CN106009064B - A kind of graphene oxide modified thermoplastic starch composite material and preparation method thereof - Google Patents
A kind of graphene oxide modified thermoplastic starch composite material and preparation method thereof Download PDFInfo
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- CN106009064B CN106009064B CN201610475541.9A CN201610475541A CN106009064B CN 106009064 B CN106009064 B CN 106009064B CN 201610475541 A CN201610475541 A CN 201610475541A CN 106009064 B CN106009064 B CN 106009064B
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Abstract
The invention discloses a kind of graphene oxide modified thermoplastic starch composite materials and preparation method thereof, wherein composite material of the present invention is using thermoplastic starch as base-material, using graphene oxide as filler, each component is configured to by mass percentage：Thermoplastic starch 67 80%, plasticizer 19.8 26.6%, graphene oxide 0.2 6.4%.Composite material of the present invention is nontoxic, degradable, at low cost, simple for process, and compared with thermoplastic starch, tensile strength improves, thermal stability improves, thermal coefficient improves, water vapour permeability declines.
Description
One, technical field
The present invention relates to a kind of thermoplastic starch powder composite material, specifically a kind of graphene oxide modified thermoplastic forms sediment
Powder composite material and preparation method thereof belongs to technical field of composite materials.
Two, background technology
Under existing situation, environmentally protective, sustainable development development and utilization is carried out to existing resource and environment, at
For universal common recognition.Traditional plastic material has the shortcomings that be difficult to degrade, is poisonous and harmful, relying on petroleum-based energy；And it is natural high
Molecular material has the advantages such as degradable, renewable, environmental-friendly, can be used for replacing conventional plastic to solve the above problems.
Starch be it is a kind of derive from a wealth of sources, be cheap, the natural macromolecular material that the regeneration period is short, contain in strand
Great amount of hydroxy group group, these groups are formed crystalline state and amorphous state and are deposited by intramolecular and intermolecular hydrogen bond action
Aggregated structure；Since glass transition temperature is close to decomposition temperature, do not have plasticity.The plasticizings such as glycerine, ethylene glycol
Containing groups such as hydroxyl, amino, amide groups in agent small molecule, stronger hydrogen bond can be formed with the hydroxyl in starch molecular chain
Effect reduces glass transition temperature, it is made to show thermoplasticity to destroy its original structure.Starch and plasticizer are total to
After mixed, thermoplastic starch can be made by forming methods such as shearing, extrusion, molding, injection moldings under the high temperature conditions.
Compared with conventional plastic, thermoplastic starch Shortcomings in terms of mechanical property, hygroscopicity, thermal stability, this makes
Its application is restricted.It has been investigated that made by the way that the high lamellar inorganic filler of compatible degree is added into thermoplastic starch
The composite material of work, above-mentioned various aspects of performance all can get and improve.In the related art, montmorillonite, kaolin etc.
Silicate mineral with lamellar structure, as applying filler in the making of thermoplastic starch-based composite material.
Graphene oxide is a kind of stratified nano materials with huge specific surface area and abundant surface functional group, stone
The owned excellent heat of black alkene, power, electric property.After being introduced into polymer, it is remarkably improved the heating power electricity of polymer
Performance, meanwhile, the abundant functional group of surface of graphene oxide, which is homogeneously dispersed in for it in macromolecule, provides precondition.Separately
Outside, since graphene oxide is of low cost, raw material is easy to get, and competitive advantage is had more than carbon nanotube.At present with outer existing oxidation stone
The related patents of black alkene/polymer composites report that application field covers the fuel cell hydrogen storage material of energy industry,
The side such as applied fireproofing of the microporous catalyst carrier of synthetic chemical industry, conductive plastics, conductive coating and building trade
Face.
Thermoplastic starch and graphene oxide are all to have hydrophilic material.Through retrieval, in existing disclosed document
It does not find using graphene oxide as the technical solution of filler making thermoplastic starch-based composite material.
Three, invention content
The present invention is intended to provide a kind of graphene oxide modified thermoplastic starch composite material and preparation method thereof, with difference
The graphene oxide of size is filler, improves the thermodynamic property and thermal conductivity of thermoplastic starch material.The method of the present invention work
Skill is simple, easy controlled operation, of low cost, has practical value.
