WO2013183590A1 - ポリブチレンテレフタレートの製造方法 - Google Patents
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- 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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
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- C12Y101/01—Oxidoreductases acting on the CH-OH group of donors (1.1) with NAD+ or NADP+ as acceptor (1.1.1)
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- C12Y102/01—Oxidoreductases acting on the aldehyde or oxo group of donors (1.2) with NAD+ or NADP+ as acceptor (1.2.1)
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- C12Y102/04—Oxidoreductases acting on the aldehyde or oxo group of donors (1.2) with a disulfide as acceptor (1.2.4)
- C12Y102/04002—Oxoglutarate dehydrogenase (succinyl-transferring) (1.2.4.2), i.e. alpha-ketoglutarat dehydrogenase
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Definitions
- the present invention relates to a method for producing polybutylene terephthalate having good color tone from 1,4-butanediol derived from biomass resources.
- PBT Polybutylene terephthalate
- PBT can be obtained by reacting terephthalic acid or an alkyl ester thereof with 1,4-butanediol (hereinafter sometimes abbreviated as “1,4-BG”). Since BG is easily converted to tetrahydrofuran (hereinafter sometimes abbreviated as “THF”) during the reaction, there is a method for producing PBT with a high yield that suppresses the conversion of 1,4-BG to THF. Desired.
- 1,4-BG 1,4-butanediol
- the PBT is expected to move away from raw materials derived from fossil fuels as well as energy.
- raw materials derived from biomass resources that use plants and the like as raw materials are one of the promising raw material candidates, and 1,4-BG, which is a raw material for PBT, is also a 1,4-BG derived from biomass resources.
- a method for producing PBT using BG as a raw material has been studied.
- the color tone of the obtained PBT is worse than when the raw material 1,4-BG obtained from fossil fuel such as petroleum is used.
- the main cause of this color deterioration is the presence of a nitrogen atom-containing component in the PBT. Further, it is considered that there is an influence on the PBT color tone by other components than this component.
- Patent Document 1 discloses a technique for obtaining PBT using a raw material derived from biomass resources by controlling the nitrogen atom content of the raw material 1,4-BG derived from biomass resources to 0.01 to 50 ppm by mass. It describes about obtaining PBT with an atomic content of 50 mass ppm or less. Furthermore, 1-acetoxy-4-hydroxybutane (hereinafter sometimes abbreviated as “1,4-HAB”) contained in the raw material 1,4-BG delays the polycondensation reaction of PBT, and PBT However, it is described that the use of 1,4-BG having a controlled nitrogen atom concentration in the raw material 1,4-BG as a raw material can reduce PBT coloring due to polymerization delay.
- 1,4-HAB 1-acetoxy-4-hydroxybutane
- gamma-butyrolactone (hereinafter sometimes abbreviated as “GBL”) is generated as a by-product in the conventional method for producing 1,4-BG.
- GBL gamma-butyrolactone
- Patent Document 2 discloses that in a process for producing 1,4-BG from a fossil fuel-derived raw material, 1,4-BG is hydrogenated from maleic acid, succinic acid, maleic anhydride and / or fumaric acid, and the like. It is described that gamma-butyrolactone is produced as a by-product in obtaining a crude hydrogenation product containing BG.
- Patent Document 3 produces 1,4-BG by performing chemical reduction or biotechnological hydrogenation of succinic acid derived from biomass resources.
- Patent Document 4 describes a method for obtaining 1,4-BG by direct fermentation from bacterial cells.
- Patent Document 3 involves hydrogenation similar to that of Patent Document 2, there is a high possibility that GBL by-product will proceed.
- Patent Document 4 there is a high possibility that GBL is generated as a by-product from a metabolic pathway or the like. Further, Patent Documents 1 to 4 do not describe the relationship between gamma-butyrolactone contained in the raw material 1,4-BG and the nitrogen atom-containing compound.
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a method for efficiently producing PBT with good color tone using 1,4-BG derived from biomass resources as a raw material.
- the present inventors have found that gamma-butyrolactone contained in the raw material 1,4-BG reacts with the nitrogen atom-containing compound in the raw material 1,4-BG during the production of PBT. It was found that the compound produced in this way causes a new coloration of PBT.
- the color tone is good by controlling the content of gamma-butyrolactone in 1,4-BG to a specific amount.
- the present inventors have found that it is possible to obtain a reliable PBT and have completed the present invention. That is, the gist of the present invention resides in the following [1] to [6].
- a method for producing polybutylene terephthalate which comprises a step (a) of reacting or transesterifying, and a polycondensation reaction step (b) for obtaining a polybutylene terephthalate by polycondensation reaction of the reaction product obtained in the step (a).
- a method for producing polybutylene terephthalate wherein the content of gamma-butyrolactone in the raw material 1,4-butanediol is 1 to 100 ppm by mass.
- the method for producing polybutylene terephthalate according to [2] wherein the content of gamma-butyrolactone in the crude 1,4-butanediol is 101 mass ppm to 2 mass%.
- Non-naturally occurring microbial biocatalyst at least one exogenous encoding 4-hydroxybutanoate dehydrogenase, succinyl-CoA synthase, CoA-dependent succinic semialdehyde dehydrogenase, or ⁇ -ketoglutarate decarboxylase
- a microbial biocatalyst comprising a microorganism having a 4-hydroxybutanoic acid biosynthetic pathway comprising a nucleic acid, wherein said microorganism comprises a sufficient amount of said exogenous nucleic acid to secrete said 4-hydroxybutanoic acid monomer
- PBT having a good color tone can be efficiently produced using 1,4-BG derived from biomass resources as a raw material.
- FIG. 1 shows the relationship between the color tone of PBT obtained by the PBT production method (nitrogen atom-containing biomethod) and the conventional PBT production method (the petrification method) of the present invention and the GBL content of raw material 1,4-BG.
- FIG. 1 shows the relationship between the color tone of PBT obtained by the PBT production method (nitrogen atom-containing biomethod) and the conventional PBT production method (the petrification method) of the present invention and the GBL content of raw material 1,4-BG.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the lower limit value or the upper limit value in the present specification means a range including the value of the lower limit value or the upper limit value.
- “weight%”, “weight ppm”, “part by weight”, and “weight ratio” are synonymous with “mass%”, “mass ppm”, “part by weight”, and “mass ratio”, respectively. .
- ppm when “ppm” is simply described, it means “ppm by weight”.
- PBT is obtained by subjecting a dicarboxylic acid component containing terephthalic acid or an alkyl ester of terephthalic acid to a diol component containing raw material 1,4-butanediol derived from biomass resources, It can be obtained by subjecting the reaction product to a polycondensation reaction.
- the alkyl group of the terephthalic acid alkyl ester is preferably an alkyl group having 1 to 3 carbon atoms.
- the terephthalic acid or terephthalic acid alkyl ester used as a raw material is preferably 80 mol% or more, more preferably 90 mol% or more, and most preferably 100 mol% of the total dicarboxylic acid component.
- the biomass resource-derived raw material 1,4-BG is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 99 mol% or more of the total diol component.
- the mechanical strength, heat resistance, fragrance retaining property and the like as a molded product are preferable.
- the dicarboxylic acid component used as a raw material may contain a dicarboxylic acid component other than terephthalic acid or terephthalic acid alkyl ester as a main component, and other dicarboxylic acid components together with terephthalic acid or terephthalic acid alkyl ester in a reactor. May be supplied.
- dicarboxylic acid components include phthalic acid, isophthalic acid, dibromoisophthalic acid, sodium sulfoisophthalate, phenylenedioxydicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 4 , 4′-diphenylketone dicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and the like, and ester-forming derivatives thereof Alicyclic dicarboxylic acids such as hexahydroterephthalic acid and hexahydroisophthalic acid and their ester-forming derivatives; succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic
- the diol component as a raw material may contain a diol component other than the biomass resource-derived raw material 1,4-BG, and other diol components may be reacted with the biomass resource raw material 1,4-BG. May be supplied to the vessel.
- Examples of other diol components include ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, 1,2- Butanediol, 1,3-butanediol, 2,3-butanediol, 1,3-pentanediol, 2,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, polyethylene glycol, poly Aliphatic chain diols such as tetramethylene glycol; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedimethylol, 2,5-norbornane dimethylol, etc.
- Alicyclic Diols xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-hydroxyphenyl) propane, 2,2-bis (4′- ⁇ -hydroxyethoxyphenyl) propane, bis (4-hydroxy Aromatic diols such as phenyl) sulfone and bis (4′- ⁇ -hydroxyethoxyphenyl) sulfonic acid; ethylene oxide adduct or propylene oxide adduct of 2,2-bis (4′-hydroxyphenyl) propane; derived from biomass resources 1,4-BG etc. which are not. These may be used alone or in combination of two or more.
- the following components may be further used as a copolymerization component in addition to the dicarboxylic acid component and the diol component.
- the copolymer component include glycolic acid, p-hydroxybenzoic acid, hydroxycarboxylic acid such as p- ⁇ -hydroxyethoxybenzoic acid, alkoxycarboxylic acid, stearyl alcohol, heneicosanol, octacosanol, benzyl alcohol, stearic acid, behen.
- Monofunctional components such as acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid, tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetetracarboxylic acid, gallic acid, trimethylolethane, trimethylolpropane , Trifunctional or higher polyfunctional components such as glycerol, pentaerythritol and sugar ester. Regarding these copolymer components, one kind may be used alone, or two or more kinds may be mixed and used.
- the raw material 1,4-BG used in the production of the PBT of the present invention is derived from biomass resources and is preferable from the viewpoint of environmental protection.
- Biomass resources are those that are stored by converting the light energy of the sun into forms such as starch and cellulose by the photosynthetic action of plants, animals that grow by eating plants, and plants and animals that are processed. Products that can be produced. Specifically, wood, rice straw, rice bran, old rice, corn, sugar cane, cassava, sago palm, okara, corn cob, tapioca cass, bagasse, vegetable oil residue, buckwheat, buckwheat, soybean, oil and fat, waste paper, paper residue, marine product residue, Examples include livestock excrement, sewage sludge, and food waste.
- plant resources such as wood, rice straw, old rice, corn, sugar cane, cassava, sago palm, okara, corn cob, tapioca cass, bagasse, vegetable oil residue, potato, buckwheat, soybeans, fats and oils, waste paper, papermaking residue, etc. are more preferable.
- Preferred examples include wood, rice straw, old rice, corn, sugar cane, cassava, sago palm, straw, oil and fat, waste paper, papermaking residue, and the like, and most preferred are corn, sugar cane, cassava, and sago palm.
