WO2017183550A1 - Résine à base de poly(téréphtalate de butylène) - Google Patents

Résine à base de poly(téréphtalate de butylène) Download PDF

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Publication number
WO2017183550A1
WO2017183550A1 PCT/JP2017/015096 JP2017015096W WO2017183550A1 WO 2017183550 A1 WO2017183550 A1 WO 2017183550A1 JP 2017015096 W JP2017015096 W JP 2017015096W WO 2017183550 A1 WO2017183550 A1 WO 2017183550A1
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Prior art keywords
polybutylene terephthalate
terephthalate resin
ppm
acid
compound
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PCT/JP2017/015096
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English (en)
Japanese (ja)
Inventor
壮一郎 南
伸行 廣中
大橋　英人
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東洋紡株式会社
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Priority to JP2017543398A priority Critical patent/JPWO2017183550A1/ja
Publication of WO2017183550A1 publication Critical patent/WO2017183550A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—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
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof

Definitions

  • the present invention relates to polybutylene terephthalate in which the amount of tetrahydrofuran (hereinafter referred to as THF) and 1,4-butanediol (hereinafter referred to as BD), which are outgas generated during molding, is reduced, thermal stability, color tone,
  • THF tetrahydrofuran
  • BD 1,4-butanediol
  • the present invention relates to a polybutylene terephthalate resin excellent in hydrolysis resistance and transparency, and further relates to a polybutylene terephthalate resin excellent in moldability, which can be suitably used for films, monofilaments, fibers, electrical and electronic parts, automobile parts and the like.
  • Polybutylene terephthalate a typical engineering plastic among thermoplastic polyester resins, has excellent physical and chemical properties such as ease of molding, mechanical properties, heat resistance, chemical resistance, fragrance retention, etc. Therefore, it is widely used for injection molded products such as automobile parts, electrical / electronic parts, precision equipment parts. In recent years, it has come to be widely used in the fields of films, sheets, monofilaments, fibers, etc., taking advantage of its characteristics.
  • Polybutylene terephthalate production methods are roughly classified into, for example, a transesterification method using dimethyl terephthalate as a terephthalic acid component as a raw material and a direct esterification method using terephthalic acid as a raw material.
  • the transesterification method has a drawback that distillation separation after recovery is difficult because the boiling points of methanol and THF generated as by-products of the reaction are close.
  • the direct esterification method methanol is not generated and the raw material basic unit is better than that in the transesterification method. Therefore, the production of polybutylene terephthalate by the direct esterification method has become the mainstream.
  • the titanium catalyst used in the direct esterification method significantly accelerates the decomposition reaction that generates THF and BD at the time of molding, so that THF and BD are mixed into the polybutylene terephthalate to be a product, so that the thermal stability, There is a problem that the quality such as color tone, hydrolysis resistance, and transparency is deteriorated.
  • THF and BD are used to generate oligomers and additives derived from polybutylene terephthalate, metal compounds derived from additives, compounds derived from stabilizers, compounds derived from mold release agents, etc. (Degraded component) is carried to the mold and deposited, which deteriorates the appearance of the molded product, and further increases the frequency of mold cleaning, resulting in decreased productivity. Newly found.
  • Patent Document 1 a method for reducing the amount of titanium compound used as a catalyst
  • Patent Document 2 a method for defining the intrinsic viscosity and carboxy group concentration of polybutylene terephthalate
  • Patent Documents 3 and 4 a method for defining the intrinsic viscosity and carboxy group concentration of polybutylene terephthalate
  • the above method is not sufficient to suppress the generation amount of THF and BD at a temperature (for example, around 265 ° C.) applied during molding.
  • the object of the present invention is to reduce the generation amount of THF and BD, which have an effect of transporting a decomposition component causing mold contamination to the mold during molding, and also has thermal stability, color tone, hydrolysis resistance and transparency. It is an object of the present invention to provide a polybutylene terephthalate which is excellent in moldability and can be suitably used for films, monofilaments, fibers, electrical and electronic parts, automobile parts and the like, which are further excellent in moldability.
