CN103304887B - High-strength conductive polypropylene particles that a kind of graphene is modified and preparation method thereof - Google Patents
High-strength conductive polypropylene particles that a kind of graphene is modified and preparation method thereof Download PDFInfo
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- CN103304887B CN103304887B CN201210056012.7A CN201210056012A CN103304887B CN 103304887 B CN103304887 B CN 103304887B CN 201210056012 A CN201210056012 A CN 201210056012A CN 103304887 B CN103304887 B CN 103304887B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention belongs to technical field of polymer materials, discloses high-strength conductive polypropylene particles that a kind of graphene is modified and preparation method thereof.The polypropylene particles are made up of the component including following parts by weight：0 40 parts of 100 parts of polypropylene particles, 0.1 20 parts of single-layer graphene, 0.01 1 parts of antioxidant, 0.1 10 parts of plasticizer, 1 10 parts of light stabilizer, 1 10 parts of lubricant and filler.Preparation method is as follows：100 parts of polypropylene particles, 0.1 20 parts are added in high-speed mixer and are well mixed by the single-layer graphene of pretreatment, 0.01 1 parts of antioxidant, 0.1 10 parts of plasticizer, 1 10 parts of light stabilizers, 1 10 parts of lubricants and 0 40 parts of fillers, is placed in vacuum drying oven and dries；Dried material is pumped into double screw extruder by metering and carries out melting mixing, after die head extruding pelletization, obtains the high-strength conductive polypropylene particles of graphene modification.The polypropylene particles of the present invention have the advantages that intensity is high, electrical conductivity is high.
Description
Technical field
The invention belongs to technical field of polymer materials, is related to the high-strength conductive polypropylene particles that a kind of graphene is modified
And preparation method thereof.
Background technology
Polypropylene have nontoxic, tasteless, density is small, excellent resistance to water soak, excellent antiacid caustic corrosion, excellent antilysis
The advantages that, it is widely used in auto industry, household electrical appliance, tubing, machine components making etc. as a kind of conventional engineering plastics
Aspect.But polypropylene also have two it is bigger the shortcomings that, insufficient strength, electric conductivity extreme difference, in use easily production
Raw electrostatic hazard, therefore limit application of the polypropylene in fields such as electronics, medical treatment.
At present, conductive plastics is mainly to be combined by matrix and electroconductive stuffing of plastics.Electroconductive stuffing is main
It is metallic fiber, metal dust, carbon fiber or carbon black, and the addition of these fillers is general higher could produce excellent conduction
Performance, this not only substantially increases cost of material, it is often more important that filler dispersion effect is bad.It has impact on when addition is higher
The original mechanical property of plastic substrate, makes the mechanical property of plastics significantly decline.And graphene is to be currently known in material most
Thin one kind, while be also mankind's known strength highest material, very rigid, also harder than diamond, intensity compares the world
Upper taller upper 100 times best of steel.On an atomic scale, the structure of graphene is very special, and as simple substance, it is in room temperature
The speed of lower transmission electronics is all faster than known conductor.Therefore the addition of a small amount of graphene is only needed to increase substantially plastics
Intensity and electric conductivity.
The content of the invention
The defects of for prior art, it is an object of the invention to provide the high-strength conductive polypropylene that a kind of graphene is modified
Particle, by into polypropylene particles add graphene obtain modified polypropylene material, have it is nontoxic, tasteless, density is small, excellent
The features such as resistance to water soak, excellent antiacid caustic corrosion, excellent antilysis, particularly with the characteristics of intensity is high, electrical conductivity is high.
It is a further object to provide a kind of preparation method of above-mentioned polypropylene particles.
Technical scheme is as follows：
The invention provides a kind of graphene be modified high-strength conductive polypropylene particles, the polypropylene particles by including with
The component of lower parts by weight is made：
100 parts of polypropylene particles,
Single-layer graphene 0.1-20 parts,
Antioxidant 0.01-1 parts,
Plasticizer 0.1-10 parts,
Light stabilizer 1-10 parts,
Lubricant 1-10 parts,
Filler 0-40 parts.
Described polypropylene particles are HOPP, and isotacticity 60%-95%, molecular weight is 10-30 ten thousand.
Described single-layer graphene thickness is 1-100nm.
Described antioxidant is selected from 2,6- three-level butyl -4- methylphenols, diphenylamines, 3,5- three-level butyl -4- hydroxy benzenes
One or more in base thioether, p-phenylenediamine or EEDQ.
