CN107841105A - Heat-proof combustion-resistant PLA graphene composite material and preparation method thereof - Google Patents
Heat-proof combustion-resistant PLA graphene composite material and preparation method thereof Download PDFInfo
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- CN107841105A CN107841105A CN201610834239.8A CN201610834239A CN107841105A CN 107841105 A CN107841105 A CN 107841105A CN 201610834239 A CN201610834239 A CN 201610834239A CN 107841105 A CN107841105 A CN 107841105A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention provides a kind of heat-proof combustion-resistant PLA graphene composite material, it is characterised in that it is made up of the raw material of following parts by weight：50~100 parts of PLA, 4~10 parts of chitosan, 2~8 parts of graphene nanometer sheet, 8~14 parts of carbon fiber, 8~16 parts of glass fibre, 6~10 parts of nano imvite, 1~5 part of Ludox, 1~5 part of four glycidyl amine of MDA, 1~3 part of silane coupler；Wherein, the specific surface area of the graphene nanometer sheet reaches 80~100m2/ g, and treated by the glycidyl amine of MDA four.The present invention also provides a kind of preparation method of above-mentioned heat-proof combustion-resistant PLA graphene composite material.Heat-proof combustion-resistant PLA graphene composite material provided by the invention has the advantages of excellent fire-retardancy, excellent toughness, resistance to elevated temperatures are good, comprehensive mechanical intensity is high.
Description
Technical field
The present invention relates to a kind of lactic acid composite material, and in particular to a kind of heat-proof combustion-resistant PLA graphene composite material
And preparation method thereof.
Background technology
PLA（English abbreviation：PLA）It is a kind of thermoplastic aliphatic's polyester, produces the lactic acid and third required for PLA
Lactide can be fermented by renewable resource, be dehydrated, be obtained after purification, resulting PLA typically have good machinery and
Processing characteristics, and poly-lactic acid products it is discarded after can be that one kind possesses good performance by various mode fast degradations
Green plastic.But PLA material is more crisp in itself, and heat resistance is poor, and this significantly limit its application.
Graphene nanometer sheet, guide number Ss（Graphene nanosheets）Or GNFs (Graphene
NanoFlakes), it is to be formed by single layer of carbon atom planar structure graphene stacking, thickness is the bidimensional Nano graphite of nanoscale
Material, its extreme case are single-layer graphenes, and it has larger specific surface area and layer structure, can be formed in the base very
Good supporting network structure, there is far-reaching Research Significance for improving PLA properties.
The content of the invention
In view of this, it is a kind of good, comprehensive with excellent fire-retardancy, excellent toughness, resistance to elevated temperatures it is necessory to provide
Heat-proof combustion-resistant PLA graphene composite material of high mechanical strength and preparation method thereof, to solve the above problems.
The present invention provides a kind of heat-proof combustion-resistant PLA graphene composite material, is made up of the raw material of following parts by weight：It is poly-
50~100 parts of lactic acid, 4~10 parts of chitosan, 2~8 parts of graphene nanometer sheet, 8~14 parts of carbon fiber, 8~16 parts of glass fibre,
6~10 parts of nano imvite, 1~5 part of Ludox, 9~14 parts of expanded graphite, 2~6 parts of attapulgite, MDA
Four 1~5 part of glycidyl amines, 1~3 part of silane coupler；Wherein, the specific surface area of the graphene nanometer sheet reach 80~
100m2/ g, and treated by the glycidyl amine of MDA four.
Based on above-mentioned, it is made up of the raw material of following parts by weight：70~90 parts of PLA, 5~8 parts of chitosan, graphene
It is 3~6 parts of nanometer sheet, 10~12 parts of carbon fiber, 10~14 parts of glass fibre, 7~9 parts of nano imvite, 2~4 parts of Ludox, swollen
Swollen 10~12 parts of graphite, 3~5 parts of attapulgite, 2~4 parts of four glycidyl amine of MDA, silane coupler 1~3
Part.
Based on above-mentioned, the silane coupler is Silane coupling agent KH550, silane coupler KH560, silane coupler
KH570 or silane coupler KH792.
Based on above-mentioned, the weight average molecular weight of the PLA is 100,000~800,000, and fusing point is 60 DEG C.
Based on above-mentioned, the carbon fiber is treated through silane coupler.
Based on above-mentioned, the glass fibre is treated through silane coupler.
Wherein, the particle diameter of the silicon dioxide granule in the Ludox is 580nm, and the content of silicon dioxide granule is
20%~30%.
Based on above-mentioned, the particle diameter of the nano imvite is less than 40 μm.
