CN102391628B - Polylactic acid/ polyamide 11 alloy material - Google Patents
Polylactic acid/ polyamide 11 alloy material Download PDFInfo
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- CN102391628B CN102391628B CN 201110287355 CN201110287355A CN102391628B CN 102391628 B CN102391628 B CN 102391628B CN 201110287355 CN201110287355 CN 201110287355 CN 201110287355 A CN201110287355 A CN 201110287355A CN 102391628 B CN102391628 B CN 102391628B
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- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical group [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a polylactic acid/polyamide 11 alloy material. The polylactic acid/polyamide 11 alloy material is mainly prepared by melting and blending polylactic acid, polyamide 11, and a third component by using melting and mixing equipment; based on the mass of the polylactic acid and the polyamide 11, the polylactic acid is 5 to 95 mass percent, and the polyamide 11 is 5 to 95 mass percent; and the third component is 0 to 15 percent based on the total mass of the polylactic acid and the polyamide 11, wherein 0 infinitely approaches 0 but is not 0; and the third component is an elastomer containing an epoxide group. The polylactic acid/polyamide 11 alloy material is high in hardness, modulus and tensile strength, the impact resistance is greatly improved and the polylactic acid/polyamide 11 alloy material meets the performance using requirements of a structural material.
Description
Technical field
The present invention relates to Polymer Technology and ecological environment material nd field, relate in particular to the polylactic acid/polyamide 11 alloy material in a kind of high-performance full biomass source and preparation method thereof.
Background technology
Resources and environment is the great major issue of facing mankind.The tradition macromolecular material derives from non-renewable petrochemical industry resource, and before non-renewable petroleum resources dry spells arrived, macromolecular material reproducible, that particularly derive from biomass had caused global concern.In the past in 10 years, poly-lactic acid material is subject to the broad interest of industry member, and reason comprises: the one, and the poly(lactic acid) raw materials for production come from plant, do not rely on oil, before non-renewable petroleum resources dry spells arrived, reproducible product will become the well sold and in short supply product of global range.The 2nd, under certain condition can biological degradation after poly(lactic acid) is used, do not produce white pollution, this is particularly important for wrapping material.The 3rd, poly(lactic acid) belongs to a kind of less energy-consumption product, than the low 30%-50% energy consumption of the polymkeric substance take petroleum products as raw material production.The 4th, the CO2 emissions in the production of poly(lactic acid), processing and the consumption last handling process is also than general polymer material low about 20%.Therefore, the widespread use of poly-lactic acid products not only has great significance for reducing human dependence to limited resources such as oil and building low-carbon (LC) society, and can reduce white pollution, alleviates the environmental problem of facing mankind.Yet the toughness of poly(lactic acid) itself is not enough, erosion-resisting characteristics is poor, and this has greatly limited the widespread adoption of poly-lactic acid material.
Center on the toughness reinforcing of poly(lactic acid), both at home and abroad existing numerous patent documentations.Patent CN101955639A discloses a kind of method of utilizing the polyurethane elastomer plasticizing polylactic acid, and CN101168617 and CN101935390A then use aliphatic polyester to improve the shock resistance of poly(lactic acid) as toughner.JP 2007-63435 discloses a kind of method of using the polyethylene elastomer plasticizing polylactic acid.Yet none other rubber that all uses of all these documents improves the toughness of poly(lactic acid) as toughner, and for reaching preferably toughening effect, rubber content is usually greater than 15%.Although the adding of rubber has improved the toughness of material, reduced inevitably modulus and the intensity of material, in addition, it is synthetic that used rubber all derives from petrochemical material.How when improving poly(lactic acid) impelling strength, excessively do not reduce its intensity is a major issue of poly-lactic acid material modification always.The macromolecular material for preparing simultaneously full biomass source and excellent performance also is the important directions of high score Materials.