- Biomass resources generally contain many alkali metals and alkaline earth metals such as nitrogen atoms, Na, K, Mg, and Ca.
- the method of these biomass resources is not particularly limited.
- the biomass resources are subjected to known pretreatment and saccharification processes such as chemical treatment with acids and alkalis, biological treatment using microorganisms, physical treatment, and the like. Induced to carbon source.
- the process often includes a refinement process by pretreatment such as chipping, scraping, or crushing biomass resources, and further includes a grinding process by a grinder or a mill as necessary.
- the refined biomass resources are usually guided to a carbon source through further pretreatment and saccharification steps.
- Specific methods include chemical methods such as acid treatment with strong acids such as sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid, alkali treatment, ammonia freeze steaming explosion method, solvent extraction, supercritical fluid treatment, oxidizing agent treatment; Examples thereof include physical methods such as pulverization, steam explosion, microwave treatment, and electron beam irradiation; biological treatments such as hydrolysis by microorganisms and enzyme treatment.
- Carbon sources derived from the above biomass resources usually include hexoses such as glucose, mannose, galactose, fructose, sorbose, tagatose; pentoses such as arabinose, xylose, ribose, xylulose, ribulose; pentose, saccharose, starch, cellulose Disaccharides and polysaccharides such as butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, rirenonic acid, monoctinic acid, arachidic acid, eicosene Fats and oils such as acid, arachidonic acid, behenic acid, erucic acid, docosapentaenoic acid, docosahexaenoic acid, lignoceric acid and ceracolonic acid; poly
- hexose such as glucose, fructose, xylose, saccharose, pentose or disaccharide is preferable, and glucose is particularly preferable.
- cellulose which is a main component of paper is also preferable.
- these carbon sources are used as a raw material by fermentation methods by microbial conversion, chemical conversion methods including reaction steps such as hydrolysis, dehydration reaction, hydration reaction, oxidation reaction, etc., and combinations of these fermentation methods and chemical conversion methods.
- 1,4-BG is synthesized.
- the fermentation method by microbial conversion is preferable.
- the microorganism used in the fermentation method by microbial conversion is not particularly limited, and examples thereof include coryneform bacteria, Escherichia coli, Anaerobiospirillum genus, Actinobacillus genus, filamentous fungi and yeast. Can be mentioned. Among the microorganisms, coryneform bacteria, Escherichia coli, Anaerobiospirillum genus and yeast are preferable, coryneform bacteria, Escherichia coli and yeast are more preferable, and Escherichia coli is particularly preferable.
- the raw material 1,4-BG derived from biomass resources used in the present invention may be produced directly from a carbon source such as glucose, fructose, xylose and saccharose described above by a fermentation method, or obtained by a fermentation method. It may be obtained by converting succinic acid, succinic anhydride, succinic acid ester, gamma butyrolactone and its derivatives into 1,4-BG by chemical reaction. Further, 1,4-BG may be produced from propylene, butadiene, butane, acetylene, synthesis gas and the like obtained by fermentation. Among these, the method of directly obtaining the raw material 1,4-BG by fermentation is efficient and preferable.
- Examples of the reduction catalyst for hydrogenating succinic acid include Pd, Ru, Re, Rh, Ni, Cu, Co and compounds thereof. Specifically, Pd / Ag / Re, Ru / Ni / Co / ZnO, Cu / Zn oxide, Cu / Zn / Cr oxide, Ru / Re, Re / C, Ru / Sn, Ru / Pt / Sn , Pt / Re / alkali, Pt / Re, Pd / Co / Re, Cu / Si, Cu / Cr / Mn, ReO / CuO / ZnO, CuO / CrO, Pd / Re, Ni / Co, Pd / CuO / CrO 3 , phosphoric acid Ru, Ni / Co, Co / Ru / Mn, Cu / Pd / KOH, Cu / Cr / Zn, and the like. Among these, Ru / Sn or Ru / Pt / Sn is preferable in terms of catalytic
- raw material 1,4-BG from biomass resources by a combination with a known organic chemical catalytic reaction
- a method of producing raw material 1,4-BG from biomass resources by a combination with a known organic chemical catalytic reaction is also used.
- raw material 1,4-BG can be easily produced by a combination of a known dehydration reaction and catalytic reaction.
- the raw material 1,4-BG derived from biomass resources contains nitrogen atom-containing compounds as impurities due to the fermentation process and the purification process including the acid neutralization step. Specifically, nitrogen atom-containing compounds such as amino acids, proteins, ammonia, urea, and fermenting bacteria are included.
- the nitrogen atom content of the raw material 1,4-BG obtained from biomass resources, which is a raw material for PBT is a mass ratio with respect to the raw material 1,4-BG, and the upper limit is usually 50 ppm, preferably 20 ppm, more preferably 10 ppm, more preferably 5 ppm. Further, the lower limit is usually 0.01 ppm, preferably 0.1 ppm, and particularly preferably 0.2 ppm from the viewpoint of economy of the purification process. As the nitrogen atom content in the raw material 1,4-BG decreases, the color tone of the produced PBT tends to be more favorable.
- the larger the number the easier the purification process becomes and it is economically advantageous, and the conversion rate of 1,4-BG to THF during the PBT production reaction is also easily suppressed.
- the nitrogen atom content in 1,4-BG can be measured by the method described in the Examples section below, but the measuring method is not limited to this.
- the reason why the nitrogen atom content of the raw material 1,4-BG used in the production of PBT in the present invention is 0.01 to 50 ppm by mass is not certain in terms of the polycondensation reaction rate and color tone.
- a coloring attractant that deteriorates the color tone of PBT by inhibiting the polycondensation reaction in the purification process including distillation and treatment for controlling the nitrogen atom content of the raw material 1,4-BG It is presumed that the generation of can be suppressed.
- the raw material 1,4-BG used in the present invention contains GBL, which is considered to generate a nitrogen atom-containing compound and various amides, amines, amino acids and other derivatives. Therefore, it is considered that a component that strongly deteriorates the color tone of PBT exists in these derivatives.
- the nitrogen atom content in the raw material 1,4-BG derived from the biomass resource is, for example, when hydrogenated succinic acid obtained by fermentation of the biomass resource to obtain the raw material 1,4-BG, its fermentation conditions, ammonia It is possible to adjust the amount of the nitrogen atom-containing compound in succinic acid according to the neutralization conditions by succinic acid and the crystallization conditions of succinic acid. Further, 1,4-BG obtained by hydrogenating succinic acid can adjust its nitrogen atom content according to purification conditions including distillation. Also, when the raw material 1,4-BG is obtained directly by fermentation of biomass resources, it should be adjusted according to the fermentation conditions, neutralization conditions with ammonia, purification conditions including distillation of the obtained 1,4-BG, etc. Can do.
- the raw material 1,4-BG derived from biomass resources usually contains GBL as an impurity.
- GBL an impurity
- the raw material 1,4-BG is produced by hydrogenation via maleic acid, succinic acid, succinic anhydride, succinic acid ester, etc. as an intermediate, or when 2-hydroxytetrahydrofuran is contained as an impurity and dehydrogenated
- the raw material 1,4-BG contains GBL as an impurity.
- the raw material 1,4-BG used for the production of PBT is crude 1,4-BG containing a large amount of by-product GBL as described above
- the crude 1,4-BG is purified.
- Raw material 1,4-BG can be obtained.
- the GBL content in the crude 1,4-BG is a mass ratio to the crude 1,4-BG
- the upper limit is usually 2% by mass, preferably 1% by mass, more preferably 1000 ppm, particularly preferably 200 ppm. Most preferably, it is 180 ppm.
- the lower limit is usually 101 ppm, preferably 120 ppm, and the lower limit is particularly preferably 150 ppm from the viewpoint of economy of the fermentation process and the hydrogenation process.
- the GBL content of the raw material 1,4-BG used for the production of PBT in the present invention is a mass ratio with respect to the raw material 1,4-BG, and the upper limit is usually 100 ppm, preferably 50 ppm, more preferably Is 40 ppm, particularly preferably 30 ppm, most preferably 20 ppm. Further, the lower limit is usually 1 ppm, preferably 2 ppm, and in particular, the lower limit is preferably 5 ppm from the viewpoint of economy of the purification process. As the GBL content in the raw material 1,4-BG containing a nitrogen atom-containing compound decreases, the polycondensation reaction rate in the production of PBT, the color tone of the produced PBT, and the like tend to be preferable.
- the color tone of the obtained PBT can be adjusted by adjusting the GBL content of the raw material 1,4-BG within the above range.
- the content of GBL in the raw material 1,4-BG or crude 1,4-BG is measured by the method described in the Examples section below.
- the content of GBL in the raw material 1,4-BG derived from biomass resources is determined by, for example, the fermentation conditions and ammonia when the raw material 1,4-BG is obtained by hydrogenating succinic acid obtained by fermentation of biomass resources.
- the amount of GBL in succinic acid can be adjusted by neutralizing conditions, succinic acid crystallization conditions, and the like.
- GBL is an intermediate in the synthesis of 1,4-BG, and it is difficult to accurately control the amount of GBL. Therefore, it is preferable to adjust the GBL content in the raw material 1,4-BG by purifying it in advance before supplying the raw material 1,4-BG derived from biomass resources to the reactor for the production of PBT.
- GBL is a component having a lighter boiling point than 1,4-BG
- the GBL content in the raw material 1,4-BG is obtained by performing separation distillation of the light-boiling component in the purification process of 1,4-BG.
- 1,4-BG is obtained directly by fermentation of biomass resources
- the GBL content is adjusted by the fermentation conditions, neutralization conditions with ammonia, purification conditions including distillation of the resulting crude 1,4-BG, etc.
- the separation distillation of GBL and crude 1,4-BG can be performed by multistage distillation using a packing and / or tray. At this time, GBL can be distilled off from the top of the separation distillation column. However, under high temperature conditions, GBL reacts with 1,4-BG and becomes highly boiling. Since this high boiling point component is decomposed into GBL in the next step, it is preferable to reduce the generation of the high boiling point component in the light distillation component separation distillation column. From such a point of view, the temperature at the top of the separation distillation column is usually preferably 40 to 180 ° C, more preferably 50 to 160 ° C, and particularly preferably 60 to 150 ° C.
- the content of 1-acetoxy-4-hydroxybutane (1,4-HAB) in the biomass resource-derived raw material 1,4-BG used for the production of PBT in the present invention is based on the raw material 1,4-BG.
- the upper limit is preferably 99 ppm, more preferably 90 ppm, particularly preferably 80 ppm, and most preferably 70 ppm.
