CN102603994A - Glycidyl methacrylate grafted polylactic acid copolymer material, preparation method for same and application thereof - Google Patents
Glycidyl methacrylate grafted polylactic acid copolymer material, preparation method for same and application thereof Download PDFInfo
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- CN102603994A CN102603994A CN2012100626590A CN201210062659A CN102603994A CN 102603994 A CN102603994 A CN 102603994A CN 2012100626590 A CN2012100626590 A CN 2012100626590A CN 201210062659 A CN201210062659 A CN 201210062659A CN 102603994 A CN102603994 A CN 102603994A
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- glycidyl methacrylate
- graft copolymer
- lactic acid
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- methacrylate graft
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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
- B29C48/92—Measuring, controlling or regulating
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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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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a glycidyl methacrylate grafted polylactic acid copolymer material, which is made of, in weight percentage, 93%-97% of polylactic resin, 1%-5% of glycidyl methacrylate and 1%-2% of radical initiator. The glycidyl methacrylate grafted polylactic acid copolymer material can serve as a novel efficient coupling agent to be applied to polyester based composite materials, so that the polyester based composite materials embody excellent performances. The invention further discloses a preparation method for the glycidyl methacrylate grafted polylactic acid copolymer material, which includes the steps: weighing the polylactic resin, the glycidyl methacrylate and the radical initiator according to the weight percentage, and uniformly mixing to serve as mixed materials; and adding the mixed materials into a double-screw extruder for melt extrusion and granulation so as to obtain a granular product. The method has the advantages of high production efficiency, low cost, no solvent pollution, high grafting ratio and the like, is easy in large-scale industrial production and has good economic benefit.
Description
Technical field
The present invention relates to modifying plastics and Composite Preparation field, particularly a kind of glycidyl methacrylate graft copolymer of poly lactic acid material.
Background technology
POLYACTIC ACID is a kind of biodegradable bio-based thermoplasticity aliphatic polyester plastics.POLYACTIC ACID derives from some recuperable natural resourcess such as W-Gum.With respect to other biological base plastics, POLYACTIC ACID has relative higher modulus, intensity, thereby it is widely used in key areas such as biomedicine, packaging industry.
But POLYACTIC ACID also exists some shortcomings, and, poor heat resistance big like fragility, price are high, and these shortcomings have restricted its application in daily life.Usually improve its performance through in POLYACTIC ACID, adding the method that fillers such as wood powder, natural fiber, starch prepare polylactic acid-base composite material, reduce its price.A subject matter that exists in the existing polylactic acid-base composite material is exactly that interface consistency difference causes the polylactic acid-base composite material over-all properties to descend between POLYACTIC ACID matrix and filler.
The method of at present the polylactic acid-base composite material interface performance being improved comprises: stuffing surface modification, POLYACTIC ACID matrix modification, coupling agent modified; Wherein, be a kind of simple, effective means through the method for in the polylactic acid-base composite material course of processing, directly adding coupling agent.
Publication number is that CN1371921A, CN102250359A one Chinese patent application disclose through the synthetic chitin of solution method and the graft copolymer of POLYACTIC ACID or the graft copolymer of starch and POLYACTIC ACID, is used to improve the interface compatibility of chitin or starch filled polylactic acid blend.But being of limited application of these two kinds of graft copolymers, and solution method prepares, and polylactic acid graft copolymer method efficient is low, solvent contamination is big.
Publication number improves the interface binding ability with natural fiber for the CN101200579A one Chinese patent application discloses through to the modification of POLYACTIC ACID matrix grafted maleic anhydride.Though this technical scheme can improve the mechanical property of polylactic acid-base composite material, because the POLYACTIC ACID matrix is carried out modification, destroyed the molecular structure of POLYACTIC ACID itself, and the percentage of grafting of maleic anhydride and reactive behavior can not guarantee all.
Publication number is that CN101333330A, CN101962468A one Chinese patent application disclose the interface compatibility that small molecules coupling agents such as using silane improves the natural fibre reinforced polylactic acid based composites.Though these technical schemes can improve the mechanical property of polylactic acid-base composite material to a certain extent, these coupling agents all do not have to consider and the dependent interaction of POLYACTIC ACID matrix, and the small molecules coupling agent oozes out in material easily, influence the over-all properties of material.
Summary of the invention
The invention provides a kind of glycidyl methacrylate graft copolymer of poly lactic acid material, can be used as a kind of efficient coupling agent and be applied in the polyester based matrix material.
