WO2007114459A1 - ポリ乳酸組成物 - Google Patents
ポリ乳酸組成物 Download PDFInfo
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- WO2007114459A1 WO2007114459A1 PCT/JP2007/057515 JP2007057515W WO2007114459A1 WO 2007114459 A1 WO2007114459 A1 WO 2007114459A1 JP 2007057515 W JP2007057515 W JP 2007057515W WO 2007114459 A1 WO2007114459 A1 WO 2007114459A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/005—Processes for mixing polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the present invention relates to a composition containing polylactic acid. More specifically, the present invention relates to a composition containing polylactic acid, excellent in thermal stability, mechanical strength, and hue, and capable of long-term storage.
- plastics are light and tough, have excellent durability, and can be easily and arbitrarily molded, so they have been mass-produced to support our lives.
- plastic when plastic is disposed of in the environment, it accumulates without being easily decomposed. Incineration releases a large amount of carbon dioxide, which has spurred global warming.
- Biodegradable plastics have aliphatic carboxylic acid ester units and are easily degraded by microorganisms.
- the thermal stability is poor, and the molecular weight is decreased or the hue is deteriorated in processes exposed to high temperatures such as melt spinning, injection molding, and melt film formation.
- Patent Document 1 proposes that when a molecular weight reaches 50,000 or more, a phosphoric acid compound or a phosphorous acid compound is added to polylactic acid as a catalyst deactivator.
- Patent Documents 2 and 3 teach that an acid phosphate ester or a chelating agent is added as a catalyst deactivator to improve the thermal stability of polylactic acid.
- Patent Document 1 adding a catalyst deactivator to low molecular weight polylactic acid hinders the subsequent polymerization reaction, resulting in a high molecular weight. It means that the body cannot be obtained.
- the acidic phosphoric acid esters described in Patent Documents 2 and 3 cause corrosion of the production equipment or decrease the hydrolysis resistance of the resin due to its acidity.
- the chelating agents exemplified are generally poor in heat resistance and are burned before supplementing the metal catalyst, causing serious coloring and odor.
- Patent Document 1 Japanese Patent No. 2 8 6 2 0 7 1
- Patent Document 2 Japanese Patent No. 3 4 8 7 3 8 8
- Patent Document 3 Japanese Patent Application Laid-Open No. Hei 10-3 6 6 5 1 Disclosure of Invention
- An object of the present invention is to provide a composition containing polylactic acid and having excellent thermal stability and hue. Another object of the present invention is to provide a composition having a high stereocomplex crystal content and excellent heat resistance.
- the present inventors have found that by adding a phosphono fatty acid ester to polylactic acid, the residual catalyst in the polylactic acid can be effectively deactivated, and the thermal stability and hue of polylactic acid can be improved. completed.
- the present invention contains 0.001 to 0.1 parts by weight of a metal catalyst and 0.001 to 0.5 parts by weight of a phosphono fatty acid ester with respect to 100 parts by weight of polylactic acid. It is a composition. Moreover, this invention is a molded object which consists of this composition. Furthermore, the present invention relates to a method for producing a composition comprising stereocomplex crystals comprising mixing poly-L-lactic acid and poly-D-lactic acid, comprising: poly-L-lactic acid and poly-D-lactic acid. At least one contains a metal catalyst, and vigorously, the mixture is mixed in an amount of 0.001 to 0.5 parts by weight with respect to 100 parts by weight of poly-L-lactic acid and poly-D-lactic acid. It is a manufacturing method of the composition performed in presence of phosphono fatty acid ester of this. BEST MODE FOR CARRYING OUT THE INVENTION
- composition (Polylactic acid)
- Polylactic acid is a polymer mainly composed of lactic acid units represented by the following formula.
- the polylactic acid is preferably poly-L-lactic acid, poly-D-lactic acid or a mixture thereof.
- Poly-L-lactic acid is a polymer mainly containing L-lactic acid units
- poly-D-lactic acid is a polymer mainly containing D-lactic acid units.
- Poly-L-lactic acid preferably contains 90 to 100 mol%, more preferably 95 to 100 mol%, and still more preferably 98 to 100 mol% of lactic acid units.
- Examples of other units include D-lactic acid units and units other than lactic acid.
- the D-lactic acid unit and the units other than lactic acid are preferably 0 to 10 mol%, more preferably 0 to 5 mol%, still more preferably 0 to 2 mol%.
- the poly-D-lactic acid preferably contains 90 to 100 mol%, more preferably 95 to 100 mol%, and still more preferably 98 to 100 mol% of 0-lactic acid units.
