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WO2007007893A1 - Composition contenant un acide polylactique stéréocomplexe - Google Patents

Composition contenant un acide polylactique stéréocomplexe Download PDF

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Publication number
WO2007007893A1
WO2007007893A1 PCT/JP2006/314128 JP2006314128W WO2007007893A1 WO 2007007893 A1 WO2007007893 A1 WO 2007007893A1 JP 2006314128 W JP2006314128 W JP 2006314128W WO 2007007893 A1 WO2007007893 A1 WO 2007007893A1
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WO
WIPO (PCT)
Prior art keywords
poly
acid
weight
lactic acid
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/314128
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English (en)
Japanese (ja)
Inventor
Hirotaka Suzuki
Kiyotsuna Toyahara
Midori Ikegame
Zhen Tang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Teijin Ltd
Mutual Corp
Musashino Chemical Laboratory Ltd
Original Assignee
Teijin Ltd
Mutual Corp
Musashino Chemical Laboratory Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2005203540A external-priority patent/JP2007023393A/ja
Priority claimed from JP2005203541A external-priority patent/JP2007023083A/ja
Priority claimed from JP2005255514A external-priority patent/JP5007032B2/ja
Priority claimed from JP2005255515A external-priority patent/JP5007033B2/ja
Application filed by Teijin Ltd, Mutual Corp, Musashino Chemical Laboratory Ltd filed Critical Teijin Ltd
Publication of WO2007007893A1 publication Critical patent/WO2007007893A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D01F6/625—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from 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
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds

Definitions

  • the present invention relates to a composition containing stereocomplex polylactic acid. More specifically, the present invention relates to a composition containing stereocomplex polylactic acid, which has excellent thermal stability, mechanical strength, and hue and can be stored for a long period of time. The present invention also relates to a fiber comprising the composition. Background art
  • polylactic acid has excellent heat resistance and has a good balance of hue and mechanical strength, but compared to petroleum-based resins such as polyethylene terephthalate and polyamide.
  • petroleum-based resins such as polyethylene terephthalate and polyamide.
  • cloud and mud there is still a difference between cloud and mud regarding thermal stability.
  • the polylactic acid studied in these documents is a polylactic acid having a melting point of less than 20.0 ° C mainly composed of either L-monolactic acid or D-lactic acid, and heat stability before and after 20.00 sexuality is being studied.
  • poly-L-lactic acid and poly-D-lactic acid are mixed at a ratio of about 1: 1 in a solution or in a molten state to obtain a stereocomplex polylactic acid having a high melting point and high crystallinity. It is known (Japanese Patent Laid-Open No. 6 3-2 4 1 0 2 4).
  • the melting point of this stereocomplex polylactic acid is 2 15-230 ° C., which is higher than that of polylactic acid mainly composed of either L monolactic acid or D-lactic acid. Therefore, the stereocomplex polylactic acid can be used at high temperatures and is expected to be used in various fields.
  • the catalyst deactivator used for stereocomplex polylactic acid expected to be used at high temperature is the catalyst deactivator used for polylactic acid based on one of L-lactic acid and D-lactic acid disclosed in the above-mentioned literature. Compared to the above, a catalyst deactivation effect is required. However, catalyst deactivators that provide sufficient thermal stability at high temperatures have not yet been fully studied, and there is room for further study.
  • a fiber made of stereocomplex polylactic acid and having a strength of about 0.5 c NZ dtex is disclosed (Japanese Patent Laid-Open No. 6 3-2 4 10 2 4).
  • a fiber obtained by melt-spinning poly (L-lactic acid) and poly (D-lactic acid) and heat-treating the same has been disclosed (Journal of the Fiber Science Society, 1980). This fiber relaxes the molecular orientation inside the fiber during heat treatment, and the strength of the fiber is 2.3 cN / dtex.
  • An object of the present invention is to provide a composition containing stereocomplex polylactic acid, having excellent thermal stability, mechanical strength and hue, and capable of being stored for a long period of time, a fiber comprising the composition, and a method for producing them.
  • the inventors have found that (1) a phosphoric acid-based quencher and a phenolic antioxidant or (i i) imine compound are effective, and completed the present invention.
  • the present invention is a composition containing stereocomplex polylactic acid, a metal polymerization catalyst, and (i) a phosphoric acid-based deactivator and a phenolic anti-oxidation agent or (ii) an imine compound.
  • the present invention also provides: (1) a process for producing poly-L-lactic acid by polymerizing L-lactide in the presence of a metal polymerization catalyst;
  • a method for producing a composition containing stereocomplex polylactic acid comprising a step of melt-kneading a poly-L-lactic acid composition and a poly-D-lactic acid composition.
  • the present invention includes a fiber comprising the above composition and a fiber product containing the fiber.
  • the present invention provides a composition containing poly-L-lactic acid, poly-D-lactic acid, a metal polymerization catalyst, and (i) a phosphoric acid-based deactivator and a phenolic anti-oxidation agent or (ii) an imine compound. It includes a method for producing a fiber comprising melt kneading and spinning a product.
  • Stereocomplex polylactic acid is formed from poly-L monolactic acid and poly_D-lactic acid.
  • Poly-L-lactic acid (poly-D-lactic acid) consists essentially of L-lactic acid units (D-lactic acid units) represented by the following formula.
  • the poly-L-lactic acid is preferably composed of 90 to 100 mol%, more preferably 95 to 100 mol%, and even more preferably 98 to 100 mol% of L-lactic acid units. Configured. Examples of other units include D-lactic acid units and copolymer component units other than lactic acid.
  • the D-lactic acid unit and the copolymer component unit other than lactic acid are preferably 0 to 10 mol%, more preferably 0 to 5 mol%, and still more preferably 0 to 2 mol%.
  • the poly-D-lactic acid is preferably composed of 90-; L 0 0 mol%, more preferably 95-1000 mol%, and even more preferably 98-10.0 mol% of 0-lactic acid units. Made. Examples of other units include L monolactic acid units and copolymer component units other than lactic acid.