The present invention also provides a kind of preparation method of above-mentioned heat-proof combustion-resistant PLA graphene composite material, specific preparation side
Method step is as follows：
（1）The processing of graphene nanometer sheet
Graphene nanometer sheet is positioned in DMF solvent together with the glycidyl amine of MDA four, mechanical agitation is held
It is continuous 1~3 hour, 500~1500rpm of rotating speed, after being well mixed, it is positioned in drying oven, temperature control is at 45 DEG C~55 DEG C
Persistently dry 6 hours, obtain the graphene nanometer sheet of surface modification；
（2）The graphene nanometer sheet that the surface is modified and PLA mix particles is uniform, in three-roll grinder grind 20~
30 min, obtain PLA graphene mixture；
（3）By the PLA graphene mixture and chitosan, nano imvite, silane coupler, Ludox, expansion stone
Ink, attapulgite, the glycidyl amine of MDA four in the min of high-speed mixer and mixing 10~30, mix according to said ratio
Added after closing uniformly in the hopper of double screw extruder, by carbon fiber and glass fibre by a certain percentage from double screw extruder
Plus fine mouth in add, extruded through melt blending, extruded material dries up pelletizing after cold go, be made the heat-proof combustion-resistant PLA
Graphene composite material.
Compared with prior art, heat-proof combustion-resistant PLA graphene composite material provided by the invention has advantages below：
First, the graphene nanometer sheet of the glycidyl amine of MDA four surface treatment, energy are prepared using solution blended process
Enough make graphene nanometer sheet and matrix resin that there is good compatibility；Secondly, the glycidyl amine of MDA four is gathered around
There is larger relative molecular mass, but show very low viscosity, therefore be used to reduce the melt viscosity of polymer, improve poly-
The fluidity of molten of compound；In addition, having active hydroxyl and amino in chitosan macromolecular, they have stronger chemical reaction
Ability, by producing interaction with other radical reactions or with matrix, toughening effect is splendid；The addition of nano imvite then may be used
To improve the mechanical strength of polymer, heat resistance and anti-flammability；Ludox can increase the heat resistance and intensity of polymer；It is swollen
Swollen graphite is the phyllosilicate nano material compositional flame-retardant such as expansion type flame retardant and attapulgite, nano imvite, Neng Gou
Matrix surface forms continuous and fine and close layer of charcoal, and will not produce and melt drop；Graphene have high temperature resistant, excellent pliability and
The advantages that high intensity；Therefore, heat-proof combustion-resistant PLA graphene composite material provided by the invention has excellent fire-retardancy, good
The advantages that good toughness, resistance to elevated temperatures are good, comprehensive mechanical intensity is high.
Embodiment
Below by embodiment, technical scheme is described in further detail.
Embodiment 1
The embodiment of the present invention provides a kind of heat-proof combustion-resistant PLA graphene composite material, its by following parts by weight raw material system
Into：50 parts of PLA, 4 parts of chitosan, 2 parts of graphene nanometer sheet, 8 parts of carbon fiber, 8 parts of glass fibre, 6 parts of nano imvite,
1 part of Ludox, 9 parts of expanded graphite, 2 parts of attapulgite, 1 part of four glycidyl amine of MDA and silane coupler
1 part of KH550；Wherein, the weight average molecular weight of the PLA is 100,000, and fusing point is 60 DEG C；Carbon fiber and glass fibre be all through
Cross what Silane coupling agent KH550 treated.
The preparation method for the above-mentioned heat-proof combustion-resistant PLA graphene composite material that the present embodiment provides comprises the following steps：
（1）Graphene nanometer sheet is positioned in DMF solvent together with the glycidyl amine of MDA four, mechanical agitation
Continue 1 hour, the rpm of rotating speed 700, after being well mixed, be positioned in drying oven, temperature control 45 DEG C persistently drying it is 6 small
When, the graphene nanometer sheet of surface modification is obtained, and its specific surface area reaches 87 m2/g；
（2）The graphene nanometer sheet that the surface is modified and PLA mix particles is uniform, 20 are ground in three-roll grinder
Min, obtain PLA graphene mixture；
（3）By the PLA graphene mixture and chitosan, nano imvite, Silane coupling agent KH550, Ludox, swollen
Swollen graphite, attapulgite, the glycidyl amine of MDA four in the min of high-speed mixer and mixing 10, mix according to said ratio
Added after closing uniformly in the hopper of double screw extruder, by carbon fiber and glass fibre by a certain percentage from double screw extruder
Plus fine mouth in add, extruded through melt blending, extruded material dries up pelletizing after cold go, be made the heat-proof combustion-resistant PLA
Graphene composite material.
