CN102675804A - Thermoplastic konjac glucomannan/graphene oxide compound material and preparation method thereof - Google Patents
Thermoplastic konjac glucomannan/graphene oxide compound material and preparation method thereof Download PDFInfo
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- CN102675804A CN102675804A CN2012101536680A CN201210153668A CN102675804A CN 102675804 A CN102675804 A CN 102675804A CN 2012101536680 A CN2012101536680 A CN 2012101536680A CN 201210153668 A CN201210153668 A CN 201210153668A CN 102675804 A CN102675804 A CN 102675804A
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Abstract
The invention discloses a thermoplastic konjac glucomannan/graphene oxide compound material and a preparation method thereof. The invention is characterized in that the compound material comprises the following components according to parts by weight: 1 to 99 parts of thermoplastic konjac glucomannan, 0.001 to 2 parts of graphene oxide, 0 to 10 parts of cross-linking agent and 0 to 10 parts of plasticizing agent; and the preparation method comprises the following steps of: proportioning; adding the thermoplastic konjac glucomannan into an ethanol or water solution of the graphene oxide, stirring for 5 to 10 hours, filtering and drying solid substances; then, drying after stirring and mixing with the cross-linking agent and the plasticizing agent in a mixing machine evenly; and afterwards, placing into a double-screw extrusion machine, extruding after carrying out melt blending at the temperature of 100 to 140 DEG C for 5 to 15 minutes, and granulating so as to prepare the compound material. The compound material has favorable processing performance, has excellent adsorbability, thermal stability and mechanical toughness, can be biologically degraded, can be regenerated, has no pollution to the environment and can be widely applied to the fields of chemical engineering, medicine, environmental protection, capital construction and the like.
Description
Technical field
The invention belongs to matrix material and preparation method thereof, relate to a kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material and preparation method thereof.Thermoplasticity Rhizoma amorphophalli glucomannan provided by the invention/graphene oxide matrix material has good adsorptivity, thermostability and mechanical tenacity; And biodegradable, renewable, environmentally safe can be used as fire retardant material, structured material, sorbing material and are widely used in chemical industry, medicine, environmental protection, machine and the field such as build.
Background technology
The annual production in the whole world surpasses 200,000,000 tons of plastics confession people consumption.Synthesized polymer material is with its good weather resistance, anti-medium property, HS and be easy to premium propertiess such as processing and become indispensable part in industrial production and the daily life; But exhausted day by day along with fossil resources such as the main raw material oil of macromolecule chemical industry, coals; Cause the oil coal price to skyrocket; And traditional nondegradation macromolecular material waste is increasing, causes great environmental pollution, and direct threats is to human Sustainable development.In order to realize the Sustainable development of world economy; One of correlative study both domestic and external forward position is to utilize clearer production technology with reproducible Biological resources, modification, the synthetic environment friendly novel property macromolecular material that satisfies request for utilization, infinitely develops to the pollution of environment with to resource to reduce.For this reason, utilize environment friendly natural polymer novel material preparation to come into one's own day by day based on renewable resources.
Rhizoma amorphophalli glucomannan is a kind of natural macromolecule amylose, comprises glucose and seminose in its molecule, and with β-1, the 4-glycosidic link connects, and also has acetyl group simultaneously.As a kind of renewable natural resource; The Rhizoma amorphophalli glucomannan source is sufficient; Biodegradable; Multifrequency natures such as possess hydrophilic property, gelation, film-forming properties, bacterinertness, low heat value property and the physiological function that some are special, and chemical modifiable functional group can be widely used in food, medicine, chemical industry and biological field.The thermoplasticity Rhizoma amorphophalli glucomannan is that a kind of process is by Rhizoma amorphophalli glucomannan and various organic monomer radical polymerization; Grafting, but the thermoplastic material of a kind of fully biodegradable that chemical process such as crosslinked obtains has very strong hydrophobicity; Can combine with organic molecule with inorganic; Form a kind of new property matrix material,, gather around to have broad application prospects for alternative petrochemical complex plastics provide new thinking.But, limited its application because thermoplasticity Rhizoma amorphophalli glucomannan comprehensive mechanical property is relatively poor.
Graphene oxide is a kind of important growth of Graphene; The Graphene that also is called as functionalization; Its structure is identical substantially with Graphene, just on two-dimentional basal plane, is connected with some functional groups, mainly is some oxygen-containing functional groups; Like many activity functional groups such as hydroxyl, carboxyl, epoxy group(ing) and carbonyls; Wherein hydroxyl and epoxy-functional mainly are positioned on the basal plane of graphite, and carboxyl, oxygen base and carbonyl then are in the edge of Graphene, and this makes it can be combined into new property matrix material with some other macromolecular compound.Therefore; Insert graphene oxide in the organic polymer as a kind of inorganic molecule; Can improve heat conduction, conduction and the mechanical property of macromolecular material, improve heat-resistant stability, chemical resistant properties and the mechanical property of matrix material, for matrix material provides more wide Application Areas.At present, along with the maturation utilization that mechanically peel prepares the graphene oxide technology, people have realized the synthetic of graphene oxide/high molecule nano composite material, and the preparation method mainly contains blending method, sol-gel method, graft process and situ aggregation method.Macromolecule matrix commonly used has PS, polyaniline, and the Vestolen PP 7052 phthalein, Z 150PH etc., but, cause the environmentally friendly relatively poor of matrix material because the polymerization macromolecule degraded is difficult.