  • the L monolactic acid unit and the copolymer component unit other than lactic acid are 0 to 10 mol%, preferably 0 to 5 mol%, more preferably 0 to 2 mol%.
  • the copolymer component unit is a dicarbonate having a functional group capable of forming two or more ester bonds.
  • Examples include units derived from rubonic acid, polyhydric alcohols, hydroxycarboxylic acids, lactones, and the like, and units derived from various polyesters, various polyethers, and various polycarbonates composed of these various components.
  • Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid.
  • Examples of polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, pendiol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, etc.
  • aromatic polyhydric alcohols such as those obtained by adding ethylene oxide to bisphenol.
  • Examples of the hydroxycarboxylic acid include daricholic acid and hydroxybutyric acid.
  • lactone examples include glycolide, ⁇ -force prolactone glycolide, ⁇ -force prolactone, / 3_propiolacton, ⁇ -butyrolactone,] 3- or r_ptyrolactone, pivalolactone, monovalerolactone, and the like.
  • Both poly-L-lactic acid and poly-D-lactic acid preferably have a weight average molecular weight of 10,000 to 500,000, more preferably 150,000 to 350,000.
  • Poly-L monolactic acid and poly-mono-D-lactic acid can be produced by a known method.
  • L- or D-lactide can be produced by heating and ring-opening polymerization in the presence of a metal polymerization catalyst.
  • low-molecular-weight polylactic acid containing a metal polymerization catalyst is crystallized, it can be produced by solid phase polymerization by heating under reduced pressure or in 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 an 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 stirring blade for high viscosity, such as a helical ribbon blade, and a horizontal reactor can be used alone or in parallel. it can.
  • Alcohol may be used as a polymerization opening agent. Such alcohol is preferably non-volatile without inhibiting the polymerization of polylactic acid.
  • decanol, Decanol, tetradecanol, hexadenool, octadecanol, etc. can be suitably used.
  • a lactic acid polyester having a relatively low molecular weight obtained by the above-described reverse polymerization method or direct polymerization method of lactic acid is used as a prepolymer.
  • the prepolymer is preferably crystallized in advance in the temperature range of the glass transition temperature (Tg) or higher and lower than the melting point (Tm) from the viewpoint of preventing fusion.
  • the crystallized prepolymer is filled in a fixed vertical reaction vessel, or a reaction vessel in which the vessel itself rotates, such as a tumbler or kiln, and the prepolymer has a glass transition temperature (Tg) or higher and lower than the melting point (Tm). Heated to a temperature range.
  • Stereocomplex polylactic acid is a mixture of poly-L-lactic acid and poly-D-lactic acid, and at least a part of them forms a stereocomplex crystal. That is, the stereocomplex polylactic acid is not a mixture of poly 1-L-lactic acid and poly 1-D-lactic acid and contains stereocomplex crystals. .
  • the weight ratio of poly (L-monolactic acid) to poly (mono-D-lactic acid) is preferably the former Z, the latter being preferably 90 to 10/90, more preferably 75/25 to 25/75, More preferably, it is 60 40 to 40 60, and still more preferably 55Z45 to 45/55.
  • the weight average molecular weight of stereocomplex polylactic acid is 100,000 to 500,000. More preferably, it is 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 chloroform as an eluent.
  • the content of the stereocomplex crystal of the composition of the present invention is preferably 80 to 100%, more preferably 95 to 100%.
  • the composition of the present invention has a differential running In the calorimetry (DSC) measurement, the ratio of the melting peak at 195 ° C or higher in the melting peak in the temperature rising process is preferably 80% or higher, more preferably 90% or higher, and still more preferably 9 5% or more.
  • the melting point is preferably in the range of 2200 to 2500, more preferably in the range of 2200 to 2200C.
  • the melting enthalpy is not less than 20 J Zg, preferably not less than 30 J Zg.
  • the proportion of melting peaks at 1 95 ° C or higher among melting peaks in the temperature rising process is 90% or more, and the melting point is 195-2. It is preferably in the range of 50 ° C., and the B insect enthalpy is 20 J Zg or more.
  • the metal polymerization catalyst is a compound of at least one metal selected from the group consisting of alkaline earth metals, rare earth elements, third-period transition metals, aluminum, germanium, tin, antimony, and titanium.
  • alkaline earth metals include magnesium, calcium, and strontium.
  • rare earth elements include scandium, yttrium, lanthanum, and cerium.
  • Third-period transition metals include iron, connort, and nickel.
  • the metal polymerization catalyst is preferably a carboxylate, alkoxide, halide, oxide, carbonate, enolate salt or trifluoromethanesulfonate of the above metal.
  • tin octylate, titanium tetraisopropoxide, and aluminum triisopropoxide are particularly preferable.
  • the composition of the present invention contains a stereocomplex polylactic acid formed from poly-L-monolactic acid-poly-D-lactic acid polymerized in the presence of a metal polymerization catalyst. Therefore, the composition of the present invention is preferably 0.001 to 1 part by weight, more preferably 0.05 to 0.1 part by weight with respect to 100 parts by weight of the stereocomplex polylactic acid. Contains a metal polymerization catalyst. If the amount of the metal polymerization catalyst added is too small, the polymerization rate is significantly prolonged, which is not preferable. On the other hand, if the amount is too large, depolymerization and ester exchange reaction are accelerated, so that the thermal stability of the resulting composition deteriorates.
  • Phosphate-based quenchers are compounds that have the ability to form salts or complexes with metal polymerization catalysts. It is a thing.
  • the phosphate deactivator at least one selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, alkyl esters thereof, and aryl esters thereof is preferable. From the viewpoint of the deactivation ability of the metal polymerization catalyst, phosphoric acid, phosphorous acid, pyrophosphoric acid, and polyphosphoric acid are more preferable.
