CN1613889A - Method for preparing high-polymer polylactic on Bitruder - Google Patents
Method for preparing high-polymer polylactic on Bitruder Download PDFInfo
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- CN1613889A CN1613889A CNA2004100664564A CN200410066456A CN1613889A CN 1613889 A CN1613889 A CN 1613889A CN A2004100664564 A CNA2004100664564 A CN A2004100664564A CN 200410066456 A CN200410066456 A CN 200410066456A CN 1613889 A CN1613889 A CN 1613889A
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- lactic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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Abstract
A process for preparing high molecular poly-lactic acid on the twin screw extruder is achieved by increasing the molecular weight of the poly-lactic acid by extending the chains of lactic acid preformed polymer on the twist screw extruder, which contains two steps: firstly, the preformed polymer of lactic acid whose weight mean molecular weight is 3000-50000 is produced by fasculation of lactic acid in the batch polymerization-autoclave; secondly, increasing the molecular weight of the produced preformed polymer to 180000 through chain extending. Its advantages include: improving the traditional synthetic method of the poly-lactic acid, settling the problem of low molecular weight, high price, no batch production, the manufacturing facility, and simple process with rapid reaction speed and high productive efficiency.
Description
Technical field
The present invention relates to the preparation method of high molecular biodegradable material poly(lactic acid), relate to specifically and produce poly-lactic acid in high molecular weight fast and continuously and its process for granulating, this method comprises by cheap lactic acid polycondensation reaction and prepares lactic acid prepolymer, and with the process of prepolymer chain extension on twin screw extruder.
Background technology
Poly(lactic acid) synthetic has two kinds of methods, i.e. ring-opening polymerization method and direct polycondensation methods.The ring-opening polymerization method prepares poly(lactic acid) by the rac-Lactide ring-opening polymerization at first by synthesis of lactide from lactic acid, mainly contains cationoid polymerisation, these three kinds of approach of anionoid polymerization and polycoordination, can synthetic molecular weight up to 700,000 to 1,000,000 PLA.The ring-opening polymerization method reaches its maturity in the laboratory, and for example, patent documentation WO90/01521, JP59-14688 have introduced the process by rac-Lactide ring-opening polymerization production poly(lactic acid).But the ring-opening polymerization complex manufacturing of rac-Lactide needs repeatedly to purify and recrystallization in particularly lactide refined, and reaction process is slower, consumes a large amount of reagent, produces discontinuously, and product yield is low, causes poly(lactic acid) to cost an arm and a leg.Patent documentation US5310865, JP59-96123, US4273920 have introduced the method that direct polycondensation method prepares poly(lactic acid), but no matter be solution direct condensation or body direct condensation exist free acid, water, polyester and rac-Lactide in system balance, reaction time is long, all also is difficult to obtain high molecular weight polymers.
It is a kind of new technology of just rising after the sixties in 20th century that reaction is extruded, and reacting and extruding polymerization has several outstanding advantages with respect to other polymerization process: production unit and technical process are simple, the level of automation height, and energy consumption is low; Speed of response is fast, and the production efficiency height can be continuously produced; Residual monomer can directly remove in process of production, and the energy recycling; Product residence time in forcing machine is short, and extent of thermal degradation is low; Can directly strengthen in process of production or chemical modification, strengthen maleic anhydride graft etc. as glass.But the control of reaction extrusion process condition has considerable influence to molecular weight of product, difficult control.The controlled degradation of the graft reaction that can be used for polymkeric substance, polyreaction, blend increase-volume reaction, polyolefinic crosslinking reaction, polymkeric substance etc. is extruded in reaction.
Extrude the existing abroad institute of synthesizing polylactic acid with reaction and study, German IKT (Institute FuerKunststofftechnologie) institute has synthesized poly(lactic acid) with rac-Lactide and its performance has been characterized on twin screw extruder.Patent documentation US5574129 has introduced the method for lactic acid prepolymer melt phase polycondensation synthesizing polylactic acid on twin screw extruder, and molecular weight can reach about 100,000, but technology is complicated, and industrialization is difficult.Patent documentation US5470944 has introduced the method that the chain extension legal system is equipped with poly-lactic acid in high molecular weight, and molecular weight is 25000～100000, but suitability for industrialized production is undesirable.
The inventor finds by a large amount of tests, make the method for lactic acid prepolymer chain extension on twin screw extruder can be fast and produce poly-lactic acid in high molecular weight continuously and by the control reaction conditions, thereby solve a series of problems that the puzzlement poly(lactic acid) is used as general-purpose plastics its granulation.
