CN101296993B - Polylactic acid composition - Google Patents
Polylactic acid composition Download PDFInfo
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- CN101296993B CN101296993B CN2006800371170A CN200680037117A CN101296993B CN 101296993 B CN101296993 B CN 101296993B CN 2006800371170 A CN2006800371170 A CN 2006800371170A CN 200680037117 A CN200680037117 A CN 200680037117A CN 101296993 B CN101296993 B CN 101296993B
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Abstract
Disclosed is a composition containing a polylactic acid, which is excellent in thermal stability, hue, and hydrolysis resistance. The composition contains (i) a polylactic acid, (ii) a metal catalyst and (iii) a phosphinic acid type quencher or a metaphosphoric acid type quencher.
Description
Technical field
The present invention relates to contain the composition of poly(lactic acid).More specifically, relate to excellent and the composition that can prolonged preservation of thermostability, physical strength, tone.
Background technology
Most of plastics are light and tough, and excellent in te pins of durability can be easily and at random carry out moulding, so mass production and support our life in many aspects always.Yet, when plastics go out of use in the environment, be not easy to be decomposed and accumulate.In addition, a large amount of carbonic acid gas of discharging quickens global warming during burning.
In view of described present situation, the biodegradable plastic of research microbiological deterioration in vogue.Biodegradable plastic has the aliphatic carboxylic acid ester units, easily by microbiological degradation.But there is following shortcoming in it: lack thermostability, be exposed in the pyritous operation at melt-spinning, injection molding, fusion system film etc., molecular weight reduces, the easy variation of tone.
Poly(lactic acid) is the plastics of the balance excellence of excellent heat resistance, color harmony physical strength in biodegradable plastic, but about thermostability, compares with the petroleum resinoid that with polyethylene terephthalate, polymeric amide is representative, and difference is very big.In order to change this present situation, the thermostability that improves poly(lactic acid) various researchs have been carried out.
For example, in patent documentation 1, proposed to reach moment more than 50,000, in poly(lactic acid), added scheme as the phosphate compound or the phosphorons acid compound of catalyst passivating agent at molecular weight.Yet, as patent documentation 1, in low-molecular-weight poly(lactic acid), add catalyst passivating agent, mean thereafter polyreaction of obstruction, can't obtain high molecular weight polymers.
In addition, in patent documentation 2 and 3, proposed to add the scheme of the thermostability that acid phosphoric acid ester or sequestrant as catalyst passivating agent improve poly(lactic acid).The acid phosphoric acid ester of record is not owing to guarantee toxic security in the patent documentation 2 and 3, thus not only pollute the environment during waste resin, and also the use in food uses is limited.In addition, sequestrant generally speaking lacks thermotolerance, burns till before catching metal catalyst, becomes main coloration reason.
On the other hand, the thermostability of known poly(lactic acid) is not only relevant with polymerizing catalyst, and is subjected to the influence (with reference to non-patent literature 1 and 2) of spontaneous backbone breaking.Spontaneous backbone breaking homolysis ground carries out; produce carbon radicals, acyl group free radical, carbonyl free radical (オ キ ソ ラ ジ カ Le) or carboxyl free radical; cause that not only the rac-Lactide that causes because of depolymerization generates, and by bonding, dehydrogenation reaction or non-homogenizing are reacted the increase that causes as the coloring components of pyruvic acid derivative again.
As mentioned above, in order to improve thermostability, tone, hydrolytic resistance in the security that keeps poly(lactic acid), the inhibition that the inhibition of the depolymerization that must cause residual catalyst, the molecular weight that backbone breaking causes reduce further improves.
Patent documentation 1: No. 2862071 communique of Japan's special permission
Patent documentation 2: No. 3487388 communique of Japan's special permission
Patent documentation 3: Japanese kokai publication hei 10-36651 communique
Non-patent literature 1:Polymer Degradation and Stability, 1985, the 11st volume, p309～326I.C.McNeill etc.
Non-patent literature 2:Journal of Analytical and Applied Pyrolysis, 1997,40-41 volume, p43～53, F.D.Kopinke etc.
Summary of the invention
The object of the present invention is to provide the composition that contains poly(lactic acid), excellent heat stability.The object of the present invention is to provide the composition that contains poly(lactic acid), tone excellence.The object of the present invention is to provide the composition that contains poly(lactic acid), hydrolytic resistance excellence.
The inventor has studied intensively making the effective passivator of residual catalyst inactivation (inactivation drug) in the poly(lactic acid).Found that, make poly(lactic acid) contain Hypophosporous Acid, 50 class passivator, can make the residual catalyst inactivation in the poly(lactic acid) efficiently, obtain the composition of thermostability and tone excellence, thereby finished the present invention.
In addition, the inventor finds, makes poly(lactic acid) contain metaphosphoric acid class passivator, can make residual catalyst and moisture inactivation in the poly(lactic acid) effectively, obtains the composition of thermostability, hydrolytic resistance excellence, thereby has finished the present invention.
That is, the present invention is for containing (i) poly(lactic acid), the (ii) metal catalyst and the (iii) composition of Hypophosporous Acid, 50 class passivator or metaphosphoric acid class passivator.
In addition, the present invention comprises formed body, and described formed body comprises said composition.
And then, the present invention relates to the preparation of compositions method, its be comprise mix poly--L-lactic acid and poly--D-lactic acid contain stereoscopic composite crystalline preparation of compositions method, it is characterized in that, at least one side in poly--L-lactic acid and poly--D-lactic acid is contained metal catalyst, and described being blended under the condition that Hypophosporous Acid, 50 class passivator or metaphosphoric acid class passivator exists carried out.
Embodiment
Below describe the present invention in detail.
＜composition 〉
Poly(lactic acid) mainly comprises the lactic acid units that following formula is represented.Poly(lactic acid) preferably contains 90～100 moles of % of lactic acid units that following formula is represented, more preferably contains 95～100 moles of %, further preferably contains 98～100 moles of %.
The weight-average molecular weight of poly(lactic acid) (Mw) is preferably 100,000～500,000, and more preferably 150,000～350,000.Weight-average molecular weight in this specification sheets (Mw) is by adopting chloroform to measure the polystyrene standard conversion weight-average molecular weight value that obtains as the gel permeation chromatography (GPC) of elutriant.
Poly(lactic acid) is poly--L-lactic acid, poly--D-lactic acid or their mixture preferably.Poly--L-lactic acid is preferably 90: 10 with the weight ratio of poly--D-lactic acid～and 10: 90, more preferably 75: 25～25: 75, further preferred 60: 40～40: 60.