  • the content of the phosphoric acid deactivator is from 0.001 to 5 parts by weight, preferably from 0.1 to 0.5 parts by weight, based on 100 parts by weight of the stereocomplex polylactic acid. If the content of the phosphoric acid deactivator is too small, the reaction efficiency with the remaining polymerization catalyst is extremely poor, resulting in uneven deactivation of the polymerization catalyst. On the other hand, if the amount is too large, the plasticization of the composition by the phosphate deactivator will cause a significant decrease in hydrolysis resistance.
  • the phenolic antioxidant is preferably a compound represented by the following formula (1).
  • 1 ⁇ to 1 ⁇ 3 are the same or different and each represents a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, one O— Ra or one S— Rb .
  • Ru include alkyl groups of from 1 to 6 carbon.
  • Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group and a t-butyl group.
  • As 1 ⁇ to 1 3 of the alicyclic hydrocarbon group a cycloalkyl group having a carbon number of 6 to 1 2 it is mentioned up.
  • R a of Kiichi O-R a represents a hydrogen atom, an aliphatic hydrocarbon group or alicyclic hydrocarbon group.
  • the aliphatic hydrocarbon group include an alkyl group having 1 to 6 carbon atoms
  • examples of the alicyclic hydrocarbon group include a cycloalkyl group having 6 to 12 carbon atoms.
  • R b in R b represents a hydrogen atom, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.
  • an aliphatic hydrocarbon group an alkyl group having from 6 to 6 carbon atoms
  • an alicyclic hydrocarbon examples of the basic group include cycloalkyl groups having 6 to 12 carbon atoms.
  • Phenolic antioxidants have the property of terminating the chain reaction by drawing out the hydrogen atom on the hydroxyl group to the radical, and as such, themselves become very stable phenoxy radicals or quinone derivatives. Do not start a new chain reaction.
  • substituent on the aromatic ring in the phenolic antioxidant it is desirable to satisfy the following two points from both electronic and stereochemical viewpoints in order to activate the hydroxyl group.
  • At least one of the 2, 4, and 6 positions is substituted with an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an ether group.
  • phenolic antioxidants 2,6-dimethylphenol, 2,6-di-t-butylphenol, 2,4-dimethylphenol, 2,4-di-t-butylphenol, 2, 4,6- Trimethylphenol, 2, 4, 6-tri-t-butyl roofenol, 2, 6-di t-butyl mono 4-methylphenol, 2, 2, mono-methylenebis (4-methyl-6-t monobutyl phenol) 2, 2, thiobis (41-methyl-6-tert-butylphenol), 3,5-di-tert-butylcatechol, lignin and the like.
  • 6-ji tert-butyl _4 monomethyl phenol, 2, 4, 6-tri-tert-butyl phenol, 2, 2'-methylene bis (4-methyl mono) are volatile and easy to handle.
  • 6-t-butylphenol is preferred.
  • the use of lignin, which is a plant-derived component, is also a preferable example from the viewpoint of safety and reduction of environmental burden.
  • the content of the phenolic antioxidant is preferably from 0.001 to 10 parts by weight, more preferably from 0.1 to 1 part by weight, based on 100 parts by weight of the stereocomplex polylactic acid. If the content is too small, it is difficult to efficiently deactivate radicals that are generated at any time during heating. If the amount is too large, radicals can be deactivated, but new problems such as plasticization of the composition and coloring with the quinone derivative produced arise. It is preferable that the phosphate deactivator is phosphoric acid and the phenolic antioxidant is 2,6-di-tert-butyl and 4-methylphenol.
  • a compound represented by the following formula (2) is preferable.
  • the imine compound represented by the formula (2) is not a Brenstead acid base like a conventional catalyst deactivator, the thermal stability can be improved without deteriorating the hydrolysis resistance of the composition. It is.
  • n in the formula (2) is an integer of 1 to 4, but is preferably 2 or more because it becomes a chelate ligand and can form a more stable complex with the catalytic metal element.
  • X is a single bond or a hydrocarbon group having!
  • the hydrocarbon group is preferably an alkylene group such as a methylene group or an ethylene group.
  • Y is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or an alicyclic group having 6 to 12 carbon atoms.
  • Examples of the aliphatic hydrocarbon group include an alkyl group and an alkenyl group.
  • Examples of the alicyclic hydrocarbon group include a cycloalkyl group.
  • the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and naphthyl group. Among these, hydrogen and a methyl group are preferable.
  • W is an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 6 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a carbon atom, a nitrogen atom, or an oxygen atom.
  • a sulfur atom or a phosphorus atom examples include an alkyl group, an alkylene group, an alkaryl group, and an alkanetetrayl group.
  • Examples of the alicyclic hydrocarbon group include a cycloalkyl group, a cycloalkylene group, a cycloalkanetril group, and a cycloalkanetetrayl group.
  • aromatic hydrocarbon group examples include a substituted or non-substituted phenyl group, a phenylene group, a phenylsilyl group, a phenyltetrayl group, a naphthyl group, a naphthylene group, a naphthalenetriyl group, and a naphthalenetetrayl group.
  • a methylene group, an ethylene group, a 1,3-propylene group, a 1,2-cyclohexanediyl group, an o-phenylene group, and an m-phenylene group are preferably selected.
  • the imine compound has a multi-legged structure starting from W when W is a carbon atom, nitrogen atom, oxygen atom, sulfur atom or phosphorus atom.
  • X in the formula (2) is a hydrocarbon group having 1 to 3 carbon atoms.
  • an alkylene group such as a methylene group or an ethylene group is preferable as the hydrocarbon group.
  • n 2
  • X is a single bond
  • Y is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • Z is a hydroxy group or cyan group
  • W is an alkylene group having 1 to 6 carbon atoms. Is preferred.
  • n is an integer of 2 to 4
  • X is an alkylene group having 1 to 3 carbon atoms
  • Y is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • Z is a hydroxy group or cyan group
  • W Is preferably a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
  • W include an alkylene group having 1 to 6 carbon atoms such as an ethylene group and a propylene group, a cycloalkylene group such as a cyclohexylene group, and a phenylene group.