（Fen Mo/Ke Li） Nylon11 in powder/granular form is a kind of engineering plastics of excellent performance, has excellent shock resistance, higher modulus and tensile strength, good oil resistant solvent resistance.Particularly importantly, the synthesis material of （Fen Mo/Ke Li） Nylon11 in powder/granular form is Viscotrol C, also is a kind of macromolecular material that comes from completely biomass.In view of the complementarity on poly(lactic acid) and the （Fen Mo/Ke Li） Nylon11 in powder/granular form physical and mechanical property and the recyclability of raw material, the alloy material of preparation poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form has important using value.(polymer 2011 for non-patent literature, 52,1417-1425) poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form are carried out the high molecule alloy material that melt blending prepares the full biomass source, yet because poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form lack consistency, preparation material phase region size is large, bonding interface is poor, thereby the material mechanical mechanical property is not improved.
The present invention is by adding the 3rd a small amount of component in poly(lactic acid) and blend of nylon, working method by reasonable adjusting alloy material, the microtexture of controlled material, the processability mechanical strength is high, the full biomass poly(lactic acid) of tenacity excellent/（Fen Mo/Ke Li） Nylon11 in powder/granular form alloy, is expected to use in electronics, building materials, automobile and other industries.
Summary of the invention
The technical problem of solution required for the present invention is to improve two kinds of consistencies that come from biomass macromolecular material (being poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form), prepares the polylactic acid/polyamide 11 alloy material of physical and mechanical property excellence.The invention provides a kind of polymer alloy material based on poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form and preparation method thereof.The alloy material modulus of inventing and mechanical strength are high, excellent shock resistance, are expected to obtain to use in electronics, building materials, automobile and other industries.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of polylactic acid/polyamide 11 alloy material, described polylactic acid/polyamide 11 alloy material mainly carries out melt blending by poly(lactic acid), （Fen Mo/Ke Li） Nylon11 in powder/granular form and the 3rd component through melting mixing equipment and obtains, based on described poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form, the massfraction of poly(lactic acid) is 5-95%, the massfraction of （Fen Mo/Ke Li） Nylon11 in powder/granular form is 5-95%, the quality of described the 3rd component be poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form total mass 0～15%, preferred 3-9%, 0 expression wherein is infinitely close to 0 but be not 0; Described the 3rd component is the elastomerics that contains epoxide group, is the elastomerics that can react under mixing condition with poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form.
Here polylactic acid/polyamide 11 alloy material is mainly prepared by poly(lactic acid), （Fen Mo/Ke Li） Nylon11 in powder/granular form and the 3rd component, the connotation of " mainly " is that the requisite main composition of polylactic acid/polyamide 11 alloy material has these three kinds, only have these three kinds of compositions passable, but allowing also to contain in the polylactic acid/polyamide 11 alloy material some does not have influential additive to major function yet yet.
The present invention also can not doping, described polylactic acid/polyamide 11 alloy material carries out melt blending by poly(lactic acid), （Fen Mo/Ke Li） Nylon11 in powder/granular form and the 3rd component through melting mixing equipment and obtains, based on described poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form, the massfraction of poly(lactic acid) is 5-95%, the massfraction of （Fen Mo/Ke Li） Nylon11 in powder/granular form is 5-95%, the quality of described the 3rd component be poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form total mass 0～15%, 0 expression wherein is infinitely close to 0 but be not 0.
In the described polylactic acid/polyamide 11 alloy material of the present invention, based on described poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form, the massfraction of poly(lactic acid) is 5-95%, and the massfraction of （Fen Mo/Ke Li） Nylon11 in powder/granular form is 5-95%, the massfraction of preferred poly(lactic acid) is 30-80%, and the massfraction of nylon is 20-70%.
Further, it is one of following that described the 3rd component is preferably: polyethylene-glycidyl methacrylate graft polystyrene-propylene is fine, polyethylene-glycidyl methacrylate copolymer, glycidyl methacrylate graft polyethylene, glycidyl methacrylate graft polypropylene, glycidyl methacrylate graft ethene-1-octene copolymer, glycidyl methacrylate graft ethylene-vinyl acetate copolymer.
