was obtained in the same manner. As a result of GC measurement, residual monomer was not confirmed.
• the evaluation result of the thermal decomposition rate by the NMR method was A.
• the evaluation result of solvent solubility was A.
• Example 4 As raw materials, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), 2-methyl-1,3-propanediol, 1,4-benzenedimethanol, sebacic acid and titanium tetraisopropoxide are listed. A polyester polyol was obtained in the same manner as in Example 1, except that the composition of No. 1 was used. As a result of GC measurement, residual monomer was not confirmed. The evaluation result of the thermal decomposition rate by the NMR method was A. The evaluation result of solvent solubility was A.
• Example 5 As raw materials, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), 3-methyl-1,5-pentanediol, dimer acid and titanyl acetylacetonate were used in the formulation shown in Table 1. A polyester polyol was obtained in the same manner as in Example 1. As a result of GC measurement, residual monomer was not confirmed. The evaluation result of the thermal decomposition rate by the NMR method was A. The evaluation result of solvent solubility was A.
• Example 6 After carrying out in the same manner as in Example 4, the inside of the reaction vessel was brought into a highly depressurized state to continue the reaction, and by-product water and glycol were continuously removed to obtain a polyester polyol.
• the solvent solubility evaluation results were as shown in Table 2.
• Example 1 A polyester polyol was obtained in the same manner as in Example 1 except that the holding temperature was changed to 180°C. The thermal decomposition rate was evaluated as C by the NMR method.
• Table 1 summarizes the reaction conditions of Examples 1-6 and Comparative Examples 1-2.
• the reactions of Examples 1-6 and Comparative Examples 1-2 correspond to the following method (ii).
• -Dicarboxylic acid- Dimer acid a compound (Cas number: 61788-89-4) having the following structure as a main component, trade name: Tsuno Dime 395, manufactured by Tsuno Food Industry Co., Ltd.
• Example 7 100 parts of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), 3-methyl- 206 parts of 1,5-pentanediol, 294 parts of sebacic acid and 0.700 parts of titanium tetraisopropoxide were charged, and the internal temperature was maintained at 145° C. under nitrogen stream. The reaction was terminated when the acid value became 2 mgKOH/g or less to obtain a polyester polyol. As a result of GC measurement, residual monomer was not confirmed. The evaluation result of the thermal decomposition rate by the NMR method was A. The evaluation result of solvent solubility was A.
• Example 8 As raw materials, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), 2-methyl-1,3-propanediol, 1,4-benzenedimethanol, sebacic acid and titanium tetraisopropoxide are listed. A polyester polyol was obtained in the same manner as in Example 7 except that it was used in the formulation of No. 3. As a result of GC measurement, residual monomer was not confirmed. The evaluation result of the thermal decomposition rate by the NMR method was A. The evaluation result of solvent solubility was A.
• Example 9 After carrying out in the same manner as in Example 8, the inside of the reaction vessel was brought into a highly depressurized state to continue the reaction, and by-product water and glycol were continuously removed to obtain a polyester polyol.
• the solvent solubility evaluation results were as shown in Table 4.
• Example 4 A polyester polyol was obtained in the same manner as in Example 8 except that the holding temperature was changed to 180°C. The thermal decomposition rate was evaluated as C by the NMR method.
• Examples 7-9 and Comparative Examples 3-4 are summarized in Table 3.
• the reactions of Examples 7-9 and Comparative Examples 3-4 correspond to the following method (i).
• Example 10 100 parts of diethylene glycol, 163 parts of sebacic acid, and 0.088 parts of titanium tetraisopropoxide are charged into a batch-type polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc., and a nitrogen stream is introduced.
• the inner temperature was maintained at 220° C. under the lower temperature, and dehydration condensation was performed for a total of 9 hours to obtain a polyester resin (PE1).
• the viscosity of the polyester resin (PE1) at 135°C was 0.167 Pa ⁇ s. Viscosity was measured by the following method. The same applies to Examples 11-16 and Comparative Examples 5-7.
• the viscosity of the polyester resin was measured using a rotational rheometer. Specifically, using a rotational rheometer "MCR-102" manufactured by Anton-Paar, the measurement temperature was set to be the same as the reaction temperature. It was measured under the condition of a shear rate of 10 s -1 .
• polyester resin 500 parts of this polyester resin (PE1) was charged together with 100 parts of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and 0.060 parts of dioctyltin into a similar batch-type reactor, and the internal reaction was carried out under a nitrogen stream. The temperature was kept at 135°C. When the molecular weight did not change by GPC, the reaction was terminated to obtain a polyester polyol. As a result of GC measurement, residual monomer was not confirmed. The evaluation result of the thermal decomposition rate by the NMR method was A. The evaluation result of solvent solubility was A.
• Example 11 A polyester resin (PE2) was obtained in the same manner as in Example 10, except that the diol, dicarboxylic acid and catalyst were changed to the types and blending amounts shown in Table 5. The viscosity of the polyester resin (PE2) at 145°C was 0.008 Pa ⁇ s.