In the prior art, the bibliographical information of the relevant thermoplasticity Rhizoma amorphophalli glucomannan of Shang Weijian/graphene oxide matrix material.
Summary of the invention
The object of the invention is intended to overcome deficiency of the prior art, and a kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material and preparation method thereof is provided.The present invention is a raw material with the natural polymer Rhizoma amorphophalli glucomannan; Add new property inorganic materials graphene oxide, obtain a kind of composite material, this matrix material has good adsorptivity, thermostability and mechanical tenacity; And it is biodegradable, renewable; Environmentally safe, processing characteristics is good in extrusion molding, blowing, injection moulding and foaming process, can be widely used in chemical industry, medicine, environmental protection, machine and the field such as build.
Content of the present invention is: a kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material, it is characterized in that: component and weight part consist of: 0～10 part in 1～99 part of thermoplasticity Rhizoma amorphophalli glucomannan, 0.001～2 part of graphene oxide, 0～10 part of linking agent and softening agent.
In the content of the present invention: said component and weight part are formed and are preferably: 0.5～10 part in 1～99 part of thermoplasticity Rhizoma amorphophalli glucomannan, 0.001～2 part of graphene oxide, 0.5～10 part of linking agent and softening agent.
In the content of the present invention: the preparation method of said thermoplasticity Rhizoma amorphophalli glucomannan can be: by weight ratio 100 parts of konjaku powders being swollen in concentration of volume percent is in 500 parts of 40% the aqueous ethanolic solutions; Stir (dissolving) after adding 2 parts of NaOH, mix; Under 70 ℃ temperature, carry out (deacetylation) reaction 4 hours; Filter, solids with ethanol or/and water washing 2～5 times (to neutral, the pH of the washings after promptly washing is 6.5～7.5) swell in again after 24 hours in 500 parts of water 40 ℃ of dryings then; Add 50 parts of 5 parts of ammonium persulphates, 50 parts of methyl acrylates and vinyl-acetic esters again, under 70 ℃ temperature, carry out (graft copolymerization) reaction 5 hours; Filter, solids or/and water washing 2～5 times, 40 ℃ of dryings 24 hours, promptly makes the thermoplasticity Rhizoma amorphophalli glucomannan with ethanol; The preparation of this thermoplasticity Rhizoma amorphophalli glucomannan or acquisition methods also can be other methods of the prior art.
In the content of the present invention: said linking agent can be one or more the mixture in MALEIC ANHYDRIDE, tributyl citrate, the ethylene bis stearic acid amide.
In the content of the present invention: said softening agent can be one or more the mixture in USP Kosher, polyoxyethylene glycol, the dimethyl phthalate.
Another content of the present invention is: the preparation method of a kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material is characterized in that comprising the following steps:
A, batching: press 1～99 part of component and weight part proportioning heat-obtaining plasticity Rhizoma amorphophalli glucomannan, 0.001～2 part of graphene oxide, 0～10 part of linking agent, 0～10 part in softening agent;
B, combination drying: the thermoplasticity Rhizoma amorphophalli glucomannan is joined the ethanol or the aqueous solution of graphene oxide, and mechanical stirring 5～10 hours mixes it, filter, solids under 80～110 ℃ temperature dry 1～3 hour, dry mixture;
The ethanol of said graphene oxide or the preparation method of the aqueous solution can be: graphene oxide is dissolved in ethanol or the water, is mixed with the ethanol or the aqueous solution that concentration is the graphene oxide of 0.01～20g/L; Using power then is that the ultrasonic device of 300～1000W carries out ultrasonic (peeling off) to the ethanol of said graphene oxide or the aqueous solution and handled 1～5 hour, promptly obtains the ethanol or the aqueous solution of (homogeneous stability) graphene oxide;
C, blend are dry: with dry mixture and linking agent, softening agent stirring and evenly mixing after 5～30 minutes in mixing machine, and under 20～60 ℃ temperature dry 8～12 hours, must blend;
D, granulation: with blend drop in the twin screw extruder, in melt blending under 100～140 ℃ the temperature after 5～15 minutes, under the pressure of 0.1～1MPa, extrude, granulation, promptly make thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material.
In another content of the present invention: component described in the step a and weight part proportioning are 1～99 part of thermoplasticity Rhizoma amorphophalli glucomannan preferably, 0.001～2 part of graphene oxide, 0.5～10 part of linking agent, 0.5～10 part in softening agent.
