CN106243651A - A kind of preparation method of porous graphene/PEG SA/PLA composite - Google Patents
A kind of preparation method of porous graphene/PEG SA/PLA composite Download PDFInfo
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- CN106243651A CN106243651A CN201610623604.0A CN201610623604A CN106243651A CN 106243651 A CN106243651 A CN 106243651A CN 201610623604 A CN201610623604 A CN 201610623604A CN 106243651 A CN106243651 A CN 106243651A
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- 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
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Abstract
The invention discloses the preparation method of a kind of porous graphene/PEG SA/PLA composite, it is specially, first prepare porous graphene/PEG SA and compound nucleator, then use the nucleator prepared and PLA to be prepared as porous graphene/PEG SA/PLA composite.The preparation method of one porous graphene of the present invention/PEG SA/PLA composite, utilize the PEG of low-molecular-weight as plasticizer, increase the gap of molecule interchain, improve the motor capacity of strand, porous graphene is as heterogeneous nucleation point, in the controlled preparation facilities of organic composite phase-changing energy storage material, under the perfusion effect of sonic oscillation coupled vacuum, it is prepared for porous graphene/PEG SA compounds nucleator, by the reciprocal action of organic-inorganic, improve the crystal property of PLA with this, thus strengthen the heat resistance of PLA.
Description
Technical field
The invention belongs to high-fire resistance degradation material preparing technical field, be specifically related to a kind of porous graphene/PEG-
The preparation method of SA/PLA composite.
Background technology
Since the mankind enter 21 century, science and technology development further, economic development is more swift and violent, but thus brought
Oil crisis problem and problem of environmental pollution are day by day serious, and therefore exploitation degradable biological macromolecular material has grand strategy meaning
Justice.Polylactic acid (PLA) has biogenetic derivation and the big characteristic of Wholly-degradable two concurrently, and because of prominent combination property be gradually lowered
Production cost, substitutes, by becoming, the environmentally friendly macromolecular material that conventional petroleum base plastics are ideal.At present, PLA is
Be widely used in the field such as biological medicine and environmental protection, but due in it in fragility, crystalline rate slowly, poor heat stability etc.
Problem, seriously limits its application in field more widely.The crystallization behavior of polylactic acid is with its mechanical property, degradability
Energy and thermostability etc. are the most directly related, and the extensively application of polylactic acid can be played good by the crystal property improving polylactic acid
Impetus.The most effectively accelerate the crystallization rate of PLA, improve the heat resistance important in inhibiting of PLA.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of porous graphene/PEG-SA/PLA composite, solve
Existing PLA crystalline rate is slowly and the problem of low heat resistant.
The technical solution adopted in the present invention is, the preparation method of a kind of porous graphene/PEG-SA/PLA composite,
Specifically, first prepare porous graphene/PEG-SA to compound nucleator, the nucleator prepared then is used to be prepared as with PLA
Porous graphene/PEG-SA/PLA composite.
The feature of the present invention also resides in:
Particularly as follows: first porous graphene/PEG-SA compounds the preparation method of nucleator, and with PEG as plasticizer, SA is high
Temperature decomposition components, with graphene oxide as carrier, wherein PEG accounts for mass fraction is that to account for mass fraction be 10-for 30-50%, SA
30%, it is 20-60% that graphene oxide accounts for mass fraction, and the mass percent sum of above each constituent content is 100%;Utilize
The controlled preparation facilities of organic composite phase-changing energy storage material carries out graphite oxide, PEG, SA three's melt blending, thus obtains oxygen
Functionalized graphene/PEG-SA blend, then carries out high temperature by Muffle furnace to graphene oxide/PEG-SA blend and quickly locates
Reason, leaves substantial amounts of cavity owing to high-temperature process makes the peroxy-radical of graphene oxide depart from rapidly, the lowest decomposition
The SA of temperature decomposes generation substantial amounts of gas expansion and porous graphene is uniformly dispersed, and finally prepares porous graphene/PEG-
SA compounds nucleator.