For realizing above purpose, technical scheme of the present invention is following:
A kind of glycidyl methacrylate graft copolymer of poly lactic acid material, process by following raw materials by weight percent:
Polylactic resin 93%～97%;
SY-Monomer G 1%～5%;
Radical initiator 1%～2%.
Better invent effect in order to obtain the present invention, below as of the present invention preferred:
The number-average molecular weight of described polylactic resin is 50,000～300,000.Further preferred, the number-average molecular weight of described polylactic resin is 80,000～120,000.The glycidyl methacrylate graft copolymer of poly lactic acid material of the polylactic resin preparation of this number-average molecular weight can improve the interface compatibility between body material and the filler to a greater degree.Polylactic resin can be selected the commercially available prod for use.
Said SY-Monomer G (GMA) is a colourless transparent liquid, relative molecular weight 142.15, and 189 ℃ of boiling points, specific density 1.073,76 ℃ of flash-points are selected the commercially available prod for use.
Described radical initiator is peroxidized t-butyl perbenzoate (TBPB), selects for use this peroxidized t-butyl perbenzoate as radical initiator, can efficiently, stably cause the reaction of polylactic resin and SY-Monomer G.
The present invention also provides a kind of glycidyl methacrylate graft copolymer of poly lactic acid preparation methods, and preparation is simple, and production efficiency is high.
Described glycidyl methacrylate graft copolymer of poly lactic acid preparation methods may further comprise the steps:
Take by weighing polylactic resin, SY-Monomer G and radical initiator by weight percentage, mix, as mixture; Mixture added in the twin screw extruder melt extrude, granulation obtains glycidyl methacrylate graft copolymer of poly lactic acid material.
Described glycidyl methacrylate graft copolymer of poly lactic acid material mainly comprises the glycidyl methacrylate graft copolymer of poly lactic acid, also comprises a spot of SY-Monomer G monomer, radical initiator, SY-Monomer G homopolymer etc.
The oxirane value of described glycidyl methacrylate graft copolymer of poly lactic acid is 0.05mol/100g～0.2mol/100g; Under this oxirane value; Glycidyl methacrylate graft copolymer of poly lactic acid material is applied in the polyester based matrix material as a kind of efficient coupling agent, makes the polyester based matrix material have better interface compatibility.
The temperature of described mixture each section in said twin screw extruder is respectively: 165 ℃～175 ℃ of feeding section temperature, 175 ℃～185 ℃ of compression section temperature, 180 ℃～185 ℃ of metering zone temperature, 185 ℃～195 ℃ of head temperatures.The rotating speed of described twin screw extruder is 300 rev/mins～400 rev/mins.Under these conditions, on the one hand, help large-scale industrialization production, on the other hand, help preparing the glycidyl methacrylate graft copolymer of poly lactic acid, percentage of grafting is high.
In this preparation method; Polylactic resin, SY-Monomer G and radical initiator three obtain glycidyl methacrylate graft copolymer of poly lactic acid material after the twin screw extruder reaction; Use in the polyester based matrix material as coupling agent, make this polyester based matrix material embody excellent properties.
Among this preparation method, the reaction that relates generally to is following:
Wherein, n is 700～4000 integer; M is 10～100 integer.
The glycidyl methacrylate graft copolymer of poly lactic acid material of described preparing method's preparation can be widely used in field of high polymer material processing; Be particularly suitable for the application in preparation polyester based matrix material, can be used as efficient coupling agent and be applied in the polyester based field of compound material.Have polyester segment and epoxide group simultaneously on the glycidyl methacrylate graft copolymer of poly lactic acid molecular chain of preparing method's preparation of the present invention; It can be used as coupling agent; Can effectively improve the interface compatibility between the body material and filler in the polyester based matrix material, improve the mechanical property of polyester based matrix material.
A kind of polyester based matrix material, form by following components in weight percentage:
POLYACTIC ACID 50%～89%;
Bamboo powder 10%～40%;
Described glycidyl methacrylate graft copolymer of poly lactic acid material 1%～10%.
The number-average molecular weight of described POLYACTIC ACID is preferably 50,000～300,000.
Compared with prior art, the present invention has following advantage:
Glycidyl methacrylate graft copolymer of poly lactic acid material of the present invention; Adopt polylactic resin, SY-Monomer G and three kinds of material prepns of radical initiator; Can be used as a kind of novel efficient coupling agent; Be applied in the polyester based matrix material, make the polyester based matrix material embody excellent properties, have very wide application prospect.