Embodiment 2
The embodiment of the present invention provides a kind of heat-proof combustion-resistant PLA graphene composite material, its by following parts by weight raw material system
Into：70 parts of PLA, 5 parts of chitosan, 3 parts of graphene nanometer sheet, 10 parts of carbon fiber, 10 parts of glass fibre, nano imvite 7
It is part, 2 parts of Ludox, 10 parts of expanded graphite, 3 parts of attapulgite, 2 parts of four glycidyl amine of MDA, silane coupled
2 parts of agent KH560；Wherein, the weight average molecular weight of the PLA is 300,000, and fusing point is 60 DEG C；Carbon fiber and glass fibre are all
Treated by silane coupler KH560.
The preparation method for the above-mentioned heat-proof combustion-resistant PLA graphene composite material that the present embodiment provides comprises the following steps：
（1）Graphene nanometer sheet is positioned in DMF solvent together with the glycidyl amine of MDA four, mechanical agitation
Continue 2 hours, the rpm of rotating speed 800, after being well mixed, be positioned in drying oven, temperature control 50 DEG C persistently drying it is 6 small
When, the graphene nanometer sheet of surface modification is obtained, and its specific surface area reaches 91 m2/g；
（2）The graphene nanometer sheet that the surface is modified and PLA mix particles is uniform, 20 are ground in three-roll grinder
Min, obtain PLA graphene mixture；
（3）By the PLA graphene mixture and chitosan, nano imvite, silane coupler KH560, Ludox, swollen
Swollen graphite, attapulgite, the glycidyl amine of MDA four in the min of high-speed mixer and mixing 15, mix according to said ratio
Added after closing uniformly in the hopper of double screw extruder, by carbon fiber and glass fibre by a certain percentage from double screw extruder
Plus fine mouth in add, extruded through melt blending, extruded material dries up pelletizing after cold go, be made the heat-proof combustion-resistant PLA
Graphene composite material.
Embodiment 3
The embodiment of the present invention provides a kind of heat-proof combustion-resistant PLA graphene composite material, its by following parts by weight raw material system
Into：80 parts of PLA, 7 parts of chitosan, 5 parts of graphene nanometer sheet, 11 parts of carbon fiber, 12 parts of glass fibre, nano imvite 8
It is part, 3 parts of Ludox, 11 parts of expanded graphite, 3 parts of attapulgite, 4 parts of four glycidyl amine of MDA, silane coupled
2 parts of agent KH570；Wherein, the weight average molecular weight of the PLA is 500,000, and fusing point is 60 DEG C；Carbon fiber and glass fibre are all
Treated by silane coupler KH570.
The preparation method for the above-mentioned heat-proof combustion-resistant PLA graphene composite material that the present embodiment provides comprises the following steps：
（1）Graphene nanometer sheet is positioned in DMF solvent together with the glycidyl amine of MDA four, mechanical agitation
Continue 2 hours, the rpm of rotating speed 1000, after being well mixed, be positioned in drying oven, temperature control 50 DEG C persistently drying it is 6 small
When, the graphene nanometer sheet of surface modification is obtained, and its specific surface area reaches 98 m2/g；
（2）The graphene nanometer sheet that the surface is modified and PLA mix particles is uniform, 25 are ground in three-roll grinder
Min, obtain PLA graphene mixture；
（3）By the PLA graphene mixture and chitosan, nano imvite, silane coupler KH570, Ludox, swollen
Swollen graphite, attapulgite, the glycidyl amine of MDA four in the min of high-speed mixer and mixing 20, mix according to said ratio
Added after closing uniformly in the hopper of double screw extruder, by carbon fiber and glass fibre by a certain percentage from double screw extruder
Plus fine mouth in add, extruded through melt blending, extruded material dries up pelletizing after cold go, be made the heat-proof combustion-resistant PLA
Graphene composite material.
Embodiment 4
The embodiment of the present invention provides a kind of heat-proof combustion-resistant PLA graphene composite material, its by following parts by weight raw material system
Into：90 parts of PLA, 8 parts of chitosan, 6 parts of graphene nanometer sheet, 12 parts of carbon fiber, 14 parts of glass fibre, nano imvite 9
It is part, 4 parts of Ludox, 12 parts of expanded graphite, 4 parts of attapulgite, 4 parts of four glycidyl amine of MDA, silane coupled
3 parts of agent KH792；Wherein, the weight average molecular weight of the PLA is 700,000, and fusing point is 60 DEG C；Carbon fiber and glass fibre are all
Treated by silane coupler KH792.