Poly--L-lactic acid mainly comprises the L-lactic acid units.Poly--L-lactic acid preferably contain 90～100 moles of %, more preferably contain 95～100 moles of %, further preferably contain the L-lactic acid units of 98～100 moles of %.As other unit, can enumerate D-lactic acid units, the unit except that lactic acid.D-lactic acid units, the unit except that lactic acid are preferably 0～10 mole of %, more preferably 0～5 mole of %, more preferably 0～2 mole of %.
Poly--D-lactic acid mainly comprises the D-lactic acid units.Poly--D-lactic acid preferably contain 90～100 moles of %, more preferably contain 95～100 moles of %, further preferably contain the D-lactic acid units of 98～100 moles of %.As other unit, can enumerate L-lactic acid units, the unit except that lactic acid.L-lactic acid units, the unit except that lactic acid are preferably 0～10 mole of %, more preferably 0～5 mole of %, more preferably 0～2 mole of %.
Unit except that lactic acid can enumerate derive from have the dicarboxylic acid that can form the functional group of ester bond more than 2, the unit of polyvalent alcohol, hydroxycarboxylic acid, lactone etc. and derive from the unit of the various polyester that form by these various constituents, various polyethers, various polycarbonate etc.
As dicarboxylic acid, can enumerate succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, terephthalic acid, m-phthalic acid etc.As polyvalent alcohol, can enumerate aromatic polyols such as polyvalent alcohol that aliphatic polyols such as ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, ethohexadiol, glycerol, sorbitan, neopentyl glycol, glycol ether, triglycol, polyoxyethylene glycol, polypropylene glycol etc. or oxyethane and bis-phenol addition obtain etc.As hydroxycarboxylic acid, can enumerate oxyacetic acid, hydroxybutyric acid etc.As lactone, can enumerate glycollide, 6-caprolactone glycollide, 6-caprolactone, beta-propiolactone, δ-butyrolactone, β-or gamma-butyrolactone, pivalolactone, δ-Wu Neizhi etc.
Poly--L-lactic acid and poly--D-lactic acid can prepare by known method.For example, can under the condition that metal catalyst exists, its ring-opening polymerization be prepared L-or the heating of D-rac-Lactide.In addition, can also make the low molecular weight crystallization that contains metal catalyst after, heating makes the incompatible preparation of its solid polycondensation under reduced pressure or under inert gas flow.And then, can also prepare by the direct polymerization method that makes the acid by dehydrating lactic condensation existing or not existing under the condition of organic solvent.
Polyreaction can implemented in the known reaction vessel in the past, can use independent or arranged side by side for example has the vertical response container of high viscosity such as hurricane band with agitating wing.
Can use alcohol as polymerization starter.As described alcohol, preferably do not hinder poly lactic acid polymerized, for nonvolatile, preferably use for example decyl alcohol, dodecanol, tetradecanol, cetyl alcohol, Stearyl alcohol etc.
In solid phase polymerization method, the lower molecular weight lactic polyester that the direct polymerization method by above-mentioned ring-opening polymerization method, lactic acid is obtained uses as prepolymer.Consider from the angle that prevents to merge, preferably make prepolymer more than its second-order transition temperature (Tg) and less than the temperature range of fusing point (Tm), carry out crystallization in advance.With crystallization prepolymer be filled in the fixed vertical response container or be filled in the reaction vessel of container self rotation as rotary drum (tumbler), stove (kiln), it is above and less than the temperature range of fusing point (Tm) to be heated to the second-order transition temperature (Tg) of prepolymer.Polymerization temperature is along with polymeric carries out heating up also without any problem interimly.In addition, in order to remove the water that generates in the solid state polymerization efficiently, preferably will be to the inner pressure relief of above-mentioned reaction vessel class, the method that makes warmed-up inert gas flow circulation and usefulness.
(stereoscopic composite poly(lactic acid))
Poly(lactic acid) is the mixture of poly--L-lactic acid, poly--D-lactic acid, preferably contains the so-called stereoscopic composite poly(lactic acid) of stereoscopic composite crystalline.The stereoscopic composite crystallization is poly-by mixing-and L-lactic acid, poly--D-lactic acid forms, in this case, poly--L-lactic acid is preferably 90: 10 with the weight ratio of poly--D-lactic acid～and 10: 90, more preferably 75: 25～25: 75, more preferably 60: 40～40: 60.The weight-average molecular weight (Mw) of poly--L-lactic acid and poly--D-lactic acid is preferably 100,000～500,000 respectively, and more preferably 150,000～350,000.
The stereoscopic composite crystallization containing ratio (X) of composition of the present invention is preferably 80～100%, and more preferably 95～100%.Stereoscopic composite crystallization containing ratio (X) is represented with following formula.
X＝{ΔHB/(ΔHA+ΔHB)}×100(％)
In the formula, Δ HA be in the differential scanning calorimeter (DSC) more than 150 ℃ and less than the entropy of fusion of the crystalline melt point of 190 ℃ of appearance, Δ HB is more than 190 ℃ and less than the entropy of fusion of the crystalline melt point of 250 ℃ of appearance.
Said stereoscopic composite poly(lactic acid) among the present invention, in differential scanning calorimeter (DSC) was measured, in the fusion peak of temperature-rise period, the fusion peak ratio more than 195 ℃ was preferably more than 80%, more preferably more than 90%, more preferably more than 95%.Fusing point is 195～250 ℃, more preferably 200～220 ℃.Entropy of fusion is more than the 20J/g, to be preferably more than the 30J/g.Particularly, be preferably as follows: in differential scanning calorimeter (DSC) was measured, in the fusion peak of temperature-rise period, the fusion peak ratio more than 195 ℃ was more than 90%, and fusing point is 195～250 ℃, and entropy of fusion is more than the 20J/g.
The stereoscopic composite crystallization can coexist, mix and make with the weight ratio of poly--D-lactic acid with regulation by-L-lactic acid poly-by making.
Mixing can be carried out under the condition that solvent exists.In addition, mixing can also be carried out under the condition that does not have solvent.That is, can adopt to gather-carry out the method for melting mixing after L-lactic acid and poly--D-lactic acid mix with specified amount, make to add remaining the opposing party after either party fusion in poly--L-lactic acid and poly--D-lactic acid and carry out mixing method.