In the controlled preparation facilities of organic composite phase-changing energy storage material between hot pressing cavity temperature 40-70 DEG C, ultrasonic power
For 150-300W, duration of oscillation 5-20min, the relative vacuum degree 20-40kPa of vacuum pump.
Muffle furnace carries out high temperature when quickly processing to graphene oxide/PEG-SA blend, muffle furnace temperature 300-450
DEG C, process time 30-120s.
Porous graphene/PEG-SA compounds nucleator and prepares porous with PLA by double screw extruder melting mixing
Graphene/PEG-SA/PLA composite, wherein, melt temperature 160-200 DEG C, porous graphene/PEG-SA compounds nucleator
Accounting for mass fraction is that to account for mass fraction be 93-99% for 1-7%, PLA, and the mass percent sum of above each constituent content is
100%.
The invention has the beneficial effects as follows: the preparation method of one porous graphene/PEG-SA/PLA composite of the present invention,
Utilize the PEG of low-molecular-weight as plasticizer, increase the gap of molecule interchain, improve the motor capacity of strand, porous graphite
Alkene is as heterogeneous nucleation point, and in the controlled preparation facilities of organic composite phase-changing energy storage material, the perfusion of sonic oscillation coupled vacuum is made
It is prepared for porous graphene/PEG-SA under with and compounds nucleator, by the reciprocal action of organic and inorganic, improve PLA's with this
Crystal property, thus strengthen the heat resistance of PLA.
Accompanying drawing explanation
Fig. 1 be one of the present invention porous graphene/PEG-SA/PLA composite preparation method in graphene oxide/
The macrograph of PEG-SA blend;
Fig. 2 be one of the present invention porous graphene/PEG-SA/PLA composite preparation method in graphene oxide/
The microgram of PEG-SA blend;
Fig. 3 be one of the present invention porous graphene/PEG-SA/PLA composite preparation method in porous graphene/
PEG-SA compounds the macrograph of nucleator;
Fig. 4 be one of the present invention porous graphene/PEG-SA/PLA composite preparation method in porous graphene/
PEG-SA compounds the microgram of nucleator;
Fig. 5 be one of the present invention porous graphene/PEG-SA/PLA composite preparation method in porous graphene/
The thermal deformation figure of PEG-SA/PLA composite.
Detailed description of the invention
The present invention is described in detail with detailed description of the invention below in conjunction with the accompanying drawings.
Embodiment 1
The preparation method of one porous graphene/PEG-SA/PLA composite of the present invention, first prepare porous graphene/
PEG-SA compounds nucleator:
With PEG (Polyethylene Glycol) as plasticizer, SA (stearic acid) is pyrolytic component, with graphene oxide as carrier,
Wherein PEG accounts for mass fraction is 30%, and it is 10% that SA accounts for mass fraction, and it is 60% that graphene oxide accounts for mass fraction;Utilization has
The controlled preparation facilities of machine composite phase-change energy storage material carries out graphite oxide, PEG, SA three's melt blending, thus is aoxidized
Graphene/PEG-SA blend, graphene oxide/PEG-SA blend macrograph is as it is shown in figure 1, microgram is as in figure 2 it is shown, so
By Muffle furnace, graphene oxide/PEG-SA blend being carried out high temperature afterwards quickly to process, muffle furnace temperature 300 DEG C, during process
Between 120s, leave substantial amounts of owing to high-temperature process makes the peroxy-radical (-COOH ,-OH) of graphene oxide depart from rapidly
Cavity, the SA of the lowest decomposition temperature decomposes generation substantial amounts of gas expansion and porous graphene is uniformly dispersed, finally prepares
Porous graphene/PEG-SA compounds nucleator, and porous graphene/PEG-SA compounds the macrograph of nucleator as it is shown on figure 3, microcosmic
Figure is as shown in Figure 4.