The preparation method for the above-mentioned heat-proof combustion-resistant PLA graphene composite material that the present embodiment provides comprises the following steps：
（1）Graphene nanometer sheet is positioned in DMF solvent together with the glycidyl amine of MDA four, mechanical agitation
Continue 2 hours, the rpm of rotating speed 1100, after being well mixed, be positioned in drying oven, temperature control 50 DEG C persistently drying it is 6 small
When, the graphene nanometer sheet of surface modification is obtained, and its specific surface area reaches 81 m2/g；
（2）The graphene nanometer sheet that the surface is modified and PLA mix particles is uniform, 30 are ground in three-roll grinder
Min, obtain PLA graphene mixture；
（3）By the PLA graphene mixture and chitosan, nano imvite, silane coupler KH792, Ludox, swollen
Swollen graphite, attapulgite, the glycidyl amine of MDA four in the min of high-speed mixer and mixing 25, mix according to said ratio
Added after closing uniformly in the hopper of double screw extruder, by carbon fiber and glass fibre by a certain percentage from double screw extruder
Plus fine mouth in add, extruded through melt blending, extruded material dries up pelletizing after cold go, be made the heat-proof combustion-resistant PLA
Graphene composite material.
Embodiment 5
The embodiment of the present invention provides a kind of heat-proof combustion-resistant PLA graphene composite material, its by following parts by weight raw material system
Into：100 parts of PLA, 10 parts of chitosan, 8 parts of graphene nanometer sheet, 14 parts of carbon fiber, 16 parts of glass fibre, nano imvite
10 parts, 5 parts of Ludox, 14 parts of expanded graphite, 5 parts of attapulgite, 5 parts of four glycidyl amine of MDA, silane it is even
Join 3 parts of agent KH560；Wherein, the weight average molecular weight of the PLA is 800,000, and fusing point is 60 DEG C；Carbon fiber and glass fibre are all
It is treated by silane coupler KH560.
The preparation method for the above-mentioned heat-proof combustion-resistant PLA graphene composite material that the present embodiment provides comprises the following steps：
（1）Graphene nanometer sheet is positioned in DMF solvent together with the glycidyl amine of MDA four, mechanical agitation
Continue 3 hours, the rpm of rotating speed 1400, after being well mixed, be positioned in drying oven, temperature control 55 DEG C persistently drying it is 6 small
When, the graphene nanometer sheet of surface modification is obtained, and its specific surface area reaches 94 m2/g；
（2）The graphene nanometer sheet that the surface is modified and PLA mix particles is uniform, 30 are ground in three-roll grinder
Min, obtain PLA graphene mixture；
（3）By the PLA graphene mixture and chitosan, nano imvite, silane coupler KH560, Ludox, swollen
Swollen graphite, attapulgite, the glycidyl amine of MDA four in the min of high-speed mixer and mixing 30, mix according to said ratio
Added after closing uniformly in the hopper of double screw extruder, by carbon fiber and glass fibre by a certain percentage from double screw extruder
Plus fine mouth in add, extruded through melt blending, extruded material dries up pelletizing after cold go, be made the heat-proof combustion-resistant PLA
Graphene composite material.
According to national standard, the heat-proof combustion-resistant PLA graphene composite material that above-described embodiment 1~5 provides is carried out each
Item performance test, test result are as shown in the table：
| Project | Tensile strength（MPa） | Bending strength（MPa） | Unnotched impact strength (KJ/m2) | Heat distortion temperature (0.18MPa/ DEG C) | Strength retention（%） | Oxygen index (OI) |
| Embodiment 1 | 93.2 | 82.1 | 28.9 | 83 | 84.4 | 32 |
| Embodiment 2 | 97.5 | 86.3 | 33.1 | 87 | 81.9 | 33 |
| Embodiment 3 | 116.9 | 91.7 | 39.6 | 90 | 80.5 | 35 |
| Embodiment 4 | 112.6 | 96.1 | 40.8 | 89 | 80.1 | 36 |
| Embodiment 5 | 104.2 | 84.8 | 36.9 | 82 | 79.6 | 38 |
Note：It is strong that strength retention refers to that obtained composite soaks 24 h drying process post-tensioning in 80 DEG C of waters bath with thermostatic control
Spend the rate of change relative to untreated composite.
Finally it should be noted that：The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof；To the greatest extent
The present invention is described in detail with reference to preferred embodiments for pipe, those of ordinary skills in the art should understand that：Still
The embodiment of the present invention can be modified or equivalent substitution is carried out to some technical characteristics；Without departing from this hair
The spirit of bright technical scheme, it all should cover among the claimed technical scheme scope of the present invention.
