CN104619745A - Method for producing block copolymer - Google Patents
Method for producing block copolymer Download PDFInfo
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- CN104619745A CN104619745A CN201380046383.XA CN201380046383A CN104619745A CN 104619745 A CN104619745 A CN 104619745A CN 201380046383 A CN201380046383 A CN 201380046383A CN 104619745 A CN104619745 A CN 104619745A
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- resin
- segmented copolymer
- polylactic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
Abstract
Provided is a method for producing a polylactic acid block copolymer with reduced residual lactide. A polylactic acid resin, a resin having at least one hydroxyl group in the molecule (hereinafter, a resin having at least one hydroxyl group in the molecule is called a resin (A)) and a transesterification catalyst are melted at normal pressure in this method for producing a block copolymer of a polylactic acid resin and a resin (A).
Description
Technical field
The present invention relates to the manufacture method of segmented copolymer, it is characterized in that, described segmented copolymer is by the resin formation in polylactic acid based resin and molecule with at least one hydroxyl, as the manufacturing condition of this segmented copolymer, resin and the transesterification catalyst melting at ambient pressure of at least one hydroxyl will be had in polylactic acid based resin, molecule.
Background technology
In recent years, due to the raising of Environmental awareness, so the burning of the soil contamination problem that brings of plastics discarded or plastics causes carbonic acid gas increase thus cause greenhouse effects of the earth problem to receive publicity.As for the former countermeasure, extensively carry out about the research of the Biodegradable resin being decomposed into carbon dioxide molecule and water molecules under the environment in soil completely, exploitation, as the countermeasure for the latter, also can not to the research of the biomass resin bringing new carbonic acid gas to bear in air, exploitation about being derived from biological Material synthesis burning by plant etc. even if extensively carried out.
As being applicable to both and resin also more favourable in cost, the concern of polylactic acid based resin is improved.If owing to being used alone polylactic acid based resin, flexibility is not enough, so be such as wound around in the purposes such as film, stretched film at Farm mulch, shopping bag, packaging, have studied and carries out softness by use poly lactic acid series multipolymer, interpolation softening agent.
Poly lactic acid series segmented copolymer, by being used alone or mixing with polylactic acid based resin, can use as the resin of flexibility.Particularly, when mixing with polylactic acid based resin, segmented copolymer can play function as softening agent.Such as, the softening agent formed by poly(lactic acid)-polyether block copolymer described in patent documentation 1, because polylactic acid chain segment contributes to the plasticization that prevents from oozing out, polyether segment contributes to poly(lactic acid), so compared with existing polylactic acid based resin softening agent, there is the feature that resistance to exudative excellence is such.
The manufacture method of these poly lactic acid series segmented copolymers, as Patent Document 1, usual method is, the hydroxyl in molecule with the resin of at least one hydroxyl, as starting point, makes cyclic dimer and the rac-Lactide ring-opening polymerization of lactic acid.As other method, as shown in patent documentation 2, the manufacture method of known a kind of poly lactic acid series segmented copolymer, it is characterized in that, make the resin melting in polylactic acid based resin and molecule with at least one hydroxyl, then add transesterification catalyst, under reduced pressure carry out transesterification reaction.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent No. 4363325 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2004-231773 publication
Summary of the invention
The problem that invention will solve
In the rac-Lactide ring-opening polymerization method described in patent documentation 1, there are the following problems: in polymerization, sublimed rac-Lactide deposition occurs and causes the pollution of reactor, a unreacted rac-Lactide part to remain in obtained poly lactic acid series segmented copolymer thus cause resin to produce rac-Lactide stink, hydrolytic resistance worsens.In addition, in the method described in patent documentation 2, owing under reduced pressure reacting, so promote because of the intramolecular ester permutoid reaction of polylactic acid based resin to generate rac-Lactide, thus produce problem similar to the above.
The present invention solves described existing problem, obtains the method manufacturing the few specific segmented copolymer of residual lactide thus.
Solve the means of problem
In order to solve above-mentioned problem, the present invention proposes following manufacture method.Namely, as described below.
(1) segmented copolymer of a kind of polylactic acid based resin and resin (A) is (following, the segmented copolymer of polylactic acid based resin and resin (A) is called segmented copolymer) manufacture method, it is characterized in that, by (following for the resin in polylactic acid based resin, molecule with at least one hydroxyl, the resin in molecule with at least one hydroxyl is called resin (A)) and transesterification catalyst melting at ambient pressure (following, to incite somebody to action melting at ambient pressure and be called normal pressure melting operation).
(2) manufacture method of the segmented copolymer Gen Ju (1), is characterized in that, described normal pressure melting operation is carried out in twin screw extruder (following, this twin screw extruder is called twin screw extruder 1).
(3) manufacture method of basis (1) or the segmented copolymer described in (2), it is characterized in that, described resin (A) is polyalkylene glycol resin.
(4) according to the manufacture method of the segmented copolymer according to any one of (1) ~ (3), it is characterized in that, described transesterification catalyst is the organic acid salt of metal and/or the halide salts of metal.
(5) manufacture method of the mixture of a kind of polylactic acid based resin and segmented copolymer, it is characterized in that, the segmented copolymer that will be manufactured by the method described in (2) is directly imported in other twin screw extruder in twin screw extruder 1, mixes with polylactic acid based resin.
(6) manufacture method of the mixture of a kind of polylactic acid based resin and segmented copolymer, it is characterized in that, with respect to the segmented copolymer that the method described in (2) manufactures, drop into polylactic acid based resin from the side feeder of the same twin screw extruder manufacturing this segmented copolymer, thus in the same twin screw extruder manufacturing this segmented copolymer, this segmented copolymer and polylactic acid based resin are mixed.
Invention effect
By being used as the normal pressure melting operation of feature of the present invention, the segmented copolymer that remaining rac-Lactide is few can be obtained.The segmented copolymer that the present invention obtains, by being used alone and mixing with polylactic acid based resin, can use in the formed bodys such as film as the resin of flexibility, also can use as the resistance to exudative softening agent that has of polylactic acid based resin well in addition.
Embodiment
The present invention is that the segmented copolymer of polylactic acid based resin and resin (A) is (following, the segmented copolymer of polylactic acid based resin and resin (A) is called segmented copolymer) manufacture method, it is characterized in that, by (following for the resin in polylactic acid based resin, molecule with at least one hydroxyl, the resin in molecule with at least one hydroxyl is called resin (A)) and transesterification catalyst melting at ambient pressure (following, to incite somebody to action melting at ambient pressure and be called normal pressure melting operation).
Below the manufacture method of segmented copolymer of the present invention is described.