Described plasticizer is selected from terephthalic acid (TPA) methyl esters, trioctyl trimellitate (TOTM), the own ester of tri trimellitate, citric acid three
One or more in butyl ester, triethyl citrate or ATEC.
One kind in dihydroxy benaophenonel, hydroxybenzotriazole or salicylic acid of described light stabilizer or it is a kind of with
On.Described lubricant is in stearic acid, calcium stearate, zinc stearate, Tissuemat E, polypropylene wax or magnesium stearate etc.
It is one or more kinds of.
The one kind or one of described filler in calcium carbonate, talcum powder, barium sulfate, silica, carbon black or calcium sulfate
More than kind.
A kind of preparation method for the high-strength conductive polypropylene particles being modified present invention also offers above-mentioned graphene, the party
Method comprises the following steps：
By the single-layer graphene, 0.01-1 parts antioxidant, 0.1- of 100 parts of polypropylene particles, 0.1-20 parts by pretreatment
10 parts of plasticizer, 1-10 parts light stabilizer, 1-10 parts lubricant and 0-40 parts filler are added in high-speed mixer and are well mixed, and are put
Dried in vacuum drying oven；Dried material is pumped into double screw extruder by metering and carries out melting mixing, by mould
After head extruding pelletization, the high-strength conductive polypropylene particles of graphene modification are obtained.
The single-layer graphene processing method of described pretreatment is as follows：Single-layer graphene is dissolved in ethanol, ethanol and stone
The weight of black alkene is 10-100: 1 than scope, high-speed stirred, mixing speed 150-1000rpm, and stirring is placed on super simultaneously
In sound pond, after supersonic frequency 30-45KHz, ultrasonic disperse 20-60min；Finely dispersed single-layer graphene is placed in 90-120
DEG C drying in oven 8-24h, the ethanol solution being attached on single-layer graphene is removed, it is standby.
Described well mixed mixing temperature is 100-150 DEG C, incorporation time 5-20min.
Described drying temperature is 100-120 DEG C, drying time 10-24h.
Described double screw extruder draw ratio be 30: 1-70: 1, twin-screw temperature setting be 140 DEG C, 160 DEG C, 180
DEG C, 200 DEG C, 220 DEG C, 240 DEG C, extruder rotating speed is 10-50rpm.
The present invention compared with prior art, has advantages below and beneficial effect：
1st, because graphene addition is few in the present invention so that polypropylene particles not only maintain the original superiority of polypropylene
Can, also by a relatively large margin improve its mechanical property.
2nd, the polypropylene particles of graphene are added in the present invention, substantially increase its electric conductivity, and its density is true much
Less than using extensive metal material at present, therefore the polypropylene particles of the present invention can be with substituted metal material in electronics, medical treatment
It is used widely Deng field.
Embodiment
The invention will be further described with reference to embodiments.
Embodiment 1
The pretreatment of single-layer graphene：The single-layer graphene that thickness is 1nm is dissolved in ethanol, the weight of ethanol and graphene
Amount is than being 10, high-speed stirred, mixing speed 150rpm, and stirring is placed in ultrasonic pond simultaneously, supersonic frequency 30KHz,
After ultrasonic disperse 20min；Finely dispersed graphene is placed in 90 DEG C of drying in oven 24h, removing is attached on graphene
Ethanol solution, it is standby.
It is the HOPP particle, 0.1 part of pretreated list that 60% molecular weight is 10-30 ten thousand by 100 parts of isotacticities
Layer graphene, 0.01 part of 2,6- three-level butyl -4- methylphenols, 0.1 part of terephthalic acid (TPA) methyl esters, 1 part of dihydroxy benaophenonel, 1
Part stearic acid, which is added in high-speed mixer, to be well mixed, and mixing temperature is 100 DEG C, incorporation time 5min, is subsequently placed in 100 DEG C
10h is dried in vacuum drying oven.The material mixed is sent into double screw extruder after measuring pump, draw ratio 30: 1, carried out
Melting mixing, twin-screw temperature setting are 140 DEG C, and 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C, extruder rotating speed is
10rpm.Finally after die head extruding pelletization.The correlated performance of made sample is shown in Table 1.