The effect of the 3rd component of the present invention is to improve two alternate bonding interfaces, realizes the mutual supplement with each other's advantages of poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form performance, and preparation intensity is high, the alloy material of good toughness.
Further, polylactic acid/polyamide 11 alloy material of the present invention can obtain by one of following two kinds of methods:
(1) polylactic acid/polyamide 11 alloy material is after being mixed by poly(lactic acid), （Fen Mo/Ke Li） Nylon11 in powder/granular form and the 3rd component, adds together that melt blending obtains in the melting mixing equipment.
(2) polylactic acid/polyamide 11 alloy material by poly(lactic acid) with add first melt blending in the melting mixing equipment after the 3rd component mixes, mixes with （Fen Mo/Ke Li） Nylon11 in powder/granular form after again the blend that obtains being pulverized and adds afterwards that melt blending obtains in the melting mixing equipment.
The preparation method's of above-mentioned bi-material difference is the difference of raw material order by merging, and if （Fen Mo/Ke Li） Nylon11 in powder/granular form and the 3rd component are carried out first melt blending, carry out melting mixing with poly(lactic acid) again, the resulting materials poor performance does not have any improved performance.
Polylactic acid/polyamide 11 alloy material of the present invention can also add various additives, and described polylactic acid/polyamide 11 alloy material can obtain by one of following two kinds of methods:
1. after polylactic acid/polyamide 11 alloy material is mixed by poly(lactic acid), （Fen Mo/Ke Li） Nylon11 in powder/granular form, the 3rd component and additive, adding together melting mixing equipment carries out melt blending and obtains, described additive is pigment, softening agent or toughener or their arbitrary combination, the quality of described additive is the 0-40% of the total mass of poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form, and 0 expression wherein is infinitely close to 0 but be not 0.
2. polylactic acid/polyamide 11 alloy material adds first melt blending in the melting mixing equipment after being mixed by poly(lactic acid) and the 3rd component, after again the pellet that obtains being pulverized and after （Fen Mo/Ke Li） Nylon11 in powder/granular form and additive mix, adding melting mixing equipment carries out melt blending and obtains, described additive is pigment, softening agent or toughener or their arbitrary combination, the quality of described additive is the 0-40% of the total mass of poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form, and 0 expression wherein is infinitely close to 0 but be not 0.
In the additive of the present invention, the pigment of often selecting such as carbon black, white carbon black; The softening agent of often selecting such as polyoxyethylene glycol, dioctyl phthalate (DOP), polypropylene etc.; The toughener of often selecting such as clay, layered silicate, cage modle siloxanes.
Additive of the present invention is one of following or their arbitrary combination more preferably: layered silicate, carbon black, white carbon black, clay or cage modle siloxanes.
Melting mixing equipment of the present invention can be the various industrial melting mixing devices commonly used such as Banbury mixer, single screw extrusion machine, twin screw extruder or injector, its use-pattern as well known to those skilled in the art.When melting mixing, the smelting temperature of equipment is set in more than the melt temperature of all raw materials usually, keep the molten state of all raw materials to get final product, but smelting temperature should be lower than the thermal degradation temperature (being generally 300 ℃) of poly(lactic acid), those skilled in the art should set suitable smelting temperature according to the melting temperature of raw material.
Polylactic acid/polyamide 11 alloy material provided by the invention can by various forming technologies (such as extrusion moulding, injection molding, blow molding or calendering formation etc.) preparation alloy product, comprise film, pipe, rod, fiber yarn, plastic components etc.Goods not only can be used as wrapping material, building material, and can be used as the fields such as building materials, electronics, appliance material.