  • Compounds represented by the formula (2-1) include N, N'-bis (salicylidene) ethylenediamine, N, N'-bis (salicylidene) propanediamine, N, N, -bis (salicylidene) — cis-cyclohexanediamine , N, N, One Bis (salicylidene) One tr an s—Cyclohexanediamine, N, ' ⁇ ' — Bis (salicylidene) One ⁇ —Phenylenediamine, ⁇ , N '— Bis (salicylidene) One m One Hue Nylene diamine, N, N'-bis (salicylidene), 1p-phendiamine, and the like.
  • W include an alkylene group having 1 to 6 carbon atoms such as an ethylene group and a propylene group, a cycloalkylene group such as a cyclohexylene group, and a phenylene group.
  • the compound of formula (2) is represented by the following formula (2-3).
  • W can be exemplified by an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group and a t-butyl group.
  • Examples of the compound represented by the formula (2-3) include N-methyliminomethylphenol, N-ethyliminomethylphenol, N-isopropyliminomethylphenol, and N-t-petitliminomethylphenol. It can be illustrated.
  • X is an alkylene group
  • Y is a hydrogen atom
  • Z is a hydroxy group
  • W is a nitrogen atom
  • N, N, N '—tris (salicylidene) trialkylenetetramine is an example of a compound of formula (2) it can.
  • ⁇ , ⁇ 'bis (salicylidene) alkylene diamine or ⁇ , ⁇ , N'-tris (salicylidene) trialkylenetetramine is preferred.
  • N, N'-bis (salicylidene) ethylenediamine, ⁇ , N'-bis (salicylidene) propanediamine are particularly preferred.
  • the content of the imine compound in the composition of the present invention is as follows.
  • the amount is 0.001 to 5 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the acid.
  • the amount of the imine compound added is too small relative to polylactic acid, the reaction efficiency with the remaining polymerization catalyst is extremely poor, and the metal polymerization catalyst cannot be sufficiently deactivated.
  • the amount is too large, plasticization and coloring of the composition by the imine compound becomes remarkable.
  • the composition of the present invention preferably has a weight change rate of ⁇ 10% or less, more preferably 5% or less, still more preferably ⁇ 0.5% or less in the black mouth form test.
  • the composition of the present invention can be used in applications requiring solvent resistance.
  • the chloroform resistance test is performed by immersing a test piece of length 10 mm, width 10 mm, and thickness 2 mm in black mouth form at 25 ° C for 1 hour. Evaluation is based on the rate of change in the weight of the test piece.
  • Stereocomplex polylactic acid can be produced by coexisting poly 1 L monolactic acid and poly 1 D-lactic acid in a predetermined weight ratio.
  • the solvent is not particularly limited as long as Li-L monolactic acid and poly-D-lactic acid are soluble.
  • the solvent is not particularly limited as long as Li-L monolactic acid and poly-D-lactic acid are soluble.
  • black mouth form methylene chloride, dichloroethane, tetrachloroethane, phenol, 'Tetrahydrofuran, N-methylpyrrolidone, N, N-dimethylformamide, ptylolactone, trioxane, hexafluoroisopropanol and the like are preferably used alone or in combination.
  • Mixing can be performed in the absence of a solvent. That is, 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 employed.
  • composition of the present invention comprises:
  • composition of the present invention comprises:
  • the poly-L-lactic acid composition and the poly-D-lactic acid composition can be produced by a melt-kneading step.
  • Poly-L-Lactic acid, Poly-D-lactic acid, Metal polymerization catalyst, Phosphate-based deactivator, Phenol-based antioxidant, Imine compound, and their amounts used are the same as in the composition section.
  • component (i) Phosphoric acid deactivator and phenolic acid antioxidant (hereinafter sometimes referred to as component (i)) or (ii) imine compound (hereinafter sometimes referred to as component (ii))
  • component (ii) Phosphoric acid deactivator and phenolic acid antioxidant
  • component (ii) imine compound
  • the ring-opening polymerization method it can be directly added and kneaded in the reaction vessel at the latter stage of polymerization. After forming into chips, they may be kneaded with an extruder or kneader. 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 component (i) or the component (i i) is added from the side feeder.
  • the polylactic acid solid obtained at the end of the polymerization and the component (i) or component (ii) are kneaded with an extruder or kneader, the polylactic acid solid and the component (i ) Or a master batch containing the component (ii) can be kneaded with an extruder or a reader.
  • the usual additives that is, UV absorbers, antioxidants, heat stabilizers, lubricants, nucleating agents, plasticizers, hydrolysis-resistant agents, Release agents, dyes, pigments, antibacterial anti-pastes, etc.
  • the composition can be widely used as a molded product. Molded products include films, sheets, fibers, fabrics, non-woven fabrics, injection molded products, extrusion molded products, vacuum / pressure air molded products, blow molded products, agricultural materials, horticultural materials, fishery materials, civil engineering / architecture Materials, stationery, medical supplies, electrical / electronic parts.
  • This invention includes the fiber which consists of the said composition.
  • the fiber preferably has a strength of 4.5 c NZ d t ex or more. Fibers with a strength of 4.5 c NZd t e x are preferred for clothing and industrial applications.
  • the fiber preferably has a weight average molecular weight decrease rate of 15% or less at 260 ° C. for 10 minutes.
  • the usual additives that is, an ultraviolet absorber, an antioxidant, a heat stabilizer, a lubricant, a mold release agent, a dye, a pigment, and an antibacterial antifungal agent are used within the range not detracting from the purpose. Etc. can be blended.
  • the fiber of the present invention can be produced by melt spinning the composition of the present invention. That is, the fiber of the present invention contains poly 1 L monolactic acid, poly 1 D lactic acid, a metal polymerization catalyst, and (i) a phosphate deactivator and a phenolic antioxidant or (ii) an imine compound.