(metal catalyst)
Metal catalyst when making poly--L-lactic acid or poly--D-lactic acid is preferably selected from the compound of at least a metal in transition metal, aluminium, germanium, tin and the antimony of alkaline-earth metal, rare earth element, period 3.As alkaline-earth metal, can enumerate magnesium, calcium, strontium etc.As rare earth element, can enumerate scandium, yttrium, lanthanum, cerium etc.As the transition metal of period 3, can enumerate titanium, iron, cobalt, nickel, zinc.
The carboxylate salt of the preferred above-mentioned metal of metal catalyst, alkoxide, halogenide, oxide compound, carbonate, enolate, fluoroform sulphonate.When considering the tone of polymerization activity, resulting composition, special preferably octanoic acid tin, zinc acetate, tetraisopropoxy titanium, aluminium isopropoxide.
Composition of the present invention contains the poly(lactic acid) that polymerization obtains under the condition that above-mentioned metal catalyst exists.Therefore, to contain with respect to poly(lactic acid) 100 weight parts be the metal catalyst of 0.001～1 weight part, preferred 0.005～0.1 weight part to composition of the present invention.The addition of metal catalyst crosses at least that polymerization velocity significantly reduces, so not preferred.Otherwise, the addition of metal catalyst cross at most because of reaction heat painted or since depolymerization, transesterification reaction quicken, so the color harmony thermostability variation of resulting composition.
(Hypophosporous Acid, 50 class passivator)
Hypophosporous Acid, 50 class passivator is to have the compound that forms the ability of salt or title complex with metal catalyst.In addition, bonding has two hydrogen atoms that show strong reducing power, the free radical that produces in the time of can suppressing high temperature, the increase of oxidation products on the phosphorus atom of Hypophosporous Acid, 50 class passivator.As Hypophosporous Acid, 50 class passivator, be preferably selected from the alkali earth metal salt of an alkali metal salt, Hypophosporous Acid, 50 of Hypophosporous Acid, 50, Hypophosporous Acid, 50 and Hypophosporous Acid, 50
At least a in the salt.
As an alkali metal salt of Hypophosporous Acid, 50, can enumerate sodium salt, sylvite of Hypophosporous Acid, 50 etc.As the alkali earth metal salt of Hypophosporous Acid, 50, can enumerate calcium salt, magnesium salts of Hypophosporous Acid, 50 etc.As Hypophosporous Acid, 50
Salt can be enumerated Hypophosporous Acid, 50 tetraethyl-ammonium salt, Hypophosporous Acid, 50 tetra-n-butyl ammonium salt, Hypophosporous Acid, 50 tetraethyl-
Salt, Hypophosporous Acid, 50 tetra-n-butyl
Salt etc.As described Hypophosporous Acid, 50 class passivator, preferred Hypophosporous Acid, 50, sodium hypophosphite, potassium hypophosphite, magnesium hypophosphite, calcium propionate, ammonium hypophosphite.Consider preferred especially Hypophosporous Acid, 50 from the deactivation of metal catalyst and the angle of inhibited oxidation product.
The content of Hypophosporous Acid, 50 class passivator is 0.001 weight part～5 weight parts with respect to poly(lactic acid) 100 weight parts, preferred 0.01～0.5 weight part.If the content of Hypophosporous Acid, 50 class passivator is crossed at least the reaction efficiency extreme difference with residual polymerizing catalyst, the inactivation of polymerizing catalyst produces fluctuation.In addition, if the content of Hypophosporous Acid, 50 class passivator is too much, the reduction of the then plasticising of the composition that causes of dimension phosphoric acid class passivator, hydrolytic resistance that the water-intake rate increase causes becomes remarkable.
Hypophosporous Acid, 50 class passivator can be in the ring-opening polymerization method in the polymerization later stage directly add to carry out in the reaction vessel mixing.In addition, it is mixing with forcing machine, kneader to be shaped to sheet (チ Star Block shape) back.The uniform distribution of consideration in poly(lactic acid) then preferably uses forcing machine, kneader.In addition, go back the method that the preferred portion of spuing with reaction vessel directly is connected with forcing machine, adds Hypophosporous Acid, 50 class passivator from the side feeder.When adding Hypophosporous Acid, 50 class passivator by aforesaid method, making the method for adding behind the solution of the such polar organic solvent of the aqueous solution or alcohol, tetrahydrofuran (THF) also is preferred mode.
On the other hand, in solid phase polymerization method, can be that poly(lactic acid) solid and the Hypophosporous Acid, 50 class passivator that obtains when polymerization is finished carries out mixing method in forcing machine, kneader, the solid of poly(lactic acid) and the masterbatch (masterbatch) that contains Hypophosporous Acid, 50 class passivator are carried out mixing method etc. in forcing machine or kneader.
The stereocomplex of poly--L-lactic acid and poly--D-lactic acid needs the high temperature more than 180 ℃, so preferably before stereocomplex, add Hypophosporous Acid, 50 class passivator in advance with any method in the aforesaid method.
(metaphosphoric acid class passivator)
The metaphosphoric acid class passivator that uses among the present invention is the compound that about 3～200 phosphoric acid unit cyclic condensation shape obtains, and has the ability that forms title complex with metal catalyst or water.Metaphosphoric acid class passivator is the ring-type polydentate ligand, compare with monodentate or catenate polydentate ligand phosphoric acid, phosphorous acid, tetra-sodium, Tripyrophosphoric acid and their ester class, the big (Wrong of ligand stability constant permanence fixed number), can be efficiently and catch metal catalyst, moisture securely.As described metaphosphoric acid class passivator, be preferably selected from metaphosphoric acid, its an alkali metal salt, its alkali earth metal salt, its
At least a in the salt.As an alkali metal salt of metaphosphoric acid, can enumerate sodium salt, sylvite of metaphosphoric acid etc.As the alkali earth metal salt of metaphosphoric acid, can enumerate calcium salt, magnesium salts of metaphosphoric acid etc.As metaphosphoric acid
Salt can be enumerated metaphosphoric acid tetraethyl-ammonium salt, metaphosphoric acid tetra-n-butyl ammonium salt, metaphosphoric acid tetraethyl-
Salt, metaphosphoric acid tetra-n-butyl
Salt etc.
Metaphosphoric acid class passivator preferably be selected from the compound shown in the following formula, its an alkali metal salt, its alkali earth metal salt with and
At least a in the salt.
In the formula, n is 1～200 integer.
The compound that following formula is represented normally n is the mixture of the compound of 1～200 integer.In following formula, n is preferably 1～100 integer, 1～50 integer more preferably, further 1～12 integer more preferably.