- Other units include L monolactic acid units and units other than lactic acid.
- the L monolactic acid unit and the units other than lactic acid are 0 to 10 mol%, preferably 0 to 5 mol%, more preferably 0 to 2 mol%.
- units other than lactic acid units derived from dicarboxylic acid, polyhydric alcohol, hydroxycarboxylic acid, lactone, etc. having functional groups capable of forming two or more ester bonds, various polyesters composed of these various components, various types Examples are units derived from polyethers, various polycarbonates and the like.
- dicarboxylic acid examples include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isofuric acid.
- Polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol Examples thereof include aliphatic polyhydric alcohols such as polyol and polypropylene glycol, and aromatic polyhydric alcohols obtained by adding ethylene oxide to bisphenol.
- Examples of the hydroxycarboxylic acid include glycolic acid and hydroxybutyric acid.
- Examples of the lactone include glycolide, ⁇ -strength prolactone glycolide, ⁇ -strength prolactone,; 6-propiolactone, ⁇ _ptyrolactone, / 3- or r-ptyrolactone, piperolactone, ⁇ -valerolactone, and the like.
- the weight average molecular weight (Mw) of poly_L-lactic acid or poly-D-lactic acid is preferably 50,000 to 500,000, more preferably 150,000 to 350,000.
- the weight average molecular weight is a standard polystyrene equivalent weight average molecular weight value measured by gel permeation chromatography (GPC) using black mouth form as an eluent.
- Poly 1-L-lactic acid and Poly 1-D-lactic acid can be produced by known methods.
- L- or D-lactide can be produced by heating and ring-opening polymerization in the presence of a metal catalyst.
- a metal catalyst for example, after crystallizing a low molecular weight polylactic acid containing a metal catalyst, it can be produced by solid phase polymerization by heating under reduced pressure or under an inert gas stream.
- it can be produced by a direct polymerization method in which lactic acid is dehydrated and condensed in the presence of organic solvent Z in the absence of Z.
- the polymerization reaction can be carried out in a conventionally known reaction vessel.
- a vertical reaction vessel equipped with a high-viscosity stirring blade such as a helical rib blade can be used alone or in parallel.
- Alcohol may be used as a polymerization initiator.
- Such an alcohol is preferably non-volatile without inhibiting the polymerization of polylactic acid.
- decanol, dodecanol, tetradecanol, hexadenol, decanol decanol, ethylene glycol, triethylene Glycol, benzyl alcohol and the like can be suitably used.
- a relatively low molecular weight lactic acid polyester obtained by the above-described ring-opening polymerization method or direct polymerization method of lactic acid is used as a prepolymer.
- Prepolymers can be said to be a preferred form from the viewpoint of preventing fusion, because they are pre-crystallized in the temperature range above the glass transition temperature (T g) and below the melting point (Tm).
- the crystallized prepolymer can be fixed in a vertical reaction vessel, or the vessel itself like a tumbler or kiln. Filled in a rotating reaction vessel, heated to a temperature range above the glass transition temperature (Tg) of the prepolymer and below the melting point (Tm).
- a method of reducing the pressure inside the reaction vessel and a method of circulating a heated inert gas stream are also preferably used in combination.
- the polylactic acid contains a stereocomplex crystal.
- the polylactic acid containing this stereocomplex crystal is called stereocomplex polylactic acid.
- Stereocomplex polylactic acid has a high melting point and excellent heat resistance.
- Stereocomplex crystals are formed by mixing poly 1-L-lactic acid and poly 1-D-lactic acid. In this case, the weight ratio of poly-L monolactic acid to poly-D-lactic acid is the former Z, the latter being preferably 90/10 to 10Z90, more preferably 75/25 to 25Z75, more preferably 60 Z 40 ⁇ 40 Z 6 0.
- the weight average molecular weight of the stereocomplex polylactic acid is preferably 100,000 to 500,000, more preferably 100,000 to 300,000.
- the weight average molecular weight is a standard polystyrene equivalent weight average molecular weight value measured by gel permeation chromatography (GPC) using black mouth form as an eluent.
- the content of stereocomplex crystals is preferably 80 to 100%, more preferably 95 to 100%.
- the stereocomplex polylactic acid referred to in the present invention preferably has a melting peak ratio of 195 ° C or higher, preferably 80% or higher, of melting peaks in the temperature rising process in differential scanning calorimetry (DSC) measurement. Is 90% or more, more preferably 95% or more.