  • the polybutylene terephthalate resin is at 265 ° C. for 10 minutes for an inert gas atmosphere.
  • the aluminum compound contains 10-50 ppm as aluminum atoms and 20-150 ppm as phosphorus atoms with respect to the mass of the polybutylene terephthalate resin.
  • the polybutylene terephthalate resin according to [1].
  • the decomposition component is prevented from being deposited in the mold, and the frequency of mold contamination during molding is reduced. I can do things. As a result, the production efficiency can be improved, and the film, monofilament, fiber, electric / electronic component, and automobile component can be provided with excellent thermal stability, color tone, hydrolysis resistance, transparency, and moldability.
  • the “polybutylene terephthalate resin” includes a polymerization catalyst compound described later. Although it can be said to be a kind of “composition” in that it contains a substance other than a chemical substance called “polybutylene terephthalate”, since the amount of the polymerization catalyst compound is very small, in the present invention, “polybutylene terephthalate resin” It expresses. In addition, in order to simplify or to describe a chemical substance called “polybutylene terephthalate”, it may be called “polybutylene terephthalate”.
  • the polybutylene terephthalate according to the present invention has a structure in which terephthalic acid units and 1,4-butanediol units are bonded by esterification or transesterification, and 70 mol% or more of dicarboxylic acid units are terephthalic.
  • the proportion of terephthalic acid units in all dicarboxylic acid units is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and the proportion of BD units in all diol units is preferably Is 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more.
  • an acid component other than terephthalic acid can be copolymerized within a range that does not impair the physical properties of polybutylene terephthalate.
  • phthalic acid isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, 4,4 ′ -Arocyclic dicarboxylic acids such as diphenylsulfone dicarboxylic acid, aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid And aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid,
  • diol components other than BD can be copolymerized within a range that does not impair the physical properties of polybutylene terephthalate.
  • hydroxycarboxylic acids such as lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p- ⁇ -hydroxyethoxybenzoic acid, stearyl alcohol
  • Monofunctional components such as benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid, tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane, trimethylolpropane
  • Trifunctional or higher polyfunctional components such as glycerol and pentaerythritol can be used as the copolymerization component.
  • the polybutylene terephthalate resin of the present invention can be obtained by combining an aluminum compound and a phosphorus compound as a catalyst in the polymerization reaction between terephthalic acid and BD. Compared with the case where a conventional titanium compound is used, the decomposition reaction during molding can be suppressed, so that the amount of THF and BD generated from the hydroxyl group end of polybutylene terephthalate can be greatly reduced.
  • the aluminum compound and phosphorus compound constituting the polymerization catalyst known compounds can be used without limitation.
  • the aluminum compound examples include carboxylates such as aluminum acetate, basic aluminum acetate and aluminum lactate, inorganic acid salts such as aluminum chloride, aluminum hydroxide and aluminum hydroxide chloride, and chelate such as aluminum acetylacetonate.
  • carboxylates such as aluminum acetate, basic aluminum acetate and aluminum lactate
  • inorganic acid salts such as aluminum chloride, aluminum hydroxide and aluminum hydroxide chloride
  • chelate such as aluminum acetylacetonate.
  • organic aluminum compounds such as compounds and aluminum oxalate, and partial hydrolysates thereof.
  • carboxylate, inorganic acid salt and chelate compound are preferable, and among these, aluminum acetate, basic aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are more preferable, Aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide and aluminum hydroxide chloride are more preferred, and aluminum acetate and basic aluminum acetate are most preferred.
  • the amount of the aluminum compound used in the polymerization catalyst according to the present invention is preferably 10 to 50 ppm, more preferably 15 to 45 ppm, as aluminum atoms with respect to the total mass of the resulting polybutylene terephthalate resin. More preferably, it is 20 to 40 ppm, and particularly preferably 30 to 40 ppm.
  • the catalytic activity is remarkably inferior, and the polymerization rate may decrease. If it exceeds 50 ppm, aluminum-based foreign matter (foreign matter derived from an aluminum compound) is generated, and in the case of a molded product that requires transparency, the aluminum-based foreign matter may deteriorate transparency. Moreover, since the crystallization speed of the polybutylene terephthalate resin also changes, there is a possibility that the molding process will be affected.