  • the composition can be produced by melt-kneading and spinning.
  • Stereocomplex polylactic acid is formed by melt-kneading poly 1-L-lactic acid and poly 1-D-lactic acid. Spinning promotes the growth of stereocomplex crystals. Melt kneading can be performed with a melt extruder. Spinning can be performed by discharging from a spinneret.
  • the present invention also provides
  • L-lactide is polymerized in the presence of a metal polymerization catalyst to produce poly (L-lactic acid), (i) a phosphoric acid-based quencher and phenolic antioxidant or (ii) an imine compound is added.
  • a metal polymerization catalyst to produce poly (L-lactic acid)
  • a phosphoric acid-based quencher and phenolic antioxidant or (ii) an imine compound is added.
  • Poly-D-lactic acid is produced by polymerizing D-lactide in the presence of a metal polymerization catalyst, and then (i) a phosphate deactivator and a phenolic antioxidant or (ii) an imine compound is added.
  • the total amount of the metal polymerization catalyst is 0.001 to 1 part by weight, preferably 0.005 to 0.1 part by weight, based on 100 parts by weight of the total of poly-L monolactic acid and poly-D-lactic acid.
  • the total amount of the phosphate deactivator is 0.001 to 5 parts by weight, preferably 0.01 to 0.05 parts by weight, based on 100 parts by weight of the total of poly-L-lactic acid and poly-D-lactic acid. It is.
  • the total amount of the phenolic antioxidant is 0.001 to 10 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total of poly 1 L monolactic acid and poly 1 D lactic acid.
  • the total amount of the imine compound is 0.001 to 5 parts by weight, preferably 0.01 to L parts by weight based on 100 parts by weight of the total of poly-L monolactic acid and poly-D-lactic acid.
  • the fiber of the present invention comprises, for example, 0.001 to 1 part by weight of a metal polymerization catalyst with respect to 100 parts by weight of the total of poly 1 L monolactic acid and poly 1 D lactic acid, and A composition containing -5 parts by weight of a phosphate deactivator and 0.001 to 10 parts by weight of a phenolic antioxidant or (ii) 0.0 to 1 to 5 parts by weight of an imine compound; It can be manufactured by spinning.
  • the composition used for spinning is preferably dried.
  • the composition preferably has a moisture content of 0 to 200 ppm, more preferably 0 to 100 ppm, and still more preferably 0 to 60 ppm.
  • the melting temperature at the time of spinning is preferably 2200 to 2800 ° C, more preferably 2220 ° C to 265 ° C, and further preferably 235 to 25 Ot :.
  • the winding speed at the time of spinning is preferably 100 to 8, 0 OmZ, more preferably 50 OmZ or more, and further preferably 1,50 OmZ or more.
  • the lactide content in the composition used for spinning is preferably 4 O O p pm or less.
  • a lactide content of 400 ppm or less is preferable because spinnability and stretchability are improved.
  • the lactide contained in the polylactic acid obtained by the lactide method may vaporize during melt spinning and cause thread spots. Lactide can be reduced by solvent washing or vacuum high temperature drying.
  • melt extruder As the melt extruder, a normal melt extruder such as a pressure melter type or a single-screw or twin-screw extruder type can be used. However, when forming a stereocomplex crystal, it is important to mix poly-L monolactic acid and poly-D-lactic acid sufficiently. From this point of view, the uniaxial or biaxial extruder type is used. preferable. In order to improve mixing, it is preferable to incorporate a static kneader in the polymer flow path.
  • the composition is melted, weighed by a gear pump, filtered in a pack, and then discharged from a nozzle provided in the base.
  • the shape of the base and the number of bases are not particularly limited, and any of round, irregular, solid, hollow, etc. can be adopted.
  • the discharged yarn is immediately cooled and solidified, then converged, added with oil, and wound.
  • the winding speed is not particularly limited, but is preferably between 30 O mZ and 5, 0 O OmZ because a stereo complex crystal is easily formed. '
  • the undrawn yarn that has been wound is used in the drawing process. However, it is not necessary to separate them, and it is possible to adopt a direct spinning drawing method in which the drawing is continued without winding after spinning.
  • the drawing may be one-step drawing or multi-step drawing of two or more steps. From the viewpoint of producing a high-strength fiber, the draw ratio is 3.5 times or more, preferably 3.5 to 5.5 times. However, if the draw ratio is too high, the fiber is devitrified and whitened, which is not preferable because the strength of the fiber is lowered.
  • Preheating for stretching is preferably performed at 70 to 100 ° (:, preferably 70 to 90 ° C.
  • Preheating is performed by raising the temperature of a roll, by using a plate-type or pin-type contact heating heater, or by non-contact type heat. It can be carried out by using a plate, a heat medium bath, etc.
  • the fibers of the present invention can be suitably used for various textile products such as woven fabrics, nonwoven fabrics, knitted fabrics, base yarns, long fibers, cut fibers, fishing yarns, and button yarns.
  • textile products such as woven fabrics, nonwoven fabrics, knitted fabrics, base yarns, long fibers, cut fibers, fishing yarns, and button yarns.
  • EXAMPLES The present invention will be described more specifically with reference examples and examples. However, the present invention is not limited to the following examples. Each physical property was evaluated by the following methods.
  • 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. of black mouth form.
  • the weight average molecular weight (Mw) was calculated as a polystyrene equivalent value.
  • Composition 1 Og was placed in a Pyrex test tube equipped with a cock, and the interior was purged with nitrogen and maintained at 260 ° C. for 10 minutes to evaluate thermal stability.
  • the weight average molecular weight (Mw) of the composition before and after the test is measured by GPC, and the thermal stability is evaluated by comparing them. I was worth it.
  • the lactide content in the composition was determined using the JEOL Co., Ltd. nuclear magnetic resonance apparatus J NM—EX270 spectrum meter in the double-mouthed form. The ratio was calculated as the ratio of the lactide-derived quadrupole peak (4.98-5.05 ppm) to 10-5.20 p pm).