Glycidyl methacrylate graft copolymer of poly lactic acid preparation methods of the present invention has production efficiency height, low, the solvent-free pollution of cost, percentage of grafting advantages of higher, is easy to large-scale industrialization production, has favorable economic benefit.
Description of drawings
Fig. 1 is the infrared spectrogram of the glycidyl methacrylate graft copolymer of poly lactic acid among the embodiment 1.
Embodiment
Among the present invention, the performance test of gained sample is carried out as follows:
1, the purification of glycidyl methacrylate graft copolymer of poly lactic acid:
Take by weighing and extrude back particulate product 1g,, sample is placed round-bottomed flask, add the stirring of 100ml chloroform and make sample dissolution, the chloroformic solution that is dissolved with sample is poured in the 200ml ethanol, sample is separated out as sample.Above step repeats 3 times to remove remaining monomer, initiator, SY-Monomer G homopolymer.At last, the sample of purifying 75 ℃ of drying for standby in vacuum drying oven.
2, molecular weight and molecular weight distribution determination:
Getting the good sample 10mg of purifying, is solvent with the chloroform, is configured to 5mg/ml solution.Adopt waters-1515 type gel chromatograph to measure molecular weight and MWD, moving phase is chloroform, and velocity of flow is 0.8ml/min, and column temperature is 20 ℃.
3, oxirane value is measured:
Adopt hydrochloric acid-pyridine method test sample article oxirane value.Take by weighing sample 0.5～1.0g behind the purifying, place the 250ml Erlenmeyer flask, accurately insert 20ml pyridine hydrochloride solution, place 128 ℃ of oil bath pan reflux 20min to make the sample dissolution reaction.After cooling, add 4～5 of phenolphthalein indicators, with the standard solution of sodium hydroxide titration extremely pink (when being acid number) of 0.2mol/L.Blank test is done in same operation.Following formula ring oxygen value (X):
In the formula: V
0The milliliter number (ml) of the standard solution of sodium hydroxide that-blank test consumes;
V
1The milliliter number (ml) of the standard solution of sodium hydroxide that-sample consumes;
V
2The milliliter number (ml) of the standard solution of sodium hydroxide that-sample consumes when measuring acid number;
The volumetric molar concentration of C-standard solution of sodium hydroxide (mol/L);
m
1The quality of-sample (g);
m
2Quality (g) when-sample is measured acid number;
4, infrared spectrogram:
With the sample of purifying with the methylene dichloride dissolving after; Adopt the coating method sample preparation; Carrying out infrared spectrogram characterizes; Fig. 1 is the infrared spectrogram of the glycidyl methacrylate graft copolymer of poly lactic acid among the embodiment 1, and the infrared spectrogram of glycidyl methacrylate graft copolymer of poly lactic acid is consistent with embodiment 1 among the embodiment 2～5.
Understand for technical problem, the embodiment that will solve the present invention are had more clearly,, the present invention is further elaborated below in conjunction with embodiment.
Embodiment 1
(number-average molecular weight is 100,000, Natureworks4032D, LD mixed type POLYACTIC ACID to take by weighing polylactic resin by weight percentage; The L type is 97%, and the D type is 3%) 96.0%, SY-Monomer G 3.0%; Peroxidized t-butyl perbenzoate 1.0% is as mixture; Mixture added in the twin screw extruder melt extrude, granulation obtains particulate product (being glycidyl methacrylate graft copolymer of poly lactic acid material).Wherein, mixture temperature of each section in twin screw extruder is respectively: 165 ℃ of feeding section temperature, and 175 ℃ of compression section temperature, 180 ℃ of metering zone temperature, 185 ℃ of head temperatures, the rotating speed of twin screw extruder are 300 rev/mins.Sample molecule amount, MWD and oxirane value are seen table 1.
Embodiment 2
(number-average molecular weight is 100,000, Natureworks4032D, LD mixed type POLYACTIC ACID to take by weighing polylactic resin by weight percentage; The L type is 97%, and the D type is 3%) 94.0%, SY-Monomer G 5.0%; Peroxidized t-butyl perbenzoate 1.0% is after mixing, as mixture; Mixture added in the twin screw extruder melt extrude, granulation obtains particulate product (being glycidyl methacrylate graft copolymer of poly lactic acid material).Wherein, mixture temperature of each section in twin screw extruder is respectively: 165 ℃ of feeding section temperature, and 175 ℃ of compression section temperature, 180 ℃ of metering zone temperature, 185 ℃ of head temperatures, twin screw extruder rotating speed are 300 rev/mins.Sample molecule amount, MWD and oxirane value are seen table 1.