Graphene oxide modified thermoplastic starch composite material of the present invention is using thermoplastic starch as base-material, to aoxidize stone
Black alkene is filler, and each component is configured to by mass percentage：
Thermoplastic starch 67-80%, plasticizer 19.8-26.6%, graphene oxide 0.2-6.4%.
The plasticizer is glycerine.
The lamella area of the graphene oxide is not less than 1 μm, and lamellar spacing is not more than 500nm.
The preparation method of graphene oxide modified thermoplastic starch composite material of the present invention, includes the following steps：
1, thermoplastic starch and plasticizer are added in high-speed mixer, mix 2-3 minutes, graphite oxide is then added
Alkene continues mixing 1-2 minutes, obtains mixture；
2, step 1 gained mixture is transferred in hermetic bag, at ambient temperature closed placement 6-10 hours；
3, it will be sent into screw rod plastic extruder through step 2 treated mixture, extrusion molding obtains after being cooled to room temperature
Obtain graphene oxide modified thermoplastic starch composite material.
The temperature of extrusion molding in step 3 is controlled at 110-135 DEG C.
Further, mixture passes through four regions altogether from screw rod plastic extrusion machine inlet to discharge port in step 3, right
The temperature range answered is followed successively by 120 DEG C, 130-135 DEG C, 130-135 DEG C, 110-120 DEG C.
Starch of the present invention is natural material, nontoxic, degradable, of low cost.
Graphene oxide used in the present invention is prepared as follows to obtain：
Graphite powder is aoxidized using Hummers methods, graphene oxide is made, specific preparation process is as follows：In ice-water bath and stir
Mix it is lower 3g graphite powders and 1.5g sodium nitrate are added in the 70mL98wt% concentrated sulfuric acids, 9g potassium permanganate is slowly added into batches
To ensure that solution temperature is less than 20 DEG C in above-mentioned solution, potassium permanganate adds in 2-3h；35 DEG C are then raised temperature to be stirred to react
24h；After reaction, 140mL deionized waters are added in reaction solution, and continue to stir 15min, 500mL is then added and goes
The hydrogen peroxide of 20mL30wt% is slowly added dropwise in ionized water, is eventually adding the hydrochloric acid solution of 200mL 1M.Product by filtering and it is more
Secondary to wash away metal ion and extra acid, obtained solid dispersion is in deionized water and continual ultrasonic 2h, gained brown are divided
Dispersion liquid centrifuges 20min by 4500rpm, removes sediment, collects upper liquid, dialyses 1 week, and freeze-drying obtains graphene oxide
Powder solid.
In the present invention, it is dispersed in thermoplastic starch matrix to graphene oxide uniform filling.Due to graphene oxide with
There is strong interaction of hydrogen bond, the addition of graphene oxide to significantly improve the drawing of thermoplastic starch between thermoplastic starch
Intensity is stretched, while in thermoplastic starch process, since with higher temperature, a part of graphene oxide is reduced,
So that the heat-resistant stability and thermal coefficient of thermoplastic starch are all significantly improved.Starch of the present invention is can be again
Raw, degradable natural material can make thermoplastic starch be more suitable for substituting traditional modeling by the improvement in heating power and electric property
Expect material.
Graphene oxide of the present invention is a kind of stratified nano materials with huge specific surface area, and surface contains
There is abundant hydrophilic functional group, hydrogen bond action can occur between the hydroxyl group in starch molecular chain, pass through extrusion molding
Technique prepares thermoplastic starch-graphene oxide composite material.Tests prove that after oxidized graphene filling enhancing, heat
The tensile strength of plastic starch improves, thermal stability improves, thermal coefficient improves, water vapour permeability declines.
Four, specific implementation mode
Below in conjunction with the embodiment of the present invention, clear, complete description is carried out to the technical solution of invention, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
The every other embodiment that those of ordinary skill in the art are obtained without creative efforts, belongs to this hair
The range of bright protection.
Graphene oxide used in the embodiment of the present invention is prepared as follows to obtain：
Graphite powder is aoxidized using Hummers methods, graphene oxide is made, specific preparation process is as follows：In ice-water bath and stir
Mix it is lower 3g graphite powders and 1.5g sodium nitrate are added in the 70mL98wt% concentrated sulfuric acids, 9g potassium permanganate is slowly added into batches
To ensure that solution temperature is less than 20 DEG C in above-mentioned solution, potassium permanganate adds in 2-3h；35 DEG C are then raised temperature to be stirred to react
24h；After reaction, 140mL deionized waters are added in reaction solution, and continue to stir 15min, 500mL is then added and goes
The hydrogen peroxide of 20mL30wt% is slowly added dropwise in ionized water, is eventually adding the hydrochloric acid solution of 200mL 1M.Product by filtering and it is more
Secondary to wash away metal ion and extra acid, obtained solid dispersion is in deionized water and continual ultrasonic 2h, gained brown are divided
Dispersion liquid centrifuges 20min by 4500rpm, removes sediment, collects upper liquid, dialyses 1 week, and freeze-drying obtains graphene oxide
Powder solid.