(polylactic acid based resin)
In the present invention, as the manufacture raw material of segmented copolymer, use polylactic acid based resin.Polylactic acid based resin refers to, using Pfansteihl unit and/or D-ALPHA-Hydroxypropionic acid unit as the polymkeric substance of main composition composition.Here, main composition composition refers to, in all 100mol% of monomeric unit in the polymer, the ratio of lactic acid units is the maximum meaning, and preferably in whole monomeric unit 100mol%, lactic acid units is 70 ~ 100mol%.
Poly (l-lactic acid) in the present invention refers to, in the whole lactic acid units 100mol% in polymkeric substance, Pfansteihl unit be greater than 50mol% and at below 100mol% containing proportional.On the other hand, the poly-D-ALPHA-Hydroxypropionic acid in the present invention refers to, in the whole lactic acid units 100mol% in polymkeric substance, D-ALPHA-Hydroxypropionic acid unit be greater than 50mol% and at below 100mol% containing proportional.
But, in the polylactic acid based resin in the present invention, do not contain the block copolymerization polylactic acid based resin of resin (A).In addition, when resin (A) and polylactic acid based resin copolymerization, segmented copolymer is referred to as.
For poly (l-lactic acid), proportional according to containing of D-ALPHA-Hydroxypropionic acid unit, the crystallinity of resin self can change.If that is, in poly (l-lactic acid) D-ALPHA-Hydroxypropionic acid unit containing increasing proportion, then the crystallinity step-down of poly (l-lactic acid), close to amorphous, on the contrary, if in poly (l-lactic acid) D-ALPHA-Hydroxypropionic acid unit containing proportional minimizing, then the crystallinity of poly (l-lactic acid) increases.Similarly, for poly-D-ALPHA-Hydroxypropionic acid, proportional according to containing of Pfansteihl unit, the crystallinity of resin self can change.If that is, in poly-D-ALPHA-Hydroxypropionic acid Pfansteihl unit containing increasing proportion, then the crystallinity step-down of poly-D-ALPHA-Hydroxypropionic acid, close to amorphous, on the contrary, if in poly-D-ALPHA-Hydroxypropionic acid Pfansteihl unit containing proportional minimizing, then the crystallinity of poly-D-ALPHA-Hydroxypropionic acid increases.
In poly (l-lactic acid) used in the present invention Pfansteihl unit containing proportional, or in poly-D-ALPHA-Hydroxypropionic acid used in the present invention D-ALPHA-Hydroxypropionic acid unit containing proportional, can at random regulate.When segmented copolymer formation the present invention obtained needs the formed body of physical strength, in whole lactic acid units 100mol%, preferred Pfansteihl unit is 90 ~ 100mol%, or D-ALPHA-Hydroxypropionic acid unit is 90 ~ 100mol%, preferably Pfansteihl unit is 95 ~ 100mol% further, or D-ALPHA-Hydroxypropionic acid unit is 95 ~ 100mol%.In addition, when the softening agent using the segmented copolymer that obtains of the present invention as crystalline polylactic acid system resin, suppress the object of oozing out of segmented copolymer from making the polylactic acid chain segment of polylactic acid based resin and segmented copolymer form eutectic, Pfansteihl and D-ALPHA-Hydroxypropionic acid containing proportional preferably as described above.On the contrary, when segmented copolymer the present invention obtained or the segmented copolymer that obtains containing the present invention are used for the hot sealing layer of film as the polylactic acid based resin of softening agent, because preferred resin is low-crystalline or amorphism, so in whole lactic acid units 100mol%, Pfansteihl unit and D-ALPHA-Hydroxypropionic acid unit are preferably 10 ~ 90mol%.
Crystalline polylactic acid system resin in the present invention refers to, this polylactic acid based resin is placed 1 hour under the heating of 100 DEG C, when then measuring by differential scanning calorimeter (DSC) under the condition of the heat-up rate of 20 DEG C/min, observe the polylactic acid based resin of the crystalline fusion heat being derived from poly(lactic acid) composition.
On the other hand, amorphism polylactic acid based resin alleged in the present invention refers to, when having carried out in the same fashion measuring, does not show the polylactic acid based resin of fusing point.
Polylactic acid based resin used in the present invention, also can random copolymerization other monomeric unit except lactic acid.As other monomer, can enumerate, ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, ethohexadiol, nonanediol, decanediol, 1, 4-cyclohexanedimethanol, neopentyl glycol, glycerine, tetramethylolmethane, dihydroxyphenyl propane, polyoxyethylene glycol, the diol compound such as polypropylene glycol and polytetramethylene glycol, oxalic acid, hexanodioic acid, sebacic acid, nonane diacid, dodecanedioic acid, propanedioic acid, pentanedioic acid, cyclohexane cyclohexanedimethanodibasic, terephthalic acid, m-phthalic acid, phthalic acid, naphthalic acid, two (p-hydroxybenzene) methane, anthracene dioctyl phthalate, 4, 4 '-diphenyl ether dioctyl phthalate, 5-sulfo group sodium m-phthalic acid, the 5-tetrabutyl
the dicarboxylic acid such as m-phthalic acid, the hydroxycarboxylic acids such as oxyacetic acid, hydroxy-propionic acid, hydroxybutyric acid, hydroxypentanoic acid, hydroxycaproic acid, hydroxy-benzoic acid, the lactone such as caprolactone, valerolactone, propiolactone, undecalactone, 1,5-oxepane-2-ketone.As for the copolymerization amount of other monomeric unit as described above, relative to all 100mol% of the monomeric unit in the polymkeric substance of polylactic acid based resin, be preferably 0 ~ 30mol%, be more preferably 0 ~ 10mol%.In addition, in above-mentioned monomeric unit, preferably select the composition with biological degradability according to purposes.
The matter average molecular weight of polylactic acid based resin used in the present invention, from the view point of operability when molecular weight and the melting of reacted segmented copolymer, be preferably 5000 ~ 1000000, more preferably 10000 ~ 500000, most preferably be 100000 ~ 300000.In addition, the matter average molecular weight in the present invention refers to, measures, the molecular weight calculated by polymethylmethacrylate scaling method with gel permeation chromatography (GPC) in the good solvents such as hexafluoroisopropanol.
As manufacturing the method for polylactic acid based resin used in the present invention, can by the method for lactic acid and other raw material Direct Dehydration condensation or the method that makes rac-Lactide and other cyclic ester intermediate carry out ring-opening polymerization be obtained.Such as, when manufacturing in Direct Dehydration condensation, lactic acid class or lactic acid class and hydroxycarboxylic acid is made preferably under the existence of organic solvent, particularly phenylate series solvent, to carry out azeotropic dehydration condensation, particularly preferably by the solvent that distillates from azeotropic except to anhydrate and the method making to become in fact the solvent Returning reacting system of anhydrous state is polymerized, thus obtain the polymkeric substance of high molecular.