The invention has the advantages that: 1) used poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form main raw material all come authigenic material, thereby the petrochemical industry Resource Dependence degree of preparation alloy is low, is environment-friendly material.2) large, the modulus of preparation alloy material hardness and tensile strength is large, shock resistance significantly improves satisfies the performance service requirements of structured material.3) preparation only need be used melting mixing equipment commonly used, and the industry preparation is simple.
Polylactic acid/polyamide 11 alloy material provided by the invention has significantly improved the impelling strength mechanical mechanics property of poly-lactic acid material in the hardness and intensity that keep poly-lactic acid material.
Description of drawings
The stress-strain curve of different content EGMA-g-SAN in Fig. 1 poly(lactic acid)/（Fen Mo/Ke Li） Nylon11 in powder/granular form=55/45 blend (the mixing preparation material of single stage method).
The stereoscan photograph of different content EGMA-g-SAN in Fig. 2 poly(lactic acid)/（Fen Mo/Ke Li） Nylon11 in powder/granular form=55/45 blend (the mixing preparation material of single stage method).(a) EGMA-g-SAN content is 0% of PLLA and （Fen Mo/Ke Li） Nylon11 in powder/granular form total mass among the figure; (b) EGMA-g-SAN content is 3% of PLLA and （Fen Mo/Ke Li） Nylon11 in powder/granular form total mass; (c) EGMA-g-SAN content is 6% of PLLA and （Fen Mo/Ke Li） Nylon11 in powder/granular form total mass; (d) EGMA-g-SAN content is 9% of PLLA and （Fen Mo/Ke Li） Nylon11 in powder/granular form total mass.
The stress-strain curve of poly(lactic acid)/（Fen Mo/Ke Li） Nylon11 in powder/granular form under Fig. 3 different blended smelting method=55/45 alloy material (EGMA-g-SAN content be PLLA and （Fen Mo/Ke Li） Nylon11 in powder/granular form total mass 6%).
The stereoscan photograph of poly(lactic acid)/（Fen Mo/Ke Li） Nylon11 in powder/granular form under Fig. 4 different blended smelting method=55/45 material (EGMA-g-SAN content be PLLA and （Fen Mo/Ke Li） Nylon11 in powder/granular form total mass 6%).(a) single stage method while mixing (embodiment 7) among the figure; (b) （Fen Mo/Ke Li） Nylon11 in powder/granular form and EGMA-g-SAN go ahead of the rest mixing after and poly(lactic acid) mixing (embodiment 13); (c) poly(lactic acid) and EGMA-g-SAN go ahead of the rest mixing after and （Fen Mo/Ke Li） Nylon11 in powder/granular form mixing (Comparative Examples 2).
Embodiment
In order further to understand the present invention, the present invention is described further below in conjunction with embodiment, but protection scope of the present invention is not limited in this.
Used poly-lactic acid material is that Japanese UNITIKA company produces in the embodiment of the invention, and trade names are TP4000, and its number-average molecular weight is 108000, and molecular weight distribution is 4.14,60.5 ℃ of second-order transition temperatures (DSC nitrogen atmosphere 10K/min heat up mensuration).
Used （Fen Mo/Ke Li） Nylon11 in powder/granular form is that French Arkema company produces in the embodiment of the invention, and commodity are called Rilsan.
All elastomericss are EGMA-g-SAN (polyethylene-glycidyl methacrylate graft polystyrene-propylene is fine) in the embodiment of the invention, are produced by Nof Corp., and commodity are called Modiper A4400.The EGMA mass content is that the mass content of glycidyl methacrylate among 70%, the EGMA is 15% in the graftomer.
Resulting materials tension test of the present invention is that 25 ℃, relative humidity are to carry out in 50% the environment in temperature, uses the dumbbell shape sample, tests by ASTM D412-80 method, and tensile testing machine is Tensilon UMT-300, and draw speed is 10mm/min.
The film shock test is tested by the standard of JIS K7160 under same envrionment conditions.