Embodiment 2
The pretreatment of single-layer graphene：The single-layer graphene that thickness is 25nm is dissolved in ethanol, ethanol and graphene
Weight ratio is 25, high-speed stirred, mixing speed 200rpm, and stirring is placed in ultrasonic pond simultaneously, and supersonic frequency is
After 32KHz, ultrasonic disperse 30min；Finely dispersed graphene is placed in 100 DEG C of drying in oven 16h, removing is attached to graphite
Ethanol solution on alkene, it is standby.
It is that HOPP particle, 0.5 part that 65% molecular weight is 10-30 ten thousand pass through pretreatment by 100 parts of isotacticities
Single-layer graphene, 0.1 part of diphenylamines, 1 part of trioctyl trimellitate (TOTM), 2 parts of hydroxybenzotriazoles, 2 parts of calcium stearates and 5 parts of carbonic acid
Calcium is added in high-speed mixer and is well mixed, and mixing temperature is 110 DEG C, incorporation time 8min, is subsequently placed in 110 DEG C of vacuum and is dried
12h is dried in case.The material mixed is sent into double screw extruder after measuring pump, draw ratio 50: 1, it is mixed to carry out melting
Refining, twin-screw temperature setting are 140 DEG C, and 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C, extruder rotating speed is 30rpm, finally
After die head extruding pelletization.The correlated performance of made sample is shown in Table 1.
Embodiment 3
The pretreatment of single-layer graphene：The single-layer graphene that thickness is 50nm is dissolved in ethanol, ethanol and graphene
Weight ratio is 50, high-speed stirred, mixing speed 300rpm, and stirring is placed in ultrasonic pond simultaneously, and supersonic frequency is
After 35KHz, ultrasonic disperse 40min；Finely dispersed graphene is placed in 120 DEG C of drying in oven 8h, removing is attached to graphite
Ethanol solution on alkene, it is standby.
It is that HOPP particle, 2 parts that 70% molecular weight is 10-30 ten thousand pass through the list of pretreatment by 100 parts of isotacticities
Layer graphene, 0.2 part of 3,5- three-level butyl -4- hydroxy phenyls thioether, the own ester of 2 parts of tri trimellitates, 4 parts of salicylic acids, 3 parts of tristearin
Sour zinc and 10 parts of talcum powder are added in high-speed mixer and are well mixed, and mixing temperature is 120 DEG C, incorporation time 10min, then
It is placed in 110 DEG C of vacuum drying ovens and dries 14h.The material mixed is sent into double screw extruder after measuring pump, draw ratio is
60: 1, carry out melting mixing, twin-screw temperature setting be 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C, extruder
Rotating speed is 40rpm, finally after die head extruding pelletization.The correlated performance of made sample is shown in Table 1.
Embodiment 4
The pretreatment of single-layer graphene：The single-layer graphene that thickness is 70nm is dissolved in ethanol, ethanol and graphene
Weight ratio is 70, high-speed stirred, mixing speed 400rpm, and stirring is placed in ultrasonic pond simultaneously, and supersonic frequency is
After 37KHz, ultrasonic disperse 50min；Finely dispersed graphene is placed in 100 DEG C of drying in oven 12h, removing is attached to graphite
Ethanol solution on alkene, it is standby.
It is that HOPP particle, 5 parts that 75% molecular weight is 10-30 ten thousand pass through the list of pretreatment by 100 parts of isotacticities
Layer graphene, 0.3 part of p-phenylenediamine, 4 parts of ATBCs, 5 parts of salicylic acids, 5 parts of Tissuemat Es and 15 parts of barium sulfate add
It is well mixed in high-speed mixer, mixing temperature is 130 DEG C, incorporation time 12min, is subsequently placed in 100 DEG C of vacuum drying ovens
Dry 16h.The material mixed is sent into double screw extruder after measuring pump, draw ratio 70: 1, carries out melting mixing, it is double
Extruder temperature is arranged to 140 DEG C, and 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C, extruder rotating speed is 50rpm, is finally passed through
After die head extruding pelletization.The correlated performance of made sample is shown in Table 1.
Embodiment 5
The pretreatment of single-layer graphene：The single-layer graphene that thickness is 80nm is dissolved in ethanol, ethanol and graphene
Weight ratio is 80, high-speed stirred, mixing speed 550rpm, and stirring is placed in ultrasonic pond simultaneously, and supersonic frequency is
After 40KHz, ultrasonic disperse 60min；Finely dispersed graphene is placed in 100 DEG C of drying in oven 12h, removing is attached to graphite
Ethanol solution on alkene, it is standby.