  • Stereocomplex crystal content is a differential scanning calorimeter (DSC) smell melting of crystal melting point which appears to ⁇ less than 190 ° C 0.99 ° C or higher Te Entarupi .DELTA..eta Alpha, appear in 250 ° less C than 190 ° C crystals was Ji calculated from the melting point of the melting Entarupi ⁇ ⁇ by the following equation.
  • Melting points and melting enthalpies were performed using a differential scanning calorimeter (DSC). 5 to 1 Omg of the composition was put into an aluminum pan, and the temperature rising rate was 10 ° C per minute, and scanning was performed in the range of 30 to 250. The melting point was determined from the obtained DSC curve, and the melting enthalpy was calculated from the area surrounded by the melting peak and the baseline.
  • DSC differential scanning calorimeter
  • the moisture content was measured using a Karl Fischer moisture meter (with Mitsubishi Chemical CA-1100 vaporizer). '
  • Strength and elongation The strength and elongation were measured using a tensile tester Tensilon manufactured by Orientec equipped with a 1 ON standard load cell, using a 35 mm test single yarn. The tension test conditions were a chuck separation of 25 mm and a pulling speed of 1 O mmZ. Strength and elongation were obtained from a stress-strain (S—S) curve obtained by this measurement, with the vertical axis representing tensile stress and the horizontal axis representing elongation. That is, strength is stress at break (c N) / fineness (dtex), and elongation is elongation at break (%) '.
  • test piece by cutting a resin piece with a length of 10 mm, a width of 10 mm, and a thickness of 2 mm, and wipe the surface with a cloth moistened with methyl alcohol. After that, the test piece was weighed. The test piece was completely immersed in a container containing 5 mL of the test solution chloroform, and the container was sealed and allowed to stand at 25 ° C. for 1 hour. However, the test solution was gently mixed several times within 30 minutes after immersion. After 1 hour, the test piece was taken out from the test solution, and the liquid adhering to the surface of the test piece was wiped lightly with dry filter paper, and immediately put into a scale and weighed.
  • the weight change rate M () of the test piece before and after the test is expressed by the following formula.
  • 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. Continued Then, the inside of the reaction vessel was purged with nitrogen five times, and L-lactide was melted at 190 ° C. When L-lactide was completely melted, 0.05 part by weight of 2-ethyl hexanoate was added together with 500 L of toluene from the raw material charging port, and polymerized at 190 ° C. for 1 hour.
  • 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-X-tilhexanoate was added together with 500 L of toluene from the raw material charging port, and polymerized at 190 ° C for 1 hour. .
  • the obtained composition was granulated using a powder grinder, and 10 g thereof was put into a Pyrex test tube with a cock. Next, the inside of the Pyrex test tube was purged with nitrogen, and maintained at 2600 ° C. for 10 minutes to conduct a thermal stability test. After completion of the test, the composition was taken out and the Mw and lactide contents were measured. Table 1 shows the measurement results. (Black mouth form test)
  • the resulting composition has an absolute value of weight change rate in a chloroform resistance test.
  • Example 1 except that 0.02 part by weight of phosphorous acid was used as a phosphoric acid-based deactivator and 0.1,2 parts by weight of 2,4,6-tree-teptyl roof enol was used as a phenolic antioxidant.
  • a composition was produced in the same manner as described above. Table 1 shows the Mw and lactide contents of the obtained composition before and after the thermal stability test. The resulting composition had a stereocomplex crystal content of 97.2%.
  • Example 1 except that 0.03 6 parts by weight of pyrophosphoric acid as a phosphoric acid-based quenching agent and 0.12 parts by weight of 2,4,6-tri-tert-butylphenol as a phenolic antioxidant were used.
  • a composition was produced in the same manner as described above. Table 1 shows the Mw and lactide contents before and after the thermal stability test of the obtained composition. The resulting composition had a stereocomplex crystal content of 98.9%.
  • Poly-L-Lactic acid was prepared in the same manner as in Example 1 except that the phosphoric acid deactivator and the phenolic anti-oxidation agent were not added.
  • the poly-L monolactic acid was subjected to heat stability and property tests, the poly-L monolactic acid after the thermal stability test was crystallized in the pyrex test tube used in the paddle test. Was attached. Table 1 shows the Mw and lactide contents after the thermal stability test.
  • Example 2 In the same manner as in Example 1, a poly L-lactic acid composition containing no phenolic antioxidant was prepared. When this poly-L-lactic acid composition was subjected to a thermal stability test, the composition was not colored, but the Mw slightly decreased. Table 1 shows the Mw and lactide contents after the thermal stability test. table 1
  • 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 L-lactide was completely melted, 0:05 parts by weight of 2-ethyl hexanoate was added together with 500 L of toluene from the raw material charging port, and polymerization was carried out at 190 for 1 hour.
  • the weight average molecular weights of the obtained composition (L) and composition (D) were 210,000 and 220,000, respectively.
  • Example 6 Using the fiber obtained in Example 4, a knitted fabric was prepared with a cylindrical knitting machine. This cloth had elasticity, was strong, and could be used practically.
  • Example 6 Using the fiber obtained in Example 4, a knitted fabric was prepared with a cylindrical knitting machine. This cloth had elasticity, was strong, and could be used practically.
  • 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 was completely melted, 500 L of 0.05-part by weight of toluene solution of 0.05 parts by weight of tin xanthate was added from the raw material charging port and polymerized at 190 ° C for 1 hour.
  • Toyo Seiki Kneader Rapoplast Mill 50C150 is used under a nitrogen gas stream. The mixture was kneaded at 230 ⁇ for 10 minutes to obtain a composition containing stereocomplex polylactic acid.
  • the obtained composition had a melting point of 217.0 ° C. in DSC, and its melting index was 22. O JZg.