The controlled preparation facilities of the organic composite phase-changing energy storage material employed in the present invention is Application No.:
2015204073124, filing date: 2015.06.12, notification number is: 204727838, and the day for announcing is: 2015.10.28's is special
The device that profit is protected, in the controlled preparation facilities of organic composite phase-changing energy storage material between hot pressing cavity temperature 40 DEG C, ultrasonic
Power is 200W, duration of oscillation 13min, the relative vacuum degree 30kPa of vacuum pump.
Then use the porous graphene/PEG-SA prepared to compound nucleator to be squeezed by twin screw with PLA (polylactic acid)
Go out machine melting mixing and prepare porous graphene/PEG-SA/PLA composite, wherein, melt temperature 160 DEG C, porous graphite
Alkene/PEG-SA compounds nucleator and accounts for mass fraction is 1%, and it is 99% that PLA accounts for mass fraction.
Embodiment 2
The preparation method of one porous graphene/PEG-SA/PLA composite of the present invention, first prepare porous graphene/
PEG-SA compounds nucleator:
With PEG (Polyethylene Glycol) as plasticizer, SA (stearic acid) is pyrolytic component, with graphene oxide as carrier,
Wherein PEG accounts for mass fraction is 50%, and it is 30% that SA accounts for mass fraction, and it is 20% that graphene oxide accounts for mass fraction;Utilization has
The controlled preparation facilities of machine composite phase-change energy storage material carries out graphite oxide, PEG, SA three's melt blending, thus is aoxidized
Graphene/PEG-SA blend, then carries out high temperature by Muffle furnace to graphene oxide/PEG-SA blend and quickly processes,
Muffle furnace temperature 400 DEG C, processes time 70s, owing to high-temperature process makes the peroxy-radical (-COOH ,-OH) of graphene oxide fast
Speed departs from and leaves substantial amounts of cavity, and the SA of the lowest decomposition temperature decomposes the substantial amounts of gas expansion of generation and makes porous graphite
Alkene is uniformly dispersed, and finally prepares porous graphene/PEG-SA and compounds nucleator.
The controlled preparation facilities of the organic composite phase-changing energy storage material employed in the present invention is Application No.:
2015204073124, filing date: 2015.06.12, notification number is: 204727838, and the day for announcing is: 2015.10.28's is special
The device that profit is protected, in the controlled preparation facilities of organic composite phase-changing energy storage material between hot pressing cavity temperature 60 DEG C, ultrasonic
Power is 300W, duration of oscillation 20min, the relative vacuum degree 20kPa of vacuum pump.
Then use the porous graphene/PEG-SA prepared to compound nucleator to be squeezed by twin screw with PLA (polylactic acid)
Go out machine melting mixing and prepare porous graphene/PEG-SA/PLA composite, wherein, melt temperature 180 DEG C, porous graphite
Alkene/PEG-SA compounds nucleator and accounts for mass fraction is 4%, and it is 96% that PLA accounts for mass fraction.
Embodiment 3
The preparation method of one porous graphene/PEG-SA/PLA composite of the present invention, first prepare porous graphene/
PEG-SA compounds nucleator:
With PEG (Polyethylene Glycol) as plasticizer, SA (stearic acid) is pyrolytic component, with graphene oxide as carrier,
Wherein PEG accounts for mass fraction is 40%, and it is 20% that SA accounts for mass fraction, and it is 40% that graphene oxide accounts for mass fraction;Utilization has
The controlled preparation facilities of machine composite phase-change energy storage material carries out graphite oxide, PEG, SA three's melt blending, thus is aoxidized
Graphene/PEG-SA blend, then carries out high temperature by Muffle furnace to graphene oxide/PEG-SA blend and quickly processes,
Muffle furnace temperature 450 DEG C, processes time 30s, owing to high-temperature process makes the peroxy-radical (-COOH ,-OH) of graphene oxide fast
Speed departs from and leaves substantial amounts of cavity, and the SA of the lowest decomposition temperature decomposes the substantial amounts of gas expansion of generation and makes porous graphite
Alkene is uniformly dispersed, and finally prepares porous graphene/PEG-SA and compounds nucleator.