- the lower limit is preferably 1 ppm, more preferably 2 ppm, and particularly preferably 5 ppm from the viewpoint of economic efficiency of the purification process.
- 1,4-HAB content in 1,4-BG containing a nitrogen atom-containing compound decreases, the polycondensation reaction rate in the production of PBT, the color tone of the produced PBT, and the like tend to be more favorable.
- the larger the number the easier the purification process becomes and the more economical it becomes.
- the content of 1,4-HAB in the raw material 1,4-BG is measured by the method described in the Examples section below.
- the 1,4-HAB content in the biomass resource-derived raw material 1,4-BG is, for example, when hydrogenated succinic acid obtained by fermentation of biomass resources to obtain the raw material 1,4-BG. It can also be adjusted by adjusting the amount of 1,4-HAB in succinic acid according to the conditions, neutralization conditions with ammonia, crystallization conditions of succinic acid, and the like. However, before supplying crude 1,4-BG derived from biomass resources to the reactor for the production of PBT, the 1,4-HAB content in the raw material 1,4-BG is adjusted by pre-purification. It is preferable.
- 1,4-HAB is a component having a lighter boiling point than 1,4-BG
- the raw material 1,4-BG is obtained by separating and distilling the light-boiling component in the purification step of crude 1,4-BG.
- the 1,4-HAB content in it can be adjusted.
- 1,4-BG is obtained directly by fermentation of biomass resources, it contains 1,4-HAB depending on the fermentation conditions, neutralization conditions with ammonia, purification conditions including distillation of the obtained 1,4-BG, etc. The amount can be adjusted, but in this case as well, it is preferable to purify crude 1,4-BG to remove light-boiling components containing 1,4-HAB.
- the separation distillation of 1,4-HAB and crude 1,4-BG can be performed simultaneously with the above-described separation distillation of GBL and crude 1,4-BG.
- the method for producing the PBT of the present invention is not particularly limited as long as the PBT can be produced.
- Known production methods of PBT are roughly classified into a so-called direct polymerization method using terephthalic acid as a main raw material and a transesterification method using terephthalic acid alkyl ester as a main raw material.
- water is produced in the initial esterification reaction
- alcohol is produced in the initial transesterification reaction.
- the direct polymerization method is preferred from the viewpoint of the height of the polymer and the improvement effect of the present invention.
- a dicarboxylic acid component containing terephthalic acid and a diol component containing raw material 1,4-BG are carried out in the presence or absence of an esterification reaction catalyst in a single or multi-stage esterification reaction tank.
- the temperature is usually 180 ° C. or higher, preferably 200 ° C. or higher, particularly preferably 210 ° C. or higher, usually 260 ° C. or lower, preferably 250 ° C. or lower, particularly preferably 245 ° C. or lower.
- the pressure is usually 10 kPa or more, preferably 13 kPa or more, particularly preferably 50 kPa or more, usually 133 kPa or less, preferably 120 kPa or less, particularly preferably 110 kPa or less.
- the reaction time is usually 0.5 hours or longer, preferably 1 hour or longer, usually 5 hours or shorter, preferably 3 hours or shorter.
- the esterification reaction is carried out continuously under the above conditions, and the resulting oligomer as an esterification reaction product is transferred to a polycondensation reaction tank, and in the presence of a polycondensation reaction catalyst in a multistage polycondensation reaction tank. A polycondensation reaction is continuously performed.
- the reaction temperature is usually 210 ° C.
- the pressure is usually not more than 27 kPa, preferably not more than 20 kPa, more preferably not more than 13 kPa, and particularly preferably not more than 2 kPa in at least one polycondensation reaction tank, and usually 2 to 12 with stirring under reduced pressure of the above conditions. Examples thereof include a method of performing a polycondensation reaction in a time, preferably 2 to 10 hours.
- a dicarboxylic acid component containing a terephthalic acid ester such as dimethyl terephthalate and a diol component containing a raw material 1,4-BG are transesterified in a single or multi-stage esterification reaction tank. Performed in the presence of a catalyst.
- the temperature is usually 110 ° C. or higher, preferably 140 ° C. or higher, particularly preferably 180 ° C. or higher, usually 260 ° C. or lower, preferably 245 ° C. or lower, particularly preferably 220 ° C. or lower.
- the pressure is usually 10 kPa or more, preferably 13 kPa or more, particularly preferably 60 kPa or more, usually 133 kPa or less, preferably 120 kPa or less, particularly preferably 110 kPa or less.
- the reaction time is usually 0.5 hours or longer, preferably 1 hour or longer, usually 5 hours or shorter, preferably 3 hours or shorter.
- the transesterification is carried out continuously under the above conditions, and the resulting oligomer as the transesterification product is transferred to a polycondensation reaction tank, and in the presence of a polycondensation reaction catalyst in a multistage polycondensation reaction tank. A polycondensation reaction is continuously performed.
- the reaction temperature is usually 210 ° C.
- the pressure is usually not more than 27 kPa, preferably not more than 20 kPa, more preferably not more than 13 kPa, and particularly preferably not more than 2 kPa in at least one polycondensation reaction tank, and usually 2 to 12 with stirring under reduced pressure of the above conditions. Examples include a method of polycondensation reaction for a time, preferably 2 to 10 hours.
- esterification reaction or transesterification reaction catalyst examples include antimony compounds such as diantimony trioxide; germanium compounds such as germanium dioxide and germanium tetroxide; titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate; Titanium compounds such as phenyl titanate such as phenyl titanate; dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexahexyl distinoxide, didodecyltin oxide, triethyltin hydroxide, triphenyltin hydro Oxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trickle Ride, tributyltin chloride, dibutyltin sulfide, buty
- the amount of the esterification reaction or transesterification catalyst used is not particularly limited, but the metal concentration (mass) in the PBT is usually 1 ppm or more, preferably 5 ppm or more, more preferably 10 ppm or more, particularly preferably 20 ppm or more, and most preferably. Is 30 ppm or more, usually 300 ppm or less, preferably 200 ppm or less, more preferably 150 ppm or less, still more preferably 100 ppm or less, particularly preferably 90 ppm or less, and most preferably 60 ppm or less.
- the metal concentration (mass) in the PBT is less than or equal to the above upper limit, it is less likely to cause foreign matters, and there is a tendency that deterioration reaction and gas generation during the thermal residence of the PBT do not easily occur.
- the reaction rate is fast and side reactions are unlikely to occur.
- a catalyst for esterification reaction or transesterification reaction may be used as it is as a polycondensation reaction catalyst, or the catalyst may be further added.
- metal concentration (mass) in PBT it is 0.5 ppm or more normally, Preferably it is 1 ppm.
- the titanium metal concentration (mass) in the PBT is preferably 250 ppm or less, and more preferably 100 ppm or less, from the viewpoint of suppressing foreign matter. 60 ppm or less is particularly preferable, and 50 ppm or less is most preferable.
- the metal concentration (mass) in PBT can be measured by using atomic emission, inductively coupled plasma (ICP) method, etc. after recovering the metal in PBT by a method such as wet ashing.
- ICP inductively coupled plasma
- esterification reaction transesterification reaction and polycondensation reaction
- phosphorus compounds such as orthophosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid and esters and metal salts thereof
- sodium hydroxide Reaction aids such as sodium compounds such as sodium benzoate, lithium compounds such as lithium acetate, alkali metal compounds such as potassium compounds such as potassium hydroxide and potassium acetate; alkaline earth metal compounds such as magnesium acetate and calcium acetate, etc.
- Reaction phenols such as 2,6-di-t-butyl-4-octylphenol and pentaerythrityl-tetrakis [3- (3 ′, 5′-t-butyl-4′-hydroxyphenyl) propionate] Dilauryl-3,3′-thiodipropionate, pentaerythrityl-tetrakis (3-La Thioether compounds such as rylthiodipropionate); antioxidants such as phosphorus compounds such as triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite; paraffin Wax, microcrystalline wax, polyethylene wax, long-chain fatty acids such as montanic acid and montanic acid esters and esters thereof; release agents such as silicone oils may be used.
- antioxidants such as phosphorus compounds such as triphenyl phosphite, tris
- Examples of the polycondensation reaction tank include known ones such as a vertical stirring polymerization tank, a horizontal stirring polymerization tank, and a thin film evaporation polymerization tank.
- mass transfer tends to be the controlling factor of molecular weight increase rather than reaction rate, so in order to proceed with the main reaction while suppressing side reactions, as much as possible Lowering the temperature and increasing the surface renewability is advantageous for achieving the object of the present invention. Therefore, it is preferable to select one or a plurality of horizontal stirring polymerization machines having a thin film evaporation function excellent in surface renewability, plug flow property, and self-cleaning property.
- the PBT obtained by the production method of the present invention can be subsequently subjected to solid phase polycondensation by a known method to increase the molecular weight.
- the PBT obtained by the polycondensation reaction is usually transferred from the bottom of the polycondensation reaction tank to a polymer extraction die and extracted into a strand shape, and is cooled with water or cooled with water and then cut with a cutter to form pellets or chips. It is made into a granular material.
- the granular material can be subsequently subjected to solid phase polycondensation by a known method or the like to increase its intrinsic viscosity.
- the PBT produced by the present invention includes a structural unit derived from terephthalic acid and a structural unit derived from 1,4-butanediol, and comprises 1,4-butane.
- the diol has a nitrogen atom content of 0.01 to 50 ppm by mass and a gamma butyrolactone content of 1 to 100 ppm by mass.
- the upper limit of the nitrogen atom content (mass ratio) in the PBT of the present invention is preferably 10 ppm, more preferably 2 ppm, and the lower limit is preferably 0.05 ppm, more preferably 0.1 ppm.
- gamma butyrolactone is converted into other components such as amide, amine, amino acid and the like that cause PBT color deterioration, and is contained in PBT. It is considered a thing.
- the PBT having a nitrogen atom content within the above range is made from the above-mentioned preferred biomass resource-derived raw material 1,4-butanediol and terephthalic acid or terephthalic acid alkyl ester in accordance with the production method according to the present invention described above. Can be obtained.
- the intrinsic viscosity of PBT of this invention is 0.50 dL / g or more, More preferably, it is 0.70 dL / g or more, Preferably it is 1.50 dL / g or less, More preferably, it is 1.35 dL / g or less.
- the intrinsic viscosity of PBT is not less than the above lower limit, it is preferable from the viewpoint of mechanical properties of the molded product, and when it is not more than the above upper limit, it tends to be preferable from the viewpoint of moldability.