  • the residual amount (content) of aluminum atoms in the polybutylene terephthalate resin of the present invention is preferably 10 to 50 ppm, more preferably 15 to 45 ppm, still more preferably 20 to 40 ppm based on the total mass of the polybutylene terephthalate resin. Particularly preferred is 30 to 40 ppm.
  • the phosphorus compound used for the polymerization catalyst is not particularly limited, but the use of a phosphonic acid compound or a phosphinic acid compound is highly preferable for improving the catalytic activity. Among these, the use of a phosphonic acid compound is effective for improving the catalytic activity. Is particularly large and preferred.
  • phosphorus compounds having a phenol moiety in the same molecule are preferred. It is not particularly limited as long as it is a phosphorus compound having a phenol structure, but it is a catalyst if one or more compounds selected from the group consisting of phosphonic acid compounds and phosphinic acid compounds having a phenol moiety in the same molecule are used.
  • the effect of improving the activity is large and preferable.
  • the use of a phosphonic acid compound having a phenol moiety in one or two or more of the same molecules is particularly preferable because the effect of improving the catalytic activity is particularly large.
  • examples of the phosphorus compound having a phenol moiety in the same molecule include compounds represented by the following general formulas (1) and (2).
  • R 1 is a hydrocarbon group having 1 to 50 carbon atoms including a phenol part, a hydroxyl group, a halogen group, an alkoxyl group, an amino group or the like, and a carbon number 1 including a phenol part.
  • R 4 represents a hydrocarbon group having 1 to 50 carbon atoms, including a substituent such as hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group.
  • R 2 and R 3 each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as a hydroxyl group or an alkoxyl group.
  • the group may contain a branched structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl, and the ends of R 2 and R 4 may be bonded to each other.
  • Examples of the phosphorus compound having a phenol moiety in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, diphenyl p-hydroxyphenylphosphonate, bis ( p-hydroxyphenyl) phosphinic acid, methyl bis (p-hydroxyphenyl) phosphinate, phenyl bis (p-hydroxyphenyl) phosphinate, p-hydroxyphenylphenylphosphinic acid, methyl p-hydroxyphenylphenylphosphinate, p-hydroxy Examples include phenyl phenylphenylphosphinate, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, and phenyl p-hydroxyphenylphosphinate.
  • phosphorus compounds represented by the following general formula (3) can be exemplified.
  • X 1 and X 2 each represent hydrogen, an alkyl group having 1 to 4 carbon atoms, or a monovalent or higher metal. Moreover, X 1 is metal be two or more valences, X 2 may be absent. Furthermore, an anion corresponding to the surplus valence of the metal may be arranged with respect to the phosphorus compound.
  • the metal Li, Na, K, Ca, Mg, and Al are preferable.
  • the catalytic activity of the aluminum compound is improved and the thermal stability of the polymerized polybutylene terephthalate resin is also improved.
  • the heat resistance of resin can be improved by using a phosphorus compound, it becomes possible to suppress the decomposition reaction at the time of shaping
  • the phosphorus compound that is preferably used as the polymerization catalyst is at least one phosphorus compound selected from the compounds represented by chemical formula (4) and chemical formula (5).
  • Irgamod 295 manufactured by BASF
  • Irganox 1425 manufactured by BASF
  • the amount of the phosphorus compound used in the polymerization catalyst according to the present invention is preferably 20 to 150 ppm, more preferably 30 to 120 ppm, remaining as phosphorus atoms with respect to the total mass of the resulting polybutylene terephthalate resin. More preferably, it is 40 to 100 ppm, and particularly preferably 50 to 90 ppm.
  • Residual amounts of phosphorus atoms that deviate from the above upper and lower limits may reduce the polymerization activity.
  • the phosphorus compound When the phosphorus compound is placed under reduced pressure conditions during polymerization of polybutylene terephthalate, about 10 to 60% of the addition amount (use amount) is removed from the system depending on the conditions. Therefore, in practice, it is necessary to determine the amount of addition after conducting trial experiments several times and determining the residual ratio of phosphorus atoms to the polybutylene terephthalate resin.