- the melting point is preferably in the range of 195 to 250 ° C, more preferably in the range of 200 to 220.
- the melting enthalpy is preferably 20 J "g or more, more preferably 30 JZg or more.
- Stereocomplex polylactic acid can be produced by coexisting poly 1 L monolactic acid and poly 1 D-lactic acid in a predetermined weight ratio. Mixing can be performed in the presence of a solvent.
- the solvent is not particularly limited as long as it can dissolve poly L-lactic acid and poly D-lactic acid.
- chloroform methylene chloride, dichloroethane, tetrachloroethane, phenol, tetrahydrofuran N-methylpyrrolidone, N, N-dimethylformamide, ptyrolactone, trioxane, hexafluoroisopropanol, etc., or a mixture of two or more thereof is preferred.
- Mixing can be performed in the absence of a solvent. That is, it can be carried out by melt-kneading poly 1 L monolactic acid and poly 1 D-lactic acid.
- a method of melt kneading after mixing a predetermined amount of poly 1-L-lactic acid and poly 1-D-lactic acid, and a method of adding and kneading one of them after melting one of them can be adopted.
- the metal catalyst is preferably a compound containing at least one metal selected from the group consisting of alkaline earth metals, rare earth metals, transition metals of the third period, aluminum, germanium, tin, and antimony.
- alkaline earth metals include magnesium, calcium, and strontium.
- rare earth metals include scandium, yttrium, lanthanum, and cerium.
- transition metals in the third period include iron, cobalt, nickel, and zinc.
- the metal catalyst can be added to polylactic acid, for example, as a carboxylate, alkoxide, aryloxide, or -3-diketone enolate of these metals.
- a carboxylate for example, as a carboxylate, alkoxide, aryloxide, or -3-diketone enolate of these metals.
- tin octylate, titanium tetraisopropoxide, and aluminum triisopropoxide are particularly preferable.
- the content of the metal catalyst is from 0.001 to 0.1 part by weight, preferably from 0.05 to 0.05 part by weight, based on 100 parts by weight of polylactic acid. If the content of the metal catalyst is too small, the polymerization rate is remarkably lowered, which is not preferable. On the other hand, if the amount is too large, coloring due to heat of reaction, or open polymerization or transesterification reaction is accelerated, so that the hue and thermal stability of the resulting composition deteriorate.
- the content of the metal catalyst with respect to polylactic acid 1 0 0 part by weight, 2 X 1 0 over 4 to 0.0 5 parts by weight as the metal element, preferably 1 X 1 0- 3 ⁇ 0. 0 3 part by weight It is.
- the amount of metal elements can be quantified by ICP emission spectrometry.
- the phosphono fatty acid ester used in the present invention is a compound in which a phosphonic acid diester moiety and a carboxylic acid ester moiety are bonded via an aliphatic hydrocarbon group. Since such a phosphono fatty acid ester is colorless and transparent and excellent in heat resistance, The hue of the resulting composition is good.
- a phosphono fatty acid ester having a chemical structure represented by the following formula (1) gives good results for the purpose of the present invention.
- R 2 and R 3 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.
- alkyl group include ethyl group, propyl group, butyl group, pentyl group, hexyl group, decyl group, and octadecyl group.
- aryl groups include phenyl and naphthenyl groups.
- the aryl group may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.
- the halogen atom to be substituted include a fluorine atom, a chlorine atom, and a bromine atom.
- R i to R 3 may be the same or different.
- N is an integer of 1 to 3.
- Examples of the compound represented by the formula (1) include: ethyl ethyl phosphonoacetate, di-n-propyl phosphonoacetate ethyl, di-n-butyl phosphonoacetate ethyl, di-n-hexylphosphonoacetate ethyl, di-n-tetyl phosphonoacetate ethyl Di-n-decylphosphonoacetate ethyl, di-n-dodecylphosphonoacetate ethyl, di-n-octyl decylphosphonoacetate ethyl, diphenylphosphonoacetate ethyl, decylphosphonoacetate decyl, jetylphosphonoacetate dodecyl, jetylphosphonoacetate Decyl, Jetylphosphonopropionate, Di-n-propylphosphonopropio Ethyl nit
- ethyl phosphonoacetate ethyl di-n-propyl phosphonoacetate ethyl, di-n-butyl phosphonoacetate ethyl, di-n-hexyl phosphonoacetate ethyl, decyl phosphonoacetate decyl, jetyl phosphono octadecyl acetate is preferred.