Consider the deactivation of metal catalyst, moisture, with the consistency of poly(lactic acid) and when handling easiness, the pH that preferably 1g is dissolved in the aqueous solution that obtains in the 100ml water is below 6, be preferably below 4, the more preferably metaphosphoric acid below 2 or its sodium salt.
Metaphosphoric acid class passivator must have P (=O) the OH position of the metal catalyst that is used for catching poly(lactic acid).Its index of clear expression is the pH that 1g metaphosphoric acid class passivator is dissolved in the aqueous solution that obtains in the 100ml water, for make P (=O) the OH position fully exists, above-mentioned pH is preferably below 6.Above-mentioned pH surpasses at 6 o'clock, and metaphosphoric acid class passivator can't fully make the metal catalyst inactivation, perhaps needs can not suppress the thermolysis of poly(lactic acid) for a long time.The content of metaphosphoric acid class passivator is 0.001～10 weight part with respect to poly(lactic acid) 100 weight parts, is preferably 0.01～0.5 weight part.The content of metaphosphoric acid class passivator is crossed the inactivation efficient extreme difference of metal remained catalyzer at least, produces the inactivation fluctuation.In addition, plasticising, the water-intake rate after the forming process that the content of metaphosphoric acid class passivator is crossed the composition that metaphosphoric acid class passivator at most causes increase, and long-term hydrolytic resistance reduces and becomes remarkable.
How much metaphosphoric acid class passivator has difference because of preparation section is different, but second-order transition temperature is all at 130～150 ℃, second-order transition temperature is that the metaphosphoric acid class passivator more than 100 ℃ heats under solid state that to carry out drying be easy, carrying out mixingly in the reaction vessel so can directly add in the polymerization later stage in the ring-opening polymerization method, thereby is preferred.In addition, can also in forcing machine or kneader, carry out mixing with the form that is shaped to flaky masterbatch.The uniform distribution of consideration in poly(lactic acid) preferably uses forcing machine or kneader.In addition, also preferably the portion of spuing of reaction vessel directly is connected with forcing machine, from the method for the solution of the aqueous solution of side feeder interpolation metaphosphoric acid class passivator or polar organic solvent.As described polar organic solvent, ethers such as glycol dimethyl ether, tetrahydrofuran (THF), alcohols such as methyl alcohol, ethanol are suitable.On the other hand, in solid phase polymerization method, poly(lactic acid) solid that obtains when polymerization is finished and metaphosphoric acid class passivator carry out mixing method in forcing machine or kneader, the solid of poly(lactic acid) and the masterbatch etc. that contains metaphosphoric acid class passivator are carried out mixing method etc. in forcing machine or kneader be possible.
In metaphosphoric acid, sodium-metaphosphate has been established security as foodstuff additive, is preferred.In addition, sodium-metaphosphate has following advantage: be solid and need not to add in the poly(lactic acid) with the form of the aqueous solution at normal temperatures, can not use the water that promotes hydrolysis.In addition, sodium-metaphosphate has the fusing point lower than poly(lactic acid), even directly add in the poly(lactic acid) with solid form, also can easily be distributed in the poly(lactic acid) in the temperature fusion lower than poly(lactic acid).In addition, sodium-metaphosphate is compared with highly acid metaphosphoric acid, and is acid low, preventing on the corrosion of equipment this point it is preferred.
The weight-average molecular weight of composition of the present invention (Mw) is 100,000～500,000, is preferably 150,000～350,000, is being excellent aspect thermostability, tone, the hydrolytic resistance, can perform well in melt-spinning, fusion system film, injection molding.
The manufacture method of＜composition 〉
The present invention includes the preparation of compositions method, its be comprise mix poly--L-lactic acid and poly--D-lactic acid contain stereoscopic composite crystalline preparation of compositions method, it is characterized in that, at least one side in poly--L-lactic acid and poly--D-lactic acid is contained metal catalyst, and this is blended under the condition that Hypophosporous Acid, 50 class passivator or metaphosphoric acid class passivator exists and carries out.
Poly--L-lactic acid, poly--D-lactic acid, metal catalyst, Hypophosporous Acid, 50 class passivator, metaphosphoric acid class passivator such as in the combination items record.
Therefore, metal catalyst preferably contains the compound of at least a metal in transition metal-type, aluminium, germanium, tin and the antimony that is selected from alkaline-earth metal, rare earth element, period 3.
With respect to total 100 weight parts of poly--L-lactic acid and poly--D-lactic acid, the content of metal catalyst is preferably 0.001～1 weight part.
Hypophosporous Acid, 50 class passivator preferably is selected from the alkali earth metal salt of an alkali metal salt, Hypophosporous Acid, 50 of Hypophosporous Acid, 50, Hypophosporous Acid, 50 and Hypophosporous Acid, 50
At least a in the salt.
Preferably there is Hypophosporous Acid, 50 class passivator 0.001～5 weight part in total 100 weight parts with respect to poly--L-lactic acid and poly--D-lactic acid.
Metaphosphoric acid class passivator preferably be selected from the compound shown in the following formula, its an alkali metal salt, its alkali earth metal salt with and
At least a in the salt.
In the formula, n is 1～200 integer.
The pH that preferred 1g metaphosphoric acid class passivator is dissolved in the aqueous solution that obtains in the 100ml water is below 6.
Preferably there is metaphosphoric acid class passivator 0.001～10 weight part in total 100 weight parts with respect to poly--L-lactic acid and poly--D-lactic acid.
Mixing can be carried out under the condition that solvent exists.Solvent so long as dissolving poly--solvent of L-lactic acid and poly--D-lactic acid then is not particularly limited, but preferably use for example chloroform, methylene dichloride, ethylene dichloride, tetrachloroethane, phenol, tetrahydrofuran (THF), N-Methyl pyrrolidone, N separately, dinethylformamide, butyrolactone, three
Alkane, hexafluoroisopropanol etc. or with mixing more than 2 kinds in them.In addition, mixing can be carried out under the condition that does not have solvent.That is, can adopt to gather-carry out the method for melting mixing after L-lactic acid and poly--D-lactic acid mix with specified amount, make to add remaining the opposing party after either party fusion in poly--L-lactic acid and poly--D-lactic acid and carry out mixing method.
As the mode of aforesaid method, can enumerate following will gathering-L-lactic acid and poly--D-lactic acid blended mode.It is as follows to abridge.
(L) poly--L-lactic acid of containing metal catalyzer not in fact.
(Lc) contain gathering-L-lactic acid of metal catalyst.