  • the residual amount (content) of phosphorus atoms in the polybutylene terephthalate resin of the present invention is preferably 20 to 150 ppm, more preferably 30 to 120 ppm, still more preferably 40 to 100 ppm based on the total mass of the polybutylene terephthalate resin. Particularly preferred is 50 to 90 ppm.
  • a metal-containing polymerization catalyst such as an antimony compound, a titanium compound, a tin compound, or a germanium compound may be used in combination in order to further improve the catalytic activity.
  • the antimony compound is preferably 30 ppm or less as an antimony atom with respect to the mass of the resulting polybutylene terephthalate resin
  • the germanium compound is preferably 10 ppm or less as a germanium atom with respect to the mass of the obtained polybutylene terephthalate resin.
  • the titanium compound is preferably 3 ppm or less as a titanium atom with respect to the mass of the resulting polybutylene terephthalate resin, and the tin compound has 3 ppm or less as a tin atom with respect to the mass of the resulting polybutylene terephthalate resin.
  • these metal-containing polymerization catalysts such as antimony compounds, titanium compounds, tin compounds and germanium compounds are not used as much as possible.
  • a small amount of alkali metal, alkaline earth metal and at least one selected from the compound may coexist as the second metal-containing component.
  • the terminal group of polybutylene terephthalate resin can be stabilized, and there is an effect of suppressing the generation amount of THF and BD.
  • the residual amount is preferably 50 ppm or less as an alkali metal atom or an alkaline earth metal atom.
  • the intrinsic viscosity of the polybutylene terephthalate resin of the present invention is required to be 0.5 to 1.3 dL / g.
  • the intrinsic viscosity is preferably 0.6 to 1.2 dL / g, more preferably 0.7 to 1.15 dL / g, and still more preferably 0.8 to 1.1 dL / g.
  • the method for producing the polybutylene terephthalate resin is classified into a continuous type and a batch type from the raw material supply or polymer discharge mode.
  • a continuous system in which raw materials are continuously supplied and an esterification reaction and a polycondensation reaction are continuously performed.
  • Continuous reaction equipment is a reaction vessel for esterification and a melt polycondensation reaction vessel connected by piping, and the raw materials are continuously charged without emptying each reaction vessel. In this method, the resin is removed from the transfer and melt polycondensation reaction vessel.
  • the esterification reaction may be performed in one stage or may be performed in multiple stages.
  • the melt polycondensation reaction may be performed in one stage or may be performed in multiple stages.
  • An example of the polymerization method according to the polybutylene terephthalate resin of the present invention is as follows. That is, the dicarboxylic acid component containing terephthalic acid as a main component and the diol component containing BD as a main component are mixed in a raw material mixing tank to form a slurry to suppress intramolecular dehydration cyclization reaction of BD to THF. Therefore, preferably at a temperature of 210 to 235 ° C.
  • the esterification is continuously carried out for 2.5 to 8 hours, more preferably 3 to 6 hours.
  • the obtained esterification reaction product (hereinafter sometimes referred to as an oligomer) is transferred to a polycondensation reaction tank, and is usually 210 to 280 ° C., preferably 220 to 270 ° C., more preferably 230 to 260 ° C.
  • the polycondensation reaction is usually performed for 1 to 15 hours, preferably 2 to 10 hours, more preferably 3 to 6 hours under stirring under a reduced pressure of 10 kPa or less, preferably 5 kPa or less, more preferably 1 kPa or less.
  • the polymer obtained by the polymerization reaction is usually transferred from the bottom of the polycondensation reaction tank to a polymer extraction die and extracted in the form of a strand, while being cooled with water or after being cooled with water, cut with a cutter, pellets, chips, etc. It is made of granular material.
  • the polymerization catalyst for polybutylene terephthalate used in the present invention can be added to the reaction system at any stage of the polymerization reaction.
  • it can be added to the reaction system at any stage before the start of the esterification reaction and during the reaction, immediately before the start of the polycondensation reaction, or at any stage during the polycondensation reaction.
  • it is preferable to add the aluminum compound and the phosphorus compound immediately before the start of the polycondensation reaction.