  • Thermal stability test The obtained composition containing stereocomplex polylactic acid was granulated using a powder mill, and 10 g thereof was put into a Pyrex test tube with a cock. Next, the inside of a Pyrex test tube was replaced with nitrogen, and a thermal stability test was performed at 260 ° C for 10 minutes. After completion of the test, the composition was removed and the Mw and lactide contents were measured. Table 3 shows the measurement results. .
  • the obtained composition had an absolute value of weight change of 1% or less in the chloroform resistance test.
  • N, N, N, thotris (salicylidene)
  • a composition was prepared in the same manner as in Example 1 except that triethylenetetramine was used, and a heat stability test was conducted at 260 ° (10 minutes).
  • the resulting composition had a melting point of 218'.5 ° C in DSC and its melting enthalpy was 22.2 JZg After the test was completed, the composition was taken out and the Mw and lactide contents were measured. The results are shown in Table 3.
  • Example 6 When N, N′-bis (salicylidene) ethylenediamine obtained in Example 6 was not included, the thermal stability test was conducted on poly-L-monolactic acid. The poly-L-lactic acid after the thermal stability test was conducted. The Pyrex test tube used in the test had crystals of lactide as a decomposition product. Table 3 shows the Mw and lactide contents after the thermal stability test. 'Table 3
  • composition of the present invention has excellent thermal stability at high temperature (260 ° C.).
  • poly-D-lactic acid was synthesized in the same manner. That is, 100 parts by weight of D-lactide and 0.15 parts by weight of stearyl alcohol were charged. Subsequently, the inside of the reaction vessel was purged with nitrogen five times, and D-lactide was melted at 190 ° C. When D-lactide was completely melted, 0.05 part by weight of 2-ethyl hexanoate was added together with 50 L of toluene from the raw material charging port, and polymerized at 190 ° C. for 1 hour. After the polymerization was completed, strand-shaped poly-D-lactic acid was discharged from the discharge port of the reaction vessel, and was cut into pellets while cooling. The obtained poly-D-lactic acid had a weight average molecular weight (Mw) of 2 20 and 0 0 0.
  • Mw weight average molecular weight
  • Poly-L-lactic acid 50 parts by weight obtained in Reference Example 2 and Poly-D-lactic acid 50 parts by weight are mixed well in a pelleted state and placed in a vacuum dryer at 100 ° C for 8 hours. And dried to reduce the moisture content to 80 ppm. With respect to 100 parts by weight of this mixture, 0 ⁇ 15 parts by weight of N, N′-bis (salicylidene) ethylenediamine was mixed well.
  • the fibers of Examples 8 and 9 had high melting points characteristic of stereocomplex polylactic acid, and were high heat-resistant fibers made of stereocomplex polylactic acid.
  • Weight average molecular weight after spinning 190, 000 195, 000
  • a knitted fabric was prepared from the fiber obtained in Example 9 using a cylindrical knitting machine. This cloth had elasticity, was strong, and could be used practically. The invention's effect
  • the composition of the present invention is excellent in thermal stability at high temperature, hardly decreases in molecular weight upon heating, and is hardly colored. That is, the composition of the present invention hardly produces lactide, cyclic oligomers, and chain low molecules in processes requiring heating such as melt spinning, melt film formation, and injection molding, and has little molecular weight reduction and hue deterioration.
  • the composition of the present invention is excellent in hydrolysis resistance and can be stored for a long time. According to the method for producing a composition of the present invention, a composition containing stereocomplex polylactic acid having excellent thermal stability can be produced.
  • the fiber of the present invention is composed of a composition having excellent thermal stability at high temperatures, it is excellent in thermal stability and strength. According to the fiber manufacturing method of the present invention, a fiber excellent in thermal stability can be manufactured. Industrial applicability
  • composition of the present invention is useful as a raw material for fibers, films, and molded articles.
  • the fiber of the present invention can be used for various textile products.

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Abstract

La présente invention concerne une composition qui contient un acide polylactique stéréocomplexe et qui possède des propriétés excellentes de stabilité thermique, de résistance mécanique et de tonalité chromatique. L'invention concerne spécifiquement une composition qui contient un acide polylactique stéréocomplexe, un catalyseur de polymérisation métallique et (i) un modérateur phosphaté et un antioxydant phénolé ou (ii) un composé imine. L'invention concerne également une fibre comprenant une telle composition et des procédés permettant de les préparer.