Summary of the invention
The purpose of this invention is to provide a kind of method that on twin screw extruder, prepares poly-lactic acid in high molecular weight, can be fast and produce poly-lactic acid in high molecular weight continuously.
The present invention is achieved in that
A kind of method that on twin screw extruder, prepares poly-lactic acid in high molecular weight, form by following two steps:
1) in an intermittent reaction polymeric kettle, it is 3000～50000 lactic acid prepolymer that the lactic acid monomer direct condensation obtains weight-average molecular weight, and the lactic acid prepolymer that obtains is pulverized sealing and preserved;
2) lactic acid prepolymer of above-mentioned gained is carried out chain extension on twin screw extruder, the acquisition weight-average molecular weight is 15000～180000 poly(lactic acid).
The first step of the present invention need prepare lactic acid prepolymer.The lactic acid that uses among the present invention can be that what to have optical activity (as D-or L-lactic acid) also can be non-optical activity (as D, L-lactic acid), perhaps is optical activity and non-optical active mixture.The purity of lactic acid monomer preferably is not less than 85%.
The processed of the present invention in the intermittent reaction polymeric kettle can adopt reduced pressure distillation technique, and dehydration temperaturre is 70～150 ℃, and more excellent temperature is 90～110 ℃.Vacuum tightness is 0.05～0.2Mpa, is good with 0.1～0.15Mpa wherein.Dewatering time is 0.5～3 hour, and the more excellent time is 1～2 hour.Under nitrogen, dewatering, not only can accelerate dewatering speed but also can reduce the generation of side reaction.In the decompression dehydration process, adopt agitator to stir to increase dewatering speed.
In lactic acid precondensation process, employed catalyzer mainly is divided three classes, 1) metal of II, III, IV and V family in the periodictable is as magnesium, aluminium, titanium, zinc, tin etc.; (2) oxide compound of II, III, IV and V family metal is as antimonous oxide, magnesium oxide, titanium dioxide, zinc oxide, titanium dioxide pick, aluminum oxide etc.; (3) salt of the metal of II, III, IV and V family is as tin protochloride, stannous octoate, zinc ethyl, etheric acid aluminium, tin acetate, manganese acetate, Cobaltous diacetate etc.; The above-mentioned catalyzer of enumerating can be used in combination.For example, manganese acetate is used for the catalysis lactic acid polycondensation reaction and antimonous oxide is used for stoping side reaction, and the chemical equilibrium between polymkeric substance and the monomer is transformed towards the direction that generates polymkeric substance.
Catalyst levels is calculated by weight at 0.001～1 part, is preferably in 0.1～0.5 part, and unit weight is as the criterion with the lactic acid monomer that begins to add.
The temperature of lactic acid precondensation is 90～200 ℃, and more excellent temperature of reaction is 120 ℃～170 ℃.Temperature is low excessively, and reactive behavior is not enough; Temperature is too high, and decomposition reaction takes place, and cyclization quickens.Vacuum tightness is 0.05～0.2Mpa, and more excellent vacuum tightness is 0.1～0.15Mpa.Reaction times is 10～30 hours, and the more excellent reaction times is 15～25 hours.Adopt the operational path of low temperature high vacuum, middle temperature high vacuum and high temperature high vacuum in the reaction process, progressively heat up and carry out polymerization.Feed rare gas element (as nitrogen) in the reaction process at times, so not only can accelerate reaction process, and can reduce the generation of side reaction.Through polycondensation, can obtain weight-average molecular weight and be 3000～50000 lactic acid prepolymer.
The prepolymer pulverizing that obtains is convenient to feed in raw material at the forcing machine charging opening, and prepolymer is stand-by with the sealing bag encapsulation.
It is not very good that molecular weight is lower than 3000 prepolymer effect.Because in ensuing extrusion, obtain the higher molecular weight poly(lactic acid) will need the long time consequently can not fully carry out at the residence time of forcing machine internal reaction.Therefore, it is unpractiaca using the lower prepolymer of those molecular weight.And such prepolymer melt viscosity is lower, overflows from the vacuumizing and exhausting outlet easily in forcing machine, finally causes venting port to stop up, and has hindered whole process of production.
Extracting lactic acid prepolymer 1g is dissolved in chloroform, adds several 1% phenolphthalein as indicator.KOH-ethanolic soln with 0.05mol/L carries out titration, calculates its hydroxyl value.