  • the polycondensation reaction rate and the amount of THF and BD generated from the polybutylene terephthalate resin can be adjusted by adjusting the terminal composition of the oligomer before the polycondensation reaction. it can.
  • the polycondensation reaction can be efficiently carried out by setting the proportion of hydroxyl groups to 50 to 90% of the total number of terminals of the oligomer before the polycondensation reaction.
  • the proportion of hydroxyl groups in the oligomer before the polycondensation reaction is preferably in the range of 55 to 85%, more preferably 60 to 80%.
  • the polybutylene terephthalate resin of the present invention satisfies the following (1) and (2).
  • Tetrahydrofuran (THF) generated when the polybutylene terephthalate resin is heated at 265 ° C. for 10 minutes in an inert gas atmosphere is 50 ppm or less.
  • the polybutylene terephthalate resin is heated at 265 ° C. for 10 minutes.
  • 1,4-butanediol (BD) generated when heated in an active gas atmosphere is 10 ppm or less
  • the above (1) and (2) can be measured by the method described in detail in (Methods for measuring THF and BD generation) described in the Examples section below. Specifically, a thermal desorption apparatus (TD-20) / gas chromatograph mass spectrometer (QP-2010UItra) manufactured by Shimadzu Corporation, column Rxi-1 ms (length 60 m, inner diameter 0.32 mm, film thickness 0) .25 ⁇ m), a polybutylene terephthalate resin sample is heat-treated at 265 ° C. for 10 minutes, and the collected components are analyzed. As the inert gas, helium gas is preferably used.
  • the polybutylene terephthalate resin satisfying the above (1) and (2) employs a direct esterification method using an aluminum compound and a phosphorus compound as a polymerization catalyst, and before the polycondensation reaction. It can obtain by making the ratio which a hydroxyl group occupies among the terminal total number of an oligomer into a specific range.
  • the amount of THF generated is preferably 40 ppm or less, more preferably 30 ppm or less, and still more preferably 20 ppm or less.
  • the amount of BD generated is preferably 5 ppm or less.
  • the polybutylene terephthalate resin of the present invention includes 2,6-di-tert-butyl-4-octylphenol, pentaerythrityl-tetrakis [3- (3 ′, 5′-tert-butyl-4′-hydroxyphenyl) propionate ], Phenol compounds such as dilauryl-3,3′-thiodipropionate, thioether compounds such as pentaerythrityl-tetrakis (3-laurylthiodipropionate), triphenyl phosphite, tris (nonylphenyl) phosphite, Antioxidants such as phosphorus compounds such as tris (2,4-di-t-butylphenyl) phosphite, paraffin wax, microcrystalline wax, polyethylene wax, long chain fatty acids represented by montanic acid and montanic acid ester, and the like Release of esters, silicone oil, etc. Or the like may be added
  • 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.
  • other fillers can be blended together with the reinforcing filler.
  • Other fillers to be blended include, for example, plate-like inorganic fillers, ceramic beads, asbestos, wollastonite, talc, clay, mica, zeolite, kaolin, potassium titanate, barium sulfate, titanium oxide, silicon oxide, oxidation Aluminum, magnesium hydroxide, etc. are mentioned.
  • the plate-like inorganic filler By blending the plate-like inorganic filler, the anisotropy and warpage of the molded product can be reduced.
  • the plate-like inorganic filler include glass flakes, mica, and metal foil. Among these, glass flakes are preferably used.
  • a flame retardant can be blended to impart flame retardancy.
  • 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.
  • the polybutylene terephthalate resin of the present invention can be blended with conventional additives as required.
  • additives are not particularly limited and include, for example, stabilizers such as antioxidants and heat stabilizers, lubricants, mold release agents, catalyst deactivators, crystal nucleating agents, crystallization accelerators, and the like. It is done. These additives can be added during the polymerization or after the polymerization.
  • stabilizers such as UV absorbers and weathering stabilizers, colorants such as dyes and pigments, antistatic agents, foaming agents, plasticizers, impact modifiers. Etc. can be blended.