In another content of the present invention: the preparation method of the Rhizoma amorphophalli glucomannan of thermoplasticity described in the step a can be: by weight ratio 100 parts of konjaku powders being swollen in concentration of volume percent is in 500 parts of 40% the aqueous ethanolic solutions; Stir (dissolving) after adding 2 parts of NaOH, mix; Under 70 ℃ temperature, carry out (deacetylation) reaction 4 hours; Filter, solids with ethanol or/and water washing 2～5 times (to neutral, the pH of the washings after promptly washing is 6.5～7.5) swell in again after 24 hours in 500 parts of water 40 ℃ of dryings then; Add 50 parts of 5 parts of ammonium persulphates, 50 parts of methyl acrylates and vinyl-acetic esters again, under 70 ℃ temperature, carry out (graft copolymerization) reaction 5 hours; Filter, solids or/and water washing 2～5 times, 40 ℃ of dryings 24 hours, promptly makes the thermoplasticity Rhizoma amorphophalli glucomannan with ethanol; The preparation of this thermoplasticity Rhizoma amorphophalli glucomannan or acquisition methods also can be other methods of the prior art.
In another content of the present invention: linking agent described in the step a can be one or more the mixture in MALEIC ANHYDRIDE, tributyl citrate, the ethylene bis stearic acid amide.
In another content of the present invention: step a softening agent can be one or more the mixture in USP Kosher, polyoxyethylene glycol, the dimethyl phthalate.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) adopts the present invention; But the thermoplastic material of a kind of fully biodegradable that the thermoplasticity Rhizoma amorphophalli glucomannan is a kind of process to be obtained by Rhizoma amorphophalli glucomannan and various organic monomer radical polymerization, grafting, chemical process such as crosslinked; Very strong hydrophobicity is arranged, can combine with organic molecule with inorganic; Graphene oxide is connected with some oxygen-containing functional groups on two-dimentional basal plane, like many activity functional groups such as hydroxyl, carboxyl, epoxy group(ing) and carbonyls, make it can be combined into environmentally friendly property matrix material with the thermoplasticity Rhizoma amorphophalli glucomannan; The present invention utilizes simple melt blending process; Generation between the main activity functional groups of thermoplastics type's Rhizoma amorphophalli glucomannan and graphene oxide is connected or associating chemical reaction; The chemical reaction that combines as between the hydroxyl of the hydroxyl on graphene oxide surface and thermoplastic glucomannan glycan becomes a kind of novel complexes; Therefore; Insert graphene oxide in thermoplastics type's Rhizoma amorphophalli glucomannan as a kind of inorganic nanoparticles; Mono-layer graphite oxide alkene high-specific surface area, HS, high-modulus, good characteristics such as chemical thermotolerance have been made full use of; Thermoplastics type's Rhizoma amorphophalli glucomannan is improved a lot in aspect performances such as mechanical, heat-resisting, absorption, thereby improve mechanical property, thermal stability and the absorption property etc. of macromolecular material;
(2) adopt the present invention, Rhizoma amorphophalli glucomannan is as a kind of natural high moleculer eompound, and belongs to renewable resources, and the source is sufficient and biodegradable, environmentally friendly, and it is carried out graft modification, becomes thermoplastic glucomannan, has improved its thermostability; Graphene oxide has many particular performances, behind thermoplastic glucomannan formation mixture, has improved mechanical tenacity, adsorptivity and the thermostability of material; Thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material, process operation is simple and easy to control, can use conventional equipment to carry out suitability for industrialized production;
What (3) the present invention provided thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material is a kind of new property matrix material, has good adsorptivity, thermostability and mechanical tenacity, high comprehensive performance; And it is biodegradable; Renewable, environmentally friendly, environmentally safe; Processing characteristics is good in extrusion molding, blowing, injection moulding and foaming process, can be widely used in chemical industry, medicine, environmental protection, machine and the field such as build; Preparation technology is simple, and operation is easy, and operation is practical easily.
Embodiment
Embodiment given below intends so that the present invention is described further; But can not be interpreted as it is restriction to protection domain of the present invention; The technician in this field to some nonessential improvement and adjustment that the present invention makes, still belongs to protection scope of the present invention according to the content of the invention described above.
Embodiment 1:
Take by weighing graphene oxide 0. 1g by weight; Be dissolved in the ethanol; Being mixed with concentration is the graphene oxide ethanolic soln of 0.1g/L; Use power said graphene oxide ethanolic soln to be carried out supersound process 2 hours then, obtain the graphene oxide ethanolic soln of homogeneous stability as the ultrasonic device of 500W; In the graphene oxide ethanolic soln that 50 parts of thermoplasticity Rhizoma amorphophalli glucomannans is joined homogeneous stability after the supersound process, mechanical stirring is 10 hours then then, mix mixing after, filtering solution, with mixture 80 ℃ dry 3 hours down; Then mixture and MALEIC ANHYDRIDE were stirred 5 minutes in high-speed mixer for 10 parts; 60 ℃ of dryings of temperature 8 hours; Temperature control in 100 ℃ with intermingling material melt blending 5 minutes in the duplex extruding machine; At the 1MPa extruding pelletization, promptly make thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material.