- n is preferably an integer of 1 to 3.
- the content of the phosphono fatty acid ester is 0.001 to 0.5 part by weight, preferably 0.02 to 0.2 part by weight, based on 100 parts by weight of polylactic acid. If the content of the phosphono fatty acid ester is too small, the deactivation efficiency of the remaining metal catalyst is extremely poor and a sufficient effect cannot be obtained. On the other hand, if the amount is too large, the mold and die used during molding and spinning will be significantly contaminated.
- a method of mixing phosphono fatty acid ester with polylactic acid Either the method of adding without dilution or the method of adding after dilution may be used.
- a liquid or solid phosphono fatty acid ester having a melting point of less than 150 ° C. is used, in the ring-opening polymerization method, it can be directly added and kneaded in the reaction vessel at the latter stage of polymerization. It is also possible to knead with an extruder or kneader as a master batch formed into chips. Considering the uniform distribution in polylactic acid, use of an extruder or a kneader is preferable.
- a method in which the discharge part of the reaction vessel is directly connected to the extruder and the phosphono fatty acid ester is added from the side feeder is also preferred.
- the solid-phase polymerization method a method of kneading a polylactic acid solid obtained at the end of polymerization and a phosphono fatty acid ester with an ex-luder or two-in-one, a polylactic acid solid, and a master batch containing a phosphono fatty acid ester
- a kneading method using an extruder or a kneader a method of bringing the chips into contact with steam of a phosphono fatty acid ester, a method of immersing or spraying the phosphono fatty acid ester in a solution, and the like are possible.
- the present invention relates to a method for producing a composition comprising a stereocomplex crystal comprising mixing poly-L-lactic acid and poly-D-lactic acid, comprising at least poly-L-lactic acid and poly-D-lactic acid.
- One of them contains a metal catalyst, and the mixture is added to 0.001 to 0.5 parts by weight, preferably ⁇ with respect to 100 parts by weight of poly-L-lactic acid and poly-D-lactic acid.
- a method for producing a composition in the presence of 0.2 to 0.2 parts by weight of a phosphono fatty acid ester is included.
- the production method of poly-L-lactic acid, poly-D-lactic acid, metal catalyst, and phosphono fatty acid ester is as described in the section of the composition.
- the solvent is not particularly limited as long as it can dissolve poly-L-monolactic acid and poly-D-lactic acid.
- the solvent is not particularly limited as long as it can dissolve poly-L-monolactic acid and poly-D-lactic acid.
- chloroform, salt methylene chloride, dichloroethane, tetrachloroethane, phenol, Tetrahydrofuran, N-methylpyrrolidone, N, N-dimethylformamide, ptyrolactone, trioxane, hexafluoroisopropanol, etc. are used alone or in combination of two or more.
- Mixing should be done in the absence of solvent. Can do. That is, it can be performed by melt-kneading poly-L monolactic acid and poly-D-lactic acid.
- poly-L-lactic acid and poly-D-lactic acid are mixed in a predetermined amount and then melt-kneaded, or a method in which one of them is melted and the remaining one is added and kneaded can be adopted. it can.
- Embodiment 1 (L) and (Dc p) are mixed.
- Embodiment 2 (L), (Dc) and (P) are mixed.
- Embodiment 3 (Lc), (D) and (P) are mixed.
- Embodiment 4 (Lc), (Dc) and (P) are mixed.
- Embodiment 5 (Lc) and (Dc p) are mixed.
- Embodiment 6 (Lc p) and (D) are mixed.
- Embodiment 7 (Lcp) and (Dc) are mixed.
- Embodiment 8 (Lc p) and (Dc p) are mixed.
- the method includes (i) a composition obtained by adding a phosphono fatty acid ester to poly (mono-L) monolactic acid produced in the presence of a metal catalyst, —It is preferably produced by mixing a composition obtained by adding a phosphono fatty acid ester to lactic acid. Mixing can be performed in the presence of a solvent. It can also be carried out by melt-kneading in the absence of a solvent.
- the composition of the present invention is excellent in hue and heat stability, dramatically lowers the molecular weight during heat processing, and can be suitably used for melt spinning, melt film formation, injection molding, and the like.
- the composition of the present invention can be used satisfactorily by molding into a fiber, a film, various molded articles and the like.
- the molded product may contain additives used for ordinary resin molded products. For example, antioxidants, weathering agents, light-proofing agents, hydrolysis-resistant agents, etc., various deterioration inhibitors, flame retardants, nucleating agents, etc. Examples include lubricants, talc, glass fibers, natural fibers, chemical fibers, cut fibers, whiskers, and other molding aids, pigments, dyes, and the like.