- the intrinsic viscosity of PBT is measured by the method described in the Examples section below.
- the terminal carboxyl group concentration of the PBT of the present invention is not particularly limited, but the lower limit is preferably 1 equivalent / ton, more preferably 2 equivalent / ton, and particularly preferably 3 equivalent / ton. Most preferably, it is 5 equivalents / ton, and the upper limit is preferably 50 equivalents / ton, more preferably 40 equivalents / ton, particularly preferably 30 equivalents / ton, and 25 equivalents / ton. Most preferably.
- the terminal carboxyl group concentration of PBT can be determined by dissolving the resin in an organic solvent and titrating with an alkali solution such as sodium hydroxide. More specifically, it can be determined by the method described in the Examples section below.
- PBT color tone> Usually, PBT produced using the raw material 1,4-BG derived from biomass resources tends to deteriorate in color tone, but the PBT of the present invention has good color tone. Further, as described above, it is possible to adjust the color tone of PBT obtained by adjusting the content of GBL in raw material 1,4-BG in the purification process of crude 1,4-BG. .
- the PBT of the present invention can be made into a PBT composition containing components other than PBT as long as the effects of the present invention are not significantly impaired.
- components other than the PBT include various resins such as thermoplasticity and thermosetting, fillers such as mold release agents and reinforcing fillers, flame retardants, and other various additives.
- thermoplastic resin examples include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polymethacrylic acid ester, polyacrylic acid ester, ABS resin, polycarbonate, polyamide, polyphenylene sulfide, polyethylene terephthalate, liquid crystal polyester, polyacetal, polyphenylene oxide, and the like.
- thermosetting resin a thermosetting resin, a phenol resin, a melamine resin, a silicone resin, an epoxy resin etc. are mentioned. These resins may be used alone or in combination of two or more. Of these, a thermoplastic resin is often used.
- the blending amount (mass) is not particularly limited as long as the excellent effect of the present invention is expressed, but the ratio of PBT to the total amount of the resin is usually 0.1% by mass. Above, preferably 1% by mass or more, more preferably 10% by mass or more, usually 99.9% by mass or less, preferably 99% by mass or less, more preferably 90% by mass or less.
- the release agent is not particularly limited, and examples thereof include 2,6-di-t-butyl-4-octylphenol, pentaerythrityl-tetrakis [3- (3 ′, 5′-t-butyl-4′-hydroxy Phenolic compounds such as phenyl) propionate]; Thioether compounds such as dilauryl-3,3′-thiodipropionate, pentaerythrityl-tetrakis (3-laurylthiodipropionate); paraffin wax, microcrystalline wax, polyethylene wax, Examples include long-chain fatty acids represented by montanic acid and montanic acid esters and esters thereof; silicone oils and the like. These may be used alone or in combination of two or more.
- the reinforcing filler is not particularly limited.
- inorganic fibers such as glass fiber, carbon fiber, silica / alumina fiber, zirconia fiber, boron fiber, boron nitride fiber, silicon nitride potassium titanate fiber, and metal fiber; aromatic Organic fibers such as polyamide fibers and fluororesin fibers can be mentioned.
- inorganic fibers, particularly glass fibers are preferably used. Only one type of reinforcing filler may be used, or two or more types may be used in combination.
- the average fiber diameter is not particularly limited, but is usually 1 to 100 ⁇ m, preferably 2 to 50 ⁇ m, more preferably 3 to 30 ⁇ m, and particularly preferably 5 to 20 ⁇ m.
- the average fiber length is not particularly limited, but is usually 0.1 to 20 mm, preferably 1 to 10 mm.
- a reinforcing filler that has been surface-treated with a sizing agent or a surface treating agent in order to improve the interfacial adhesion with the PBT.
- the sizing agent or surface treatment agent include functional compounds such as epoxy compounds, acrylic compounds, isocyanate compounds, silane compounds, and titanate compounds.
- the treatment with the sizing agent or the surface treatment agent may be performed by previously treating the reinforcing filler, or may be brought into contact with the sizing agent or the surface treatment agent when preparing the PBT composition.
- a reinforcing filler When a reinforcing filler is used, its blending amount is usually 150 parts by mass or less, preferably 5 to 100 parts by mass with respect to 100 parts by mass of the resin component containing PBT.
- fillers include plate-like inorganic fillers, ceramic beads, asbestos, wollastonite, talc, clay, mica, zeolite, kaolin, potassium titanate, barium sulfate, titanium oxide, silicon oxide, aluminum oxide, and hydroxide.
- fillers include plate-like inorganic fillers, ceramic beads, asbestos, wollastonite, talc, clay, mica, zeolite, kaolin, potassium titanate, barium sulfate, titanium oxide, silicon oxide, aluminum oxide, and hydroxide.
- magnesium magnesium.
- the plate-like inorganic filler include glass flakes, mica, and metal foil. Among these, glass flakes are preferably used.
- the flame retardant is not particularly limited, and examples thereof include organic halogen compounds, antimony compounds, phosphorus compounds, other organic flame retardants, and inorganic flame retardants.
- organic halogen compound include brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, polypentabromobenzyl acrylate and the like.
- the antimony compound include antimony trioxide, antimony pentoxide, sodium antimonate, and the like.
- phosphorus compound phosphate ester, polyphosphoric acid, ammonium polyphosphate, red phosphorus etc. are mentioned, for example.
- organic flame retardants include nitrogen compounds such as melamine and cyanuric acid.
- inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, silicon compound, and boron compound. These flame retardants may be used alone or in combination of two or more.
- additives examples include, but are not limited to, stabilizers such as antioxidants and heat stabilizers, lubricants, catalyst deactivators, crystal nucleating agents, and crystallization accelerators. These additives may be added during or after polycondensation.
- stabilizers such as ultraviolet absorbers and weathering stabilizers, colorants such as dyes and pigments, antistatic agents, foaming agents, plasticizers, and impact resistance improvers.
- the method of blending the above-mentioned other components is not particularly limited, but for example, a method of using a uniaxial or biaxial extruder having equipment that can be devolatilized from a vent port as a kneader is preferable.
- Each component including an additional component may be supplied to the kneader in a lump or sequentially.
- two or more components selected from each component including the additional components can be mixed in advance.
- the method of molding the PBT of the present invention and the PBT composition containing the PBT is not particularly limited, and is a molding method generally used for thermoplastic resins, specifically, injection molding, hollow molding, extrusion molding, Press molding can be applied.
- the PBT of the present invention and the PBT composition containing the PBT are excellent in color tone, thermal stability, transparency and quality stability, and are injection molded products such as electric, electronic parts and automotive parts, films, monofilaments, fibers and the like. It can be suitably used in extrusion molded article applications.
- Terminal carboxyl group concentration (AB) ⁇ 0.1 ⁇ f / W (equivalent / ton)
- A is the amount ( ⁇ L) of 0.01N sodium benzyl alcohol solution required for titration
- B is 0.01 mol / L sodium benzyl alcohol solution required for titration with a blank.
- W is the amount of PBT sample (g)
- f is the titer of 0.01 mol / L sodium hydroxide.
- ⁇ PBT color tone (b value)> Pellet-shaped PBT was filled into a cylindrical powder measurement cell having an inner diameter of 30 mm and a depth of 12 mm, and measured by a reflection method using a colorimetric color difference meter Color Meter ZE2000 (manufactured by Nippon Denshoku Industries Co., Ltd.). The cell was rotated by 90 degrees and obtained as a simple average value of values measured at four points. The color tone was evaluated by the b value in the L, a, b color system. A lower b value indicates less yellowing and a better color tone.
- the raw material 1,4-BG for the petrochemical process an industrially available product was used.
- the raw material 1,4-BG (C) obtained by the butane method includes maleic acid, succinic acid, maleic anhydride formed by oxidation of butane and / Or obtained by hydrogenating them using fumaric acid as a raw material.
- the raw material 1,4-BG (D) obtained by the butadiene method (hereinafter sometimes abbreviated as “butadiene method (D)”) is obtained by carrying out an acetoxylation reaction using butadiene, acetic acid and oxygen, It can be obtained by obtaining diacetoxybutene as a body, hydrogenating and hydrolyzing the diacetoxybutene.
- the raw material 1,4-BG (E) obtained by the propylene method (hereinafter sometimes abbreviated as “propylene method (E)”) is obtained by an oxo reaction of allyl alcohol obtained by oxidation of propylene.
- the raw material 1,4-BG of the biomethod (B) is obtained by the method described in US Patent Application Publication No. 2011/0003355, that is, the total amount of bacterial cells and salt or each of them by filtration, centrifugation and ion exchange resin. After removing at least a part, water was removed by distillation to obtain crude 1,4-BG before purification shown in Table-1. This crude 1,4-BG before purification was dehydrated and concentrated using a glass rotary evaporator. The pressure was 10.7 kPa, and the internal temperature was 175 ° C. The distillation rate was 10% by mass, and 90% by mass of the crude 1,4-BG solution was recovered with respect to the charged amount remaining in the flask.
- the dehydrated crude 1,4-BG solution is used as a raw material, and batch distillation is performed using a glass instrument, and the fraction is separated into a plurality of fractions to obtain a high-boiling fraction and a light fraction from the crude 1,4-BG. Boiling separation was performed.
- a multistage distillation column corresponding to three stages was used as a theoretical stage.
- the column top pressure was 13.3 kPa and the column bottom temperature was controlled at 182 ° C.
- the distillation temperature rose with removal of light boiling and then stabilized at 175 ° C.
- the fraction having a stable top temperature was collected as 1,4-BG. 80% by mass of 1,4-BG fraction was recovered with respect to the raw material charge.
- the composition of this purified 1,4-BG fraction is also shown in Table 1.
- 1,4-BG having the composition after purification shown in Table 1 was further separated into a plurality of fractions using the same batch distillation apparatus, and 5 lots of GBL and purified biomethod (B) having different nitrogen atom contents were obtained. Obtained. The lots are designated as Lot 1, Lot 2, Lot 3, Lot 4, and Lot 5 in order from the first stop.
- Table 2 shows the GBL content, nitrogen atom content, 1,4-HAB content, and BGTF content in each lot. Note that GBL may be regenerated from high-boiling components, and GBL is increased in lots 1 to 5 shown in Table 2 as compared to 1,4-BG after purification in Table-1.
- the temperature was raised to 245 ° C. over 0.75 hour and held.
- the pressure was reduced to 0.07 kPa over 1.5 hours from the start of polymerization, and the polycondensation reaction was performed for 0.8 hours under the same reduced pressure, and the reaction system was returned to normal pressure to complete the polycondensation.