  • the polybutylene terephthalate resin of the present invention includes polyethylene, polypropylene, polystyrene, polyacrylonitrile, polymethacrylic acid ester, ABS resin, polycarbonate, polyamide, polyphenylene sulfide, polyethylene terephthalate, liquid crystal polyester, polyacetal, polyphenylene oxide, etc.
  • Thermosetting resins such as thermoplastic resins, phenol resins, melamine resins, silicone resins, and epoxy resins can be blended. These thermoplastic resins and thermosetting resins can be used in combination of two or more.
  • the method of blending the various additives and resins is not particularly limited, but a method of using a single or twin screw extruder having equipment capable of devolatilization from the vent port as a kneader is preferable.
  • Each component including an additional component can be supplied to the kneader in a lump or can be supplied sequentially.
  • two or more kinds of components selected from each component including an additional component can be mixed in advance.
  • the method for molding the polybutylene terephthalate resin of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, molding methods such as injection molding, hollow molding, extrusion molding, and press molding are applied. I can do things.
  • the polybutylene terephthalate resin of the present invention can reduce THF and BD generated during the molding process, the frequency of mold contamination during the molding process can be reduced. As a result, the production efficiency can be improved, and the film, monofilament, fiber, electric / electronic component, and automobile component can be provided with excellent thermal stability, color tone, hydrolysis resistance, transparency, and moldability.
  • the secondary trap tube was reheated at 280 ° C., the collected components were introduced into a gas chromatograph mass spectrometer (hereinafter referred to as GC-MS), and THF and BD were quantified from the obtained chromatogram.
  • GC-MS gas chromatograph mass spectrometer
  • quantitative_assay was performed in toluene mass conversion using the standard solution with a known density
  • a continuous molding evaluation mold (having a cavity with an outer diameter of 30 mm, an inner diameter of 20 mm and a thickness of 3 mm, the flow end is a concave portion and no gas venting) is used.
  • the mold was continuously molded by a short shot method so that inclusions such as polybutylene terephthalate decomposition products were likely to accumulate in the concave portion on the opposite side of the gate portion, and mold contamination was observed.
  • the cylinder temperature at the time of molding was 260 ° C.
  • the mold temperature was 60 ° C.
  • the cycle time was 40 seconds
  • the mold contamination after 20 shots was evaluated.
  • the evaluation was performed visually according to the following criteria. ⁇ : Dirt is hardly recognized. ⁇ : Dirt is gently recognized in the center near the concave portion on the opposite side of the gate portion. X: Dirt in the center near the recess on the opposite side of the gate portion is conspicuous in black with a clear outline.
  • the esterification reaction was performed for 2 hours.
  • the esterification reaction was completed, and 70% of the total number of oligomer ends before the polycondensation reaction was a hydroxyl group.
  • the BD solution of the aluminum compound prepared by the above method and the BD solution of the phosphorus compound 1, respectively, were added so that 40 ppm and 70 ppm remain as aluminum atoms and phosphorus atoms, The temperature of the system was raised to 250 ° C.
  • Example 2 A polybutylene terephthalate resin having an intrinsic viscosity of 0.81 dL / g was obtained in the same manner as in Example 1 except that the polycondensation reaction was changed to 2.5 hours.
  • Example 3 A polybutylene terephthalate resin having an intrinsic viscosity of 1.20 dL / g was obtained in the same manner as in Example 1 except that the polycondensation reaction was changed to 4 hours.
  • Example 4 The polybutylene terephthalate resin obtained in Example 1 was subjected to solid-phase polymerization for 24 hours under reduced pressure at 200 ° C. using a batch type solid-phase polymerization apparatus, and polybutylene terephthalate having an intrinsic viscosity of 0.83 dL / g. A resin was obtained.
  • Example 5 The polybutylene terephthalate resin obtained in Example 2 was subjected to solid phase polymerization at 200 ° C. under reduced pressure for 24 hours using a batch type solid phase polymerization apparatus, and polybutylene terephthalate having an intrinsic viscosity of 1.01 dL / g. A resin was obtained.