PCT/JP2006/314128 2005-07-12 2006-07-11 Composition contenant un acide polylactique stéréocomplexe Ceased WO2007007893A1 (fr)

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JP2005-203540 2005-07-12
JP2005203540A JP2007023393A (ja) 2005-07-12 2005-07-12 ステレオコンプレックスポリ乳酸からなる繊維およびその製造方法
JP2005-203541 2005-07-12
JP2005203541A JP2007023083A (ja) 2005-07-12 2005-07-12 ステレオコンプレックスポリ乳酸を含有する組成物
JP2005255514A JP5007032B2 (ja) 2005-09-02 2005-09-02 ステレオコンプレックスポリ乳酸組成物
JP2005255515A JP5007033B2 (ja) 2005-09-02 2005-09-02 ステレオコンプレックスポリ乳酸からなる繊維
JP2005-255515 2005-09-02
JP2005-255514 2005-09-02

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008120807A1 (fr) * 2007-03-30 2008-10-09 Teijin Limited Composition d'acide polylactique, et fibre constituée de celle-ci
WO2008120821A1 (fr) * 2007-03-29 2008-10-09 Teijin Limited Composition d'acide polylactique
WO2008120825A1 (fr) * 2007-03-30 2008-10-09 Teijin Limited Composition d'acide polylactique
JP2008248182A (ja) * 2007-03-30 2008-10-16 Teijin Ltd ポリ乳酸組成物
JP2008248184A (ja) * 2007-03-30 2008-10-16 Teijin Ltd ポリ乳酸組成物
EP2116576A4 (fr) * 2007-02-23 2011-04-06 Teijin Ltd Composition d'acide polylactique
US8937137B2 (en) 2013-03-13 2015-01-20 Exxonmobil Chemical Patents Inc. Diphenylamine salan catalyst
US8952114B2 (en) 2012-08-03 2015-02-10 Exxonmobil Chemical Patents Inc. Halogenated catalysts comprising Salan ligands
US8957171B2 (en) 2012-08-03 2015-02-17 Exxonmobil Chemical Patents Inc. Catalysts comprising salan ligands
US8957172B2 (en) 2012-08-03 2015-02-17 Exxonmobil Chemical Patents Inc. Nonsymmetric catalysts comprising salan ligands
US9045568B2 (en) 2012-08-03 2015-06-02 Exxonmobil Chemical Patents Inc. Vinyl terminated polyethylene with long chain branching
US9120879B2 (en) 2012-11-02 2015-09-01 Exxonmobil Chemical Patents Inc. Supported Salan catalysts
US9150676B2 (en) 2013-06-20 2015-10-06 Exxonmobil Chemical Patents Inc. Thio-salalen catalyst
US9193813B2 (en) 2014-03-31 2015-11-24 Exxonmobil Chemical Patents Inc. Phenylene-bridged salalen catalysts
US9200099B2 (en) 2013-06-20 2015-12-01 Exxonmobil Chemical Patents Inc. Salenol catalyst
US9200100B2 (en) 2013-06-20 2015-12-01 Exxonmobil Chemical Patents Inc. Long-bridged salen catalyst
US9290589B2 (en) 2013-12-13 2016-03-22 Exxonmobil Chemical Patents Inc. Cyclopentadienyl-substituted salan catalysts
US9365661B2 (en) 2012-08-03 2016-06-14 Exxonmobil Chemical Patents Inc. Polyalphaolefins prepared using modified salan catalyst compounds
US9382349B2 (en) 2012-08-03 2016-07-05 Exxonmobil Chemical Patents Inc. Polyalphaolefins prepared using modified Salan catalyst compounds
CN110156966A (zh) * 2012-08-16 2019-08-23 普拉克生化公司 聚(2-羟基链烷酸)及其制备方法

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JPH0931171A (ja) * 1995-07-25 1997-02-04 Shimadzu Corp ポリ乳酸の製造法
JPH0995603A (ja) * 1995-09-29 1997-04-08 Dainippon Ink & Chem Inc ヒドロキシカルボン酸系ポリエステル組成物の製造方法
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Publication number Priority date Publication date Assignee Title
EP2116576A4 (fr) * 2007-02-23 2011-04-06 Teijin Ltd Composition d'acide polylactique
WO2008120821A1 (fr) * 2007-03-29 2008-10-09 Teijin Limited Composition d'acide polylactique
JPWO2008120821A1 (ja) * 2007-03-29 2010-07-15 帝人株式会社 ポリ乳酸組成物
WO2008120807A1 (fr) * 2007-03-30 2008-10-09 Teijin Limited Composition d'acide polylactique, et fibre constituée de celle-ci
WO2008120825A1 (fr) * 2007-03-30 2008-10-09 Teijin Limited Composition d'acide polylactique
JP2008248182A (ja) * 2007-03-30 2008-10-16 Teijin Ltd ポリ乳酸組成物
JP2008248184A (ja) * 2007-03-30 2008-10-16 Teijin Ltd ポリ乳酸組成物
JPWO2008120825A1 (ja) * 2007-03-30 2010-07-15 帝人株式会社 ポリ乳酸組成物
US9045568B2 (en) 2012-08-03 2015-06-02 Exxonmobil Chemical Patents Inc. Vinyl terminated polyethylene with long chain branching
US8952114B2 (en) 2012-08-03 2015-02-10 Exxonmobil Chemical Patents Inc. Halogenated catalysts comprising Salan ligands
US8957171B2 (en) 2012-08-03 2015-02-17 Exxonmobil Chemical Patents Inc. Catalysts comprising salan ligands
US8957172B2 (en) 2012-08-03 2015-02-17 Exxonmobil Chemical Patents Inc. Nonsymmetric catalysts comprising salan ligands
US9464148B2 (en) 2012-08-03 2016-10-11 Exxonmobil Chemical Patents Inc. Vinyl terminated polyethylene with long chain branching
US9382349B2 (en) 2012-08-03 2016-07-05 Exxonmobil Chemical Patents Inc. Polyalphaolefins prepared using modified Salan catalyst compounds
US9365661B2 (en) 2012-08-03 2016-06-14 Exxonmobil Chemical Patents Inc. Polyalphaolefins prepared using modified salan catalyst compounds
CN110156966A (zh) * 2012-08-16 2019-08-23 普拉克生化公司 聚(2-羟基链烷酸)及其制备方法
US9556287B2 (en) 2012-11-02 2017-01-31 Exxonmobil Chemical Patents Inc. Vinyl terminated macromonomers
US9120879B2 (en) 2012-11-02 2015-09-01 Exxonmobil Chemical Patents Inc. Supported Salan catalysts
US8937137B2 (en) 2013-03-13 2015-01-20 Exxonmobil Chemical Patents Inc. Diphenylamine salan catalyst
US9200099B2 (en) 2013-06-20 2015-12-01 Exxonmobil Chemical Patents Inc. Salenol catalyst
US9200100B2 (en) 2013-06-20 2015-12-01 Exxonmobil Chemical Patents Inc. Long-bridged salen catalyst
US9150676B2 (en) 2013-06-20 2015-10-06 Exxonmobil Chemical Patents Inc. Thio-salalen catalyst
US9290589B2 (en) 2013-12-13 2016-03-22 Exxonmobil Chemical Patents Inc. Cyclopentadienyl-substituted salan catalysts
US9193813B2 (en) 2014-03-31 2015-11-24 Exxonmobil Chemical Patents Inc. Phenylene-bridged salalen catalysts

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