Second step of the present invention is carried out chain extension to lactic acid prepolymer on twin screw extruder.
Employed forcing machine is twin screw extruder, engagement type in the same way among the present invention; Adopt a plurality of heating unit zone heating on the machine barrel, the control of each section temperature can independently be carried out by cooling circulating water; A plurality of venting ports can allow gas and volatile component remove; Length-to-diameter ratio was 30～70 (length refers to directly refer to screw diameter by spiro rod length).When using such forcing machine, we can control the temperature in each stage in the reaction process by machine barrel different zones temperature is set effectively, and the by product that reacts each stage simultaneously can be distilled the discharge system under appropriate condition (temperature and vacuum tightness).
Barrel zone temperature is controlled at 100 ℃～200 ℃ usually, is preferably in 115 ℃～180 ℃.Be lower than 100 ℃, then speed of reaction is very low; Be higher than 200 ℃, then polymkeric substance will decompose.If barrel zone temperature is controlled in the above-mentioned scope, is reflected in 10～40 minutes and just can finishes.
Vacuum tightness in the forcing machine usually-25mbar～-200mbar, be preferably in-50～-100mbar.Vacuum tightness is low excessively, and moisture and evaporate into and grade and can not remove can delay normal reaction process.Vacuum tightness is too high, easily poly(lactic acid) is released, and makes venting port stop up.
The rotating speed of extruder screw is to the polycondensation of quickening lactic acid prepolymer and effectively to remove water byproduct also be very important.Consider this, screw speed is set in 5～160rpm usually, is preferably in 10～60rpm.
Employed catalyzer can be with reference to preparation used catalyzer during prepolymer.
Employed chainextender can be polyvalent alcohol, polyprotonic acid or isocyanate ester compound.Polyalcohols can be: tetramethylolmethane, sorbyl alcohol, polyvinyl alcohol, 1,4-butyleneglycol, hexylene glycol etc.; Polynary acids can be: adjacent benzene tetracarboxylic acid, ethylenediamine tetraacetic acid (EDTA), Succinic anhydried, hexanodioic acid, terephthalic acid, m-phthalic acid, propanedioic acid, MALEIC ANHYDRIDE etc.; Isocyanates can be: diphenylmethanediisocyanate (MDI), 2,4 toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), lysinediisocyanate (LDI) etc.Wherein, better with the chainextender effect of isocyanates.
Solid chainextender or catalyzer can with add after prepolymer mixes; The catalyzer of liquid or chainextender can add from another charging opening with peristaltic pump, can use certain amount of solvent, as benzene, toluene, acetone etc.
In extruding the chain extension process, can add certain amount of stabilizer or oxidation inhibitor, as oxidation inhibitor PL-34 (external title: Ultronox626), antioxidant 1010, oxidation inhibitor 168 etc.
Catalyst levels is calculated by weight at 0.001～1 part, is preferably in 0.1～0.5 part.The add-on of chainextender is recently calculated with mole, as MDI, in-NCO and the lactic acid prepolymer-the OH mol ratio is 0～2, more excellent is 0.8～1.2.The add-on of oxidation inhibitor is 0.2～0.8 part.
Discovering of this area, forcing machine have high efficient mixed and shearing action, compare the surfactivity that can significantly improve prepolymer with general batch reactor.The combination that the present invention carries out chain extending reaction by batch reactor and twin screw extruder makes the structure of each reactant and performance reach to optimize in each respective stage of reaction and implements reactions steps, then can produce the poly(lactic acid) of higher molecular weight.The inventor finds, if product poly(lactic acid) straight forming without granulation but under the molten state of extruding then can be eliminated because of the power loss that particle fusion again causes, the performance in the moulding process is damaged and also can be reduced simultaneously.The present invention compares with general method and greatly reduces production cost, but and makes the production serialization.
Embodiment
Below in conjunction with accompanying drawing embodiments of the present invention are further described, the example of being lifted below being to be understood that does not comprise all the elements of the present invention just in order to explain the present invention.