- a thermal stability test was carried out by placing 10 g of the composition into a Pyrex test tube with a cock and holding the nitrogen-substituted interior at 260 ° C for 10 minutes and 60 minutes.
- the weight average molecular weight (Mw) of the composition before and after the thermal stability test was measured by GPC, and the thermal stability was evaluated by comparing them.
- Mw weight average molecular weight
- GPC-11 manufactured by Shodex was used, 5 Omg of the composition was dissolved in 5 ml of black mouth form, and developed at 40 ° C. black mouth form.
- the weight average molecular weight (Mw) was calculated as a polystyrene equivalent value.
- the lactide content in the composition was determined using a JEOL nuclear magnetic resonance apparatus J NM-EX270 spectrum meter in heavy-mouthed form. It was calculated as the ratio of quadruple peak area derived from lactide (4.98-5.05 p pm) to 20 ppm).
- the stereocomplex crystal content is the melting melting enthalpy ⁇ of the crystal melting point that appears at 150 ° C or higher and lower than 190 ° C on the differential scanning calorimeter (DSC). It was calculated by the following formula (2) from the melting enthalpy ⁇ of the crystal melting point appearing at 0 ° C. or more and less than 250 ° C.
- Stereocomplex crystal content ⁇ / ( ⁇ + ⁇ ) ⁇ X 100 (%) (2)
- Hue [1] The sample that had been subjected to the thermal stability test described for 60 minutes, and the sample before the test was a 1 wt% dichloromethane solution, and the YI value was UV-visible spectroscopy by Shimadzu Corporation. Total UV—Measured with 2400 PC. The Y I value was calculated from the tristimulus values X, Y, and ⁇ ⁇ by the following formula (3). The ⁇ value, which is an index of hue, was calculated by the following formula (4).
- Jetylphosphonopropionate was synthesized in the same manner as in Reference Example 1 except that 10 parts by weight of bromoethyl propionate was used instead of 100 parts by weight of bromoethyl acetate.
- G n-hexylphosphonopropionate was synthesized in the same manner as in Reference Example 3 except that 10 parts by weight of bromoethyl propionate was used instead of 100 parts by weight of bromoethyl acetate.
- L-lactide and 0.15 parts by weight of stearyl alcohol were charged from a raw material charging port of a polymerization reaction vessel equipped with a cooling distillation pipe under a nitrogen stream. Subsequently, the inside of the reaction vessel was purged with nitrogen five times, and L-lactide was melted at 190 ° C. When the L-lactide is completely melted, 0.02 part by weight of 2-ethyl hexanoate and 500 0 L of toluene are added from the raw material charging port and polymerized at 190 ° C for 1 hour. It was.
- the obtained composition was granulated to 25 mm using a powder mill, and 10 g thereof was put into a Pyrex test tube with a cup. Next, the inside of the Pyrex test tube was purged with nitrogen, and thermal stability tests were conducted at 26 ° C. for 10 minutes and 60 minutes. After completion of the test, the composition was taken out, and Mw, lactide content, and ⁇ value were measured. Table 1 shows the measurement results.
- a composition was prepared in the same manner as in Example 1, except that 0.055 parts by weight of ethyl ethylphosphonoacetate was changed to 0.069 parts by weight of ethyl n-butylphosphonoacetate.
- Table 1 shows the Mw and lactide contents of the resulting composition.
- a thermal stability test was conducted in the same manner as in Example 1. The results are shown in Table 1.
- a composition was prepared in the same manner as in Example 1, except that 0.05 part by weight of ethyl phosphonoacetate was replaced by 0.05 part by weight of di-n-hexylphosphonoacetate.
- Table 1 shows the Mw and lactide contents of the resulting composition.
- a thermal stability test was conducted in the same manner as in Example 1. The results are shown in Table 1.
- a composition was prepared in the same manner as in Example 1, except that 0.05 part by weight of ethyl phosphonoacetate was replaced by 0.1 part by weight of octyl decyl phosphonoacetate.
- Table 1 shows the Mw and lactide contents of the resulting composition.
- a thermal stability test was conducted in the same manner as in Example 1. The results are shown in Table 1.
- Example 1 A composition was prepared in the same manner as in Example 1, except that 0.05 part by weight of ethyl phosphonoacetate was replaced by 0.05 part by weight of ethyl phosphonopropionate. Table 1 shows the Mw and lactide contents of the resulting composition. Next, real A thermal stability test was conducted in the same manner as in Example 1. The results are shown in Table 1.