It is that HOPP particle, 8 parts that 80% molecular weight is 10-30 ten thousand pass through the list of pretreatment by 100 parts of isotacticities
Layer graphene, 0.5 part of EEDQ, 5 parts of triethyl citrates, 5 parts of hydroxybenzotriazoles, 6 parts of polypropylene waxes and 20 parts of dioxies
SiClx is added in high-speed mixer and is well mixed, and mixing temperature is 130 DEG C, incorporation time 15min, is subsequently placed in 120 DEG C very
18h is dried in empty baking oven.The material mixed is sent into double screw extruder after measuring pump, draw ratio 60: 1, melted
Melt mixing, twin-screw temperature setting is 140 DEG C, and 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C, extruder rotating speed is 50rpm,
Finally after die head extruding pelletization.The correlated performance of made sample is shown in Table 1.
Embodiment 6
The pretreatment of single-layer graphene：The single-layer graphene that thickness is 90nm is dissolved in ethanol, ethanol and graphene
Weight ratio is 90, high-speed stirred, mixing speed 650rpm, and stirring is placed in ultrasonic pond simultaneously, and supersonic frequency is
After 42KHz, ultrasonic disperse 60min；Finely dispersed graphene is placed in 100 DEG C of drying in oven 12h, removing is attached to graphite
Ethanol solution on alkene, it is standby.
It is that HOPP particle, 10 parts that 85% molecular weight is 10-30 ten thousand pass through the list of pretreatment by 100 parts of isotacticities
Layer graphene, 0.7 part of 2,6- three-level butyl -4- methylphenol, 7 parts of ATECs, 6 parts of dihydroxy benaophenonels, 8 parts
Magnesium stearate and 25 parts of carbon blacks are added in high-speed mixer and are well mixed, and mixing temperature is 140 DEG C, incorporation time 16min, so
After be placed in 120 DEG C of vacuum drying ovens and dry 19h.The material mixed is sent into double screw extruder, draw ratio after measuring pump
For 50: 1, melting mixing is carried out, twin-screw temperature setting is 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C, extrusion
Machine rotating speed is 45rpm, finally after die head extruding pelletization.The correlated performance of made sample is shown in Table 1.
Embodiment 7
The pretreatment of single-layer graphene：The single-layer graphene that thickness is 100nm is dissolved in ethanol, ethanol and graphene
Weight ratio is 100, high-speed stirred, mixing speed 800rpm, and stirring is placed in ultrasonic pond simultaneously, and supersonic frequency is
After 43KHz, ultrasonic disperse 60min；Finely dispersed graphene is placed in 100 DEG C of drying in oven 12h, removing is attached to graphite
Ethanol solution on alkene, it is standby.
It is that HOPP particle, 15 parts that 90% molecular weight is 10-30 ten thousand pass through the list of pretreatment by 100 parts of isotacticities
Layer graphene, 0.8 part of EEDQ, 8 parts of ATECs, 7 parts of salicylic acids, 9 parts of Tissuemat Es and 30 parts of calcium sulfate
Add in high-speed mixer and be well mixed, mixing temperature is 150 DEG C, incorporation time 18min, is subsequently placed in 120 DEG C of vacuum and dries
20h is dried in case.The material mixed is sent into double screw extruder after measuring pump, draw ratio 50: 1, it is mixed to carry out melting
Refining, twin-screw temperature setting are 140 DEG C, and 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C, extruder rotating speed is 45rpm, finally
After die head extruding pelletization.The correlated performance of made sample is shown in Table 1.
Embodiment 8
The pretreatment of single-layer graphene：The single-layer graphene that thickness is 50nm is dissolved in ethanol, ethanol and graphene
Weight ratio is 50, high-speed stirred, mixing speed 1000rpm, and stirring is placed in ultrasonic pond simultaneously, and supersonic frequency is
After 45KHz, ultrasonic disperse 40min；Finely dispersed graphene is placed in 120 DEG C of drying in oven 8h, removing is attached to graphite
Ethanol solution on alkene, it is standby.