Embodiment 1:
Adding 8kg purity is 88% D in having the 15L batchwise polymerization still of agitator, and L-lactic acid is with Sb
2O
3With ZnO as catalyzer, each adds 0.6wt%, stirs fully.100 ℃ were dewatered 1.5 hours, and then inflated with nitrogen is warming up to 125 ℃, inflated with nitrogen 0.5 hour.Close nitrogen then and vacuumize, vacuum tightness is 0.1Mpa, and 145 ℃ were reacted 3 hours, 155 ℃ were reacted 4 hours, were raised to 165 ℃, 180 ℃ again, at last slowly cooling, total reaction time was sloughed water 2.32kg in 17 hours, obtained the 5.2kg weight-average molecular weight and be 15250 prepolymer.
Get the 1000g prepolymer, add 0.5%SnCl
2With tetramethylolmethane as chainextender, tetramethylolmethane-OH and prepolymer-the COOH mol ratio is 0.4.The three mixed with stirrer join twin screw extruder.Chain extending reaction carries out under nitrogen protection.Forcing machine is twin screw engagement type (long/directly=40, diameter 27mm), and screw rod can be in the same way or incorgruous rotation.Machine barrel comprises 11 districts altogether, and the temperature in each district can be set respectively.
Forcing machine is provided with according to following example:
Feed rate: 1.5kg/h; Screw speed: 10rpm; Vacuum tightness :-50mbar
Barrel zone temperature: 1,2 districts=150 ℃
3-7 district=175 ℃
8,9 districts=150 ℃
10,11 districts=170 ℃
The residence time of poly(lactic acid) is 10min, and the poly(lactic acid) weight-average molecular weight that is obtained is 32040.
Embodiment 2～5:
Get the 1000g performed polymer that obtains in the example 1, add 0.3%SnCl
2Make chainextender with TDI, the mol ratio of change-NCO/-OH.Performed polymer and SnCl
2Earlier with the agitator adding that is mixed, TDI adds with peristaltic pump.
Forcing machine is provided with according to following example:
Feed rate: 1.5kg/h; Screw speed: 20rpm; Vacuum tightness :-50mbar
Barrel zone temperature: 1 district=130 ℃
2 districts=140 ℃
3-7 district=150 ℃
8,9 districts=140 ℃
10,11 districts=150 ℃
The residence time of poly(lactic acid) is 12min, and (Mw) is as follows for weight-average molecular weight:
| -NCO/-OH mol ratio | ????Mw |
| ????0.5 | ????33650 |
| ????0.75 | ????40870 |
| ????1 | ????47260 |
| ????1.2 | ????43280 |
Embodiment 6～8:
Get the 1000g performed polymer that obtains in the example 1, catalyst levels is 0.3%, makes chainextender with MDI ,-NCO/-OH=1.Three's adding that is mixed.
Forcing machine is provided with according to following example:
Feed rate: 1.5kg/h; Screw speed: 10rpm; Vacuum tightness :-75mbar
Barrel zone temperature: 1,2 districts=140 ℃
3-7 district=150 ℃
8,9 districts=140 ℃
10,11 districts=150 ℃
The residence time of poly(lactic acid) is 20min, and (Mw) is as follows for weight-average molecular weight:
| Catalyzer | ????Mw |
| ????SnCl 2 | ????66450 |
| ????Sn(Oct) 2 | ????60560 |
| ????Sn | ????48230 |
Embodiment 9:
Adding 15kg purity is 88% L-lactic acid in having the 15L batchwise polymerization still of agitator, adds the Sn (Oct) of 0.5wt%
2As catalyzer, stir fully.100 ℃ were dewatered 2 hours, and then inflated with nitrogen is warming up to 130 ℃, inflated with nitrogen 0.5 hour.Close nitrogen then and vacuumize, vacuum tightness is 0.1Mpa, and 150 ℃ were reacted 4 hours, 160 ℃ were reacted 4 hours, were raised to 170 ℃, 180 ℃ again, at last slowly cooling, total reaction time was sloughed water 4.3kg in 22 hours, obtained the 9.66kg weight-average molecular weight and be 38400 prepolymer.
Get the 1000g performed polymer, add 0.3% Sn (Oct)
2Make chainextender with TDI ,-NCO/-OH=1.TDI and Sn (Oct)
2Mix after peristaltic pump adds with acetone solution.
Forcing machine is provided with according to following example:
Feed rate: 2kg/h; Screw speed: 20rpm; Vacuum tightness :-100mbar
Barrel zone temperature: 1,2 districts=140 ℃
3-7 district=150 ℃
8,9 districts=140 ℃
10,11 districts=150 ℃
The residence time of poly(lactic acid) is 16min, and weight-average molecular weight is 96080.