In addition, also known to use the catalyzer such as stannous octoate to make the cyclic ester intermediates such as rac-Lactide under reduced pressure carry out polymkeric substance that ring-opening polymerization also can obtain high molecular.Now, by the method for the removing condition of moisture during reflux in adjustment in use organic solvent and low molecular compound, polyreaction make catalyst deactivation suppress the method for depolymerization reaction, heat-treat manufactured polymkeric substance method etc. after terminating, the polymkeric substance that rac-Lactide amount is few can be obtained.
(there is in molecule the resin (resin (A)) of at least one hydroxyl)
In the present invention, use resin (A) as the manufacture raw material of segmented copolymer.In the present invention, relative to the ester bond between the lactic acid units-lactic acid units in polylactic acid based resin, be that starting point carries out transesterification reaction with the hydroxyl of resin (A), thus resin (A) for the resin in molecule with at least one hydroxyl be important.But, resin (A) for beyond polylactic acid based resin, the resin in molecule with at least one hydroxyl.In addition, for resin (A), according to purposes, preferably select the resin with biological degradability.
As resin (A), contain the resin of hydroxyl as molecular end, can enumerate, the polyester based resin beyond polylactic acid based resin, polyethers system resin, polyacetal system resin etc.In addition, the resin of hydroxyl is contained as side chain, can enumerate, the deoxidation halogenide of the carboxylate of polyvinyl alcohol resin, ethylene-vinyl alcohol copolymer resin, polyose, polyose, the etherate of polyose, polyose, the oxide compound of polyose, hydroxyl modification polyolefin-based resins etc.In order to give polylactic acid based resin flexibility, the second-order transition temperature of resin (A) is preferably-70 ~ 50 DEG C, more preferably-70 ~ 40 DEG C.
In the middle of them, high from the effect of the flexibility improving polylactic acid based resin, high with the intermiscibility of polylactic acid based resin aspect, as resin (A), be preferably the polyester based resin beyond polylactic acid based resin and/or polyethers system resin, be more preferably polyethers system resin, more preferably polyalkylene glycol resin.
As the polyalkylene glycol resin of resin (A), particularly preferably be polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol-propylene glycol copolymers, wherein most preferably polyoxyethylene glycol.Polyoxyethylene glycol, due to soft and high with the affinity of polylactic acid based resin, so the segmented copolymer of polylactic acid based resin and polyoxyethylene glycol excellence in the plasticizing efficiency of its flexibility, polylactic acid based resin.
As for the matter average molecular weight of resin used in the present invention (A), from the view point of the operability when molecular weight of reacted segmented copolymer and flexibility and melting, be preferably 1000 ~ 1000000, be more preferably 5000 ~ 500000, more preferably 5000 ~ 100000, most preferably be 5000 ~ 30000.
(transesterification catalyst)
For the present invention, polylactic acid based resin, resin (A) and transesterification catalyst is made to be important in normal pressure melting.That is, in the present invention, carried out the manufacture of segmented copolymer by ester-interchange method, now use transesterification catalyst to become important.
As the transesterification catalyst in the present invention, although be not particularly limited, can enumerate, such as metal, metal-salt, sulfur acid, nitrogenous basic cpd.
As the example of metal, can enumerate, manganese, magnesium, titanium, zinc, iron, aluminium, cerium, calcium, barium, cobalt, lithium, sodium, potassium, caesium, lead, strontium, tin, antimony, germanium, yttrium, lanthanum, indium, zirconium etc.
As metal-salt, can enumerate, the phosphoric acid salt of the organic acid salt of metal, the nitrate of metal, metal, the borate of metal, the halide salts of metal, the hydroxide salt etc. of metal.In addition, as the metal used in metal-salt, the metal same with the example of above-mentioned metal can be enumerated.As organic acid example, can enumerate, carboxylic acid, sulfur acid, carbonic acid, phenol etc.
As vitriolated example, can enumerate, sulfuric acid, sulfoacid compound, sulfinic acid compound, sulfenic acid compound.
As nitrogenous basic cpd, can enumerate, quaternary ammonium salt, tertiary amines, secondary amine class, primary amine class, pyridines, imidazoles, ammonia etc.
Wherein, from the view point of decomposition and the degree of molecular weight reduction, the effect as catalyzer of the dispersiveness in resin, resin, transesterification catalyst in the present invention is preferably metal-salt, more preferably the organic acid salt of metal and/or the halide salts of metal.Particularly, from the view point of selecting the high transesterification catalyst of the transesterify catalytic capability of the little transesterification catalyst of the corrodibility of polymeric kettle and forcing machine, unit mass and being difficult to the transesterification catalyst that occurs to ooze out from resin, as the organic acid salt of metal and/or the halide salts of metal, preferably there is the halide salts of the organic acid of the alkyl of carbonatoms 0 ~ 10 and the salt (organic acid salt of metal) of metal and/or metal.In addition, in the present invention, carbonatoms is that the alkyl of 0 refers to, does not have the meaning of alkyl in molecule.
In addition, for the segmented copolymer that the present invention obtains, if consideration needs the possibility used in the purposes of biological degradability in the purposes, refuse bag, compost bag etc. of agroforestry, then transesterification catalyst used in the present invention is preferably the catalyzer high to biological safety.If the ability taken into account thereon as transesterification catalyst and selecting, then transesterification catalyst is preferably the organic acid salt of metal and/or the halide salts of metal, as particularly preferred transesterification catalyst, can enumerate, the salt (organic acid salt of metal) of the organic acid with the alkyl of carbonatoms 0 ~ 10 as follows and metal or the halide salts of metal as follows.
Organic acid salt as metal is particularly preferred, have the organic acid of alkyl of carbonatoms 0 ~ 10 and the concrete example of the salt of metal, such as, be the carboxylic acid without the carbonatoms 1 ~ 10 of hydroxyl and the salt being selected from the metal in magnesium, titanium, tin, zinc, iron, aluminium, calcium, potassium and being formed.In addition, the concrete example of the halide salts of particularly preferred metal, such as, for being selected from the halogenide of the metal in magnesium, titanium, tin, zinc, iron, aluminium, calcium, potassium.
In addition, in the present invention, also two or more kinds may be used different transesterification catalyst.
(manufacture method of the segmented copolymer of polylactic acid based resin and resin (A))
The feature of the manufacture method of segmented copolymer of the present invention is, to reactor supply as the polylactic acid based resin of raw material, resin (A) and transesterification catalyst, carries out melting (experience normal pressure melting operation) at ambient pressure.
The present invention manufactures segmented copolymer by making polylactic acid based resin and resin (A) carry out transesterification reaction.And alleged transesterification reaction refers to, makes some ester bond and hydroxyl, carboxylic acid group or other ester bond have an effect, exchanges with the hydroxyl in ester bond or carboxylic acid group, generate the reaction with the initial different types of ester bond of ester bond here.Particularly, in the present invention, main purpose is that the ester bond of hydroxyl and polylactic acid based resin by making resin (A) is had an effect introduce ester bond between polylactic acid based resin and resin (A).