(Lcp) contain gathering-L-lactic acid of metal catalyst and Hypophosporous Acid, 50 class passivator or metaphosphoric acid class passivator.
(D) poly--D-lactic acid of containing metal catalyzer not in fact.
(Dc) contain gathering-D-lactic acid of metal catalyst.
(Dcp) contain gathering-D-lactic acid of metal catalyst and Hypophosporous Acid, 50 class passivator or metaphosphoric acid class passivator.
(P) Hypophosporous Acid, 50 class passivator or metaphosphoric acid class passivator.
Mode 1: mix (L) and (Dcp).
Mode 2: mix (L), (Dc) and (P).
Mode 3: mix (Lc), (D) and (P).
Mode 4: mix (Lc), (Dc) and (P).
Mode 5: mix (Lc) and (Dcp).
Mode 6: mix (Lcp) and (D).
Mode 7: mix (Lcp) and (Dc).
Mode 8: mix (Lcp) and (Dcp).
In addition, for this method, preferably make by mixing following composition, described composition is: added the composition of Hypophosporous Acid, 50 class passivator or metaphosphoric acid class passivator in the poly--L-lactic acid that (i) under the condition that metal catalyst exists, prepares and poly--D-lactic acid of (ii) under the condition that metal catalyst exists, preparing in added the composition of Hypophosporous Acid, 50 class passivator or metaphosphoric acid class passivator.Mixing can be carried out under the condition that solvent exists.Mixing can also be carried out by melting mixing under the condition that does not have solvent.
＜formed body 〉
The present invention includes formed body, described formed body comprises above-mentioned composition.That is, can use composition of the present invention to obtain injection-molded article, extrusion molding article, vacuum pressed moulding product, blow molding product, film, sheet non-woven fabrics, fiber, cloth, complex body, agricultural goods, materials and equipments, fishery goods, materials and equipments, building-goods, materials and equipments for building, stationery, medical treatment product or other formed body with other material.Moulding can be undertaken by ordinary method.
Embodiment
Below, be described more specifically the present invention by embodiment and comparative example.But the present invention is not subjected to any qualification of following example.The evaluation of each rerum natura is carried out by the following method.
(1) heat stability test of composition
The 10g composition is packed in パ イ レ Star Network ス (registered trademark) the system test tube of band plug, inside is replaced with nitrogen, kept assess thermal stability 10 minutes at 260 ℃.By the weight-average molecular weight (Mw) of composition before and after the GPC determination test, by relatively they come assess thermal stability.
In addition, the terminal carboxyl(group) amount (eq/t of unit) to composition before and after the heat stability test compares the evaluation hydrolytic resistance.The increasing amount of terminal carboxyl(group) is the index of expression hydrolysis degree.Terminal carboxyl(group) is following tries to achieve: the 100mg sample dissolution in the 10ml chloroform, to wherein adding 10ml ethanol, is added BTB as indicator in the solution that so modulation forms, carry out titration with 0.05N potassium hydroxide/ethanolic soln.
(2) weight-average molecular weight (Mw)
For weight-average molecular weight (Mw), use the GPC-11 of シ ヨ one デ Star Network ス system, make the 50mg sample dissolution in the 5ml chloroform, launch with 40 ℃ chloroforms.Weight-average molecular weight (Mw) is calculated with the polystyrene conversion value.
(3) lactide content in the composition
The nuclear magnetic resonance device JNM-EX270 spectrometer of the NEC system of use, with the deuterochloroform is solvent, calculate the quartet peak area that comes from rac-Lactide (4.98～5.05ppm) with respect to the quartet peak area that derives from poly(lactic acid) (5.10～5.20ppm) ratio, with this as the lactide content in the composition.
(4) computing method of stereoscopic composite crystallization containing ratio (X)
By in differential scanning calorimeter (DSC) more than 150 ℃ and less than the entropy of fusion Δ HA of the crystalline melt point of 190 ℃ of appearance, more than 190 ℃ and less than the entropy of fusion Δ HB of the crystalline melt point of 250 ℃ of appearance, calculate stereoscopic composite crystallization containing ratio (X) by following formula.
X＝{ΔHB/(ΔHA+ΔHB)}×100(％)
(5) the tone evaluation of composition
The tone evaluation of composition is undertaken by L, a, b value that the ultraviolet-visible spectrometer UV2400PC with Shimadzu Seisakusho Ltd.'s (strain) system obtains.Estimating sample is the film of 40nm, makes as the solvent cast method of stoste by 15 weight % dichloromethane solutions with composition.
(6) employed rac-Lactide
In following example,, use the rac-Lactide of the made polymerization-grade of the wild chemical research of (strain) Musashi as the L-rac-Lactide.As the D-rac-Lactide, use the rac-Lactide of the made polymerization-grade of the wild chemical research of (strain) Musashi.
Embodiment 1 poly(lactic acid)+Hypophosporous Acid, 50
Distillate the raw material loading port of the polymerization container of pipe, under nitrogen gas stream, pack into L-rac-Lactide 100 weight parts and Stearyl alcohol 0.15 weight part from having condensation.Then, make the L-rac-Lactide 190 ℃ of fusions with carrying out nitrogen displacement 5 times in the reaction vessel.At the complete fused of L-rac-Lactide constantly, from the raw material loading port 2 ethyl hexanoic acid tin 0.05 weight part is added with toluene 500 μ L, 190 ℃ of polymerizations 1 hour.
After polymerization finishes, add Hypophosporous Acid, 50 (with the pure medicine of light (strain) system) 0.02 weight part, mixing 15 minutes from the raw material loading port.Make remaining L-rac-Lactide slough (Tuo Play at last), spue gathering-the L-lactic acid composition of wire from the discharge opening of reaction vessel, limit cooling sideline judge becomes particulate state.The Mw and the lactide content of resulting composition are shown in table 1.
It is granular that resulting composition uses pulverizer to make, and its 10g is encased in the test tube with ground stopper of thermal glass " パ イ レ Star Network ス " (コ one ニ Application グ register of company trade mark) system.Then the nitrogen displacement is carried out in the test tube inside of パ イ レ Star Network ス (registered trademark) system, implement 260 ℃, 10 minutes heat stability test.After this off-test, take out composition, measure Mw and lactide content.Measurement result is shown in table 1.In addition, L, a, the b value with the composition in this moment is shown in table 2.