Embodiment 10:
Get the 1000g performed polymer that obtains in the example 9, add 0.3%SnCl
2Make chainextender with tetramethylolmethane, the molar ratio of change-NCO/-OH.Tetramethylolmethane-OH and prepolymer-the COOH mol ratio is 0.4.
Forcing machine is provided with according to following example:
Feed rate: 2kg/h; Screw speed: 10rpm; Vacuum tightness :-50mbar
Barrel zone temperature: 1,2 districts=140 ℃
3-7 district=155 ℃
8,9 districts=140 ℃
10,11 districts=150 ℃
The residence time of poly(lactic acid) is 15min, and weight-average molecular weight is 68530.
Embodiment 11～14:
Get the 1000g performed polymer that obtains in the example 9, add 0.3%SnCl
2Make chainextender with MDI, the molar ratio of change-NCO/-OH.
Forcing machine is provided with according to following example:
Feed rate: 2kg/h; Screw speed: 10rpm; Vacuum tightness :-75mbar
Barrel zone temperature: 1 district=140 ℃
2 districts=150 ℃
3-7 district=160 ℃
8,9 districts=150 ℃
10,11 districts=160 ℃
The residence time of poly(lactic acid) is that weight-average molecular weight is as follows about 24min:
| -NCO/-OH mol ratio | ????Mw |
| ????0.5 | ????86540 |
| ????0.75 | ????142500 |
| ????1 | ????173120 |
| ????1.2 | ????162430 |
Embodiment 15:
Get the 1000g performed polymer that obtains in the example 9, add 0.3%SnCl
2, add the 0.5wt%PL-34 used as stabilizers.Make chainextender with MDI ,-NCO/-OH=1.
Forcing machine is provided with according to following example:
Feed rate: 2kg/h; Screw speed: 20rpm; Vacuum tightness :-100mbar
Barrel zone temperature: 1 district=140 ℃
2 districts=150 ℃
3-7 district=165 ℃
8,9 districts=150 ℃
10,11 districts=160 ℃
The residence time of poly(lactic acid) is 18min, and product is faint yellow, and weight-average molecular weight is 182560.
Embodiment 16: simultaneous test
Get the 1000g performed polymer that obtains in the example 9, only add catalyzer and do not add chainextender, the condition that is provided with of forcing machine is the same with embodiment 10, and the poly(lactic acid) weight-average molecular weight that obtains is 48040.
Claims (13)
1. method that on twin screw extruder, prepares polymer reunion lactic acid, form by following two steps:
1) in an intermittent reaction polymeric kettle, it is 3000～50000 lactic acid prepolymer that the lactic acid monomer direct condensation obtains weight-average molecular weight, and the lactic acid prepolymer that obtains is pulverized sealing and preserved;
2) lactic acid prepolymer of above-mentioned gained is carried out chain extension on twin screw extruder, the acquisition weight-average molecular weight is 15000～180000 poly(lactic acid).
2. according to the described method of claim 1, it is characterized in that the purity of lactic acid monomer is not less than 85%.
3. according to the described method of claim 1, it is characterized in that in the batch reactor material acid being dewatered, dehydration temperaturre is 70～150 ℃, and vacuum tightness is 0.05～0.2Mpa, and the time is 0.5～3 hour.
4. according to the described method of claim 1, the temperature that it is characterized in that synthesizing lactic acid oligopolymer in the batch reactor is 90～200 ℃, and vacuum tightness 0.05～0.2Mpa carries out under protection of inert gas, and the polycondensation time is 10～30 hours.
5. method according to claim 1 is characterized in that the water byproduct of polycondensation gained in the batch reactor removes by vacuumizing and exhausting.
6. according to the described method of claim 1～5, adopt the method that progressively heats up to carry out polymerization when it is characterized in that in the batch reactor polycondensation.
7. method according to claim 1 is characterized in that described lactic acid prepolymer is carried out the used chainextender of chain extension on twin screw extruder be polyvalent alcohol, polyprotonic acid, acid anhydrides or isocyanate ester compound.
8. method according to claim 1, it is characterized in that the twin screw extruder that is used for chain extending reaction has a plurality of venting ports, adopt a plurality of heating unit zone heating on the machine barrel, the control of each section temperature can independently be carried out by cooling circulating water, and its spiro rod length is 30～70 with the screw diameter ratio.
9. according to claim 1 or 8 described methods, it is characterized in that reacting and extrude the water byproduct that produces in the chain extension process and vacuumize by exhaust and removed, and solvent is discharged by liquefaction process.