As for the melt temperature in normal pressure melting operation, although different according to the viscosity of the fusing point of the kind of reactor, polylactic acid based resin, the fusing point of resin (A), the viscosity of polylactic acid based resin and resin (A), but, if particularly consider fusing point and the heat decomposition temperature of polylactic acid based resin, temperature then in normal pressure melting operation is preferably 150 ~ 250 DEG C, is more preferably 180 ~ 240 DEG C.In addition, the polylactic acid based resin used and resin (A), hydrolysis during in order to prevent melting and painted, preferably carries out abundant drying in advance and moisture rate is reduced.The amount of moisture of polylactic acid based resin and resin (A) preferably altogether for 1200ppm (quality criteria) below, be more preferably 500ppm (quality criteria) below, more preferably 200ppm (quality criteria) below.
The mass ratio that adds of polylactic acid based resin and resin (A) is not particularly limited, but preferred scope is 95:5 ~ 5:95 by quality ratio.Particularly, when the segmented copolymer of resultant is used for the principal constituent of formed body as the resin of flexibility, the mass ratio that adds of polylactic acid based resin and resin (A) is preferably 95:5 ~ 50:50, more preferably 90:10 ~ 60:40.In addition, when the softening agent using segmented copolymer as polylactic acid based resin, the mass ratio that adds of polylactic acid based resin and resin (A) is preferably 80:20 ~ 5:95, is more preferably 75:25 ~ 10:90, more preferably 70:30 ~ 30:70.
As for the addition of transesterification catalyst, although different according to the kind, temperature of reaction, reaction times, reaction atmosphere etc. of reactor, but, relative to total 100 mass parts of polylactic acid based resin and resin (A), be preferably the scope of 0.001 ~ 5 mass parts, the more preferably scope of 0.005 ~ 1 mass parts.As long as the addition of transesterification catalyst is the scope of 0.001 ~ 5 mass parts relative to total 100 mass parts of polylactic acid based resin and resin (A), just painted, the molecular weight of obtained segmented copolymer can be reduced and the generation of rac-Lactide is limited in inferior limit.
In the present invention, in order to suppress to produce rac-Lactide during transesterification reaction, it is important for carrying out normal pressure melting operation at ambient pressure.Normal pressure in the present invention refers to, the air pressure in normal pressure melting operation is 5 × 10
4~ 1.5 × 10
5in the scope of Pa, be preferably 7 × 10
4~ 1.3 × 10
5pa, more preferably 9 × 10
4~ 1.1 × 10
5pa.In addition, in this normal pressure melting operation, in order to suppress hydrolysis and the oxygenolysis of resin, preferably make reactor under non-active gas atmosphere.
The reactor used in normal pressure melting operation is not particularly limited, and such as, as batch reactor, can enumerate, and is with the test tube of whipping appts, longitudinal type or horizontal type tank reactor or kneading machine etc.As flow reactor, can enumerate, single screw extrusion machine, twin screw extruder, other multiple screw extruder.Multiple screw extruders more than two screw rods, its screw rod sense of rotation can be equidirectional, also can be different directions.
Wherein, from the view point of Reaction time shorten and operability, the reactor of normal pressure melting operation is preferably flow reactor, more preferably twin screw extruder.That is, normal pressure melting operation, preferably carries out in flow reactor, particularly in twin screw extruder.In twin screw extruder, because the melting of polylactic acid based resin and resin (A) is not only promptly carried out, and resin distribution mixing each other and dispersing and mixing are carried out expeditiously, so the collision probability of the hydroxyl of the ester bond of polylactic acid based resin and resin (A) increases, its result, their transesterification reaction was carried out with the short period of time.
As previously mentioned, although normal pressure melting operation is preferably carried out in twin screw extruder, but form as the screw rod of such twin screw extruder, in order to ensure the resin residence time required for reaction and mixing power, the kneading disk that preferred use is reverse, screw diameter is preferably 10 ~ 400mm, and L/D is preferably 20 ~ 200.
When reactor is twin screw extruder, air pressure is measured by venting hole.
As for the time required for normal pressure melting operation, when the batch reactor using mixing property low, be preferably 30 minutes ~ 5 hours.In contrast, when taking twin screw extruder as the flow reactor of representative, the time of normal pressure melting operation is equivalent to the residence time of the resin in reactor, and it is preferably 5 ~ 30 minutes, more preferably 5 ~ 15 minutes.
By the segmented copolymer that manufacture method of the present invention obtains, by making the transesterification catalyst inactivation remained, its storage stability can be improved further.As the deactivator used with such object, can enumerate, such as amino acid, phenols, hydroxycarboxylic acid, diones, amine, oxime, phenanthroline class, pyridine compounds, dithio compound, diazonium compound, thio-alcohol, porphyrin, containing the phosphorus compound such as phenols, carboxylic acid, phosphoric acid, phosphoric acid ester, phosphate metal salt, phosphorous acid, phosphorous acid ester, phosphorous acid metal-salt of nitrogen as ligating atom.In addition, these deactivators not only can be used alone, also can be used in combination.From the aspect of the hydrolytic resistance of polylactic acid based resin, more preferably phosphorus compound in these deactivators, the further preferably phosphoric acid crystallization of more than purity 98 quality % or phosphorous acid crystallization.
As the method for adding deactivator, when batch reactor, have and temporarily make reactor stop and adding deactivator after transesterification reaction terminates, and then the method that reactor is run.When taking twin screw extruder as the flow reactor of representative, there is the method for adding deactivator from the side feeder of forcing machine.
As for the addition of deactivator, relative to transesterification catalyst 1 mass parts of adding in manufacturing process, be preferably 0.01 ~ 10 mass parts, more preferably 0.1 ~ 5 mass parts.
For the matter average molecular weight of the segmented copolymer that the present invention obtains, when using by this segmented copolymer for the purpose of the principal constituent of formed body, in order to the mechanical characteristics of satisfied practicality, its matter average molecular weight is preferably 10000 ~ 1000000, is more preferably 50000 ~ 500000.In addition, when utilizing this segmented copolymer as additives such as softening agent, in order to show softnessization and resistance to exudative, its matter average molecular weight is preferably 1000 ~ 500000, is more preferably 5000 ~ 100000, and more preferably 5000 ~ 50000.
(mixture of segmented copolymer and polylactic acid based resin)
Segmented copolymer that the present invention obtains can be used with polylactic acid based resin.In this case, segmented copolymer also can play function as the softening agent of polylactic acid based resin.Like this, when segmented copolymer the present invention obtained uses as the softening agent of polylactic acid based resin, be dispersed in polylactic acid based resin to make segmented copolymer, melting mixing can be carried out to polylactic acid based resin and segmented copolymer, also polylactic acid based resin and segmented copolymer can be made to be dissolved in the good solvents such as chloroform, to make solvent evaporates or resin is separated out in poor solvent.