- a composition was prepared in the same manner as in Example 1, except that 0.055 parts by weight of ethyl phosphonoacetate was replaced by 0.5 parts by weight of ethyl n-hexylphosphonopropionate.
- Table 1 shows the Mw and lactide contents of the resulting composition.
- a thermal stability test was conducted in the same manner as in Example 1. The results are shown in Table 1.
- a composition was prepared in the same manner as in Example 1, except that 0.05 part by weight of ethyl phosphonoacetate was replaced by 0.05 part by weight of triethyl phosphite.
- Table 1 shows the Mw and lactide contents of the resulting composition.
- a thermal stability test was conducted in the same manner as in Example 1. The results are shown in Table 1.
- a composition was prepared in the same manner as in Example 1, except that 0.05 5 parts by weight of ethyl phosphonoacetate was replaced by 0.07 parts by weight of triphenyl phosphite.
- Table 1 shows the Mw and lactide contents of the resulting composition.
- a thermal stability test was conducted in the same manner as in Example 1. The results are shown in Table 1.
- Example 1 A composition was prepared in the same manner as in Example 1, except that no ethyl ether was added. Table 1 shows the Mw and lactide contents of the resulting composition. Next, a thermal stability test was conducted in the same manner as in Example 1. The results are shown in Table 1.
- a poly-D-lactic acid composition was prepared in the same manner. That is, 100 parts by weight of D-lactide and 0.15 parts by weight of stearyl alcohol were charged, and then the inside of the reaction vessel was purged with nitrogen five times to melt D-lactide at 190 ° C. When D-lactide is completely melted, 0.05 part by weight of 2-ethyl hexanoate is added together with toluene 5 0 0 // L from the raw material charging port and polymerized at 190 ° C for 1 hour. did. After completion of the polymerization, 0.05 5 parts by weight of ethyl ethylphosphonoacetate was added from the catalyst inlet and mixed for 15 minutes. Finally, excess D-lactide was devolatilized, the strand-shaped poly-D-lactic acid composition was discharged from the discharge port of the reaction vessel, and was cut into pellets while cooling.
- the resulting composition is granulated to 2-5 mm using a pulverizer and 10 g Placed in a Pyrex test tube with a hook. Next, the inside of the Pyrex test tube was replaced with nitrogen, and a thermal stability test was conducted at 260 ° C for 10 minutes. After completion of the test, the composition was taken out, and Mw, lactide content, and ⁇ I value were measured. Table 2 shows the measurement results.
- a composition was prepared in the same manner as in Example 7 except that 0.055 parts by weight of ethyl phosphonoacetate was replaced with 0.069 parts by weight of diethyl n-butylphosphonoacetate.
- Table 2 shows the Mw, stereocomplex crystal content and lactide content of the resulting composition.
- the thermal stability test of the composition was performed in the same manner as in Example 7. The results are shown in Table 2.
- a composition was prepared in the same manner as in Example 7, except that 0.05 part by weight of ethyl phosphonoacetate was replaced by 0.08 part by weight of di-n-hexylphosphonoacetate.
- Table 1 shows the Mw, stereocomplex crystal content, and lactide content of the resulting composition.
- the thermal stability test of the composition was performed in the same manner as in Example 7. The results are shown in Table 2.
- a composition was prepared in the same manner as in Example 7 except that 0.05 part by weight of ethyl phosphonoacetate was replaced by 0.1 part by weight of octyl decyl phosphonoacetate.
- Table 2 shows the Mw, stereocomplex crystal content and lactide content of the resulting composition.
- the thermal stability test of the composition was performed in the same manner as in Example 7. The results are shown in Table 2.
- Example 1 2 A composition was prepared in the same manner as in Example 7, except that 0.055 parts by weight of ethyl phosphonoacetate was changed to 0.059 parts by weight of ethyl phosphonopropionate. Table 2 shows the Mw, stereocomplex crystal content, and lactide content of the resulting composition. The thermal stability test of the composition was performed in the same manner as in Example 7. The results are shown in Table 2.
- Example 1 2 A composition was prepared in the same manner as in Example 7, except that 0.055 parts by weight of ethyl phosphonoacetate was changed to 0.059 parts by weight of ethyl phosphonopropionate.
- Table 2 shows the Mw, stereocomplex crystal content, and lactide content of the resulting composition.