Embodiment 2:
Take by weighing graphene oxide 0.5g by weight; Be dissolved in the water; Being mixed with concentration is the graphite oxide aqueous solution of 0.5g/L, uses power as the ultrasonic device of 600W said graphite oxide aqueous solution to be carried out supersound process 3 hours then, obtains the graphite oxide aqueous solution of homogeneous stability; In the graphite oxide aqueous solution that 15 parts of thermoplasticity Rhizoma amorphophalli glucomannans is joined homogeneous stability after the supersound process, mechanical stirring is 10 hours then then, mix mixing after, filtering solution, with mixture 90 ℃ dry 3 hours down; Then mixture and USP Kosher were stirred 20 minutes in high-speed mixer for 10 parts; 50 ℃ of dryings of temperature 9 hours; Temperature control in 120 ℃ with intermingling material melt blending 10 minutes in the duplex extruding machine; At the 0.3MPa extruding pelletization, promptly make thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material.
Embodiment 3:
Take by weighing graphene oxide 1g by weight; Be dissolved in the ethanol; Being mixed with concentration is the graphene oxide ethanolic soln of 1g/L, uses power as the ultrasonic device of 400W said graphene oxide ethanolic soln to be carried out supersound process 5 hours then, obtains the graphene oxide ethanolic soln of homogeneous stability; In the graphene oxide ethanolic soln that 30 parts of thermoplasticity Rhizoma amorphophalli glucomannans is joined homogeneous stability after the supersound process, mechanical stirring is 10 hours then then, mix mixing after, filtering solution, with mixture 100 ℃ dry 1 hour down; Then 2 parts of mixture and tributyl citrates were stirred 15 minutes in high-speed mixer for 2 parts with polyoxyethylene glycol; 40 ℃ of dryings of temperature 10 hours; Temperature control in 110 ℃ with intermingling material melt blending 10 minutes in the duplex extruding machine; At the 1MPa extruding pelletization, promptly make thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material.
Embodiment 4:
Take by weighing graphene oxide 2g by weight; Be dissolved in the water; Being mixed with concentration is the graphite oxide aqueous solution of 2g/L, uses power as the ultrasonic device of 800W said graphite oxide aqueous solution to be carried out supersound process 4 hours then, obtains the graphene oxide aqueous solution of homogeneous stability; In the graphite oxide aqueous solution that 40 parts of thermoplasticity Rhizoma amorphophalli glucomannans is joined homogeneous stability after the supersound process, mechanical stirring is 10 hours then then, mix mixing after, filtering solution, with mixture 110 ℃ dry 1 hour down; Then with 3 parts of mixture and MALEIC ANHYDRIDEs; Tributyl citrate stirred 30 minutes in high-speed mixer for 4 parts; 60 ℃ of dryings of temperature 8 hours; Temperature control in 130 ℃ with intermingling material melt blending 12 minutes in the duplex extruding machine, at the 0.5MPa extruding pelletization, promptly make thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material.
Embodiment 5:
Take by weighing graphene oxide 5g by weight; Be dissolved in the ethanol; Being mixed with concentration is the graphene oxide ethanolic soln of 5g/L, uses power as the ultrasonic device of 1000W said graphene oxide ethanolic soln to be carried out supersound process 5 hours then, obtains the graphene oxide ethanolic soln of homogeneous stability; Then 60 parts of thermoplasticity Rhizoma amorphophalli glucomannans are joined in the graphene oxide ethanolic soln of homogeneous stability after the supersound process, mechanical stirring is 10 hours then, mix mixing after, filtering solution, with mixture 95 ℃ dry 2 hours down; Then with 5 parts of mixture and polyoxyethylene glycol; Dimethyl phthalate stirred 25 minutes in high-speed mixer for 3 parts; 40 ℃ of dryings of temperature 11 hours; Temperature control in 130 ℃ with intermingling material melt blending 12 minutes in the duplex extruding machine, at the 0.3MPa extruding pelletization, promptly make thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material.
Embodiment 6:
Take by weighing graphene oxide 0.01g by weight; Be dissolved in the water; Being mixed with concentration is the graphite oxide aqueous solution of 0.01g/L, uses power as the ultrasonic device of 750W said graphite oxide aqueous solution to be carried out supersound process 2.5 hours then, obtains the graphite oxide aqueous solution of homogeneous stability; In the graphite oxide aqueous solution that 40 parts of thermoplasticity Rhizoma amorphophalli glucomannans is joined homogeneous stability after the supersound process, mechanical stirring is 10 hours then then, mix mixing after, filtering solution, with mixture 85 ℃ dry 2 hours down; Then with 5 parts of mixture and MALEIC ANHYDRIDEs; 1 part of tributyl citrate, 5 parts of dimethyl phthalates stirred 25 minutes in high-speed mixer; 50 ℃ of dryings of temperature 10 hours; Temperature control in 120 ℃ with intermingling material melt blending 5 minutes in the duplex extruding machine, at the 0.6MPa extruding pelletization, promptly make thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material.