Comparative example 1
Except not adding the Hypophosporous Acid, 50, the method by similarly to Example 1 obtains composition.Said composition is carried out heat stability test, and the composition after the heat stability test is crisp as a result, and degradation production is that the crystallization of rac-Lactide is made on the test tube attached to the used パ イ レ Star Network ス (registered trademark) of test.Mw after the heat stability test and lactide content are shown in table 1.In addition, L, a, the b value with the composition in this moment is shown in table 2.
Table 1
Table 2
| L | a | b | |
| Embodiment 1 | 93.6 | 0.03 | 1.23 |
| Comparative example 1 | 93.2 | -0.04 | 3.22 |
Embodiment 2 stereoscopic composite poly(lactic acid)+Hypophosporous Acid, 50
(manufacturing of poly--L-lactic acid)
Distillate the raw material loading port of the polymerization container of pipe, under nitrogen gas stream, pack into L-rac-Lactide 100 weight parts and Stearyl alcohol 0.15 weight part from having condensation.Then, make the L-rac-Lactide 190 ℃ of fusions with carrying out nitrogen displacement 5 times in the reaction vessel.At the complete fused of L-rac-Lactide constantly, from the raw material loading port 2 ethyl hexanoic acid tin 0.05 weight part is added with toluene 500 μ L, 190 ℃ of polymerizations 1 hour.
After polymerization finishes, add Hypophosporous Acid, 50 (with the pure medicine of light (strain) system) 0.02 weight part, mixing 15 minutes from the raw material loading port.Remaining L-rac-Lactide is sloughed, and from spue poly--L-lactic acid of wire of the discharge opening of reaction vessel, limit cooling sideline judge becomes particulate state.
(manufacturing of poly--D-lactic acid)
Then, gather-D-lactic acid by same operation preparation.That is, pack into D-rac-Lactide 100 weight parts and Stearyl alcohol 0.15 weight part then with carrying out nitrogen displacement 5 times in the reaction vessel, make the D-rac-Lactide 190 ℃ of fusions.At the complete fused of D-rac-Lactide constantly, from the raw material loading port 2 ethyl hexanoic acid tin 0.05 weight part and toluene 500 μ L are added together, 190 ℃ of polymerizations 1 hour.After polymerization finishes, add Hypophosporous Acid, 50 (with the pure medicine of light (strain) system, phospho acid) 0.02 weight part, mixing 15 minutes from the raw material loading port.Remaining D-rac-Lactide is sloughed, and from spue poly--D-lactic acid of wire of the discharge opening of reaction vessel, limit cooling sideline judge becomes particulate state.
(formation of stereoscopic composite)
Make above-mentioned poly--particle 50 weight parts of L-lactic acid and the particle 50 weight part thorough mixing of poly--D-lactic acid after, use the kneader Labo Plastomill 50C150 of Japan's system machine (strain) system, mixing 10 minutes in 230 ℃ under stream of nitrogen gas.The stereoscopic composite crystallization containing ratio (X) of resulting composition is 98.8%.
(heat stability test)
It is granular that resulting composition uses pulverizer to make, and this saccharoid 10g is encased in the test tube of パ イ レ Star Network ス (registered trademark) system of being with plug.Then the nitrogen displacement is carried out in the test tube inside of パ イ レ Star Network ス (registered trademark) system, kept 10 minutes, implement heat stability test at 260 ℃.After the off-test, take out composition, measure Mw and lactide content.Measurement result is shown in table 3.In addition, L, a, the b value with the composition in this moment is shown in table 4.
Embodiment 3 stereoscopic composite poly(lactic acid)+ammonium hypophosphites
Except using ammonium hypophosphite (MP Biomedicals) 0.02 weight part as the Hypophosporous Acid, 50 class passivator, the operation by similarly to Example 2 makes composition.The stereoscopic composite crystallization containing ratio of resulting composition is 99.0%.Mw and lactide content before and after the heat stability of composition test are shown in table 3, and L, a, b value are shown in table 4.
Comparative example 2
Except not adding Hypophosporous Acid, 50 class passivator, the method by similarly to Example 2 prepares composition.Said composition is carried out heat stability test, and the composition after the heat stability test is crisp as a result, is brown, and degradation production is that the crystallization of rac-Lactide is made on the test tube attached to the used パ イ レ Star Network ス (registered trademark) of test.Mw and lactide content before and after the heat stability of composition test are shown in table 3, and L, a, b value are shown in table 4.
Table 3
Table 4
| L | a | b | |
| Embodiment 2 | 94.1 | 0.01 | 1.31 |
| Embodiment 3 | 93.8 | 0.02 | 1.08 |
| Comparative example 2 | 93.7 | -0.02 | 3.48 |
Embodiment 4 poly(lactic acid)+metaphosphoric acid
Distillate the raw material loading port of the polymerization container of pipe, under nitrogen gas stream, pack into L-rac-Lactide 100 weight parts and Stearyl alcohol 0.15 weight part from having condensation.Then, make the L-rac-Lactide 190 ℃ of fusions with carrying out nitrogen displacement 5 times in the reaction vessel.At the complete fused of L-rac-Lactide constantly, from the toluene 500 μ L solution of raw material loading port interpolation 2 ethyl hexanoic acid tin 0.05 weight part, 190 ℃ of polymerizations 1 hour.After polymerization finishes, add metaphosphoric acid (with the pure medicine of light (strain) system) 0.02 weight part from the raw material loading port, mixing 15 minutes, the pH that described metaphosphoric acid 1g is dissolved in the aqueous solution that obtains in the 100ml water was 0.85.Remaining L-rac-Lactide is sloughed, and composition spues in the reaction vessel.The Mw of resulting composition, lactide content and terminal carboxyl(group) amount are shown in table 5.
Use pulverizer to make the granular of 2～5mm resulting composition, this saccharoid 10g is encased in パ イ レ Star Network ス (registered trademark) the system test tube of band plug.Then the nitrogen displacement is carried out in the test tube inside of パ イ レ Star Network ス (registered trademark) system, be implemented in 260 ℃ of heat stability tests that keep 10 minutes and 60 minutes.After this off-test, take out composition, measure Mw, lactide content and terminal carboxyl(group) amount.Measurement result is shown in table 5.