The controlled preparation facilities of the organic composite phase-changing energy storage material employed in the present invention is Application No.:
2015204073124, filing date: 2015.06.12, notification number is: 204727838, and the day for announcing is: 2015.10.28's is special
The device that profit is protected, in the controlled preparation facilities of organic composite phase-changing energy storage material between hot pressing cavity temperature 70 DEG C, ultrasonic
Power is 150W, duration of oscillation 5min, the relative vacuum degree 40kPa of vacuum pump.
Then use the porous graphene/PEG-SA prepared to compound nucleator to be squeezed by twin screw with PLA (polylactic acid)
Go out machine melting mixing and prepare porous graphene/PEG-SA/PLA composite, wherein, melt temperature 200 DEG C, porous graphite
Alkene/PEG-SA compounds nucleator and accounts for mass fraction is 7%, and it is 93% that PLA accounts for mass fraction.
Polylactic acid (PLA) has biogenetic derivation and the big characteristic of Wholly-degradable two concurrently, and because of prominent combination property and gradually
The production cost reduced, substitutes, by becoming, the environmentally friendly macromolecular material that conventional petroleum base plastics are ideal.At present,
PLA has been widely used in the field such as biological medicine and environmental protection, but its crystalline rate slowly and degree of crystallinity low cause heat-resisting
Property difference and seriously limit its application in field more widely.Therefore, the crystal property improving polylactic acid can be to poly-
Good impetus is played in the extensively application of lactic acid.The application utilizes the PEG of low-molecular-weight as plasticizer, increases strand
Between gap, improve strand motor capacity, porous graphene is as heterogeneous nucleation point, at organic composite phase-changing energy storage material
Controlled preparation facilities in be prepared for porous graphene/PEG-SA under sonic oscillation coupled vacuum perfusion effect and compound nucleator,
By the reciprocal action of organic and inorganic, improve the crystal property of PLA with this, thus strengthen the heat resistance of PLA.
The Nano-size Porous Graphite alkene of high thermal stability is easily reunited in forming process and cannot be given full play to its induction knot
Brilliant effect, organic low molecular PEG is heated during the use of polymer product and can occur slowly to migrate and affect end article
Use.The present invention utilizes the controlled preparation facilities of organic composite phase-changing energy storage material to carry out graphite oxide, the low temperature of PEG and SA is total to
Mixed, make each component be uniformly dispersed thus develop the graphene oxide/PEG-SA blend of high dispersive.
It is illustrated in figure 5 thermal deformation (Vicat softening point) figure of porous graphene/PEG-SA/PLA composite, wherein,
In figure, A is the heat distortion temperature of pure PLA material, and B, C and D respectively with the addition of 1%, 4% and 7% porous graphene/PEG-
SA compounds the heat distortion temperature of the PLA composite of nucleator, by scheming it is found that the PLA that with the addition of compounding nucleator is heat-resisting
Property significantly improves, and it is added on about 4% heat-resistant deforming best results.
Claims (5)
1. the preparation method of porous graphene/PEG-SA/PLA composite, it is characterised in that specifically, first prepare
Porous graphene/PEG-SA compounds nucleator, then uses the nucleator prepared and PLA to be prepared as porous graphene/PEG-
SA/PLA composite.