Embodiment 7:
A kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material, the component and the weight part of this matrix material consist of: 1 part of thermoplasticity Rhizoma amorphophalli glucomannan, 0.001 part of graphene oxide.
Embodiment 8:
A kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material, the component and the weight part of this matrix material consist of: 10 parts in 99 parts of thermoplasticity Rhizoma amorphophalli glucomannans, 2 parts of graphene oxides, 10 parts of linking agents and softening agent.
Embodiment 9:
A kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material, the component and the weight part of this matrix material consist of: 5 parts in 50 parts of thermoplasticity Rhizoma amorphophalli glucomannans, 1 part of graphene oxide, 5 parts of linking agents and softening agent.
Embodiment 10:
A kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material, the component and the weight part of this matrix material consist of: 0.5 part in 1 part of thermoplasticity Rhizoma amorphophalli glucomannan, 0.001 part of graphene oxide, 0.5 part of linking agent and softening agent.
Embodiment 11:
A kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material, the component and the weight part of this matrix material consist of: 1 part in 10 parts of thermoplasticity Rhizoma amorphophalli glucomannans, 0.01 part of graphene oxide, 1 part of linking agent and softening agent.
Embodiment 12:
A kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material, the component and the weight part of this matrix material consist of: 0～10 part in 1～99 part of thermoplasticity Rhizoma amorphophalli glucomannan, 0.001～2 part of graphene oxide, 0～10 part of linking agent and softening agent;
The concrete weight part consumption of each feed composition sees the following form among each embodiment:
Embodiment 19:
A kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material, the component and the weight part of this matrix material consist of: 99 parts of thermoplasticity Rhizoma amorphophalli glucomannans, 2 parts of graphene oxides.
Embodiment 20:
A kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material, the component and the weight part of this matrix material consist of: 45 parts of thermoplasticity Rhizoma amorphophalli glucomannans, 1 part of graphene oxide.
Embodiment 21:
A kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material, the component and the weight part of this matrix material consist of: 90 parts of thermoplasticity Rhizoma amorphophalli glucomannans, 0.1 part of graphene oxide.
Embodiment 22:
A kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material, the component and the weight part of this matrix material consist of: 60 parts of thermoplasticity Rhizoma amorphophalli glucomannans, 0.5 part of graphene oxide.
Embodiment 23:
The preparation method of a kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material comprises the following steps:
A, batching: press 1～99 part of component and weight part proportioning heat-obtaining plasticity Rhizoma amorphophalli glucomannan, 0.001～2 part of graphene oxide, 0～10 part of linking agent, 0～10 part in softening agent; The concrete weight part consumption of each feed composition can be for arbitrary among the embodiment 7～22;
B, combination drying: the thermoplasticity Rhizoma amorphophalli glucomannan is joined the ethanol or the aqueous solution of graphene oxide, and mechanical stirring 5 hours mixes it, filter, solids under 80 ℃ temperature dry 3 hours, dry mixture;
The ethanol of said graphene oxide or the preparation method of the aqueous solution can be: graphene oxide is dissolved in ethanol or the water, is mixed with the ethanol or the aqueous solution that concentration is the graphene oxide of 0.01g/L; Use power the ethanol of said graphene oxide or the aqueous solution to be carried out ultrasonic (peeling off) then and handled 5 hours, promptly obtain the ethanol or the aqueous solution of (homogeneous stability) graphene oxide as the ultrasonic device of 300W;
C, blend are dry: with dry mixture and linking agent, softening agent stirring and evenly mixing after 5 minutes in mixing machine, and under 20 ℃ temperature dry 12 hours, must blend;
D, granulation: with blend drop in the twin screw extruder, in melt blending under 100 ℃ the temperature after 15 minutes, under the pressure of 0.1MPa, extrude, granulation, promptly make thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material.
Embodiment 24:
The preparation method of a kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material comprises the following steps:
A, batching: press 1～99 part of component and weight part proportioning heat-obtaining plasticity Rhizoma amorphophalli glucomannan, 0.001～2 part of graphene oxide, 0～10 part of linking agent, 0～10 part in softening agent; The concrete weight part consumption of each feed composition is arbitrary among the embodiment 7～22;
B, combination drying: the thermoplasticity Rhizoma amorphophalli glucomannan is joined the ethanol or the aqueous solution of graphene oxide, and mechanical stirring 10 hours mixes it, filter, solids under 110 ℃ temperature dry 1 hour, dry mixture;
The ethanol of said graphene oxide or the preparation method of the aqueous solution can be: graphene oxide is dissolved in ethanol or the water, is mixed with the ethanol or the aqueous solution that concentration is the graphene oxide of 20g/L; Use power the ethanol of said graphene oxide or the aqueous solution to be carried out ultrasonic (peeling off) then and handled 1 hour, promptly obtain the ethanol or the aqueous solution of (homogeneous stability) graphene oxide as the ultrasonic device of 1000W;
C, blend are dry: with dry mixture and linking agent, softening agent stirring and evenly mixing after 30 minutes in mixing machine, and under 60 ℃ temperature dry 8 hours, must blend;
D, granulation: with blend drop in the twin screw extruder, in melt blending under 140 ℃ the temperature after 5 minutes, under the pressure of 1MPa, extrude, granulation, promptly make thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material.