Embodiment 5 poly(lactic acid)+sodium-metaphosphate
Except 0.02 weight part metaphosphoric acid being changed into the pH that 1g is dissolved in the aqueous solution that obtains in the 100ml water is 1.97 metaphosphoric acid sodium salt (ラ サ rolling flourish (strain) system, acid metaphosphoric acid, polymerization degree n=1～34) outside 0.02 weight part, by method modulation group compound similarly to Example 4.The Mw of resulting composition, lactide content and terminal carboxyl(group) amount are shown in table 5.Resulting composition uses pulverizer to make the granular of 2～5mm, this saccharoid 10g is encased in the test tube of パ イ レ Star Network ス (registered trademark) system of being with plug.Then the nitrogen displacement is carried out in the test tube inside of パ イ レ Star Network ス (registered trademark) system, be implemented in 260 ℃ of heat stability tests that keep 10 minutes and 60 minutes.After this off-test, take out composition, measure Mw, lactide content and terminal carboxyl(group) amount.Measurement result is shown in table 5.
Embodiment 6 poly(lactic acid)+metaphosphoric acid Na
Except 0.02 weight part metaphosphoric acid being changed into the pH that 1g is dissolved in the aqueous solution that obtains in the 100ml water is 4.0 metaphosphoric acid sodium salt 0.02 weight part, by method modulation group compound similarly to Example 4.The metaphosphoric acid sodium salt is after with sodium hydroxide the metaphosphoric acid that uses among the embodiment 4 partly being neutralized, to carry out drying and prepare.The Mw and the lactide content of resulting composition are shown in table 5.Resulting composition uses pulverizer to make the granular of 2～5mm, this saccharoid 10g is encased in the test tube of パ イ レ Star Network ス (registered trademark) system of being with plug.Then the nitrogen displacement is carried out in the test tube inside of パ イ レ Star Network ス (registered trademark) system, be implemented in 260 ℃ of heat stability tests that keep 10 minutes and 60 minutes.After this off-test, take out composition, measure Mw and lactide content.Measurement result is shown in table 5.
Embodiment 7 poly(lactic acid)+sodium-metaphosphate
Except 0.02 weight part metaphosphoric acid being changed into the pH that 1g is dissolved in the aqueous solution that obtains in the 100ml water is 5.6 metaphosphoric acid sodium salt 0.02 weight part, and the method by similarly to Example 4 prepares composition.The metaphosphoric acid sodium salt is after with sodium hydroxide the metaphosphoric acid that uses among the embodiment 4 partly being neutralized, to carry out drying and prepare.The Mw and the lactide content of resulting composition are shown in table 5.Resulting composition uses pulverizer to make the granular of 2～5mm, this saccharoid 10g is encased in the test tube of パ イ レ Star Network ス (registered trademark) system of being with plug.Then the nitrogen displacement is carried out in the test tube inside of パ イ レ Star Network ス (registered trademark) system, be implemented in 260 ℃ of heat stability tests that keep 10 minutes and 60 minutes.After this off-test, take out composition, measure Mw and lactide content.Measurement result is shown in table 5.
Comparative example 3
Except not adding the metaphosphoric acid, the method by similarly to Example 4 obtains composition.Said composition is carried out heat stability test with method similarly to Example 4.Mw after the heat stability test, lactide content and terminal carboxyl(group) amount are shown in table 5.
Table 5
Embodiment 8 stereoscopic composite poly(lactic acid)+metaphosphoric acids
(preparation of poly--L-lactic acid)
Distillate the raw material loading port of the polymerization container of pipe, under nitrogen gas stream, pack into L-rac-Lactide 100 weight parts and Stearyl alcohol 0.15 weight part from having condensation.Then, make the L-rac-Lactide 190 ℃ of fusions with carrying out nitrogen displacement 5 times in the reaction vessel.At the complete fused of L-rac-Lactide constantly, from the raw material loading port 2 ethyl hexanoic acid tin 0.05 weight part is added with toluene 500 μ L, 190 ℃ of polymerizations 1 hour.
After polymerization finishes, add the pH that 1g is dissolved in the aqueous solution that obtains the 100ml water from the catalyzer input port and be 0.85 metaphosphoric acid 0.02 weight part, mixing 15 minutes.Remaining L-rac-Lactide is sloughed, and from spue poly--L-lactic acid of wire of the discharge opening of reaction vessel, limit cooling sideline judge becomes particulate state.
(preparation of poly--D-lactic acid)
Then, gather-D-lactic acid by same operation preparation.That is, pack into D-rac-Lactide 100 weight parts and Stearyl alcohol 0.15 weight part then with carrying out nitrogen displacement 5 times in the reaction vessel, make the D-rac-Lactide 190 ℃ of fusions.At the complete fused of D-rac-Lactide constantly, from the raw material loading port 2 ethyl hexanoic acid tin 0.05 weight part is added with toluene 500 μ L, 190 ℃ of polymerizations 1 hour.
After polymerization finishes, add the pH that 1g is dissolved in the aqueous solution that obtains the 100ml water from the catalyzer input port and be 0.85 metaphosphoric acid (with the pure medicine of light (strain) system) 0.02 weight part, mixing 15 minutes.Remaining D-rac-Lactide is sloughed, and from spue poly--D-lactic acid of wire of the discharge opening of reaction vessel, limit cooling sideline judge becomes particulate state.
(formation of stereoscopic composite)
Make above-mentioned poly--particle 50 weight parts of L-lactic acid and the particle 50 weight part thorough mixing of poly--D-lactic acid after, use the kneader Labo Plastomill 50C150 of Japan's system machine (strain) system, mixing 10 minutes in 230 ℃ under stream of nitrogen gas.The stereoscopic composite crystallization containing ratio (X) of resulting composition is 99.7%.The Mw and the lactide content of resulting composition are shown in table 6.
Use pulverizer to make the granular of 2～5mm resulting composition, this saccharoid 10g is encased in the test tube of パ イ レ Star Network ス (registered trademark) system of being with plug.Then the nitrogen displacement is carried out in the test tube inside of パ イ レ Star Network ス (registered trademark) system, implement 260 ℃, 10 minutes heat stability test.After this off-test, take out composition, measure Mw and lactide content.Measurement result is shown in table 6.
Embodiment 9 stereoscopic composite poly(lactic acid)+sodium-metaphosphates
Except 0.02 weight part metaphosphoric acid being changed into the pH that 1g is dissolved in the aqueous solution that obtains in the 100ml water is outside 1.97 metaphosphoric acid sodium salt (ラ サ rolling flourish (strain) system, acid metaphosphoric acid) 0.02 weight part, and the method by similarly to Example 8 prepares composition.The Mw of resulting composition, stereoscopic composite crystallization containing ratio (X), lactide content and terminal carboxyl(group) amount are shown in table 6.The heat stability test of composition is also implemented similarly to Example 8, and measurement result is recorded in table 6 in the lump.