Comparative example：
As the contrast standard of following each embodiment, present invention firstly provides without containing graphene oxide
Prepared thermoplastic starch material and its test result of tensile strength raising, thermal stability, thermal coefficient.
It weighs 1000g thermoplastic starch and high-speed mixer is added in 300g glycerine, it is mixed with the rotating speed of 1000-1500r/min
It closes 3 minutes and obtains mixture；Gained mixture is transferred in hermetic bag, it is closed at ambient temperature to place 8 hours；It will processing
Mixture afterwards takes out and is sent into the feed inlet of screw rod plastic extruder, from feed inlet to the four of discharge port regions according to 120
DEG C, 130 DEG C, 130 DEG C, 110 DEG C of temperature extrusion molding, the thermoplastic starch without containing graphene oxide is obtained after being cooled to room temperature
Powder material.After tested, the tensile strength of the material is 5.85MPa~6.63MPa, and heat decomposition temperature is 120 DEG C, and thermal coefficient is
0.16W.m-1.K-1。
Embodiment 1：
1, it weighs 1000g thermoplastic starch and high-speed mixer is added in 300g glycerine, with the rotating speed of 1000-1500r/min
10g graphene oxide powders are then added in mixing 3 minutes, are mixed 2 minutes, are mixed with the rotating speed of 1000-1500r/min
Material；
2, gained mixture is transferred in hermetic bag, it is closed at ambient temperature to place 8 hours；
3, the feed inlet of screw rod plastic extruder will be sent into through step 2 treated mixture, from feed inlet to discharge port
Four regions according to 120 DEG C, 130 DEG C, 130 DEG C, 120 DEG C of temperature extrusion molding, obtain graphite oxide after being cooled to room temperature
Alkene modified thermoplastic starch composite material.
The lamella area of the graphene oxide is not less than 1 μm, and lamellar spacing is not more than 500nm.After tested, with it is not oxygen-containing
The thermoplastic starch material of graphite alkene is compared, and the fracture strength of the present embodiment composite material is increased by 5.85MPa~6.63MPa
To 14.08MPa~16.36MPa, heat decomposition temperature increases to 175 DEG C by 120 DEG C, and thermal coefficient is by 0.16W.m-1.K-1Increase to
0.46W.m-1.K-1。
Embodiment 2：
1, it weighs 1000g thermoplastic starch and high-speed mixer is added in 300g glycerine, with the rotating speed of 1000-1500r/min
5g graphene oxide powders are then added in mixing 3 minutes, are mixed 2 minutes, are mixed with the rotating speed of 1000-1500r/min
Material；
2, gained mixture is transferred in hermetic bag, it is closed at ambient temperature to place 8 hours；
3, the feed inlet of screw rod plastic extruder will be sent into through step 2 treated mixture, from feed inlet to discharge port
Four regions according to 120 DEG C, 130 DEG C, 130 DEG C, 120 DEG C of temperature extrusion molding, obtain graphite oxide after being cooled to room temperature
Alkene modified thermoplastic starch composite material.
The lamella area of the graphene oxide is not less than 1 μm, and lamellar spacing is not more than 500nm.After tested, with it is not oxygen-containing
The thermoplastic starch material of graphite alkene is compared, and the fracture strength of the present embodiment composite material is increased by 5.85MPa~6.63MPa
To 8.03MPa~11.32MPa, heat decomposition temperature increases to 140 DEG C by 120 DEG C, and thermal coefficient is by 0.16W.m-1.K-1Increase to
0.29W.m-1.K-1。
Embodiment 3：
1, it weighs 1000g thermoplastic starch and high-speed mixer is added in 300g glycerine, with the rotating speed of 1000-1500r/min
20g graphene oxide powders are then added in mixing 3 minutes, are mixed 2 minutes, are mixed with the rotating speed of 1000-1500r/min
Material；
2, gained mixture is transferred in hermetic bag, it is closed at ambient temperature to place 8 hours；
3, the feed inlet of screw rod plastic extruder will be sent into through step 2 treated mixture, from feed inlet to discharge port
Four regions according to 120 DEG C, 130 DEG C, 130 DEG C, 120 DEG C of temperature extrusion molding, obtain graphite oxide after being cooled to room temperature
Alkene modified thermoplastic starch composite material.