When segmented copolymer is used as the softening agent of polylactic acid based resin, for polylactic acid based resin and segmented copolymer containing proportional, in the total 100 quality % of segmented copolymer and polylactic acid based resin, segmented copolymer preferably containing 3 ~ 70 quality %, more preferably containing 5 ~ 60 quality %, further preferably containing 5 ~ 50 quality %.As long as segmented copolymer containing proportional in above-mentioned scope, just can improve the flexibility of polylactic acid based resin and shock-resistance, the oozing out of suppression segmented copolymer.
When being used as polylactic acid based resin softening agent by segmented copolymer, except polylactic acid based resin and segmented copolymer, in resin combination, other thermoplastic resin, general particle, additive also can be mixed.
Manufacture the normal pressure melting operation of segmented copolymer, as previously mentioned, preferably carry out in twin screw extruder (following, this twin screw extruder is called twin screw extruder 1).In addition, when using segmented copolymer use etc. as the softening agent of polylactic acid based resin, manufacture the mixture of polylactic acid based resin and segmented copolymer, the manufacture method of the polylactic acid based resin be preferably as follows and the mixture of segmented copolymer, it is characterized in that, the segmented copolymer manufactured in twin screw extruder 1 is directly imported in twin screw extruder 1 other twin screw extruder (following, this other twin screw extruder is called twin screw extruder 2) in, mix with polylactic acid based resin in this twin screw extruder 2.Namely, when manufacturing the mixture of polylactic acid based resin and segmented copolymer, the segmented copolymer manufactured with twin screw extruder 1 is directly imported the stage casing of twin screw extruder 2 by preferred use polymer pipes etc. by methods such as side chargings with molten state, mix in twin screw extruder 2 with polylactic acid based resin.Here, directly the meaning refers to, when being imported in twin screw extruder 2 in twin screw extruder 1 by segmented copolymer, this block polymer imports in twin screw extruder 2 in twin screw extruder 1 when keeping more than second-order transition temperature.Such as, segmented copolymer is discharged in twin screw extruder 1, when the state becoming below second-order transition temperature with this segmented copolymer imports to such in twin screw extruder 2, can not be interpreted as alleged direct here.In addition, when segmented copolymer has multiple second-order transition temperature, import in twin screw extruder 2 in twin screw extruder 1 when remaining on making segmented copolymer more than the highest second-order transition temperature and be called directly.
When manufacturing the mixture of segmented copolymer and polylactic acid based resin, the matter average molecular weight that there is segmented copolymer is little, the situation that second-order transition temperature is low in addition, and such segmented copolymer exists the possibility being difficult to sheet stock.In this case, need, by temporary transient for obtained segmented copolymer cooling curing, then to carry out pulverization process.Relative to this, to the segmented copolymer that obtains of twin screw extruder 1 be used directly to import twin screw extruder 2 if adopted and in twin screw extruder 2, carry out the technique that mixes with polylactic acid based resin, then can omit above-mentioned cooling, the time and labor of pulverizing, so preferably.
The screw rod formation of twin screw extruder 1 and twin screw extruder 2, screw diameter, L/D and the residence time, preferably form with the preferred screw rod of aforesaid twin screw extruder, screw diameter, L/D and the residence time same.In addition, twin screw extruder 1 and twin screw extruder 2 also can be formations of the same race.
In addition, carry out the twin screw extruder 1 of the manufacture of segmented copolymer, due to aforesaid reason, need for normal pressure.The scope of normal pressure is identical with aforementioned range.On the other hand, in the method, twin screw extruder 2 is not owing to contributing to the generation of segmented copolymer, so in twin screw extruder 2, air pressure is not be necessary for normal pressure, under can being set to decompression yet.
In addition, as the method for mixture manufacturing polylactic acid based resin and segmented copolymer, also there is the manufacture method of the mixture of following polylactic acid based resin and segmented copolymer, it is characterized in that, with respect to the segmented copolymer that twin screw extruder manufactures, drop into polylactic acid based resin from the side feeder of the same twin screw extruder manufacturing this segmented copolymer, thus in the same twin screw extruder manufacturing this segmented copolymer, this segmented copolymer and polylactic acid based resin are mixed.In the method, except can omitting the time and labor of the cooling of segmented copolymer, pulverizing as described above, the twin screw extruder of needs is only 1, device can be formed and simplify, so preferably.
As the preferred screw rod formation of the twin screw extruder that present method uses, can enumerate, add kneading disk in forward side compared with dropping into the side feeder of polylactic acid based resin.In addition, for screw diameter, L/D and the residence time, preferably same with the preferred screw diameter of aforesaid twin screw extruder, L/D and the residence time.In addition, for extrusion temperature, preferably the temperature near this kneading disk is set to 200 ~ 280 DEG C, catalytic amount is preferably 0.05 ~ 5 mass parts.This is because, what mainly carry out the manufacture of segmented copolymer in the method is from the position of the main feeder of twin screw extruder to the position of side feeder adding polylactic acid based resin, namely be only a part for twin screw extruder, need to react efficiently in the portion.In addition, when adding polylactic acid based resin from side feeder, preferably add deactivator simultaneously.
In the method, be from the position of the main feeder of twin screw extruder to the position of side feeder adding polylactic acid based resin due to what mainly carry out the manufacture of segmented copolymer, in this position, due to above-mentioned reason, need to react at ambient pressure.The scope of normal pressure is identical with aforesaid scope.On the other hand, after the position from side feeder, almost do not contribute to the generation of segmented copolymer.Therefore, in this interval, air pressure is not be necessary for normal pressure, under can being set to decompression yet.
In addition, the polylactic acid based resin used in the mixture of polylactic acid based resin and segmented copolymer, can use the resin identical with the polylactic acid based resin that the raw material hereinbefore as segmented copolymer describes.
In the composition of the segmented copolymer obtained containing the present invention, also can use the additive such as known antioxidant, crystallization nucleating agent, ultra-violet stabilizer, anti-tinting material, matting agent, reodorant, fire retardant, weather resisting agent, static inhibitor, ion-exchanger, tackifier, defoamer, tinting pigment, dyestuff, lubricant, whipping agent, other resin as required.For the addition of these additives, as long as do not damaging the scope of the effect that the present invention realizes, just be not particularly limited, but relative to the composition 100 quality % containing segmented copolymer, additive is preferably 0.01 ~ 30 quality %, be more preferably 0.01 ~ 20 quality %, more preferably 0.01 ~ 10 quality %.
The segmented copolymer that the present invention obtains, from the view point of foul smell and hydrolytic resistance, its residual lactide amount is preferably below 1.00 quality %, is more preferably below 0.70 quality %, more preferably below 0.50% quality.