The preparation method of a kind of porous graphene/PEG-SA/PLA composite the most according to claim 1, its feature exists
In, particularly as follows: first described porous graphene/PEG-SA compounds the preparation method of nucleator, and with PEG as plasticizer, SA is high
Temperature decomposition components, with graphene oxide as carrier, wherein PEG accounts for mass fraction is that to account for mass fraction be 10-for 30-50%, SA
30%, it is 20-60% that graphene oxide accounts for mass fraction, and the mass percent sum of above each constituent content is 100%;Utilize
The controlled preparation facilities of organic composite phase-changing energy storage material carries out graphite oxide, PEG, SA three's melt blending, thus obtains oxygen
Functionalized graphene/PEG-SA blend, then carries out high temperature by Muffle furnace to graphene oxide/PEG-SA blend and quickly locates
Reason, leaves substantial amounts of cavity owing to high-temperature process makes the peroxy-radical of graphene oxide depart from rapidly, the lowest decomposition
The SA of temperature decomposes generation substantial amounts of gas expansion and porous graphene is uniformly dispersed, and finally prepares porous graphene/PEG-
SA compounds nucleator.
The preparation method of a kind of porous graphene/PEG-SA/PLA composite the most according to claim 1, its feature exists
In, in the controlled preparation facilities of described organic composite phase-changing energy storage material between hot pressing cavity temperature 40-70 DEG C, ultrasonic power is
150-300W, duration of oscillation 5-20min, the relative vacuum degree 20-40kPa of vacuum pump.
The preparation method of a kind of porous graphene/PEG-SA/PLA composite the most according to claim 1, its feature exists
In, described Muffle furnace graphene oxide/PEG-SA blend is carried out high temperature quickly process time, muffle furnace temperature 300-450 DEG C,
Process time 30-120s.
The preparation method of a kind of porous graphene/PEG-SA/PLA composite the most according to claim 1, its feature exists
In, described porous graphene/PEG-SA compounds nucleator and prepares many with described PLA by double screw extruder melting mixing
Hole Graphene/PEG-SA/PLA composite, wherein, melt temperature 160-200 DEG C, porous graphene/PEG-SA compounds nucleation
It is that to account for mass fraction be 93-99% for 1-7%, PLA that agent accounts for mass fraction, and the mass percent sum of above each constituent content is
100%.
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CN106928906A (en) * | 2017-05-02 | 2017-07-07 | 吉林建筑大学 | A kind of stannic oxide/graphene nano inorganic phase-changing material and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101864098A (en) * | 2010-06-03 | 2010-10-20 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
KR20130103154A (en) * | 2012-03-09 | 2013-09-23 | 충남대학교산학협력단 | Polypropylene-polylactic acid mixed resin/graphene/natural fiber bionanocomposite and manufacturing method of thereof |
CN103804661A (en) * | 2014-01-22 | 2014-05-21 | 盐城菁华新材料科技有限公司 | Graphene/polylactic acid composite material and preparation method thereof |
CN104072959A (en) * | 2014-07-15 | 2014-10-01 | 南京航空航天大学 | Oxidized graphene modified foam material and preparation method thereof |
-
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- 2016-08-02 CN CN201610623604.0A patent/CN106243651B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101864098A (en) * | 2010-06-03 | 2010-10-20 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
KR20130103154A (en) * | 2012-03-09 | 2013-09-23 | 충남대학교산학협력단 | Polypropylene-polylactic acid mixed resin/graphene/natural fiber bionanocomposite and manufacturing method of thereof |
CN103804661A (en) * | 2014-01-22 | 2014-05-21 | 盐城菁华新材料科技有限公司 | Graphene/polylactic acid composite material and preparation method thereof |
CN104072959A (en) * | 2014-07-15 | 2014-10-01 | 南京航空航天大学 | Oxidized graphene modified foam material and preparation method thereof |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106928906A (en) * | 2017-05-02 | 2017-07-07 | 吉林建筑大学 | A kind of stannic oxide/graphene nano inorganic phase-changing material and preparation method thereof |
CN106928906B (en) * | 2017-05-02 | 2019-08-02 | 吉林建筑大学 | A kind of stannic oxide/graphene nano inorganic phase-changing material and preparation method thereof |
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