- the thermal stability test of the composition was performed in the same manner as in Example 7. The results are shown in Table 2.
- Example 1 2 A composition was prepared in the same manner as in Example 7, except that 0.055 parts by weight of ethyl phosphonoa
- a composition was prepared in the same manner as in Example 7, except that 0.055 parts by weight of ethyl phosphonoacetate was changed to 0.08 parts by weight of di-n-hexylphosphonopropionate.
- Table 2 shows the Mw, stereocomplex crystal content, and lactide content of the resulting composition.
- the thermal stability test of the composition was also conducted in the same manner as in Example 7. The results are shown in Table 2.
- a composition was prepared in the same manner as in Example 7, except that 0.05 part by weight of ethyl phosphonoacetate was replaced by 0.05 part by weight of triethyl phosphite.
- Table 2 shows the Mw, stereocomplex crystal content, and lactide content of the resulting composition.
- the thermal stability test of the composition was performed in the same manner as in Example 7. The results are shown in Table 2.
- a composition was prepared in the same manner as in Example 7 except that 0.05 part by weight of ethyl phosphonoacetate was replaced by 0.07 part by weight of triphenyl phosphite.
- Table 2 shows the Mw, stereocomplex crystal content, and lactide content of the resulting composition.
- the thermal stability test of the composition was performed in the same manner as in Example 7. The results are shown in Table 2.
- Example 7 A composition was prepared in the same manner as in Example 7 without adding the phosphono fatty acid ester.
- Table 2 shows the Mw, stereocomplex crystal content, and lactide content of the resulting composition.
- the thermal stability test of the composition was performed in the same manner as in Example 7. The results are shown in Table 2.
- the composition of the present invention is excellent in thermal stability, and the molecular weight is unlikely to decrease during heating. That is, the composition of the present invention has a molecular weight reduction that makes it difficult to produce lactide, cyclic oligomers, and chain low molecules in processes that require heating of 180 ° C or higher such as melt spinning, melt film formation, and injection molding. Less is.
- the composition of the present invention has a good hue. Furthermore, the composition of the present invention containing a stereocomplex crystal has excellent heat resistance. Therefore, the composition of the present invention is suitable as a raw material for yarns, films, or resin moldings. Industrial applicability
- composition of the present invention is excellent in thermal stability, it can be melt-molded into yarns, films and various molded products.
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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)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
Claims
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES07740951.4T ES2527106T3 (es) | 2006-03-31 | 2007-03-28 | Composición de ácido poliláctico |
JP2008508708A JP4997224B2 (ja) | 2006-03-31 | 2007-03-28 | ポリ乳酸組成物 |
MX2008012147A MX2008012147A (es) | 2006-03-31 | 2007-03-28 | Composicion de acido polilactico. |
BRPI0709274-1A BRPI0709274A2 (pt) | 2006-03-31 | 2007-03-28 | composição, produto moldado, e, processo para fabricar uma composição |
AU2007232747A AU2007232747A1 (en) | 2006-03-31 | 2007-03-28 | Polylactic acid composition |
US12/294,549 US8263690B2 (en) | 2006-03-31 | 2007-03-28 | Polylactic acid composition |
EP07740951.4A EP2006331B1 (en) | 2006-03-31 | 2007-03-28 | Polylactic acid composition |
CA2647873A CA2647873C (en) | 2006-03-31 | 2007-03-28 | Polylactic acid composition |
KR1020087013897A KR101331749B1 (ko) | 2006-03-31 | 2007-03-28 | 폴리락트산 조성물 |
CN2007800123029A CN101415776B (zh) | 2006-03-31 | 2007-03-28 | 聚乳酸组合物 |