The lamella area of the graphene oxide is not less than 1 μm, and lamellar spacing is not more than 500nm.After tested, with it is not oxygen-containing
The thermoplastic starch material of graphite alkene is compared, and the fracture strength of the present embodiment composite material is increased by 5.85MPa~6.63MPa
To 10.03MPa~12.47MPa, heat decomposition temperature increases to 160 DEG C by 120 DEG C, and thermal coefficient is by 0.16W.m-1.K-1Increase to
0.50W.m-1.K-1。
Embodiment 4：
1, it weighs 1000g thermoplastic starch and high-speed mixer is added in 300g glycerine, with the rotating speed of 1000-1500r/min
10g graphene oxide powders are then added in mixing 3 minutes, are mixed 2 minutes, are mixed with the rotating speed of 1000-1500r/min
Material；
2, gained mixture is transferred in hermetic bag, it is closed at ambient temperature to place 8 hours；
3, the feed inlet of screw rod plastic extruder will be sent into through step 2 treated mixture, from feed inlet to discharge port
Four regions according to 120 DEG C, 130 DEG C, 130 DEG C, 120 DEG C of temperature extrusion molding, obtain graphite oxide after being cooled to room temperature
Alkene modified thermoplastic starch composite material.
The lamella area of the graphene oxide is not more than 500nm, and graphene film layer thickness is not more than 500nm.After tested,
Compared with the thermoplastic starch material without graphene oxide, the fracture strength of the present embodiment composite material by 5.85MPa~
6.63MPa increases to 12.05MPa~14.13MPa, and heat decomposition temperature increases to 162 DEG C by 120 DEG C, thermal coefficient by
0.16W.m-1.K-1Increase to 0.32W.m-1.K-1。
The difference of embodiment 4 and embodiment 1 is that the lamella area of graphene oxide used is different.The former is 1um, after
Person is 500nm.Tests prove that the lamella size difference of graphene oxide is for thermoplastic starch-graphene oxide composite wood
There is influence in the heating power electric property of material.
Preparation method of the present invention is dispersed in thermoplastic starch matrix to graphene oxide uniform filling.Due to aoxidizing stone
There is strong interaction of hydrogen bond, the addition of graphene oxide to significantly improve thermoplastic starch between black alkene and thermoplastic starch
The tensile strength of powder, while in thermoplastic starch process, due to higher temperature, a part of graphene oxide quilt
Reduction so that the heat-resistant stability and thermal coefficient of thermoplastic starch are all significantly improved.Starch of the present invention is
Renewable, degradable natural material can make thermoplastic starch be more suitable for substituting biography by the improvement in heating power and electric property
System plastic material.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (2)
1. a kind of preparation method of graphene oxide modified thermoplastic starch composite material, it is characterised in that include the following steps：
（1）Thermoplastic starch and plasticizer are added in high-speed mixer, graphene oxide is added after mixing, continues to mix
Uniformly, mixture is obtained；
（2）By step（1）Gained mixture is transferred in hermetic bag, at ambient temperature closed placement 6-10 hours；
（3）It will be through step（2）Treated, and mixture is sent into screw rod plastic extruder, and extrusion molding obtains after being cooled to room temperature
Obtain graphene oxide modified thermoplastic starch composite material；
Step（3）Middle mixture squeezes out machine inlet to discharge port from screw rod plastic and passes through four regions, corresponding temperature altogether
Range is followed successively by 120 DEG C, 130-135 DEG C, 130-135 DEG C, 110-120 DEG C；
The composite material be using thermoplastic starch as base-material, using graphene oxide as filler, each component structure by mass percentage
Become：
Thermoplastic starch 67-80%, plasticizer 19.8-26.6%, graphene oxide 0.2-6.4%；
The lamella area of the graphene oxide is not less than 1 μm, and lamellar spacing is not more than 500nm.
2. preparation method according to claim 1, it is characterised in that：
The plasticizer is glycerine.
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