  • Comparative Example 2 In Comparative Example 1, a polybutylene terephthalate resin having an intrinsic viscosity of 1.07 dL / g was obtained in the same manner as in Comparative Example 1 except that the polycondensation reaction was changed to 2 hours.
  • Comparative Example 3 In Comparative Example 2, the same procedure as in Comparative Example 2 was carried out except that the amount of tetrabutyl titanate was changed so that 40 ppm of titanium atoms remained with respect to the mass of the resulting polybutylene terephthalate resin, and the intrinsic viscosity was 0.83 dL / g. A polybutylene terephthalate resin was obtained.
  • Comparative Example 4 Comparative Example 3 was the same as Comparative Example 3 except that magnesium acetate tetrahydrate was added so that 40 ppm of magnesium atoms remained with respect to the mass of the resulting polybutylene terephthalate resin at the same timing as the addition of tetrabutyl titanate. And a polybutylene terephthalate resin having an intrinsic viscosity of 0.84 dL / g was obtained.
  • Comparative Example 6 The polybutylene terephthalate resin obtained in Comparative Example 1 was subjected to solid-phase polymerization at 200 ° C. under reduced pressure for 6 hours using a batch type solid-phase polymerization apparatus, and an intrinsic viscosity of 1.04 dL / g was obtained. A resin was obtained.
  • the transesterification reaction was completed, and 98% of the total number of terminals of the oligomer before the polycondensation reaction was a hydroxyl group. Subsequently, the temperature of the system is raised to 250 ° C. in 1 hour, and the pressure of the system is gradually reduced to 0.15 kPa during this time, and a polycondensation reaction is carried out for 1.5 hours under these conditions. A pellet of polybutylene terephthalate resin of .80 dL / g was obtained.
  • the transesterification reaction was completed, and 96% of the total number of oligomer ends before the polycondensation reaction was a hydroxyl group. Subsequently, the temperature of the system is raised to 250 ° C. in 1 hour, and the pressure of the system is gradually reduced to 0.15 kPa during this time, and a polycondensation reaction is performed for 2 hours under these conditions, and an intrinsic viscosity of 1.09 dL. / G of polybutylene terephthalate resin pellets were obtained.
  • the temperature of the system was raised to 250 ° C. in 1 hour, and the pressure of the system was gradually reduced to 0.15 kPa during this time, and a polycondensation reaction was performed for 4 hours under these conditions.
  • g or more of polybutylene terephthalate resin was not obtained.
  • the resulting polybutylene terephthalate resin had an intrinsic viscosity of 0.46 dL / g, but since pelletization was difficult, various evaluations were not performed.
  • Table 2 shows the results of evaluating the physical properties of the polybutylene terephthalate resin obtained in the comparative example. In Comparative Examples 10 and 11, the physical properties could not be evaluated.
  • the polybutylene terephthalate resin of the example is compared with the comparative example (a system using a titanium catalyst, a system using dimethyl terephthalate as a raw material, a system where the terminal composition of the oligomer before the polycondensation reaction is not in a specific range). It was confirmed that the generation amount of THF and BD can be reduced. This is because, as described above, the titanium catalyst that significantly accelerates the decomposition reaction that generates THF and BD is not used, and the thermal decomposition of polybutylene terephthalate is suppressed by the hindered phenol part in the phosphorus compound.
  • the proportion of the hydroxyl group of the oligomer before the polycondensation reaction is less than the system using a titanium catalyst, the system using dimethyl terephthalate as a raw material, and the ratio is in a specific range, THF, It is considered that the amount of BD generated can be reduced.
  • the polybutylene terephthalate resin of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, injection molding, hollow molding, extrusion molding, press molding, and other molding methods can be applied, Since THF and BD generated at that time can be reduced, the frequency of mold contamination during molding can be reduced. As a result, the production efficiency can be improved, and the film, monofilament, fiber, electric / electronic component, and automobile component can be provided with excellent thermal stability, color tone, hydrolysis resistance, transparency, and moldability.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une résine de poly(téréphtalate de butylène) qui contient, en tant que constituants catalytiques de polymérisation, un composé d'aluminium et un composé de phosphore et qui présente une viscosité intrinsèque de 0,5 à 1,3 dl/g et qui génère 50 ppm ou moins de tétrahydrofuranne et 10 ppm ou moins de 1,4-butanediol lorsqu'elle est chauffée à 265°C pendant 10 minutes dans une atmosphère de gaz inerte. Cette résine de poly(téréphtalate de butylène) peut réduire les quantités de tétrahydrofuranne et de 1,4-butanediol générées pendant le moulage, tout en présentant une excellente stabilité thermique, un excellent ton de couleur, une excellente résistance à l'hydrolyse et une excellente transparence.