Embodiment 25:
The preparation method of a kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material comprises the following steps:
A, batching: press 1～99 part of component and weight part proportioning heat-obtaining plasticity Rhizoma amorphophalli glucomannan, 0.001～2 part of graphene oxide, 0～10 part of linking agent, 0～10 part in softening agent; The concrete weight part consumption of each feed composition is arbitrary among the embodiment 7～22;
B, combination drying: the thermoplasticity Rhizoma amorphophalli glucomannan is joined the ethanol or the aqueous solution of graphene oxide, and mechanical stirring 7.5 hours mixes it, filter, solids under 95 ℃ temperature dry 2 hours, dry mixture;
The ethanol of said graphene oxide or the preparation method of the aqueous solution can be: graphene oxide is dissolved in ethanol or the water, is mixed with the ethanol or the aqueous solution that concentration is the graphene oxide of 10g/L; Use power the ethanol of said graphene oxide or the aqueous solution to be carried out ultrasonic (peeling off) then and handled 2.5 hours, promptly obtain the ethanol or the aqueous solution of (homogeneous stability) graphene oxide as the ultrasonic device of 500W;
C, blend are dry: with dry mixture and linking agent, softening agent stirring and evenly mixing after 17 minutes in mixing machine, and under 40 ℃ temperature dry 10 hours, must blend;
D, granulation: with blend drop in the twin screw extruder, in melt blending under 120 ℃ the temperature after 10 minutes, under the pressure of 0.5MPa, extrude, granulation, promptly make thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material.
Embodiment 26:
The preparation method of a kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material comprises the following steps:
A, batching: press 1～99 part of component and weight part proportioning heat-obtaining plasticity Rhizoma amorphophalli glucomannan, 0.001～2 part of graphene oxide, 0～10 part of linking agent, 0～10 part in softening agent; The concrete weight part consumption of each feed composition is arbitrary among the embodiment 7～22;
B, combination drying: the thermoplasticity Rhizoma amorphophalli glucomannan is joined the ethanol or the aqueous solution of graphene oxide, and mechanical stirring 5～10 hours mixes it, filter, solids under 80～110 ℃ temperature dry 1～3 hour, dry mixture;
The ethanol of said graphene oxide or the preparation method of the aqueous solution can be: graphene oxide is dissolved in ethanol or the water, is mixed with the ethanol or the aqueous solution that concentration is the graphene oxide of 0.01～20g/L; Using power then is that the ultrasonic device of 300～1000W carries out ultrasonic (peeling off) to the ethanol of said graphene oxide or the aqueous solution and handled 1～5 hour, promptly obtains the ethanol or the aqueous solution of (homogeneous stability) graphene oxide;
C, blend are dry: with dry mixture and linking agent, softening agent stirring and evenly mixing after 5～30 minutes in mixing machine, and under 20～60 ℃ temperature dry 8～12 hours, must blend;
D, granulation: with blend drop in the twin screw extruder, in melt blending under 100～140 ℃ the temperature after 5～15 minutes, under the pressure of 0.1～1MPa, extrude, granulation, promptly make thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material.
Embodiment 27:
The preparation method of a kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material comprises the following steps:
A, batching: press 1～99 part of component and weight part proportioning heat-obtaining plasticity Rhizoma amorphophalli glucomannan, 0.001～2 part of graphene oxide, 0～10 part of linking agent, 0～10 part in softening agent; The concrete weight part consumption of each feed composition is arbitrary among the embodiment 7～22;
B, combination drying: the thermoplasticity Rhizoma amorphophalli glucomannan is joined the ethanol or the aqueous solution of graphene oxide, and mechanical stirring 6 hours mixes it, filter, solids under 90 ℃ temperature dry 1.5 hours, dry mixture;
The ethanol of said graphene oxide or the preparation method of the aqueous solution can be: graphene oxide is dissolved in ethanol or the water, is mixed with the ethanol or the aqueous solution that concentration is the graphene oxide of 0.1g/L; Use power the ethanol of said graphene oxide or the aqueous solution to be carried out ultrasonic (peeling off) then and handled 2 hours, promptly obtain the ethanol or the aqueous solution of (homogeneous stability) graphene oxide as the ultrasonic device of 400W;
C, blend are dry: with dry mixture and linking agent, softening agent stirring and evenly mixing after 10 minutes in mixing machine, and under 30 ℃ temperature dry 11 hours, must blend;
D, granulation: with blend drop in the twin screw extruder, in melt blending under 110 ℃ the temperature after 8 minutes, under the pressure of 0.3MPa, extrude, granulation, promptly make thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material.