Embodiment 1-12
Poly(lactic acid) (PLA), （Fen Mo/Ke Li） Nylon11 in powder/granular form (PA11) and elastomerics (EGMA-g-SAN) are respectively in 80 ℃ of vacuum drying ovens after dry 24 hours, PLA/ （Fen Mo/Ke Li） Nylon11 in powder/granular form and elastomerics take by weighing sample by table 1 quality proportioning, add in the Banbury mixer behind the mix and blend under the room temperature, the Banbury mixer temperature is 200 ℃, the setting screw speed is 100rpm, banburying discharging after 5 minutes.
Above-mentioned mixing sample is hot pressed into the sheet that thickness is 1mm in 210 ℃ thermocompressor, carries out performance test with standard dumbbell shape punching press cutter preparation standard test batten, the result is as shown in table 1.
Comparative Examples 1
Poly(lactic acid) is added in the Banbury mixer, and the Banbury mixer temperature is 200 ℃, and the setting screw speed is 100rpm, banburying discharging after 5 minutes.
Above-mentioned mixing sample is hot pressed into the sheet that thickness is 1mm in 210 ℃ thermocompressor, carries out performance test with standard dumbbell shape punching press cutter preparation standard test batten, the result is as shown in table 1.
As can be seen from Table 1, used elastomerics (EGMA-g-SAN) has significantly improved shock resistance and the elongation at break of polylactic acid/polyamide 11 alloy material.
Embodiment 13
Poly(lactic acid) (PLA), （Fen Mo/Ke Li） Nylon11 in powder/granular form (PA11) and elastomerics (EGMA-g-SAN) are respectively in 80 ℃ of vacuum drying ovens after dry 24 hours, quantitative PLA and EGMA-g-SAN are at first mixed rear adding Banbury mixer, the Banbury mixer temperature is 200 ℃, the setting screw speed is 100rpm, banburying discharging after 5 minutes.This sample is pulverized rear and quantitative （Fen Mo/Ke Li） Nylon11 in powder/granular form mix, add Banbury mixer, the Banbury mixer temperature is 200 ℃, and the setting screw speed is 100rpm, banburying discharging after 5 minutes.The mass ratio of used three kinds of raw materials is PLA/ （Fen Mo/Ke Li） Nylon11 in powder/granular form=55g/45g, and EGMA-g-SAN is 6% of PLA and （Fen Mo/Ke Li） Nylon11 in powder/granular form total mass.
Above-mentioned mixing sample is hot pressed into the sheet that thickness is 1mm in 210 ℃ thermocompressor, carries out performance test with standard dumbbell shape punching press cutter preparation standard test batten, acquired results sees Table 2.
Comparative example 2
Poly(lactic acid) (PLA), （Fen Mo/Ke Li） Nylon11 in powder/granular form (PA11) and elastomerics (EGMA-g-SAN) are respectively in 80 ℃ of vacuum drying ovens after dry 24 hours, quantitative （Fen Mo/Ke Li） Nylon11 in powder/granular form and EGMA-g-SAN are at first mixed rear adding Banbury mixer, the Banbury mixer temperature is 200 ℃, the setting screw speed is 100rpm, banburying discharging after 5 minutes.With mixing with quantitative poly(lactic acid) after this sample pulverizing, add Banbury mixer, the Banbury mixer temperature is 200 ℃, the setting screw speed is 100rpm, banburying discharging after 5 minutes.The mass ratio of used three kinds of raw materials is PLA/ （Fen Mo/Ke Li） Nylon11 in powder/granular form=55g/45g, and EGMA-g-SAN is 6% of PLA and （Fen Mo/Ke Li） Nylon11 in powder/granular form total mass.
Above-mentioned mixing sample is hot pressed into the sheet that thickness is 1mm in 210 ℃ thermocompressor, carries out performance test with standard dumbbell shape punching press cutter preparation standard test batten, acquired results sees Table 2.