- the obtained PBT was extracted as a strand from the bottom of the reaction vessel, submerged in water at 10 ° C., and then the strand was cut with a cutter to obtain a pellet-like PBT.
- the polycondensation time was defined as the polycondensation time from the start of decompression to the end of polycondensation after the addition of magnesium acetate, and the polycondensation rate was defined as intrinsic viscosity / polycondensation time.
- the polycondensation rate was 0.37 dL / g / hour.
- the amount of THF was analyzed for the distillate during the esterification reaction, and the THF conversion rate expressed as mol% per terephthalic acid charged was 70.6 mol%.
- Example 2 PBT was produced in the same manner except that the raw material 1,4-BG was changed to lot 2 obtained by bio-method purification.
- Table 3 shows the conversion rate to THF [%] during the production of PBT, the polycondensation time [hour], the polycondensation rate [dL / g / hour], and the analysis result of the above PBT measurement method.
- Example 3 In Example 1, PBT was produced in the same manner except that the raw material 1,4-BG was changed to lot 3 obtained by bio-method purification. Table 3 shows the conversion rate to THF [%] during the production of PBT, the polycondensation time [hour], the polycondensation rate [dL / g / hour], and the analysis result of the above PBT measurement method.
- Example 4 In Example 1, PBT was produced in the same manner except that the raw material 1,4-BG was changed to lot 4 obtained by bio-method purification.
- Table 3 shows the conversion rate to THF [%] during the production of PBT, the polycondensation time [hour], the polycondensation rate [dL / g / hour], and the analysis result of the above PBT measurement method.
- Example 1 PBT was produced in the same manner except that the raw material 1,4-BG was changed to lot 5 obtained by bio-method purification.
- Table 3 shows the conversion rate to THF [%] during the production of PBT, the polycondensation time [hour], the polycondensation rate [dL / g / hour], and the analysis result of the above PBT measurement method.
- Example 2 PBT was produced in the same manner except that the raw material 1,4-BG was changed to 1,4-BG of the butane method (C) having the composition shown in Table 3.
- Table 3 shows the conversion rate to THF [%] during the production of PBT, the polycondensation time [hour], the polycondensation rate [dL / g / hour], and the analysis result of the above PBT measurement method.
- Example 3 PBT was produced in the same manner except that the raw material 1,4-BG was changed to 1,4-BG of the butadiene method (D) having the composition shown in Table 3.
- Table 3 shows the conversion rate to THF [%] during the production of PBT, the polycondensation time [hour], the polycondensation rate [dL / g / hour], and the analysis result of the above PBT measurement method.
- Example 4 PBT was produced in the same manner except that the raw material 1,4-BG was changed to 1,4-BG of the propylene method (E) having the composition shown in Table 3.
- Table 3 shows the conversion rate to THF [%] during the production of PBT, the polycondensation time [hour], the polycondensation rate [dL / g / hour], and the analysis result of the above PBT measurement method.
- FIG. 1 shows the PBT color b value relative to the GBL content in the raw materials 1,4-BG of Examples 2 to 4 and Comparative Example 1, and the GBL content in the raw materials 1,4-BG of Comparative Examples 2 to 4 It is a graph which shows the color tone b value of PBT. From FIG. 1, it is not possible to confirm the correlation between the GBL concentration and the b value in 1,4-BG (Comparative Examples 2 to 4) in which no nitrogen atom exists, but in 1,4-BG derived from biomass resources in which nitrogen atom exists.
- the coloration of PBT by GBL induces the coloration of the newly generated compound from the reaction of the nitrogen atom compound in 1,4-BG derived from biomass with GBL. Can be estimated.
- a component derived from GBL and a nitrogen atom-containing compound deteriorates the color tone, but the color tone deterioration of PBT by 2-pyrrolidone derived from ammonia and GBL supports this estimation. It is. Since the component derived from GBL and the nitrogen atom-containing compound is the cause of the color tone deterioration, in the raw material not containing the nitrogen atom-containing compound but containing only GBL, the color tone deterioration of PBT accompanying the increase in the GBL content is not confirmed. I can understand. This mechanism is not limited to 2-pyrrolidone, and the nitrogen component is not limited to ammonia.
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Abstract
Description
バイオマス資源由来の原料から1,4-BGを製造する方法では、特許文献3にバイオマス資源由来のコハク酸に対して化学的還元あるいは生物工学的な水素化を行い、1,4-BGを製造することが記載され、特許文献4には、菌体から直接発酵することで1,4-BGを得る方法が記載されている。
さらに上記特許文献1~4には、原料1,4-BG中に含まれるガンマブチロラクトンと窒素原子含有化合物との関係については記載されていない。
即ち、本発明の要旨は以下の[1]~[6]に存する。
前記原料1,4-ブタンジオールにおけるガンマブチロラクトンの含有量が1~100質量ppmである、ポリブチレンテレフタレートの製造方法。
[2] 前記工程(a)に先立ち、バイオマス資源由来の粗1,4-ブタンジオールを精製して前記原料1,4-ブタンジオールを得る工程を更に有する、前記[1]に記載のポリブチレンテレフタレートの製造方法。
[3] 前記粗1,4-ブタンジオールにおけるガンマブチロラクトンの含有量が、101質量ppm~2質量%である、前記[2]に記載のポリブチレンテレフタレートの製造方法。
[4] 前記原料1,4-ブタンジオールにおける1-アセトキシ-4-ヒドロキシブタンの含有量が1~99質量ppmである、前記[1]~[3]のいずれか1に記載のポリブチレンテレフタレートの製造方法。
[5] 前記原料1,4-ブタンジオール又は前記粗1,4-ブタンジオールを、グルコース、フルクトース、キシロース及びサッカロースからなる群より選ばれる少なくとも1の炭素源から発酵法により直接製造する工程をさらに有する、前記[1]~[4]のいずれか1に記載のポリブチレンテレフタレートの製造方法。
[6] バイオマス資源から、下記に示す天然に存在しない微生物生体触媒を用いて、前記原料1,4-ブタンジオール又は前記粗1,4-ブタンジオールを製造する工程を更に有する、前記[1]~[5]のいずれか1に記載のポリブチレンテレフタレートの製造方法。
天然に存在しない微生物生体触媒:4-ヒドロキシブタン酸脱水素酵素、スクシニル-CoA合成酵素、CoA依存性コハク酸セミアルデヒド脱水素酵素、またはα-ケトグルタル酸脱炭酸酵素をコードする少なくとも1つの外因性核酸を含む4-ヒドロキシブタン酸生合成経路を有する微生物を含み、前記微生物が前記4-ヒドロキシブタン酸の単量体を分泌するために十分な量の前記外因性核酸を含む、微生物生体触媒