In addition, the segmented copolymer that the present invention obtains, because the preferred polylactic acid based resin as raw material and resin (A) do not remain, so preferably only exist one in its GPC elution curve to be derived from high molecular peak (unimodality).In addition, when polylactic acid based resin and resin (A) residual, in its GPC elution curve exist 2 be derived from high molecular peak (bimodality) or exist more than 2.
In addition, the segmented copolymer that the present invention obtains, the resin (A) preferably as raw material does not remain.Therefore, for following defined TmA0 and TmA, preferred TmA0-TmA is more than 7.0 DEG C, is more preferably more than 9.0 DEG C.
TmA0: the melting peak temperature being derived from resin (A) read from the figure of the DSC temperature-rise period of resin (A) monomer.
TmA: the melting peak temperature being derived from resin (A) segment read from the figure of the DSC temperature-rise period of segmented copolymer.
In addition, when the mixture flaking of segmented copolymer the present invention obtained and polylactic acid based resin, for obtained sheet, in order to show sufficient flexibility, its modulus in tension is preferably 100 ~ 1000MPa.Modulus in tension is more preferably 100 ~ 950MPa, more preferably 100 ~ 900MPa.
In addition, the above-mentioned sheet containing segmented copolymer and polylactic acid based resin, needs segmented copolymer not depart from from polylactic acid based resin, namely needs it resistance to exudative.As resistance to exudative index, the hot water extraction rate of sheet is preferably in following ranges.That is, in the distilled water seethed with excitement at 1 atmosphere pressure, less than 5.0% is preferably to the rate of mass reduction that sheet has carried out when processing for 1 hour, is more preferably less than 3.0%.Embodiment
Illustrate that embodiment is specifically described the present invention below, but the present invention is not by any restriction of these embodiments.
[measuring and evaluation method]
Mensuration shown in embodiment, evaluate and carry out under condition as described below.
(1) Young's modulus (MPa)
The TENSILON UCT-100 using (strain) オ リ エ Application テ ッ Network to produce carries out stress-strain measurement, the initial straight line portion of service stress-strain curve, by the stress-difference between 2 on straight line divided by the strain differential between identical 2, thus calculate modulus in tension.Specifically, determined the rectangle sample of long 150mm, wide 10mm by compressed tablet, measure according to the method for regulation in JIS K 7127 (1999) under the condition of incipient extension spacing jig from 50mm, draw speed 200mm/ minute.In addition, mensuration is carried out 5 times, calculate its mean value.
(2) rac-Lactide amount
By the sample dissolution that generates in methylene dichloride, by concentration adjustment to 1g/20ml, then add acetone 60ml, and then carry out ultrasonic agitation and to drip hexanaphthene 320ml, thus component of polymer is separated out.By the PTFE strainer in centrifugation and 0.45 μm, aperture, precipitate is removed, be made into sample liquid.Use gas-chromatography GC-17A (society of Shimadzu Seisakusho Ltd. system) at post: DB-17MS type (J & W society system), column temperature: 80 ~ 250 DEG C, 10 DEG C/min, analyze this sample liquid under the condition of carrier gas: He.In addition, use the sample liquid production standard curve changing the lactide monomer of concentration in advance, utilize this typical curve to try to achieve the rac-Lactide amount (quality %) of test portion.
(3) hot water extraction rate
As resistance to exudative index, measure hot water extraction rate.For the damping compressed tablet of more than 1 day in the environment of temperature 23 DEG C, humidity 65%RH in advance, measure quality before treatment.Then, in the distilled water seethed with excitement at 1 atmosphere pressure, 1 h immersion process is carried out to sheet, under the condition same with before process, again carry out damping, then measure the quality after process.Then, hot water extraction rate is gone out by following formulae discovery.
Hot water extraction rate (quality %)=(quality after quality-process before treatment) × 100/ quality before treatment
(4)GPC
For matter average molecular weight, measured by gel permeation chromatography (GPC), calculated by polymethylmethacrylate scaling method.In addition, the calculating of matter average molecular weight, in the elution curve of obtained sample, only only have one when being derived from high molecular peak (unimodality) to carry out, not when having two high molecular peak (bimodality) being derived from polylactic acid based resin and resin (A), or have when being derived from plural high molecular peak and carry out.2695 types that the mensuration of GPC uses Waters company to produce carry out, and detector uses differential refractometer 2414 type of WATERS company, and pump uses the MODEL510 of WATERS company, and post uses the post be connected in series by 2 ShodexHFIP-806M to carry out.As for condition determination, flow velocity is set to 0.5mL/ minute, column temperature is set to 40 DEG C, use the hexafluoroisopropanol adding 5mM sodium trifluoroacetate as solvent, inject the solution of 0.2mL test portion concentration 0.1 quality %.
(5)DSC
Use the differential scanning calorimeter RDC220 that セ イ コ ー イ Application ス Star Le (strain) produces, the sample 5mg of generation is contained in aluminum dish, be warming up to 220 DEG C from 25 DEG C with the heat-up rate of 20 DEG C/min, at 220 DEG C, keep melting, then quenching to 25 DEG C in 5 minutes.Then, from the figure of this temperature-rise period, read the melting peak temperature TmA (DEG C) being derived from resin (A) segment.In addition, using unreacted resin (A) as sample, tried to achieve the melting peak temperature TmA0 (DEG C) of resin (A) by method similar to the above, calculate TmA0-TmA.
[polylactic acid based resin]
(4032D)
Poly (l-lactic acid), " 4032D " that Natureworks produces, matter average molecular weight 200000, D body burden 1.4mol%, fusing point 166 DEG C.Use the under reduced pressure resin of dry 5 hours at 100 DEG C in vacuum drying oven in advance.
(4060D)
Poly (l-lactic acid), " 4060D " that Natureworks produces, matter average molecular weight 200000, D body burden 12.0mol%, without fusing point.Use the under reduced pressure resin of dry 7 hours at 50 DEG C in vacuum drying oven in advance.
In addition, the Waters2695 that matter average molecular weight uses Japanese ウ ォ ー タ ー ズ (strain) to produce, uses hexafluoroisopropanol solvent to measure using polymethylmethacrylate as standard at column temperature 40 DEG C.
[resin (A)]
(PEG6000S)
Polyoxyethylene glycol, Sanyo changes into " PEG6000S " that industrial produces, and matter average molecular weight 8000, TmA0 is 64.0 DEG C.Use the under reduced pressure resin of dry 7 hours at 30 DEG C in vacuum drying oven in advance.
(Ecoflex)
Polytetramethylene glycol adipic acid ester-terephthalate, " Ecoflex F BlendC1200 " that BASF produces, matter average molecular weight 60000, TmA0 is 120.2 DEG C.Use the under reduced pressure resin of dry 7 hours at 80 DEG C in vacuum drying oven in advance.
[transesterification catalyst]
(acetic acid Mg)
As metal-salt (organic acid salt of metal), use magnesium acetate 4 hydrate (medicine industrial production pure with light).