From embodiment 7 and 13 and Comparative Examples 2 can find out that material forms in the identical situation, the preparation method of alloy material is remarkable to the performance impact of material.Mixing middle the 3rd component is mixed with poly(lactic acid) in advance in two steps, again with the best performance of the mixing resulting materials of nylon, next is the simultaneously materials of one-step melting gained of three components, and the 3rd component is mixed with nylon in advance, and is the poorest with the mixing resulting materials performance of poly(lactic acid) again.
The performance (single stage method is mixing) of table 1 poly(lactic acid) (PLA)/（Fen Mo/Ke Li） Nylon11 in powder/granular form (PA11) alloy material
The performance of poly(lactic acid)/（Fen Mo/Ke Li） Nylon11 in powder/granular form during table 2. different processing methods (=55/45) alloy material (EGMA-g-SAN content is 6%)
The stress-strain curve of the sample of different content EGMA-g-SAN as shown in Figure 1 in embodiment 5～8 gained poly(lactic acid)/（Fen Mo/Ke Li） Nylon11 in powder/granular forms=55/45 blend, can find out that the sample breakage elongation that does not add the 3rd component EGMA-g-SAN only is 5%, the adding of a small amount of EGMA-g-SAN has greatly improved the toughness of material, and the elongation at break of the 3rd constituent materials of adding 6% is up to 300%.This result shows that the adding of the 3rd component has greatly improved the mechanical mechanics property of material.
Embodiment 5～8 gained samples are carried out sem test, the gained photo as shown in Figure 2, show the sample that does not add the 3rd component, the bonding interface extreme difference of poly(lactic acid) and nylon (accompanying drawing 2 (a)), adding a small amount of the 3rd component has significantly increased by two alternate bonding, can find out simultaneously, mixing sample the 3rd component of single stage method mainly be dispersed in poly(lactic acid) mutually in, forms special Salami and constructs.
The stress-strain curve of poly(lactic acid)/（Fen Mo/Ke Li） Nylon11 in powder/granular form under the different blended smelting method=55/45 alloy material as shown in Figure 3, the result shows that the material preparation method has tremendous influence to performance, if going ahead of the rest, the 3rd component and nylon mixes with poly(lactic acid) again after mixing, the resulting materials poor performance can't satisfy service requirements; On the contrary, again that resulting materials and （Fen Mo/Ke Li） Nylon11 in powder/granular form is mixing if the 3rd component and poly(lactic acid) are in advance mixing, resulting materials intensity is high, toughness is best; Three components are carried out the mixing sample of single stage method also have preferably mechanical property.
Embodiment 7, embodiment 12, Comparative Examples 2 gained samples are carried out sem test, and the gained photo goes on foot in the material of mixing preparations two as shown in Figure 4, and in the material that the 3rd component is first with poly(lactic acid) is mixed, the density that the 3rd component is dispersed in the poly(lactic acid) is large; And if the 3rd component is mixed with nylon first, mixing with poly(lactic acid) again, in the resulting materials the 3rd component mainly be dispersed in nylon mutually in.Therefore the distribution situation of the 3rd component is the determinative that affects material property.
Claims (4)
1. polylactic acid/polyamide 11 alloy material, it is characterized in that described polylactic acid/polyamide 11 alloy material carries out melt blending by poly(lactic acid), （Fen Mo/Ke Li） Nylon11 in powder/granular form and the 3rd component through melting mixing equipment and obtains, based on described poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form, the massfraction of poly(lactic acid) is 5-95%, the massfraction of （Fen Mo/Ke Li） Nylon11 in powder/granular form is 5-95%, the quality of described the 3rd component be poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form total mass 3 ~ 9%; Described the 3rd component is the elastomerics that contains epoxide group; Described polylactic acid/polyamide 11 alloy material be by poly(lactic acid) with add first melt blending in the melting mixing equipment after the 3rd component mixes, mixes with （Fen Mo/Ke Li） Nylon11 in powder/granular form after again the blend that obtains being pulverized and adds afterwards that melt blending obtains in the melting mixing equipment.