PCT/JP2017/015096 2016-04-20 2017-04-13 Résine à base de poly(téréphtalate de butylène) WO2017183550A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020158747A (ja) * 2018-09-28 2020-10-01 日本エステル株式会社 ポリエステル樹脂
WO2022054670A1 (fr) * 2020-09-11 2022-03-17 東洋紡株式会社 Composition de résine polyester ainsi que procédé de fabrication de celle-ci, et film de polyester mettant en œuvre celle-ci
WO2022059511A1 (fr) * 2020-09-17 2022-03-24 東洋紡株式会社 Résine de polyester, objet moulé par soufflage à partir de celle-ci et procédés de production associés
WO2024070038A1 (fr) * 2022-09-30 2024-04-04 東洋紡エムシー株式会社 Résine de copolyester

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002241481A (ja) * 2001-02-21 2002-08-28 Toyobo Co Ltd 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
JP2002322254A (ja) * 2001-02-20 2002-11-08 Toyobo Co Ltd ポリエステルおよびその製造方法
JP2002363274A (ja) * 2001-04-03 2002-12-18 Toyobo Co Ltd ポリエステルおよびその製造方法
JP2005112873A (ja) * 2003-10-02 2005-04-28 Toyobo Co Ltd ポリエステルならびにポリエステルの製造方法
WO2005075539A1 (fr) * 2004-02-10 2005-08-18 Toyo Boseki Kabushiki Kaisha Catalyseur de polymérisation d’un polyester, polyester produit avec ce catalyseur et procédé de production d’un polyester
JP2006282800A (ja) * 2005-03-31 2006-10-19 Toyobo Co Ltd ポリエステルフィルム
JP2008081576A (ja) * 2006-09-27 2008-04-10 Toyobo Co Ltd ポリエステル樹脂の製造方法及びそれにより得られたポリエステル樹脂

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002322254A (ja) * 2001-02-20 2002-11-08 Toyobo Co Ltd ポリエステルおよびその製造方法
JP2002241481A (ja) * 2001-02-21 2002-08-28 Toyobo Co Ltd 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
JP2002363274A (ja) * 2001-04-03 2002-12-18 Toyobo Co Ltd ポリエステルおよびその製造方法
JP2005112873A (ja) * 2003-10-02 2005-04-28 Toyobo Co Ltd ポリエステルならびにポリエステルの製造方法
WO2005075539A1 (fr) * 2004-02-10 2005-08-18 Toyo Boseki Kabushiki Kaisha Catalyseur de polymérisation d’un polyester, polyester produit avec ce catalyseur et procédé de production d’un polyester
JP2006282800A (ja) * 2005-03-31 2006-10-19 Toyobo Co Ltd ポリエステルフィルム
JP2008081576A (ja) * 2006-09-27 2008-04-10 Toyobo Co Ltd ポリエステル樹脂の製造方法及びそれにより得られたポリエステル樹脂

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020158747A (ja) * 2018-09-28 2020-10-01 日本エステル株式会社 ポリエステル樹脂
WO2022054670A1 (fr) * 2020-09-11 2022-03-17 東洋紡株式会社 Composition de résine polyester ainsi que procédé de fabrication de celle-ci, et film de polyester mettant en œuvre celle-ci
WO2022059511A1 (fr) * 2020-09-17 2022-03-24 東洋紡株式会社 Résine de polyester, objet moulé par soufflage à partir de celle-ci et procédés de production associés
WO2024070038A1 (fr) * 2022-09-30 2024-04-04 東洋紡エムシー株式会社 Résine de copolyester

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