尚、本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。また、本明細書における、下限値または上限値は、その下限値または上限値の値を含む範囲を意味する。
ここで、“重量%”、“重量ppm”、“重量部”及び“重量比”と、“質量%”、“質量ppm”、“質量部”及び“質量比”とは、それぞれ同義である。また単に“ppm”と記載した場合は、“重量ppm”のことを示す。
本発明において、PBTは、テレフタル酸またはテレフタル酸アルキルエステルを含むジカルボン酸成分と、バイオマス資源由来の原料1,4-ブタンジオールを含むジオール成分とをエステル化反応またはエステル交換反応させた後、該反応物を重縮合反応させることにより得られる。なお、テレフタル酸アルキルエステルのアルキル基としては、炭素数1~3のアルキル基が好ましい。
また、バイオマス資源由来の原料1,4-BGは、全ジオール成分の80モル%以上であることが好ましく、90モル%以上であることが更に好ましく、99モル%以上であることが特に好ましい。
他のジカルボン酸成分としては、例えば、フタル酸、イソフタル酸、ジブロモイソフタル酸、スルホイソフタル酸ナトリウム、フェニレンジオキシジカルボン酸、4,4’-ジフェニルジカルボン酸、4,4’-ジフェニルエーテルジカルボン酸、4,4’-ジフェニルケトンジカルボン酸、4,4’-ジフェノキシエタンジカルボン酸、4,4’-ジフェニルスルホンジカルボン酸、2,6-ナフタレンジカルボン酸等の芳香族ジカルボン酸およびこれらのエステル形成性誘導体;ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸等の脂環式ジカルボン酸およびこれらのエステル形成性誘導体;コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカジカルボン酸、ドデカジカルボン酸等の脂肪族鎖式ジカルボン酸およびこれらのエステル形成性誘導体等が挙げられる。これらは1種を単独で用いてもよく、2種以上を混合して用いてもよい。
他のジオール成分としては、例えばエチレングリコール、トリメチレングリコール、ペンタメチレングリコール、ヘキサメチレングリコール、オクタメチレングリコール、デカメチレングリコール、ネオペンチルグリコール、2-メチル-1,3-プロパンジオール、1,2-ブタンジオール、1,3-ブタンジオール、2,3-ブタンジオール、1,3-ペンタンジオール、2,3-ペンタンジオール、2-エチル-2-ブチル-1,3-プロパンジオール、ポリエチレングリコール、ポリテトラメチレングリコール等の脂肪族鎖式ジオール;1,2-シクロヘキサンジオール、1,4-シクロヘキサンジオール、1,1-シクロヘキサンジメチロール、1,4-シクロヘキサンジメチロール、2,5-ノルボルナンジメチロール等の脂環式ジオール;キシリレングリコール、4,4’-ジヒドロキシビフェニル、2,2-ビス(4’-ヒドロキシフェニル)プロパン、2,2-ビス(4’-β-ヒドロキシエトキシフェニル)プロパン、ビス(4-ヒドロキシフェニル)スルホン、ビス(4’-β-ヒドロキシエトキシフェニル)スルホン酸等の芳香族ジオール;2,2-ビス(4’-ヒドロキシフェニル)プロパンのエチレンオキサイド付加物またはプロピレンオキサイド付加物;バイオマス資源由来でない1,4-BG等が挙げられる。これらは1種を単独で用いてもよく、2種以上を混合して用いてもよい。
その共重合成分としては、例えば、グリコール酸、p-ヒドロキシ安息香酸、p-β-ヒドロキシエトキシ安息香酸等のヒドロキシカルボン酸やアルコキシカルボン酸、ステアリルアルコール、ヘネイコサノール、オクタコサノール、ベンジルアルコール、ステアリン酸、ベヘン酸、安息香酸、t-ブチル安息香酸、ベンゾイル安息香酸等の単官能成分、トリカルバリル酸、トリメリット酸、トリメシン酸、ピロメリット酸、ナフタレンテトラカルボン酸、没食子酸、トリメチロールエタン、トリメチロールプロパン、グリセロール、ペンタエリスリトール、シュガーエステル等の三官能以上の多官能成分等が挙げられる。これらの共重合成分についても、1種を単独で用いてもよく、2種以上を混合して用いてもよい。
本発明のPBTの製造に用いる原料1,4-BGは、バイオマス資源由来のものであり、環境保護の点から好ましい。
具体的には、木材、稲わら、米ぬか、古米、とうもろこし、サトウキビ、キャッサバ、サゴヤシ、おから、コーンコブ、タピオカカス、バガス、植物油カス、芋、そば、大豆、油脂、古紙、製紙残渣、水産物残渣、家畜排泄物、下水汚泥、食品廃棄物等が挙げられる。この中でも、木材、稲わら、古米、とうもろこし、サトウキビ、キャッサバ、サゴヤシ、おから、コーンコブ、タピオカカス、バガス、植物油カス、芋、そば、大豆、油脂、古紙、製紙残渣等の植物資源が好ましく、より好ましくは木材、稲わら、古米、とうもろこし、サトウキビ、キャッサバ、サゴヤシ、芋、油脂、古紙、製紙残渣等が挙げられ、最も好ましくはとうもろこし、サトウキビ、キャッサバ、サゴヤシが挙げられる。
こうして微細化されたバイオマス資源は、通常、更に前処理・糖化の工程を経て炭素源へと誘導される。その具体的な方法としては、硫酸、硝酸、塩酸、リン酸などの強酸による酸処理、アルカリ処理、アンモニア凍結蒸煮爆砕法、溶媒抽出、超臨界流体処理、酸化剤処理などの化学的方法;微粉砕、蒸煮爆砕法、マイクロ波処理、電子線照射等の物理的方法;微生物や酵素処理による加水分解等の生物学的処理などが挙げられる。
原料1,4-BG中の窒素原子含有量が少なくなるほど、生成するPBTの色調などが好ましくなる傾向が強い。一方、多くなるほど、精製工程を簡便とし易く経済的に有利な上、PBT製造反応中での1,4-BGのTHFへの転化率も低く抑えやすい。
なお、本発明において、1,4-BG中の窒素原子含有量は、後掲の実施例の項に記載される方法で測定することができるが、測定法はこれに限定されない。
例えば、本発明で用いる原料1,4-BG中にはGBLが含まれるが、GBLは窒素原子含有化合物と種々のアミド、アミン、アミノ酸などの誘導体を生成すると考えられ、その誘導体は二官能以上を有する反応性に富む成分であることから、これら誘導体中に強くPBTの色調を悪化させる成分が存在するものと考えられる。
窒素原子含有化合物を含有する原料1,4-BG中のGBL含有量が少なくなるほど、PBT製造における重縮合反応速度、生成するPBTの色調などが好ましくなる傾向が強い。一方、多くなるほど、精製工程を簡便とし易く経済的に有利となる。本発明においては、原料1,4-BGのGBL含有量を上記の範囲で調節することにより、得られるPBTの色調を調整することができる。
なお、原料1,4-BG又は粗1,4-BG中のGBLの含有量は、後掲の実施例の項に記載される方法で測定される。
この場合、GBLは1,4-BGよりも軽沸点の成分であり、1,4-BGの精製工程で軽沸点成分の分離蒸留を行うことで、原料1,4-BG中のGBL含有量を調節することができる。
1,4-BGがバイオマス資源の発酵により直接得られる場合にも、その発酵条件、アンモニアによる中和条件、得られた粗1,4-BGの蒸留を含む精製条件などによりGBL含有量を調節することができるが、この場合も粗1,4-BGの精製を行って、GBLを含む軽沸点成分を除去することが好適な手段である。
このような観点から、分離蒸留塔の塔頂部温度は、通常40~180℃が好ましく、更に好ましくは50~160℃であり、特に好ましくは60~150℃の範囲である。塔頂部温度がこの下限以上の温度であることにより、水による冷却が容易となり、経済性の点から好ましい。一方、上記上限以下の温度であることにより、該高沸成分の生成が大幅に加速されることを防ぐことから好ましい。
なお、原料1,4-BG中の1,4-HABの含有量は、後掲の実施例の項に記載される方法で測定される。
この場合、1,4-HABは1,4-BGよりも軽沸点の成分であり、粗1,4-BGの精製工程で軽沸点成分の分離蒸留を行うことで、原料1,4-BG中の1,4-HAB含有量を調節することができる。
1,4-BGがバイオマス資源の発酵により直接得られる場合にも、その発酵条件、アンモニアによる中和条件、得られた1,4-BGの蒸留を含む精製条件などにより1,4-HAB含有量を調節することができるが、この場合も粗1,4-BGの精製を行って、1,4-HABを含む軽沸点成分を除去することが好適な手段である。
本発明のPBTの製造方法は、PBTを製造することができればよく、特に制限されない。
PBTの公知の製造方法は、主原料としてテレフタル酸を用いるいわゆる直接重合法と、主原料としてテレフタル酸アルキルエステルを用いるエステル交換法とに大別される。前者は、初期のエステル化反応で水が生成し、後者は初期のエステル交換反応でアルコールが生成するという違いがあるが、原料の入手安定性、留出物の処理の容易さ、原料原単位の高さ、また本発明による改良効果という観点からは直接重合法が好ましい。
上記条件下で連続的にエステル化反応させ、得られたエステル化反応生成物としてのオリゴマーを重縮合反応槽に移送し、複数段の重縮合反応槽内で、重縮合反応触媒の存在下で連続的に重縮合反応を行う。反応温度は通常210℃以上、好ましくは220℃以上、通常260℃以下、好ましくは250℃以下、特に好ましくは245℃以下である。圧力は、通常27kPa以下、好ましくは20kPa以下、より好ましくは13kPa以下、中でも少なくとも1つの重縮合反応槽においては好ましくは2kPa以下であり、上記条件の減圧下で、攪拌しながら、通常2~12時間、好ましくは2~10時間で重縮合反応させる方法等が挙げられる。
上記条件下で連続的にエステル交換反応させ、得られたエステル交換反応生成物としてのオリゴマーを重縮合反応槽に移送し、複数段の重縮合反応槽内で、重縮合反応触媒の存在下で連続的に重縮合反応を行う。反応温度は通常210℃以上、好ましくは220℃以上、通常260℃以下、好ましくは250℃以下、特に好ましくは245℃以下である。圧力は、通常27kPa以下、好ましくは20kPa以下、より好ましくは13kPa以下、中でも少なくとも1つの重縮合反応槽においては好ましくは2kPa以下であり、上記条件の減圧下で、攪拌しながら、通常2~12時間、好ましくは2~10時間、重縮合反応させる方法等が挙げられる。
また、触媒として有機チタン化合物を用いる場合には、異物抑制の観点から、最終的にはPBT中のチタン金属濃度(質量)は、250ppm以下であることが好ましく、100ppm以下であることが更に好ましく、60ppm以下であることが特に好ましく、50ppm以下であることが最も好ましい。
本発明により製造されるPBT(以下、“本発明のPBT”と称することがある。)は、テレフタル酸由来の構成単位と1,4-ブタンジオール由来の構成単位を含み、1,4-ブタンジオール中の窒素原子含有量は0.01~50質量ppm、ガンマブチロラクトン含有量は1~100質量ppmである。
本発明のPBTにおける窒素原子含有量(質量比)の上限は、好ましくは10ppm、より好ましくは2ppmで、下限は、好ましくは0.05ppm、より好ましくは0.1ppmである。本発明のPBT中のガンマブチロラクトンの含有量による影響は不明であるが、ガンマブチロラクトンはPBT色調悪化の原因となるアミド、アミン、アミノ酸などの他成分に変換されて、PBT中に含有されているものと考えられる。
PBTの固有粘度は、後掲の実施例の項に記載される方法で測定される。
PBTの末端カルボキシル基濃度は、樹脂を有機溶媒に溶解し、水酸化ナトリウム等のアルカリ溶液を用いて滴定することにより求めることができる。より具体的には、後掲の実施例の項に記載される方法で求められる。
通常、バイオマス資源由来の原料1,4-BGを用いて製造されたPBTは色調が悪化する傾向にあるが、本発明のPBTは色調が良好である。また、前述の如く、原料1,4-BG中のGBLを、粗1,4-BGの精製工程などでその含有量を調節することで、得られるPBTの色調を調節することが可能である。
本発明のPBTは、本発明の効果を大幅に損なわない範囲で、PBT以外の成分を含むPBT組成物とすることができる。そのPBT以外の成分の具体例を挙げると、熱可塑性、熱硬化性などの各種樹脂、離型剤、強化充填材等の充填材、難燃剤、その他各種添加剤などが挙げられる。
板状無機充填材を配合することにより、成形品の異方性およびソリを低減することができる。板状無機充填材としては、例えば、ガラスフレーク、雲母、金属箔などを挙げることができる。これらの中ではガラスフレークが好適に使用される。
有機ハロゲン化合物としては、例えば、臭素化ポリカーボネート、臭素化エポキシ樹脂、臭素化フェノキシ樹脂、臭素化ポリフェニレンエーテル樹脂、臭素化ポリスチレン樹脂、臭素化ビスフェノールA、ポリペンタブロモベンジルアクリレート等が挙げられる。アンチモン化合物としては、例えば、三酸化アンチモン、五酸化アンチモン、アンチモン酸ソーダ等が挙げられる。リン化合物としては、例えば、リン酸エステル、ポリリン酸、ポリリン酸アンモニウム、赤リン等が挙げられる。その他の有機難燃剤としては、例えば、メラミン、シアヌール酸などの窒素化合物等が挙げられる。その他の無機難燃剤としては、例えば、水酸化アルミニウム、水酸化マグネシウム、ケイ素化合物、ホウ素化合物などが挙げられる。これらの難燃剤は、1種を単独で用いてもよく、2種以上を混合して用いてもよい。