10. according to claim 1 or 8 described methods, it is characterized in that reacting the vacuum tightness of extruding in the chain extension process and be-25～-200mbar.
11., it is characterized in that reaction extrudes that temperature is 100～200 ℃ in the chain extension process according to claim 1 or 8 described methods, carry out segmentation control, the screw rod revolution is 5～160rpm/min.
12., it is characterized in that the reaction times in extruder is that mean residence time is 8～30 minutes according to claim 1 or 8 described methods.
13., it is characterized in that can be equipped with shaped device at extruder head extrudes the poly(lactic acid) straight forming according to claim 1 or 8 described methods.
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| CNB2004100664564A CN100395275C (en) | 2004-09-16 | 2004-09-16 | Method for preparing high-polymer polylactic on Bitruder |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100532453C (en) * | 2006-10-12 | 2009-08-26 | 同济大学 | Plastic foam sheet material of poly lactic acid for vacuum forming , and preparation method |
| CN101374883B (en) * | 2006-01-30 | 2011-06-29 | 株式会社吴羽 | Process for producing aliphatic polyester |
| CN101353417B (en) * | 2007-07-25 | 2011-08-31 | 四川琢新生物材料研究有限公司 | Multistage reaction continuous polymerization unit for synthesizing polylactic acid material with lactides monomer |
| CN101768260B (en) * | 2008-12-31 | 2011-10-26 | 上海同杰良生物材料有限公司 | Modifying method of polylactic acid |
| CN102358778A (en) * | 2011-07-29 | 2012-02-22 | 无锡碧杰生物材料科技有限公司 | Novel biodegradable master batch and preparation method thereof |
| CN101522743B (en) * | 2006-09-29 | 2012-02-22 | 富特罗股份有限公司 | Process for producing polylactide-urethane copolymers |
| CN102924700A (en) * | 2008-09-09 | 2013-02-13 | 莫立克股份有限公司 | Novel polymers with hydroxyl acid blocks |
| CN108676151A (en) * | 2018-06-07 | 2018-10-19 | 浙江臻隆新材料科技有限公司 | A kind of polylactic acid production method |
| CN111454553A (en) * | 2020-05-18 | 2020-07-28 | 长沙乐远化工科技有限公司 | Modified polylactic acid material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5574129A (en) * | 1994-05-10 | 1996-11-12 | The Japan Steel Works, Ltd. | Process for producing lactic acid polymers and a process for the direct production of shaped articles from lactic acid polymers |
| JP4048764B2 (en) * | 2001-01-31 | 2008-02-20 | トヨタ自動車株式会社 | Method for producing lactide using fermented lactic acid as raw material and method for producing polylactic acid |
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2004
- 2004-09-16 CN CNB2004100664564A patent/CN100395275C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101374883B (en) * | 2006-01-30 | 2011-06-29 | 株式会社吴羽 | Process for producing aliphatic polyester |
| CN101522743B (en) * | 2006-09-29 | 2012-02-22 | 富特罗股份有限公司 | Process for producing polylactide-urethane copolymers |
| CN100532453C (en) * | 2006-10-12 | 2009-08-26 | 同济大学 | Plastic foam sheet material of poly lactic acid for vacuum forming , and preparation method |
| CN101353417B (en) * | 2007-07-25 | 2011-08-31 | 四川琢新生物材料研究有限公司 | Multistage reaction continuous polymerization unit for synthesizing polylactic acid material with lactides monomer |
| CN102924700A (en) * | 2008-09-09 | 2013-02-13 | 莫立克股份有限公司 | Novel polymers with hydroxyl acid blocks |
| CN101768260B (en) * | 2008-12-31 | 2011-10-26 | 上海同杰良生物材料有限公司 | Modifying method of polylactic acid |
| CN102358778A (en) * | 2011-07-29 | 2012-02-22 | 无锡碧杰生物材料科技有限公司 | Novel biodegradable master batch and preparation method thereof |
| CN102358778B (en) * | 2011-07-29 | 2014-06-18 | 上海载和实业投资有限公司 | Novel biodegradable master batch and preparation method thereof |
| CN108676151A (en) * | 2018-06-07 | 2018-10-19 | 浙江臻隆新材料科技有限公司 | A kind of polylactic acid production method |
| CN111454553A (en) * | 2020-05-18 | 2020-07-28 | 长沙乐远化工科技有限公司 | Modified polylactic acid material and preparation method thereof |
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