Comparative example 4
Except not adding metaphosphoric acid class passivator, the method by similarly to Example 8 prepares composition.The Mw of resulting composition, stereoscopic composite crystallization containing ratio (X), lactide content and terminal carboxyl(group) amount are shown in table 6.The heat stability test of composition is also implemented similarly to Example 8, and measurement result is recorded in table 6 in the lump.
Table 6
X: stereoscopic composite crystallization containing ratio
The invention effect
The thermostability of composition of the present invention, tone, hydrolytic resistance excellence.Therefore, even the heating molecular weight also is difficult for reducing, and keep good color tone.In addition, even composition of the present invention heating, the increase of lactide content is also few.
That is, composition of the present invention is difficult for generating rac-Lactide, cyclic oligomer, the low molecule of chain in the operation that the needs of melt-spinning, fusion system film, injection molding and so on heat more than 180 ℃, and molecular weight reduces, tone worsens few.
Industrial applicability
Composition of the present invention is useful as the raw material of fiber, film, moulding product.
Claims (5)
1. composition, it contains (i) 100 weight part poly(lactic acid), (ii) 0.001～1 weight part metal catalyst and (iii) 0.001～10 weight part metaphosphoric acid class passivator,
Described metaphosphoric acid class passivator be an alkali metal salt that is selected from the compound shown in the following formula, its alkali earth metal salt with and
At least a in the salt,
Metal catalyst is to contain the compound that is selected from least a metal in alkaline-earth metal, rare earth element, titanium, iron, cobalt, nickel, zinc, aluminium, germanium, tin and the antimony,
The pH that 1g metaphosphoric acid class passivator is dissolved in the aqueous solution that obtains in the 100ml water is below 6,
In the formula, n is 1～200 integer.
2. the described composition of claim 1, wherein, poly(lactic acid) is poly--L-lactic acid, poly--D-lactic acid or their mixture.
3. the described composition of claim 1, wherein, poly(lactic acid) is the mixture of poly--L-lactic acid, poly--D-lactic acid, contains the stereoscopic composite crystallization.
4. formed body, it comprises each described composition in the claim 1～3.
5. preparation of compositions method, it is to comprise by mixing the stereoscopic composite crystalline preparation of compositions method that poly--L-lactic acid and poly--D-lactic acid forms, it is characterized in that, at least one side in poly--L-lactic acid and the poly--D-lactic acid is contained metal catalyst, and described being blended under the condition that metaphosphoric acid class passivator exists carried out
This metaphosphoric acid class passivator be an alkali metal salt that is selected from the compound shown in the following formula, its alkali earth metal salt with and
At least a in the salt, its amount is 0.001～10 weight part with respect to total 100 weight parts of poly--L-lactic acid and poly--D-lactic acid,
Metal catalyst is to contain the compound that is selected from least a metal in alkaline-earth metal, rare earth element, titanium, iron, cobalt, nickel, zinc, aluminium, germanium, tin and the antimony, and its content is 0.001～1 weight part with respect to total 100 weight parts of poly--L-lactic acid and poly--D-lactic acid
The pH that 1g metaphosphoric acid class passivator is dissolved in the aqueous solution that obtains in the 100ml water is below 6,
In the formula, n is 1～200 integer.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005292547A JP2007099939A (en) | 2005-10-05 | 2005-10-05 | Composition containing polylactic acid |
| JP292547/2005 | 2005-10-05 | ||
| JP2005292399A JP4958422B2 (en) | 2005-10-05 | 2005-10-05 | Composition containing polylactic acid |
| JP292399/2005 | 2005-10-05 | ||
| JP2005311553 | 2005-10-26 | ||
| JP311600/2005 | 2005-10-26 | ||
| JP2005311600 | 2005-10-26 | ||
| JP311553/2005 | 2005-10-26 | ||
| PCT/JP2006/320244 WO2007043547A1 (en) | 2005-10-05 | 2006-10-04 | Polylactic acid composition |
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| JP2009249518A (en) * | 2008-04-08 | 2009-10-29 | Teijin Ltd | Stereocomplex polylactic acid composition excellent in hue and heat resistance |
| JP5260173B2 (en) * | 2008-08-01 | 2013-08-14 | 帝人株式会社 | Method for producing polylactic acid-containing composition |
| US9920181B2 (en) | 2012-10-10 | 2018-03-20 | Toray Industries, Inc. | Polylactic acid resin composition, molded product, and method of manufacturing polylactic acid resin composition |
| CN115637032A (en) * | 2021-07-20 | 2023-01-24 | 北京服装学院 | Heat-resistant flame-retardant polylactic acid material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3404121A (en) * | 1966-07-27 | 1968-10-01 | Eastman Kodak Co | Polyester catalyst-stabilizer usage |
| US5770682A (en) * | 1995-07-25 | 1998-06-23 | Shimadzu Corporation | Method for producing polylactic acid |
| EP1354908A1 (en) * | 2000-11-30 | 2003-10-22 | DAICEL CHEMICAL INDUSTRIES, Ltd. | Aliphatic polyester copolymer and process for producing the same, biodegradable resin molding based on aliphatic polyester, and lactone-containing resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5785818A (en) * | 1980-11-18 | 1982-05-28 | Mitsubishi Chem Ind Ltd | Production of polybutylene terephthalate |
| JPH05230201A (en) * | 1992-02-24 | 1993-09-07 | Dainippon Ink & Chem Inc | Production of polyester |
| JP3622386B2 (en) * | 1996-12-25 | 2005-02-23 | トヨタ自動車株式会社 | Process for producing biodegradable block copolymer |
| JP3610780B2 (en) * | 1998-06-30 | 2005-01-19 | トヨタ自動車株式会社 | Method for producing polylactic acid stereocomplex polymer molding |
| JP2005336414A (en) * | 2004-05-31 | 2005-12-08 | Toyota Motor Corp | Resin composition and molded product therefrom |
-
2005
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3404121A (en) * | 1966-07-27 | 1968-10-01 | Eastman Kodak Co | Polyester catalyst-stabilizer usage |
| US5770682A (en) * | 1995-07-25 | 1998-06-23 | Shimadzu Corporation | Method for producing polylactic acid |
| EP1354908A1 (en) * | 2000-11-30 | 2003-10-22 | DAICEL CHEMICAL INDUSTRIES, Ltd. | Aliphatic polyester copolymer and process for producing the same, biodegradable resin molding based on aliphatic polyester, and lactone-containing resin |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平5-230201A 1993.09.07 |
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