また、その他の各種添加剤としては、紫外線吸収剤、耐候安定剤などの安定剤、染顔料などの着色剤、帯電防止剤、発泡剤、可塑剤、耐衝撃性改良剤なども挙げられる。
本発明のPBTおよびこれを含んだPBT組成物の成形加工方法は、特に制限されず、熱可塑性樹脂について一般に使用されている成形法等、具体的には、射出成形、中空成形、押し出し成形、プレス成形などを適用できる。
本発明のPBTおよびこれを含んだPBT組成物は、色調、熱安定性、透明性、品質安定性に優れ、電気、電子部品、自動車用部品などの射出成形品、フィルム、モノフィラメント、繊維などの押出し成形品用途において好適に使用できる。
<原料1,4-BGの窒素原子含有量(質量ppm)>
原料1,4-BG15mgを石英ボートに採取して、微量全窒素分析装置((株)ダイヤインスツルメンツ製 型式:「TN-10型」)を用いて試料を燃焼し、燃焼・化学発光法により定量した。また、その際に使用した標準試料には、トルエン中にアニリンを溶解し、窒素原子換算で0、0.5、1.0、2.0μg/mLのものをそれぞれ作製して使用した。
ガスクロマトグラフィー分析装置((株)島津製作所製 型式:「島津GC-2014型」)にて、DB-1カラム(無極性)を用い、修正面積百分率法により、原料1,4-BG、GBL、その他、1,4-HAB等の各ピークの成分の含有量を求め、1,4-BG中の含有量を算出した。
エステル化反応における留出液について、カールフィッシャー法(三菱化学(株)製「CA-03」で測定)にて水分量を求め、水分以外は有機成分とした。有機成分中のTHF量を上記ガスクロマトグラフ法により求め、THF生成量とした。THF生成量をテレフタル酸に対するモル%で表し、転化率とした。
ウベローデ型粘度計を使用して以下の手順で求めた。すなわち、フェノール/テトラクロロエタン(質量比1/1)の混合溶媒を使用し、30℃において、濃度1.0g/dLのPBT溶液および溶媒のみの落下秒数をそれぞれ測定し、下記式で算出した。
IV=((1+4KHηsp)0.5-1)/(2KHC)
但し、ηsp=(η/η0)-1であり、ηはPBT溶液落下秒数、η0は溶媒の落下秒数、CはPBT溶液のPBT濃度(g/dL)、KHはハギンズの定数である。KHは0.33を採用した。
ベンジルアルコール25mLにPBT0.5gを溶解し、水酸化ナトリウムの0.01モル/Lベンジルアルコール溶液を使用して滴定し、下記式で算出した。
末端カルボキシル基濃度=(A-B)×0.1×f/W(当量/トン)
但し、Aは、滴定に要した0.01Nの水酸化ナトリウムのベンジルアルコール溶液の量(μL)、Bはブランクでの滴定に要した0.01モル/Lの水酸化ナトリウムのベンジルアルコール溶液の量(μL)、WはPBT試料の量(g)、fは、0.01モル/Lの水酸化ナトリウムの力価である。
ペレット状のPBTを内径30mm、深さ12mmの円柱状の粉体測定用セルに充填し、測色色差計Color Meter ZE2000(日本電色工業(株)製)を使用して、反射法により測定セルを90度ずつ回転させて4箇所測定した値の単純平均値として求めた。色調は、L、a、b表色系におけるb値で評価した。b値が低いほど黄ばみが少なく色調が良好であることを示す。
発酵法から直接原料1,4-BGを製造する方法として、日本国特表2010-521182号公報および米国特許出願公開第2011/0003355号明細書の実施例1~4に記載の方法で得た粗1,4-ブタンジオールを精製してバイオ法1,4-ブタンジオール(B)(以下、“バイオ法(B)”と略記することがある。)を得た。
ブタン法によって得られる原料1,4-BG(C)(以下、“ブタン法(C)”と略記することがある。)は、ブタンの酸化により生成するマレイン酸、コハク酸、無水マレイン酸および/またはフマル酸を原料として、それらを水素化して得られる。
ブタジエン法によって得られる原料1,4-BG(D)(以下、“ブタジエン法(D)”と略記することがある。)は、ブタジエン、酢酸および酸素を用いてアセトキシ化反応を行って、中間体であるジアセトキシブテンを得、そのジアセトキシブテンを水添、加水分解することで得られる。
プロピレン法によって得られる原料1,4-BG(E)(以下、“プロピレン法(E)”と略記することがある。)は、プロピレンの酸化により得られるアリルアルコールのオキソ反応により得られる。
日本国特表2010-521182号公報の記載を元に有機体の発酵培地から生物学的に1,4BG含有組成物を生産したバイオ法(B)の原料1,4-BGを以下の方法で精製した。以下、「GBL」は「ガンマブチロラクトン」、「1,4-HAB」は「1-アセトキシ-4-ヒドロキシブタン」、「BGTF」は「2-(4-ヒドロキシブチルオキシ)テトラヒドロフラン」である。また、「ppm」、「%」はいずれも質量基準の値である。以下の表-2、表-3においても同様である。
この精製前粗1,4-BGに対して、ガラス製のロータリーエバポレーターを使用して脱水濃縮を行った。圧力を10.7kPaとし、内温度は175℃で実施した。留出率は10質量%であり、フラスコ内に残った仕込み量に対して90質量%の粗1,4-BG溶液を回収した。
次に、脱水後の粗1,4-BG溶液を原料に用いてガラス製の器具を用いて回分蒸留を行い、複数のフラクションに分離して粗1,4-BGからの高沸分および軽沸分の分離を行った。この際、理論段として3段相当の多段蒸留塔を用いた。塔頂圧力を13.3kPaとし、塔底温度を182℃に制御した。留出温度は軽沸分を除去するとともに上昇し、その後175℃で安定した。この塔頂温度が安定した留分を1,4-BGとして採取した。原料仕込み量に対して1,4-BGのフラクションを80質量%回収した。この精製1,4-BGのフラクションの組成も表-1に示す。
<実施例1>
攪拌装置、窒素導入口、加熱装置、温度計、留出管、および減圧用排気口を備えた反応容器に、テレフタル酸113g、バイオ法の原料1,4-BG(ロット1)を183gおよび触媒としてテトラブチルチタネートを予め6質量%溶解させたバイオ法の原料1,4-BG(ロット1)溶液0.7gを仕込み、窒素-減圧置換によって系内を窒素雰囲気下にした。次に、系内を攪拌しながら150℃まで加温後、大気圧下、220℃に1時間で昇温させて、さらに2時間生成する水を留出させつつエステル化反応を行った。
次に、酢酸マグネシウム4水塩を水に溶解し、さらにバイオ法の原料1,4-BG(ロット1)に溶解させた酢酸マグネシウム4水塩1質量%の1,4-BG溶液(酢酸マグネシウム4水塩、水、1,4-BGの質量比1:2:97)1.3gを添加した。
酢酸マグネシウム添加後の減圧開始から重縮合終了までを重縮合時間として、固有粘度/重縮合時間を重縮合速度とした。重縮合速度は0.37dL/g/時間であった。エステル化反応中の留出液についてTHF量を分析し、仕込みテレフタル酸あたりのモル%で表したTHF転化率は、70.6モル%であった。
実施例1において、原料1,4-BGをバイオ法の精製で得られたロット2に変更した以外は全て同様にPBTを製造した。PBT製造時のTHFへの転化率[%]、重縮合時間[時間]、重縮合速度[dL/g/時間]、PBTの上記測定法による分析結果を併せて表-3に示す。
実施例1において、原料1,4-BGをバイオ法の精製で得られたロット3に変更した以外は全て同様にPBTを製造した。PBT製造時のTHFへの転化率[%]、重縮合時間[時間]、重縮合速度[dL/g/時間]、PBTの上記測定法による分析結果を併せて表-3に示す。
実施例1において、原料1,4-BGをバイオ法の精製で得られたロット4に変更した以外は全て同様にPBTを製造した。PBT製造時のTHFへの転化率[%]、重縮合時間[時間]、重縮合速度[dL/g/時間]、PBTの上記測定法による分析結果を併せて表-3に示す。
実施例1において、原料1,4-BGをバイオ法の精製で得られたロット5に変更した以外は全て同様にPBTを製造した。PBT製造時のTHFへの転化率[%]、重縮合時間[時間]、重縮合速度[dL/g/時間]、PBTの上記測定法による分析結果を併せて表-3に示す。
実施例1において、原料1,4-BGを表-3に示す組成のブタン法(C)の1,4-BGに変更した以外は全て同様にPBTを製造した。PBT製造時のTHFへの転化率[%]、重縮合時間[時間]、重縮合速度[dL/g/時間]、PBTの上記測定法による分析結果を併せて表-3に示す。
実施例1において、原料1,4-BGを表-3に示す組成のブタジエン法(D)の1,4-BGに変更した以外は全て同様にPBTを製造した。PBT製造時のTHFへの転化率[%]、重縮合時間[時間]、重縮合速度[dL/g/時間]、PBTの上記測定法による分析結果を併せて表-3に示す。
実施例1において、原料1,4-BGを表-3に示す組成のプロピレン法(E)の1,4-BGに変更した以外は全て同様にPBTを製造した。PBT製造時のTHFへの転化率[%]、重縮合時間[時間]、重縮合速度[dL/g/時間]、PBTの上記測定法による分析結果を併せて表-3に示す。
実施例1~4と比較例1を比べると、バイオマス資源由来の1,4-BG(窒素原子が存在)でも、1,4-BG中のGBLの含有量が1~100質量ppmであれば、PBTの着色は少ないことから、窒素原子含有化合物とGBLとの反応生成物による着色が抑えられていることがわかる。
比較例3で使用した原料1,4-BG(ブタジエン法(D))に2-ピロリドンを123質量ppm(窒素原子含有量20.2質量ppm)添加し、それ以外は全て比較例3の条件と同様にPBT合成を行った。その結果、得られたPBTの色調b値は2.7であり、123質量ppmの2-ピロリドン添加により色調b値が1.5増加した。尚、GBLの分子量と2-ピロリドンの分子量から、123ppmの2-ピロリドンをGBL量に換算すると、124質量ppmとなる。
尚、本機構は2-ピロリドンに限定されるものではなく、また、窒素成分をアンモニアに限定するものではない。
Claims (6)
- 窒素原子含有量が0.01~50質量ppmのバイオマス資源由来である原料1,4-ブタンジオールを含むジオール成分と、テレフタル酸またはテレフタル酸アルキルエステルを含むジカルボン酸成分とをエステル化反応またはエステル交換反応させる工程(a)と、前記工程(a)で得られた反応物を重縮合反応させてポリブチレンテレフタレートを得る重縮合反応工程(b)とを有するポリブチレンテレフタレートの製造方法であって、
前記原料1,4-ブタンジオールにおけるガンマブチロラクトンの含有量が1~100質量ppmである、ポリブチレンテレフタレートの製造方法。 - 前記工程(a)に先立ち、バイオマス資源由来の粗1,4-ブタンジオールを精製して前記原料1,4-ブタンジオールを得る工程を更に有する、請求項1に記載のポリブチレンテレフタレートの製造方法。
- 前記粗1,4-ブタンジオールにおけるガンマブチロラクトンの含有量が、101質量ppm~2質量%である、請求項2に記載のポリブチレンテレフタレートの製造方法。
- 前記原料1,4-ブタンジオールにおける1-アセトキシ-4-ヒドロキシブタンの含有量が1~99質量ppmである、請求項1~3のいずれか1項に記載のポリブチレンテレフタレートの製造方法。
- 前記原料1,4-ブタンジオール又は前記粗1,4-ブタンジオールを、グルコース、フルクトース、キシロース及びサッカロースからなる群より選ばれる少なくとも1の炭素源から発酵法により直接製造する工程をさらに有する、請求項1~4のいずれか1項に記載のポリブチレンテレフタレートの製造方法。
- バイオマス資源から、下記に示す天然に存在しない微生物生体触媒を用いて、前記原料1,4-ブタンジオール又は前記粗1,4-ブタンジオールを製造する工程を更に有する、請求項1~5のいずれか1項に記載のポリブチレンテレフタレートの製造方法。
天然に存在しない微生物生体触媒:4-ヒドロキシブタン酸脱水素酵素、スクシニル-CoA合成酵素、CoA依存性コハク酸セミアルデヒド脱水素酵素、またはα-ケトグルタル酸脱炭酸酵素をコードする少なくとも1つの外因性核酸を含む4-ヒドロキシブタン酸生合成経路を有する微生物を含み、前記微生物が前記4-ヒドロキシブタン酸の単量体を分泌するために十分な量の前記外因性核酸を含む、微生物生体触媒。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016186122A1 (ja) * | 2015-05-20 | 2016-11-24 | 東洋紡株式会社 | ポリエステル樹脂 |
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Publication number | Priority date | Publication date | Assignee | Title |
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US20200071286A1 (en) * | 2016-12-20 | 2020-03-05 | Sabic Global Technologies B.V. | Utilization of normal carbon 4 (nc4) recycle stream for secondary and tertiary products |