• a polyester polyol was obtained in the same manner as in Example 10, except that the types and amounts of the PHA, polyester resin and catalyst, and the reaction temperature were as shown in Table 6. As a result of GC measurement, residual monomer was not confirmed. The evaluation result of the thermal decomposition rate by the NMR method was A. The evaluation result of solvent solubility was B.
• Example 12 A polyester resin (PE3) was obtained in the same manner as in Example 10, except that the diol, dicarboxylic acid and catalyst were used in the types and amounts shown in Table 5. The viscosity of the polyester resin (PE3) at 145°C was 0.008 Pa ⁇ s.
• a polyester polyol was obtained in the same manner as in Example 10, except that the types and amounts of the PHA, polyester resin and catalyst, and the reaction temperature were as shown in Table 6. As a result of GC measurement, residual monomer was not confirmed. The evaluation result of the thermal decomposition rate by the NMR method was A. The solvent solubility evaluation results were as shown in Table 7.
• polyester resin (PE4). 100 parts of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(1, 6-Hexanediol adipate) and 0.205 parts of titanium tetraisopropoxide were charged, and the internal temperature was maintained at 145° C. under nitrogen flow. When the molecular weight did not change by GPC, the reaction was terminated to obtain a polyester polyol. As a result of GC measurement, residual monomer was not confirmed. The evaluation result of the thermal decomposition rate by the NMR method was A. The solvent solubility evaluation results were as shown in Table 7.
• Example 14 A polyester resin (PE5) was obtained in the same manner as in Example 10, except that the diol, dicarboxylic acid and catalyst were changed to the types and blending amounts shown in Table 5. The viscosity of the polyester resin (PE5) at 145°C was 0.9 Pa ⁇ s.
• a polyester polyol was obtained in the same manner as in Example 10, except that the types and amounts of the PHA, polyester resin and catalyst, and the reaction temperature were as shown in Table 6. As a result of GC measurement, residual monomer was not confirmed. The evaluation result of the thermal decomposition rate by the NMR method was A. The evaluation result of solvent solubility was B.
• Example 15 Poly(1,6-hexanediol adipate) having a viscosity of 4.5 Pa ⁇ s at 145° C. was used as the polyester resin (PE6).
• a polyester polyol was obtained in the same manner as in Example 13, except that the types and amounts of the PHA, polyester resin and catalyst, and the reaction temperature were as shown in Table 6.
• the evaluation result of the thermal decomposition rate by the NMR method was A.
• the evaluation result of solvent solubility was B.
• Example 16 After carrying out in the same manner as in Example 15, the inside of the reaction vessel was brought into a highly depressurized state to continue the reaction, and by-product water and glycol were continuously removed to obtain a polyester polyol.
• the solvent solubility evaluation results were as shown in Table 7.
• Example 5 A polyester resin (PE7) was obtained in the same manner as in Example 10, except that the diol, dicarboxylic acid and catalyst were changed to the types and blending amounts shown in Table 5.
• the viscosity of the polyester resin (PE7) at 145°C was 0.9 Pa ⁇ s.
• a polyester polyol was obtained in the same manner as in Example 10, except that the types and amounts of the PHA, polyester resin and catalyst, and the reaction temperature were as shown in Table 6.
• the evaluation result of solvent solubility was C.
• Example 6 A polyester resin (PE8) was obtained in the same manner as in Example 10, except that the diol, dicarboxylic acid and catalyst were changed to the types and blending amounts shown in Table 5.
• the viscosity of the polyester resin (PE8) at 145°C was 14.9 Pa ⁇ s.
• a polyester polyol was obtained in the same manner as in Example 10, except that the types and amounts of the PHA, polyester resin and catalyst, and the reaction temperature were as shown in Table 6. As a result of GC measurement, residual monomer was not confirmed. The evaluation result of solvent solubility was C.
• Example 7 Poly(1,6-hexanediol adipate) having a viscosity of 0.061 Pa ⁇ s at 180° C. was used as a polyester resin (PE9).
• a polyester polyol was obtained in the same manner as in Example 13, except that the types and amounts of the PHA, polyester resin and catalyst, and the reaction temperature were as shown in Table 6. The thermal decomposition rate was evaluated as C by the NMR method.
• the method for producing a modified polyester resin of the present invention can produce a modified polyester resin obtained by modifying a polyhydroxyalkanoic acid and having excellent solvent solubility without the need for purification of the product and suppressing thermal decomposition. It was confirmed that it can be manufactured by

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Polyesters Or Polycarbonates (AREA)
• Biological Depolymerization Polymers (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=83458352

Family Applications (1)

Country Status (5)

Cited By (1)

Citations (8)

Family Cites Families (5)

• 2022
  • 2022-02-17 JP JP2023510635A patent/JP7364116B2/ja active Active
  • 2022-02-17 EP EP22779624.0A patent/EP4317243A4/en active Pending
  • 2022-02-17 WO PCT/JP2022/006461 patent/WO2022209397A1/ja not_active Ceased
  • 2022-02-17 US US18/283,316 patent/US20240191023A1/en active Pending
  • 2022-02-17 CN CN202280022855.7A patent/CN117043224A/zh active Pending

Patent Citations (8)

Non-Patent Citations (6)

Also Published As

Similar Documents

Legal Events