HK09109555.9A HK1131402A1 (en) | 2006-03-31 | 2009-10-15 | Polylactic acid composition |
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JP2006096900 | 2006-03-31 | ||
JP2006-096900 | 2006-03-31 |
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WO2007114459A1 true WO2007114459A1 (ja) | 2007-10-11 |
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PCT/JP2007/057515 WO2007114459A1 (ja) | 2006-03-31 | 2007-03-28 | ポリ乳酸組成物 |
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US (1) | US8263690B2 (ja) |
EP (1) | EP2006331B1 (ja) |
JP (1) | JP4997224B2 (ja) |
KR (1) | KR101331749B1 (ja) |
CN (1) | CN101415776B (ja) |
AU (1) | AU2007232747A1 (ja) |
BR (1) | BRPI0709274A2 (ja) |
CA (1) | CA2647873C (ja) |
ES (1) | ES2527106T3 (ja) |
HK (1) | HK1131402A1 (ja) |
MX (1) | MX2008012147A (ja) |
TW (1) | TWI499638B (ja) |
WO (1) | WO2007114459A1 (ja) |
Cited By (9)
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JP2009209224A (ja) * | 2008-03-03 | 2009-09-17 | Toyobo Co Ltd | ポリ乳酸の製造方法 |
WO2010053167A1 (ja) | 2008-11-05 | 2010-05-14 | 帝人化成株式会社 | ポリ乳酸組成物およびその成形品 |
JP2010150393A (ja) * | 2008-12-25 | 2010-07-08 | Teijin Chem Ltd | ポリ乳酸組成物およびその成形品 |
JP2010150394A (ja) * | 2008-12-25 | 2010-07-08 | Teijin Chem Ltd | ポリ乳酸組成物およびその成形品 |
JP2010150395A (ja) * | 2008-12-25 | 2010-07-08 | Teijin Chem Ltd | ポリ乳酸組成物およびその成形品 |
JP2010150392A (ja) * | 2008-12-25 | 2010-07-08 | Teijin Chem Ltd | ポリ乳酸組成物およびその成形品 |
JP2011046842A (ja) * | 2009-08-27 | 2011-03-10 | Teijin Ltd | ポリ乳酸組成物 |
JP2011057783A (ja) * | 2009-09-08 | 2011-03-24 | Toyobo Co Ltd | ポリ乳酸系ブロック共重合体 |
US20110086998A1 (en) * | 2008-07-24 | 2011-04-14 | Tomokazu Kusunoki | An aliphatic polyester resin and a process for producing it |
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Publication number | Priority date | Publication date | Assignee | Title |
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EP2395009B1 (en) * | 2009-02-09 | 2014-12-17 | LG Chem, Ltd. | Polylactide resin and preparation method thereof |
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- 2007-03-28 AU AU2007232747A patent/AU2007232747A1/en not_active Abandoned
- 2007-03-28 US US12/294,549 patent/US8263690B2/en active Active
- 2007-03-28 CN CN2007800123029A patent/CN101415776B/zh active Active
- 2007-03-28 BR BRPI0709274-1A patent/BRPI0709274A2/pt not_active IP Right Cessation
- 2007-03-28 ES ES07740951.4T patent/ES2527106T3/es active Active
- 2007-03-28 KR KR1020087013897A patent/KR101331749B1/ko active IP Right Grant
- 2007-03-28 MX MX2008012147A patent/MX2008012147A/es unknown
- 2007-03-28 JP JP2008508708A patent/JP4997224B2/ja active Active
- 2007-03-28 EP EP07740951.4A patent/EP2006331B1/en active Active
- 2007-03-30 TW TW096111342A patent/TWI499638B/zh active
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JP2009209224A (ja) * | 2008-03-03 | 2009-09-17 | Toyobo Co Ltd | ポリ乳酸の製造方法 |
US20110086998A1 (en) * | 2008-07-24 | 2011-04-14 | Tomokazu Kusunoki | An aliphatic polyester resin and a process for producing it |
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US8642717B2 (en) | 2008-07-24 | 2014-02-04 | Toyo Boseki Kabushiki Kaisha | Aliphatic polyester resin and a process for producing it |
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TW200804504A (en) | 2008-01-16 |
AU2007232747A1 (en) | 2007-10-11 |
BRPI0709274A2 (pt) | 2011-07-12 |
CN101415776A (zh) | 2009-04-22 |
HK1131402A1 (en) | 2010-01-22 |
EP2006331A9 (en) | 2009-07-29 |
US20090062437A1 (en) | 2009-03-05 |
CA2647873A1 (en) | 2007-10-11 |
JPWO2007114459A1 (ja) | 2009-08-20 |
EP2006331B1 (en) | 2014-10-15 |
CA2647873C (en) | 2015-05-05 |
CN101415776B (zh) | 2012-10-24 |
JP4997224B2 (ja) | 2012-08-08 |
EP2006331A4 (en) | 2010-08-04 |
KR20080106161A (ko) | 2008-12-04 |
MX2008012147A (es) | 2008-11-06 |
US8263690B2 (en) | 2012-09-11 |
TWI499638B (zh) | 2015-09-11 |
EP2006331A2 (en) | 2008-12-24 |
KR101331749B1 (ko) | 2013-11-20 |
ES2527106T3 (es) | 2015-01-20 |
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