Claims (7)
1. a kind of heat-proof combustion-resistant PLA graphene composite material, it is characterised in that it is made up of the raw material of following parts by weight：It is poly-
50~100 parts of lactic acid, 4~10 parts of chitosan, 2~8 parts of graphene nanometer sheet, 8~14 parts of carbon fiber, 8~16 parts of glass fibre,
6~10 parts of nano imvite, 1~5 part of Ludox, 9~14 parts of expanded graphite, 2~6 parts of attapulgite, MDA
Four 1~5 part of glycidyl amines, 1~3 part of silane coupler；Wherein, the specific surface area of the graphene nanometer sheet reach 80~
100m2/ g, and treated by the glycidyl amine of MDA four.
2. heat-proof combustion-resistant PLA graphene composite material according to claim 1, it is characterised in that it is by following weight
The raw material of part is made：70~90 parts of PLA, 5~8 parts of chitosan, 3~6 parts of graphene nanometer sheet, 10~12 parts of carbon fiber, glass
10~14 parts of glass fiber, 7~9 parts of nano imvite, 2~4 parts of Ludox, 10~12 parts of expanded graphite, 3~5 parts of attapulgite,
2~4 parts of four glycidyl amine of MDA, 1~3 part of silane coupler.
3. heat-proof combustion-resistant PLA graphene composite material according to claim 1 or 2, it is characterised in that the silane
Coupling agent is Silane coupling agent KH550, silane coupler KH560, silane coupler KH570 or silane coupler KH792.
4. heat-proof combustion-resistant PLA graphene composite material according to claim 1 or 2, it is characterised in that the poly- breast
The weight average molecular weight of acid is 100,000~800,000, and fusing point is 60 DEG C.
5. heat-proof combustion-resistant PLA graphene composite material according to claim 1 or 2, it is characterised in that the carbon is fine
Glass fibre described in peacekeeping is treated through silane coupler.
6. heat-proof combustion-resistant PLA graphene composite material according to claim 1 or 2, it is characterised in that the nanometer
The particle diameter of montmorillonite is less than 40 μm.
7. a kind of preparation method of the heat-proof combustion-resistant PLA graphene composite material described in any one of claim 1~6, specifically
Preparation method step is as follows：
（1）Graphene nanometer sheet is positioned in DMF solvent together with the glycidyl amine of MDA four, mechanical agitation
Continue 1~3 hour, 500~1500rpm of rotating speed, after being well mixed, be positioned in drying oven, temperature control is 45 DEG C~55
DEG C persistently dry 6 hours, obtain the graphene nanometer sheet of surface modification；
（2）The graphene nanometer sheet that the surface is modified and PLA mix particles is uniform, in three-roll grinder grind 20~
30 min, obtain PLA graphene mixture；
（3）By the PLA graphene mixture and chitosan, nano imvite, silane coupler, Ludox, expansion stone
Ink, attapulgite, the glycidyl amine of MDA four in the min of high-speed mixer and mixing 10~30, mix according to said ratio
Added after closing uniformly in the hopper of double screw extruder, by carbon fiber and glass fibre by a certain percentage from double screw extruder
Plus fine mouth in add, extruded through melt blending, extruded material dries up pelletizing after cold go, be made the heat-proof combustion-resistant PLA
Graphene composite material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610834239.8A CN107841105A (en) | 2016-09-20 | 2016-09-20 | Heat-proof combustion-resistant PLA graphene composite material and preparation method thereof |
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| CN108641451A (en) * | 2018-05-21 | 2018-10-12 | 东莞市道尔新材料科技有限公司 | Coating efficient flame-retarding agent and preparation method thereof, coating |
| CN108728934A (en) * | 2018-07-14 | 2018-11-02 | 合肥盛达服装辅料有限公司 | A kind of heat-resisting ribbon of high-strength anti-flaming |
| GB2588950A (en) * | 2019-11-15 | 2021-05-19 | Tor Corp Ltd | Biodegradable polymer nanocomposite and method for production thereof |
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| CN105602216A (en) * | 2016-02-02 | 2016-05-25 | 奇瑞汽车股份有限公司 | Carbon fiber reinforced heatproof flame-retardant polylactic acid composite material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108641451A (en) * | 2018-05-21 | 2018-10-12 | 东莞市道尔新材料科技有限公司 | Coating efficient flame-retarding agent and preparation method thereof, coating |
| CN108728934A (en) * | 2018-07-14 | 2018-11-02 | 合肥盛达服装辅料有限公司 | A kind of heat-resisting ribbon of high-strength anti-flaming |
| GB2588950A (en) * | 2019-11-15 | 2021-05-19 | Tor Corp Ltd | Biodegradable polymer nanocomposite and method for production thereof |
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