Embodiment 3
(number-average molecular weight is 100,000, Natureworks4032D, LD mixed type POLYACTIC ACID to take by weighing polylactic resin by weight percentage; The L type is 97%, and the D type is 3%) 95.0%, SY-Monomer G 3.0%; Peroxidized t-butyl perbenzoate 2.0% is after mixing, as mixture; Mixture added in the twin screw extruder melt extrude, granulation obtains particulate product (being glycidyl methacrylate graft copolymer of poly lactic acid material).Wherein, mixture temperature of each section in twin screw extruder is respectively: 165 ℃ of feeding section temperature, and 175 ℃ of compression section temperature, 180 ℃ of metering zone temperature, 185 ℃ of head temperatures, twin screw extruder rotating speed are 300 rev/mins.Sample molecule amount, MWD and oxirane value are seen table 1.
Embodiment 4
(number-average molecular weight is 100,000, Natureworks4032D, LD mixed type POLYACTIC ACID to take by weighing polylactic resin by weight percentage; The L type is 97%, and the D type is 3%) 96.0%, SY-Monomer G 3.0%; Peroxidized t-butyl perbenzoate 1.0% is after mixing, as mixture; Mixture added in the twin screw extruder melt extrude, granulation obtains particulate product (being glycidyl methacrylate graft copolymer of poly lactic acid material).Wherein, mixture temperature of each section in twin screw extruder is respectively: 175 ℃ of feeding section temperature, and 185 ℃ of compression section temperature, 185 ℃ of metering zone temperature, 195 ℃ of head temperatures, twin screw extruder rotating speed are 300 rev/mins.Sample molecule amount, MWD and oxirane value are seen table 1.
Embodiment 5
(number-average molecular weight is 100,000, Natureworks4032D, LD mixed type POLYACTIC ACID to take by weighing polylactic resin by weight percentage; The L type is 97%, and the D type is 3%) 96.0%, SY-Monomer G 3.0%; Peroxidized t-butyl perbenzoate 1.0% is after mixing, as mixture; Mixture added in the twin screw extruder melt extrude, granulation obtains particulate product (being glycidyl methacrylate graft copolymer of poly lactic acid material).Wherein, mixture temperature of each section in twin screw extruder is respectively: 165 ℃ of feeding section temperature, and 175 ℃ of compression section temperature, 180 ℃ of metering zone temperature, 185 ℃ of head temperatures, twin screw extruder rotating speed are 400 rev/mins.Sample molecule amount, MWD and oxirane value are seen table 1.
Table 1
| Sample performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Molecular weight Mn | ?68000 | ?68500 | ?69200 | ?66400 | ?71400 |
| Mw/Mn | ?2.52 | ?2.63 | ?2.73 | ?2.66 | ?2.35 |
| Oxirane value mol/100g | ?0.11 | ?0.13 | ?0.16 | ?0.13 | ?0.08 |
Application examples
(number-average molecular weight is 100,000, Natureworks 4032D, LD mixed type POLYACTIC ACID with 20g bamboo powder, 80g POLYACTIC ACID; The L type is 97%, and the D type is 3%) and add and to extrude preparation bamboo powder as glycidyl methacrylate graft copolymer of poly lactic acid material blend in twin screw extruder of coupling agent and strengthen lactic acid composite material (belong in the polyester based matrix material a kind of), directly; Wherein, The temperature of each section is respectively in twin screw extruder: 180 ℃ of feeding section temperature, 185 ℃ of compression section temperature, 190 ℃ of metering zone temperature; 195 ℃ of head temperatures; The twin screw extruder rotating speed is 300 rev/mins, improves interface compatibility, presses GB/T9341-2000 after the injection moulding and detects composite materials property.
Comparative Examples 1 does not add glycidyl methacrylate graft copolymer of poly lactic acid material;
Application examples 1 adds the glycidyl methacrylate graft copolymer of poly lactic acid material of 1g embodiment 1 preparation;
Application examples 2 adds the glycidyl methacrylate graft copolymer of poly lactic acid material of 2g embodiment 1 preparation;
Application examples 3 adds the glycidyl methacrylate graft copolymer of poly lactic acid material of 5g embodiment 1 preparation;
Application examples 4 adds the glycidyl methacrylate graft copolymer of poly lactic acid material of 10g embodiment 1 preparation;
Application examples 5 adds the glycidyl methacrylate graft copolymer of poly lactic acid material of 2g embodiment 3 preparations;
Comparative Examples 2 adds 2g small molecules coupling agent diphenylmethanediisocyanate (MDI); Press GB/T9341-2000 and detect composite materials property, its concrete outcome is as shown in table 2.