Embodiment 28:
The preparation method of a kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material comprises the following steps:
A, batching: press 1～99 part of component and weight part proportioning heat-obtaining plasticity Rhizoma amorphophalli glucomannan, 0.001～2 part of graphene oxide, 0～10 part of linking agent, 0～10 part in softening agent; The concrete weight part consumption of each feed composition is arbitrary among the embodiment 7～22;
B, combination drying: the thermoplasticity Rhizoma amorphophalli glucomannan is joined the ethanol or the aqueous solution of graphene oxide, and mechanical stirring 7 hours mixes it, filter, solids under 100 ℃ temperature dry 2 hours, dry mixture;
The ethanol of said graphene oxide or the preparation method of the aqueous solution can be: graphene oxide is dissolved in ethanol or the water, is mixed with the ethanol or the aqueous solution that concentration is the graphene oxide of 1g/L; Use power the ethanol of said graphene oxide or the aqueous solution to be carried out ultrasonic (peeling off) then and handled 3 hours, promptly obtain the ethanol or the aqueous solution of (homogeneous stability) graphene oxide as the ultrasonic device of 600W;
C, blend are dry: with dry mixture and linking agent, softening agent stirring and evenly mixing after 15 minutes in mixing machine, and under 40 ℃ temperature dry 10 hours, must blend;
D, granulation: with blend drop in the twin screw extruder, in melt blending under 120 ℃ the temperature after 10 minutes, under the pressure of 0.6MPa, extrude, granulation, promptly make thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material.
Embodiment 29:
The preparation method of a kind of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material comprises the following steps:
A, batching: press 1～99 part of component and weight part proportioning heat-obtaining plasticity Rhizoma amorphophalli glucomannan, 0.001～2 part of graphene oxide, 0～10 part of linking agent, 0～10 part in softening agent; The concrete weight part consumption of each feed composition is arbitrary among the embodiment 7～22;
B, combination drying: the thermoplasticity Rhizoma amorphophalli glucomannan is joined the ethanol or the aqueous solution of graphene oxide, and mechanical stirring 8 hours mixes it, filter, solids under 110 ℃ temperature dry 2 hours, dry mixture;
The ethanol of said graphene oxide or the preparation method of the aqueous solution can be: graphene oxide is dissolved in ethanol or the water, is mixed with the ethanol or the aqueous solution that concentration is the graphene oxide of 15g/L; Use power the ethanol of said graphene oxide or the aqueous solution to be carried out ultrasonic (peeling off) then and handled 4 hours, promptly obtain the ethanol or the aqueous solution of (homogeneous stability) graphene oxide as the ultrasonic device of 800W;
C, blend are dry: with dry mixture and linking agent, softening agent stirring and evenly mixing after 25 minutes in mixing machine, and under 50 ℃ temperature dry 11 hours, must blend;
D, granulation: with blend drop in the twin screw extruder, in melt blending under 140 ℃ the temperature after 9 minutes, under the pressure of 0.9MPa, extrude, granulation, promptly make thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material.
In the foregoing description 7～29: the preparation method of the Rhizoma amorphophalli glucomannan of thermoplasticity described in the step a can be: by weight ratio 100 parts of konjaku powders being swollen in concentration of volume percent is in 500 parts of 40% the aqueous ethanolic solutions; Stir (dissolving) after adding 2 parts of NaOH, mix; Under 70 ℃ temperature, carry out (deacetylation) reaction 4 hours; Filter, solids with ethanol or/and water washing 2～5 times (to neutral, the pH of the washings after promptly washing is 6.5～7.5) swell in again after 24 hours in 500 parts of water 40 ℃ of dryings then; Add 50 parts of 5 parts of ammonium persulphates, 50 parts of methyl acrylates and vinyl-acetic esters again, under 70 ℃ temperature, carry out (graft copolymerization) reaction 5 hours; Filter, solids or/and water washing 2～5 times, 40 ℃ of dryings 24 hours, promptly makes the thermoplasticity Rhizoma amorphophalli glucomannan with ethanol; The preparation of this thermoplasticity Rhizoma amorphophalli glucomannan or acquisition methods also can be other methods of the prior art.
In the foregoing description 7～29: linking agent described in the step a can be one or more the mixture in MALEIC ANHYDRIDE, tributyl citrate, the ethylene bis stearic acid amide.
In the foregoing description 7～29: step a softening agent can be one or more the mixture in USP Kosher, polyoxyethylene glycol, the dimethyl phthalate.
In the foregoing description: each raw material that is adopted is the commercially available prod.
In the foregoing description: in the percentage that is adopted, do not indicate especially, be weight (quality) percentage; Said weight part can all be gram or kilogram.
In the foregoing description: the processing parameter in each step (temperature, time, concentration etc.) and each amounts of components numerical value etc. are scope, and any point is all applicable.
The not concrete same prior art of narrating of technology contents in content of the present invention and the foregoing description.
The invention is not restricted to the foregoing description, content of the present invention is said all can implement and have said good result.
Claims (10)
1. thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material, it is characterized in that: component and weight part consist of: 0～10 part in 1～99 part of thermoplasticity Rhizoma amorphophalli glucomannan, 0.001～2 part of graphene oxide, 0～10 part of linking agent and softening agent.