It is that HOPP particle, 20 parts that 95% molecular weight is 10-30 ten thousand pass through the list of pretreatment by 100 parts of isotacticities
Layer graphene, 1 part of 2,6- three-level butyl -4- methylphenol, 10 parts of triethyl citrates, 10 parts of hydroxybenzotriazoles, 10 parts it is hard
Resin acid zinc, 10 parts of calcium carbonate and 30 parts of talcum powder are added in high-speed mixers and are well mixed, and mixing temperature is 150 DEG C, during mixing
Between be 20min, be subsequently placed in 120 DEG C of vacuum drying ovens and dry 24h.The material mixed is sent into twin-screw after measuring pump to squeeze
Going out machine, draw ratio 50: 1 carries out melting mixing, and twin-screw temperature setting is 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C,
240 DEG C, extruder rotating speed is 45rpm, finally after die head extruding pelletization.The correlated performance of made sample is shown in Table 1.
Comparative example 1
The dosage of graphene is 0 part in the present embodiment, and other feed intake and processing step is the same as embodiment 8, the phase of made sample
Close performance and be shown in Table 1.
Table 1
It is can see by data in table 1 as the increase of graphene content, the mechanical property of polypropylene particles significantly rise；
And the decline of its resistivity is remarkably decreased, only the electric conductivity of particle improves more than 107 times after 0.1 part of graphene of addition, works as stone
When black alkene addition reaches 20 parts, its resistivity is only 1.4*10-3 Ω .m, has reached the conductive effect of semiconductor.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation here
Example, for those skilled in the art according to the announcement of the present invention, not departing from improvement that scope made and modification all should be
Within protection scope of the present invention.
Claims (4)
- A kind of 1. high-strength conductive polypropylene particles that graphene is modified, it is characterised in that：It includes the component of following parts by weight：Described polypropylene particles are HOPP, and isotacticity 60%-95%, molecular weight is 10-30 ten thousand；Described single-layer graphene thickness is 1-100nm；Described antioxidant is selected from diphenylamines, 3,5- three-level butyl -4- hydroxy phenyls thioether, p-phenylenediamine or EEDQ More than one；Described plasticizer is selected from terephthalic acid (TPA) methyl esters, trioctyl trimellitate (TOTM), the own ester of tri trimellitate, the fourth of citric acid three One or more of ester, triethyl citrate or ATEC；Described light stabilizer is selected from one or more of dihydroxy benaophenonel, hydroxybenzotriazole or salicylic acid；The preparation method of the described single-layer graphene by pretreatment comprises the following steps：Single-layer graphene is dissolved in ethanol, the weight of ethanol and graphene is (10-100) than scope：1, high-speed stirred, stirring Speed is 150-1000rpm, and stirring is placed in ultrasonic pond simultaneously, supersonic frequency 30-45KHz, ultrasonic disperse 20- After 60min；Finely dispersed single-layer graphene is placed in 90-120 DEG C of drying in oven 8-24h, it is standby；The preparation method for the high-strength conductive polypropylene particles that described graphene is modified comprises the following steps：By the single-layer graphene, 0.01-1 parts antioxidant, 0.1-10 parts of 100 parts of polypropylene particles, 0.1-20 parts by pretreatment Plasticizer, 1-10 parts light stabilizer, 1-10 parts lubricant and 0-40 parts filler are added in high-speed mixer and are well mixed, and are placed in true Dried in empty baking oven；Dried material is pumped into double screw extruder by metering and carries out melting mixing, is squeezed by die head After going out granulation, the high-strength conductive polypropylene particles of graphene modification are obtained；Described well mixed mixing temperature is 100-150 DEG C, incorporation time 5-20min；Described drying temperature is 100-120 DEG C, drying time 10-24h；Described double screw extruder draw ratio is 30:1-70:1, twin-screw temperature setting be 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C, the rotating speed of double screw extruder is 10-50rpm.
- 2. the high-strength conductive polypropylene particles that graphene according to claim 1 is modified, it is characterised in that：Described profit Lubrication prescription is selected from one or more of stearic acid, calcium stearate, zinc stearate, Tissuemat E, polypropylene wax or magnesium stearate.
- 3. the high-strength conductive polypropylene particles that graphene according to claim 1 is modified, it is characterised in that：Described fills out Material is selected from one or more of calcium carbonate, talcum powder, barium sulfate, silica, carbon black or calcium sulfate.