Table 2
Claims (10)
1. glycidyl methacrylate graft copolymer of poly lactic acid material, process by following raw materials by weight percent:
Polylactic resin 93%～97%;
SY-Monomer G 1%～5%;
Radical initiator 1%～2%.
2. glycidyl methacrylate graft copolymer of poly lactic acid material as claimed in claim 1 is characterized in that the number-average molecular weight of described polylactic resin is 50,000～300,000.
3. glycidyl methacrylate graft copolymer of poly lactic acid material as claimed in claim 2 is characterized in that the number-average molecular weight of described polylactic resin is 80,000～120,000.
4. glycidyl methacrylate graft copolymer of poly lactic acid material as claimed in claim 1 is characterized in that described radical initiator is a peroxidized t-butyl perbenzoate.
5. one kind as according to each described glycidyl methacrylate graft copolymer of poly lactic acid preparation methods of claim 1～4, it is characterized in that, may further comprise the steps:
Take by weighing polylactic resin, SY-Monomer G and radical initiator by weight percentage, mix, as mixture; Mixture added in the twin screw extruder melt extrude, granulation obtains glycidyl methacrylate graft copolymer of poly lactic acid material.
6. glycidyl methacrylate graft copolymer of poly lactic acid preparation methods as claimed in claim 5; It is characterized in that; The temperature of described mixture each section in said twin screw extruder is respectively: 165 ℃～175 ℃ of feeding section temperature; 175 ℃～185 ℃ of compression section temperature, 180 ℃～185 ℃ of metering zone temperature, 185 ℃～195 ℃ of head temperatures.
7. glycidyl methacrylate graft copolymer of poly lactic acid preparation methods as claimed in claim 5 is characterized in that, the rotating speed of described twin screw extruder is 300 rev/mins～400 rev/mins.
8. the application of glycidyl methacrylate graft copolymer of poly lactic acid material in preparation polyester based matrix material for preparing like each described preparation method of claim 5～7.
9. a polyester based matrix material is characterized in that, is made up of following components in weight percentage:
POLYACTIC ACID 50%～89%;
Bamboo powder 10%～40%;
Glycidyl methacrylate graft copolymer of poly lactic acid material 1%～10%;
Described glycidyl methacrylate graft copolymer of poly lactic acid material adopts like each described preparing method's preparation of claim 5～7.
10. polyester based matrix material as claimed in claim 9 is characterized in that, the number-average molecular weight of described POLYACTIC ACID is 50,000～300,000.
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| CN113801447A (en) * | 2021-09-29 | 2021-12-17 | 广西大学 | Preparation method of toughened and reinforced polylactic acid composite material |
| CN114395228A (en) * | 2021-12-09 | 2022-04-26 | 楷模居品（江苏）有限公司 | Antibacterial functionalized montmorillonite modified polylactic acid wood-plastic material and preparation method thereof |
| WO2023092548A1 (en) * | 2021-11-26 | 2023-06-01 | 安徽江南医疗器械股份有限公司 | Preparation method for disposable infusion hose capable of being completely biodegraded |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020780A (en) * | 2007-03-15 | 2007-08-22 | 上海交通大学 | Prepn process of polylactic acid-base thermoplastic wood-plastic composite material |
| CN101747443A (en) * | 2010-01-20 | 2010-06-23 | 华东理工大学 | Macromolecular coupling agent for bacterial cellulose surface modification as well as preparation method and application thereof |
-
2012
- 2012-03-09 CN CN201210062659.0A patent/CN102603994B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020780A (en) * | 2007-03-15 | 2007-08-22 | 上海交通大学 | Prepn process of polylactic acid-base thermoplastic wood-plastic composite material |
| CN101747443A (en) * | 2010-01-20 | 2010-06-23 | 华东理工大学 | Macromolecular coupling agent for bacterial cellulose surface modification as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 赖广兴: "聚乳酸的改性及其在聚乳酸/淀粉共混物中的应用", 《中国优秀硕士学位论文全文数据库工程科技I辑》, no. 2, 15 February 2012 (2012-02-15), pages 016 - 128 * |
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