2. by the said thermoplasticity Rhizoma amorphophalli glucomannan of claim 1/graphene oxide matrix material, it is characterized in that: said component and weight part consist of: 0.5～10 part in 1～99 part of thermoplasticity Rhizoma amorphophalli glucomannan, 0.001～2 part of graphene oxide, 0.5～10 part of linking agent and softening agent.
3. by claim 1 or 2 said thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix materials; It is characterized in that: the preparation method of said thermoplasticity Rhizoma amorphophalli glucomannan can be: by weight ratio 100 parts of konjaku powders being swollen in concentration of volume percent is in 500 parts of 40% the aqueous ethanolic solutions; Stir after adding 2 parts of NaOH, mix; Under 70 ℃ temperature, reacted 4 hours; Filter, solids with ethanol or/and water washing 2～5 times swell in again after 24 hours in 500 parts of water 40 ℃ of dryings then; Add 50 parts of 5 parts of ammonium persulphates, 50 parts of methyl acrylates and vinyl-acetic esters again, under 70 ℃ temperature, reacted 5 hours; Filter, solids or/and water washing 2～5 times, 40 ℃ of dryings 24 hours, promptly makes the thermoplasticity Rhizoma amorphophalli glucomannan with ethanol.
4. by claim 1 or 2 said thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix materials, it is characterized in that: said linking agent is one or more the mixture in MALEIC ANHYDRIDE, tributyl citrate, the ethylene bis stearic acid amide.
5. by claim 1 or 2 said thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix materials, it is characterized in that: said softening agent is one or more the mixture in USP Kosher, polyoxyethylene glycol, the dimethyl phthalate.
6. the preparation method of thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material is characterized in that comprising the following steps:
A, batching: press 1～99 part of component and weight part proportioning heat-obtaining plasticity Rhizoma amorphophalli glucomannan, 0.001～2 part of graphene oxide, 0～10 part of linking agent, 0～10 part in softening agent;
B, combination drying: the thermoplasticity Rhizoma amorphophalli glucomannan is joined the ethanol or the aqueous solution of graphene oxide, and mechanical stirring 5～10 hours mixes it, filter, solids under 80～110 ℃ temperature dry 1～3 hour, dry mixture;
The ethanol of said graphene oxide or the preparation method of the aqueous solution can be: graphene oxide is dissolved in ethanol or the water, is mixed with the ethanol or the aqueous solution that concentration is the graphene oxide of 0.01～20g/L; Using power then is that the ultrasonic device of 300～1000W carried out supersound process 1～5 hour to the ethanol or the aqueous solution of said graphene oxide, promptly obtains the ethanol or the aqueous solution of graphene oxide;
C, blend are dry: with dry mixture and linking agent, softening agent stirring and evenly mixing after 5～30 minutes in mixing machine, and under 20～60 ℃ temperature dry 8～12 hours, must blend;
D, granulation: with blend drop in the twin screw extruder, in melt blending under 100～140 ℃ the temperature after 5～15 minutes, under the pressure of 0.1～1MPa, extrude, granulation, promptly make thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix material.
7. press the preparation method of the said thermoplasticity Rhizoma amorphophalli glucomannan of claim 6/graphene oxide matrix material; It is characterized in that: component described in the step a and weight part proportioning are 1～99 part of thermoplasticity Rhizoma amorphophalli glucomannan; 0.001～2 part of graphene oxide; 0.5～10 part of linking agent, 0.5～10 part in softening agent.
8. press the preparation method of claim 6 or 7 said thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix materials; It is characterized in that: the preparation method of the Rhizoma amorphophalli glucomannan of thermoplasticity described in the step a can be: by weight ratio 100 parts of konjaku powders being swollen in concentration of volume percent is in 500 parts of 40% the aqueous ethanolic solutions; Stir after adding 2 parts of NaOH, mix; Under 70 ℃ temperature, reacted 4 hours; Filter, solids with ethanol or/and water washing 2～5 times swell in again after 24 hours in 500 parts of water 40 ℃ of dryings then; Add 50 parts of 5 parts of ammonium persulphates, 50 parts of methyl acrylates and vinyl-acetic esters again, under 70 ℃ temperature, reacted 5 hours; Filter, solids or/and water washing 2～5 times, 40 ℃ of dryings 24 hours, promptly makes the thermoplasticity Rhizoma amorphophalli glucomannan with ethanol.
9. by the preparation method of claim 6 or 7 said thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix materials, it is characterized in that: linking agent described in the step a is one or more the mixture in MALEIC ANHYDRIDE, tributyl citrate, the ethylene bis stearic acid amide.
10. by the preparation method of claim 6 or 7 said thermoplasticity Rhizoma amorphophalli glucomannan/graphene oxide matrix materials, it is characterized in that: step a softening agent is one or more the mixture in USP Kosher, polyoxyethylene glycol, the dimethyl phthalate.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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-
2012
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|---|---|---|---|---|
| CN102161711A (en) * | 2011-01-27 | 2011-08-24 | 西南科技大学 | Method for preparing absorbing material based on modified konjac glucomannan |
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