(chlorination Mg)
As metal-salt (halide salts of metal), use magnesium chloride hexahydrate (medicine industrial production pure with light).
(sad Sn)
As metal-salt (organic acid salt of metal), use 2 ethyl hexanoic acid tin (II) (medicine industrial production pure with light).
(p-TSA)
As sulfur acid, use tosic acid (medicine industrial production pure with light).
(embodiment 1)
Weigh 40 mass parts 4032D, 60 mass parts PEG6000S, 0.5 mass parts chlorination Mg, join in the test tube of band whipping appts, at air pressure 1.0 × 10
5stir while melting 4 hours at 200 DEG C in the nitrogen atmosphere of Pa, cooling, solidification thus obtain Sample A.Carry out rac-Lactide amount, matter average molecular weight and DSC to obtained Sample A to measure.
And then, weigh 30 mass parts Sample A, 20 mass parts 4032D, 50 mass parts 4060D, join in the test tube of band whipping appts, at air pressure 1.0 × 10
5stir while melting 1 hour at 240 DEG C in the nitrogen atmosphere of Pa, cooling, solidification, thus obtain sample B.Obtained sample B is pulverized, then in vacuum drying oven under reduced pressure at 50 DEG C dry 7 hours, pressurizes at 220 DEG C, thus obtain the isotropy compressed tablet of thickness 200 μm.Measure Young's modulus and the hot water extraction rate of the compressed tablet obtained.
In addition, for embodiment 2 and comparative example 1, except according to table 1 and table 2 composition of raw material and melt temperature that drop into test tube being changed, obtain sample in mode similarly to Example 1.
In addition, for comparative example 2 ~ 3, changing composition and the melt temperature of the raw material dropping into test tube according to table 2, using when obtaining Sample A vacuum pump to make invisible spectro air pressure become 1.0 × 10
3pa, in addition obtains sample in mode similarly to Example 1.
(embodiment 3)
Weigh 40 mass parts 4032D, 60 mass parts PEG6000S, 0.5 mass parts chlorination Mg, carry out blended, put in the twin screw extruder TEX30 α (L/D=35, screw diameter=30mm) of JSW's production, melting, mixing is carried out with screw speed 200rpm, inlet amount 10kg/h, discharge from mouth mould, cooling, solidification, thus obtain Sample A.In addition, the temperature for TEX30 α sets, and (measures the position of L/D=25 from screw front end) and is set as 80 DEG C, be set as 200 DEG C by after the first kneading part before from hopper bottom to the first kneading part.In addition, the venting hole be positioned at from the position of screw front end measurement L/D=20 is set to open state.The air pressure of this position is 1.0 × 10
5pa.Carry out rac-Lactide amount, matter average molecular weight and DSC to obtained Sample A to measure.
In addition, weigh 30 mass parts Sample A, 20 mass parts 4032D, 50 mass parts 4060D, join in the test tube of band whipping appts, at air pressure 1.0 × 10
5stir while melting 1 hour at 240 DEG C in the nitrogen atmosphere of Pa, cooling, solidification, thus obtain sample B.Obtained sample B is pulverized, then in vacuum drying oven under reduced pressure at 50 DEG C dry 7 hours, pressurizes at 220 DEG C, thus obtain the isotropy compressed tablet of thickness 200 μm.Measure Young's modulus and the hot water extraction rate of the compressed tablet obtained.
In addition, for embodiment 4 ~ 10, comparative example 4 ~ 7, except the composition that changes the raw material dropping into TEX30 α according to table 1 and table 2 and extrusion temperature, obtain sample in mode similarly to Example 3.
In addition, for comparative example 8, change composition and the extrusion temperature of the raw material dropping into TEX30 α according to table 2, and being positioned at of TEX30 α is connected with vacuum pump from the venting hole of the position of screw front end measurement L/D=20, make the air pressure of this position become 3.0 × 10
3pa, in addition obtains sample in mode similarly to Example 3.
The physical property of the sample obtained is shown in table 1 and table 2.
(embodiment 11)
As twin screw extruder 1, use the TEX30 α (L/D=35, screw diameter=30mm) that JSW produces, as twin screw extruder 2, use the TEX44 α (L/D=38, screw diameter=44mm) that JSW produces, the resin side of discharging from twin screw extruder 1 to be fed to the mode constituent apparatus in the stage casing (measuring the position of L/D=18 from screw front end) of twin screw extruder 2.
Weigh 40 mass parts 4032D, 60 mass parts PEG6000S, 0.5 mass parts chlorination Mg, carry out blended, put in twin screw extruder 1, carry out melting, mixing with screw speed 200rpm, inlet amount 10kg/h.In addition, the temperature for twin screw extruder 1 sets, and being set as 80 DEG C, being set as 200 DEG C by after the first kneading part by (measuring the position of L/D=25 from screw front end) before from hopper bottom to the first kneading part.In addition, make twin screw extruder 1 to be positioned at the venting hole of position measuring L/D=20 from screw front end be open state.The air pressure of this position is 1.0 × 10
5pa.
In addition, weigh 67 mass parts 4032D, 167 mass parts 4060D, carry out blended, put in twin screw extruder 2, carry out melting, mixing with screw speed 200rpm, inlet amount 23.3kg/h.In addition, the temperature for twin screw extruder 2 sets, and being set as 150 DEG C, being set as 220 DEG C by after the first kneading part by (measuring the position of L/D=28 from screw front end) before from hopper bottom to the first kneading part.In addition, make twin screw extruder 2 to be positioned at the venting hole of position measuring L/D=20 from screw front end be open state.The air pressure of this position is 1.0 × 10
5pa.The resin cooling that mouth mould from twin screw extruder 2 is discharged, solidification, thus obtain sample C.Obtained sample C is pulverized, then in vacuum drying oven under reduced pressure at 50 DEG C dry 7 hours, pressurizes at 220 DEG C, thus obtain the isotropy compressed tablet of thickness 200 μm.Measure Young's modulus and the hot water extraction rate of the compressed tablet obtained.
In addition, for embodiment 12 and comparative example 9, except change the composition of the raw material dropping into twin screw extruder 1 and 2 according to table 3 except, obtain sample in mode similarly to Example 11.
The physical property of obtained sample is illustrated in table 3.
Table 3
(embodiment 13)
As twin screw extruder, use the TEX30 α (L/D=35, screw diameter=30mm) that JSW produces, side feeder is set in the stage casing (measuring the position of L/D=18 from screw front end) of twin screw extruder.
Weigh 40 mass parts 4032D, 60 mass parts PEG6000S, 0.5 mass parts chlorination Mg, carry out blended, put into the main hopper of twin screw extruder, carry out melting, mixing with screw speed 200rpm, inlet amount 10kg/h.In addition, the temperature for twin screw extruder 1 sets, and being set as 80 DEG C, will being set as 240 DEG C from the first kneading part to side feeder by (measuring the position of L/D=25 from screw front end) before from hopper bottom to the first kneading part.In addition, make twin screw extruder 1 to be positioned at the venting hole of position measuring L/D=20 from screw front end be open state.The air pressure of this position is 1.0 × 10
5pa.