- 4. the preparation method for the high-strength conductive polypropylene particles that the graphene described in any one of claims 1 to 3 is modified, it is special Sign is：This method comprises the following steps：By the single-layer graphene, 0.01-1 parts antioxidant, 0.1-10 parts of 100 parts of polypropylene particles, 0.1-20 parts by pretreatment Plasticizer, 1-10 parts light stabilizer, 1-10 parts lubricant and 0-40 parts filler are added in high-speed mixer and are well mixed, and are placed in true Dried in empty baking oven；Dried material is pumped into double screw extruder by metering and carries out melting mixing, is squeezed by die head After going out granulation, the high-strength conductive polypropylene particles of graphene modification are obtained；The preparation method of the described single-layer graphene by pretreatment comprises the following steps：Single-layer graphene is dissolved in ethanol, the weight of ethanol and graphene is (10-100) than scope：1, high-speed stirred, stirring Speed is 150-1000rpm, and stirring is placed in ultrasonic pond simultaneously, supersonic frequency 30-45KHz, ultrasonic disperse 20- After 60min；Finely dispersed single-layer graphene is placed in 90-120 DEG C of drying in oven 8-24h, it is standby；Described well mixed mixing temperature is 100-150 DEG C, incorporation time 5-20min；Described drying temperature is 100-120 DEG C, drying time 10-24h；Described double screw extruder draw ratio is 30:1-70:1, twin-screw temperature setting be 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C, the rotating speed of double screw extruder is 10-50rpm.
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| CN201210056012.7A CN103304887B (en) | 2012-03-06 | 2012-03-06 | High-strength conductive polypropylene particles that a kind of graphene is modified and preparation method thereof |
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| CN201210056012.7A CN103304887B (en) | 2012-03-06 | 2012-03-06 | High-strength conductive polypropylene particles that a kind of graphene is modified and preparation method thereof |
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| CN103304887A CN103304887A (en) | 2013-09-18 |
| CN103304887B true CN103304887B (en) | 2017-12-05 |
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| CN103642155B (en) * | 2013-11-29 | 2016-08-17 | 中国科学院金属研究所 | A kind of composite conductive thin film with Graphene as conductive agent and preparation method thereof |
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| CN103819815A (en) * | 2014-01-28 | 2014-05-28 | 盐城纳新天地新材料科技有限公司 | Grapheme modified polypropylene master batch and preparation method thereof |
| CN104151664B (en) * | 2014-05-07 | 2016-08-24 | 武汉金牛经济发展有限公司 | The preparation method of the polyethylene composite pipe that a kind of Graphene is modified |
| CN106117747A (en) * | 2016-07-27 | 2016-11-16 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of Graphene modified poly ethylene composite |
| CN106046558A (en) * | 2016-08-09 | 2016-10-26 | 叶伟然 | Novel graphene reinforced halogen-free flame retardation PP and preparation method thereof |
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| CN107383615A (en) * | 2017-08-25 | 2017-11-24 | 江苏理工学院 | A kind of modified polypropylene material and preparation method thereof |
| CN107625229B (en) * | 2017-09-29 | 2020-05-19 | 山东接地气健康科技有限公司 | Polyurethane sole added with graphene composite material and preparation method thereof |
| CN107955260A (en) * | 2017-11-14 | 2018-04-24 | 闽南师范大学 | A kind of graphene dispersion method and application |
| CN109401057B (en) * | 2018-11-01 | 2021-12-14 | 常州工程职业技术学院 | Surface scratch-resistant polypropylene and preparation method thereof |
| CN109401058A (en) * | 2018-11-01 | 2019-03-01 | 常州工程职业技术学院 | A kind of high melt strength, propylene and preparation method thereof |
| CN109438851A (en) * | 2018-11-29 | 2019-03-08 | 广东威林工程塑料股份有限公司 | A kind of scratch-resistant, high durable, high thermal conductivity graphene modified polypropylene composite material and preparation method thereof |
| CN110194867A (en) * | 2019-07-02 | 2019-09-03 | 张志松 | A kind of antistatic high-strength polypropylene particle and preparation method thereof |
| CN111484663A (en) * | 2020-06-20 | 2020-08-04 | 上海旗华水上工程建设股份有限公司 | Graphene floating body for aquatic travel floating system |
| CN112223577A (en) * | 2020-09-24 | 2021-01-15 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | Mixing method for anti-static plastic granulation for injection molding |
| CN115011038A (en) * | 2022-06-30 | 2022-09-06 | 江西全兴化工填料有限公司 | Production process of polypropylene chemical filler |
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Denomination of invention: Graphene-modified high-strength conductive polypropylene particles and preparation method thereof Effective date of registration: 20191202 Granted publication date: 20171205 Pledgee: Chuzhou economic and Technological Development Corporation Pledgor: Shanghai Jieshijie New Materials (Group) Co., Ltd. Registration number: Y2019980000815 |