US11001706B2 (en) | 2017-02-02 | 2021-05-11 | Toyobo Co., Ltd. | Polyester resin composition, and light reflector component and light reflector including polyester resin composition |
WO2018143099A1 (ja) | 2017-02-02 | 2018-08-09 | 東洋紡株式会社 | ポリエステル樹脂組成物、これを含む光反射体用部品および光反射体 |
WO2019188921A1 (ja) | 2018-03-26 | 2019-10-03 | 東洋紡株式会社 | ポリエステル樹脂組成物、これを含む光反射体用部品および光反射体 |
JPWO2020158903A1 (ja) * | 2019-01-30 | 2021-12-02 | 三菱エンジニアリングプラスチックス株式会社 | 粉末積層造形法用の樹脂組成物、ペレット、粉末、造形物の製造方法および造形物 |
WO2023280172A1 (zh) * | 2021-07-05 | 2023-01-12 | 东丽先端材料研究开发(中国)有限公司 | 末端改性聚酯树脂、其组合物、成型品和制备方法 |
CN118108931A (zh) * | 2024-04-28 | 2024-05-31 | 康辉新材料科技有限公司 | 一种低端羧基聚对苯二甲酸丁二醇酯及其制备方法 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11240846A (ja) | 1997-12-01 | 1999-09-07 | Standard Oil Co:The | 1,4−ブタンジオールへのマレイン酸の水素化のための改良されたプロセス |
JP2006328380A (ja) * | 2005-04-26 | 2006-12-07 | Mitsubishi Chemicals Corp | ポリエステルの製造方法 |
WO2007089653A2 (en) * | 2006-01-27 | 2007-08-09 | General Electric Company | Molding compositions containing polyalkylene terephthalates and modified polybutylene terephthalate (pbt) random copolymers derived from pet |
JP2008101143A (ja) | 2006-10-19 | 2008-05-01 | Mitsubishi Chemicals Corp | ポリブチレンテレフタレート及びポリブチレンテレフタレートの製造方法 |
JP2009077719A (ja) | 2005-04-22 | 2009-04-16 | Mitsubishi Chemicals Corp | ポリエステル及びその製造方法 |
JP2010521182A (ja) | 2007-03-16 | 2010-06-24 | ジェノマティカ・インコーポレイテッド | 1,4−ブタンジオールおよびその前駆体の生合成のための組成物および方法 |
US20110003355A1 (en) | 2009-06-04 | 2011-01-06 | Genomatica, Inc | Process of separating components of a fermentation broth |
US20120046427A1 (en) * | 2010-08-19 | 2012-02-23 | Fina Technology, Inc. | "green" plastic materials and methods of manufacturing the same |
WO2013005749A1 (ja) * | 2011-07-04 | 2013-01-10 | 三菱化学株式会社 | テトラヒドロフランの製造方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU619840B2 (en) * | 1988-05-26 | 1992-02-06 | Kabushiki Kaisha Sanko Kaihatsu Kagaku Kenkyusho | A polyester and an article made of the same |
US20050209374A1 (en) * | 2004-03-19 | 2005-09-22 | Matosky Andrew J | Anaerobically biodegradable polyesters |
JP2009079057A (ja) * | 2005-04-22 | 2009-04-16 | Mitsubishi Chemicals Corp | ポリエステル及びその製造方法 |
JP2006328370A (ja) * | 2005-04-26 | 2006-12-07 | Mitsubishi Chemicals Corp | ポリエステルの製造方法 |
EP1979403B1 (en) | 2006-01-27 | 2009-12-30 | General Electric Company | Articles derived from compositions containing modified polybutylene terephthalate (pbt) random copolymers derived from polyethylene terephthalate (pet) |
JP2008163167A (ja) * | 2006-12-28 | 2008-07-17 | Toray Ind Inc | レーザー溶着用変性ポリエステル樹脂組成物およびそれを用いた複合成形体 |
US7799892B2 (en) * | 2008-05-02 | 2010-09-21 | Sabic Innovative Plastics Ip B.V. | Method of making polybutylene terephthalate and compositions and articles comprising the same |
CN109574803A (zh) * | 2012-06-05 | 2019-04-05 | 基因组股份公司 | 1,4-丁二醇的制造方法 |
EP2862886A4 (en) | 2012-06-05 | 2016-03-30 | Mitsubishi Chem Corp | METHOD FOR MANUFACTURING POLYESTER AND POLYURETHANE |
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Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11240846A (ja) | 1997-12-01 | 1999-09-07 | Standard Oil Co:The | 1,4−ブタンジオールへのマレイン酸の水素化のための改良されたプロセス |
JP2009077719A (ja) | 2005-04-22 | 2009-04-16 | Mitsubishi Chemicals Corp | ポリエステル及びその製造方法 |
JP2006328380A (ja) * | 2005-04-26 | 2006-12-07 | Mitsubishi Chemicals Corp | ポリエステルの製造方法 |
WO2007089653A2 (en) * | 2006-01-27 | 2007-08-09 | General Electric Company | Molding compositions containing polyalkylene terephthalates and modified polybutylene terephthalate (pbt) random copolymers derived from pet |
JP2008101143A (ja) | 2006-10-19 | 2008-05-01 | Mitsubishi Chemicals Corp | ポリブチレンテレフタレート及びポリブチレンテレフタレートの製造方法 |
JP2010521182A (ja) | 2007-03-16 | 2010-06-24 | ジェノマティカ・インコーポレイテッド | 1,4−ブタンジオールおよびその前駆体の生合成のための組成物および方法 |
US20110003355A1 (en) | 2009-06-04 | 2011-01-06 | Genomatica, Inc | Process of separating components of a fermentation broth |
US20120046427A1 (en) * | 2010-08-19 | 2012-02-23 | Fina Technology, Inc. | "green" plastic materials and methods of manufacturing the same |
WO2013005749A1 (ja) * | 2011-07-04 | 2013-01-10 | 三菱化学株式会社 | テトラヒドロフランの製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2857435A4 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016186122A1 (ja) * | 2015-05-20 | 2016-11-24 | 東洋紡株式会社 | ポリエステル樹脂 |
JPWO2016186122A1 (ja) * | 2015-05-20 | 2018-03-01 | 東洋紡株式会社 | ポリエステル樹脂 |
WO2019167323A1 (ja) * | 2018-03-02 | 2019-09-06 | 国立大学法人千葉大学 | 1,3-ブタジエン製造用触媒、前記触媒の製造方法、及び1,3-ブタジエンの製造方法 |
JP2019150766A (ja) * | 2018-03-02 | 2019-09-12 | 国立大学法人千葉大学 | 1,3−ブタジエン製造用触媒、前記触媒の製造方法、及び1,3−ブタジエンの製造方法 |
US11491467B2 (en) | 2018-03-02 | 2022-11-08 | Nipro Corporation | Catalyst for manufacturing 1,3-butadiene, manufacturing method of catalyst, and manufacturing method of 1,3-butadiene |
JP7427355B2 (ja) | 2018-03-02 | 2024-02-05 | 国立大学法人千葉大学 | 1,3-ブタジエン製造用触媒、前記触媒の製造方法、及び1,3-ブタジエンの製造方法 |
Also Published As
Publication number | Publication date |
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AU2013272713B2 (en) | 2017-02-02 |
MY184525A (en) | 2021-04-01 |
SG11201408099VA (en) | 2015-01-29 |
BR112014030475A8 (pt) | 2018-04-03 |
CA2875771C (en) | 2020-05-12 |
CN104540873A (zh) | 2015-04-22 |
CN104540873B (zh) | 2017-09-01 |
AU2013272713A1 (en) | 2015-01-15 |
EA201492263A1 (ru) | 2015-04-30 |
EP2857435A1 (en) | 2015-04-08 |
US20150087034A1 (en) | 2015-03-26 |
EP2857435A4 (en) | 2015-05-27 |
TWI664202B (zh) | 2019-07-01 |
KR20150035770A (ko) | 2015-04-07 |
JP6175912B2 (ja) | 2017-08-09 |
BR112014030475A2 (pt) | 2017-06-27 |
TW201402644A (zh) | 2014-01-16 |
EA039158B1 (ru) | 2021-12-13 |
BR112014030475B1 (pt) | 2020-12-22 |
IN2014DN11259A (ja) | 2015-10-09 |
JP2014012822A (ja) | 2014-01-23 |
US9556307B2 (en) | 2017-01-31 |
CA2875771A1 (en) | 2013-12-12 |
KR102086324B1 (ko) | 2020-03-09 |
EP2857435B1 (en) | 2017-07-26 |
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