2. polylactic acid/polyamide 11 alloy material as claimed in claim 1 is characterized in that described the 3rd component is one of following: polyethylene-glycidyl methacrylate graft polystyrene-vinyl cyanide, polyethylene-glycidyl methacrylate copolymer, glycidyl methacrylate graft polyethylene, glycidyl methacrylate graft polypropylene, glycidyl methacrylate graft ethene-1-octene copolymer, glycidyl methacrylate graft ethylene-vinyl acetate copolymer.
3. polylactic acid/polyamide 11 alloy material as claimed in claim 1, it is characterized in that described polylactic acid/polyamide 11 alloy material carries out melt blending by poly(lactic acid), （Fen Mo/Ke Li） Nylon11 in powder/granular form and the 3rd component through melting mixing equipment and obtains, based on described poly(lactic acid) and （Fen Mo/Ke Li） Nylon11 in powder/granular form, the massfraction of poly(lactic acid) is 30-80%, and the massfraction of nylon is 20-70%.
4. prepare alloy product film, pipe, rod, fiber yarn or plastic components such as the described polylactic acid/polyamide 11 alloy material of one of claim 1 ~ 3 by moulding process.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10160825B2 (en) | 2014-10-21 | 2018-12-25 | Samsung Electronics Co., Ltd. | Polyurethane elastomer, thermoplastic resin composition comprising the polyurethane elastomer, molded article made of the thermoplastic resin composition, and method of preparing the polyurethane elastomer |
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| CN111155191B (en) * | 2020-02-21 | 2021-09-24 | 江南大学 | Superfine polyamide 11 fiber and preparation method thereof |
| CN111205612A (en) * | 2020-03-30 | 2020-05-29 | 苏州润佳工程塑料股份有限公司 | Environment-friendly composite material for vehicles |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101023133A (en) * | 2004-09-17 | 2007-08-22 | 东丽株式会社 | Resin composition and molding comprising the same |
| CN101223239A (en) * | 2005-10-05 | 2008-07-16 | 尤尼吉可株式会社 | Biodegradable resin composition, process for production of the same, and molded article using the same |
| CN101622313A (en) * | 2007-01-29 | 2010-01-06 | 阿克马法国公司 | Composite material based on polyamide and on poly(lactic acid), manufacturing process and use thereof |
| US7723418B2 (en) * | 2003-08-29 | 2010-05-25 | Sanyo Chemical Industries, Ltd. | Antistatic resin composition |
| EP2290003A2 (en) * | 2009-08-03 | 2011-03-02 | The Yokohama Rubber Company, Limited | Thermoplastic elastomer composition |
-
2011
- 2011-09-23 CN CN 201110287355 patent/CN102391628B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7723418B2 (en) * | 2003-08-29 | 2010-05-25 | Sanyo Chemical Industries, Ltd. | Antistatic resin composition |
| CN101023133A (en) * | 2004-09-17 | 2007-08-22 | 东丽株式会社 | Resin composition and molding comprising the same |
| CN101223239A (en) * | 2005-10-05 | 2008-07-16 | 尤尼吉可株式会社 | Biodegradable resin composition, process for production of the same, and molded article using the same |
| CN101622313A (en) * | 2007-01-29 | 2010-01-06 | 阿克马法国公司 | Composite material based on polyamide and on poly(lactic acid), manufacturing process and use thereof |
| EP2290003A2 (en) * | 2009-08-03 | 2011-03-02 | The Yokohama Rubber Company, Limited | Thermoplastic elastomer composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10160825B2 (en) | 2014-10-21 | 2018-12-25 | Samsung Electronics Co., Ltd. | Polyurethane elastomer, thermoplastic resin composition comprising the polyurethane elastomer, molded article made of the thermoplastic resin composition, and method of preparing the polyurethane elastomer |
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