In addition, weigh 67 mass parts 4032D, 167 mass parts 4060D, carry out blended, put in the feeder of side, carry out melting, mixing.Temperature later for side feeder is set as 200 DEG C.In addition, the resin cooling that the mouth mould from twin screw extruder is discharged, solidification, thus obtain sample D.Obtained sample D is pulverized, then in vacuum drying oven under reduced pressure at 50 DEG C dry 7 hours, pressurizes at 220 DEG C, thus obtain the isotropy compressed tablet of thickness 200 μm.Measure Young's modulus and the hot water extraction rate of the compressed tablet obtained.
In addition, for embodiment 14 ~ 15 and comparative example 10 ~ 11, except change the composition of the raw material dropping into twin screw extruder according to table 4 except, obtain sample in mode similarly to Example 13.
The physical property of obtained sample is illustrated in table 4.
(embodiment 16)
Weigh 40 mass parts 4032D, 60 mass parts PEG6000S, 0.5 mass parts chlorination Mg, carry out blended, put in the single screw extrusion machine GT-40 (L/D=28, screw diameter=40mm) of プ ラ ス チ ッ Network engineering institute production, melting, mixing is carried out with screw speed 50rpm, inlet amount 10kg/h, discharge from mouth mould, cooling, solidification, thus obtain Sample A.In addition, the temperature for GT-40 sets, and hopper bottom is set as 80 DEG C, will be set as 200 DEG C later.In addition, the venting hole in stage casing is made to be open state.The air pressure of this position is 1.0 × 10
5pa.Carry out rac-Lactide amount, matter average molecular weight and DSC to obtained Sample A to measure.
In addition, weigh 30 mass parts Sample A, 20 mass parts 4032D, 50 mass parts 4060D, join in the test tube of band whipping appts, at air pressure 1.0 × 10
5stir while melting 1 hour at 240 DEG C in the nitrogen atmosphere of Pa, cooling, solidification, thus obtain sample B.Obtained sample B is pulverized, then in vacuum drying oven under reduced pressure at 50 DEG C dry 7 hours, pressurizes at 220 DEG C, thus obtain the isotropy compressed tablet of thickness 200 μm.Measure Young's modulus and the hot water extraction rate of the compressed tablet obtained.
In addition, for comparative example 12, except change the composition of the raw material dropping into GT-40 according to table 5 except, obtain sample in mode similarly to Example 16.
In addition, for comparative example 13, the venting hole of GT-40 is connected with vacuum pump, makes the air pressure of this position be 3.0 × 10
3pa, in addition, obtains sample in mode similarly to Example 16.
The physical property of obtained sample is illustrated in table 5.
Table 5
Utilizability in industry
By adopting the normal pressure melting operation as feature of the present invention, the segmented copolymer that residual lactide is few can be obtained.The segmented copolymer that the present invention obtains, by being used alone and mixing with polylactic acid based resin, except can using in the formed bodys such as film as the resin of flexibility, also can use as polylactic acid based resin there is the resistance to softening agent that oozes out suitably.
Claims (6)
1. the manufacture method of a segmented copolymer, described segmented copolymer is the segmented copolymer of polylactic acid based resin and resin (A), it is characterized in that, polylactic acid based resin, resin (A) and transesterification catalyst are carried out normal pressure melting operation, described resin (A) is for having the resin of at least one hydroxyl in molecule, described normal pressure melting operation refers to carries out melting at ambient pressure.
2. the manufacture method of segmented copolymer according to claim 1, is characterized in that, described normal pressure melting operation is carried out in twin screw extruder, and described twin screw extruder is twin screw extruder 1.
3. the manufacture method of segmented copolymer according to claim 1 and 2, is characterized in that, described resin (A) is polyalkylene glycol resin.
4. the manufacture method of the segmented copolymer according to any one of claims 1 to 3, is characterized in that, described transesterification catalyst is the organic acid salt of metal and/or the halide salts of metal.
5. the manufacture method of the mixture of a polylactic acid based resin and segmented copolymer, it is characterized in that, the segmented copolymer manufactured by method according to claim 2 is directly imported in other twin screw extruder in twin screw extruder 1, mixes with polylactic acid based resin.
6. the manufacture method of the mixture of a polylactic acid based resin and segmented copolymer, it is characterized in that, with respect to the segmented copolymer that method according to claim 2 manufactures, drop into polylactic acid based resin from the side feeder of the same twin screw extruder manufacturing this segmented copolymer, thus in the same twin screw extruder manufacturing this segmented copolymer, this segmented copolymer and polylactic acid based resin are mixed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012209177 | 2012-09-24 | ||
| JP2012-209177 | 2012-09-24 | ||
| PCT/JP2013/070753 WO2014045717A1 (en) | 2012-09-24 | 2013-07-31 | Method for producing block copolymer |
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| Publication Number | Publication Date |
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| CN104619745A true CN104619745A (en) | 2015-05-13 |
| CN104619745B CN104619745B (en) | 2016-11-30 |
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| CN107962757A (en) * | 2016-10-25 | 2018-04-27 | 昆山台益塑胶科技有限公司 | The production method of POM/PMMA block copolymers |
| CN107962698A (en) * | 2016-10-25 | 2018-04-27 | 昆山台益塑胶科技有限公司 | The production method of POM/PBT block copolymers |
| CN107962697A (en) * | 2016-10-25 | 2018-04-27 | 昆山台益塑胶科技有限公司 | The production method of POM/PPO block copolymers |
| CN111269373A (en) * | 2020-02-12 | 2020-06-12 | 浙江大学衢州研究院 | Preparation method of remodelable shape memory elastomer based on eutectic |
| CN112399979A (en) * | 2018-07-10 | 2021-02-23 | 东洋制罐集团控股株式会社 | Polylactic acid copolymer and method for producing same |
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| CN107001615A (en) * | 2015-06-19 | 2017-08-01 | 东丽株式会社 | Polymeric membrane and the adherence preventing material obtained using it |
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| CN111269373A (en) * | 2020-02-12 | 2020-06-12 | 浙江大学衢州研究院 | Preparation method of remodelable shape memory elastomer based on eutectic |
| CN115232628A (en) * | 2022-06-23 | 2022-10-25 | 北京晋荣农业科技有限公司 | Soil conditioner, preparation method thereof and soil conditioning method |
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| JPWO2014045717A1 (en) | 2016-08-18 |
| KR20150063367A (en) | 2015-06-09 |
| JP6119608B2 (en) | 2017-04-26 |
| WO2014045717A1 (en) | 2014-03-27 |
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