CN107880520A - High durable high abrasion PC materials based on modified graphene oxide - Google Patents
High durable high abrasion PC materials based on modified graphene oxide Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses the high durable high abrasion PC materials based on modified graphene oxide, by weight, its preparing raw material is：100 parts of PC resin, 10 30 parts of PBT resin, ELECTRODE WITH BILAYER POLYMERIC thing coats 50 80 parts of nanometer hydroxyapatite, 10 30 parts of polyether-ketone modified graphene oxide, 15 parts of ethylene bis stearamide, 13 parts of dioctyl ester base pentaerythritol diphosphites and double 13 parts of (2,4 di-tert-butyl-phenyl) pentaerythritol diphosphites.The invention also discloses the preparation method of the high durable high abrasion PC materials based on modified graphene oxide.
Description
Technical field
The invention belongs to polymer composites technical field, more particularly it relates to a kind of based on modified oxidized
The high durable high abrasion PC materials of graphene.
Background technology
PC（Makrolon）Plastics can be used for electronic apparatus, communication apparatus, modern office equipment, rail traffic vehicles interior trim
The productions such as part, automobile component.
As people are to health, the pay attention to day by day of environment and ecological protection, flame retardant of plastic standard and environmental protection standard also day
Beneficial strict, Material Burning Effluents Toxicity and smoking property problem are increasingly taken seriously, it is desirable to which plastic material or product both had
Good fire resistance, again low toxicityization and low smoke.Such as the TCO-99 of the Sweden and Ecolable-9 in Northern Europe（White swan）
Environmental mark requirement, computer material can not use Corvic and brominated flame-retardant.The blue sky of Germany makes mark
（BlueAngel）Also require that printer and copy machine housings material are free of halogen.The EbobelEU-99 in Europe requires computer
Casing plastic in be free of halogenated flame retardant.The WEEE instructions and RoHS instructions that each member state of particularly European Union in 2003 announces.
However, existing PC plastic low intensity, fire-retardant difference and wearability are bad, so as to cause short life, it is difficult to meet actual demand.
Therefore, it is necessary to carry out technological improvement, prepare have more preferable intensity and and keep high resiliency, it is and wearability, fire-retardant
The preferable PC composites of property.
The content of the invention
In order to solve the above problems, one aspect of the present invention provides the high durable high abrasion based on modified graphene oxide
PC materials, by weight, its preparing raw material is：
100 parts of PC resin, PBT resin 10-30 parts, ELECTRODE WITH BILAYER POLYMERIC thing cladding nanometer hydroxyapatite 50-80 parts, polyether-ketone are modified
Graphene oxide 10-30 parts, ethylene bis stearamide 1-5 parts, dioctyl ester base pentaerythritol diphosphites 1-3 parts and double
(2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites 1-3 parts；
Preferably, its preparing raw material is：
100 parts of PC resin, 20 parts of PBT resin, ELECTRODE WITH BILAYER POLYMERIC thing 60 parts of nanometer hydroxyapatite of cladding, silane-modified graphite oxide
20 parts of alkene, 3 parts of ethylene bis stearamide, 2 parts of dioctyl ester base pentaerythritol diphosphites and double (2,4- di-tert-butyls
Base) 2 parts of pentaerythritol diphosphites.
In one embodiment, the outer layer of the ELECTRODE WITH BILAYER POLYMERIC thing is rigid polyether-ketone, and internal layer is flexible polyether amine.
In one embodiment, the preparation method of the ELECTRODE WITH BILAYER POLYMERIC thing cladding nanometer hydroxyapatite is：
（1）In reaction vessel, sequentially add 0.044 mol 1H- imidazoles -4- ethamine, 10 g epoxy resin E-44 and
The ml of DMF 300, after leading to 30 min of nitrogen protection, heat up after 100 DEG C of 5 h of reaction, it is molten to obtain sticky polyetheramine
Liquid；
（2）Into above-mentioned sticky polyether amine solution, 100 g nanometer hydroxyapatite, 2 g silane coupler KH- are added
550, under 100 DEG C, nitrogen protection, continue after stirring 2 h, by reaction solution precipitating in 2000 ml ethanol, obtain a large amount of solids
Precipitation, solid precipitation is washed repeatedly three times with ethanol and deionized water, is then filtered, by gained solid in vacuum drying oven,
24 h are dried at 50 DEG C and obtain single polymer layer cladding nanometer hydroxyapatite；
（3）By the 4,4 ' of 0.002mol-difluoro benzophenone, 0.0021mol 4,4 '-dihydroxy benzophenone, 0.0024mol
Natrium carbonicum calcinatum, 0.012mol diphenyl sulphone (DPS) are fitted into reaction vessel, are warming up to 180 DEG C in a nitrogen atmosphere, react 6 h, so
After be warming up to 300 DEG C, react 5 h, then reaction solution separated out in deionized water, washed repeatedly with ethanol and deionized water
The solid precipitates three times, then filters, and drying 24 h by gained solid in vacuum drying oven, at 120 DEG C obtains polyether-ketone；
（4）Take step（3）The g of gained polyether-ketone 10 is dissolved in 300 ml diphenyl sulphone (DPS)s, then adds step（2）Gained individual layer gathers
Compound coats the g of nanometer hydroxyapatite 100, after being warming up to 80 DEG C of 2 h of stirring, reaction solution is separated out in deionized water, used
Ethanol and deionized water wash solid precipitation three times repeatedly, then filter, by gained solid in vacuum drying oven, at 120 DEG C
Dry 24 h and obtain ELECTRODE WITH BILAYER POLYMERIC thing cladding nanometer hydroxyapatite.
In one embodiment, the preparation method of the polyether-ketone modified graphene oxide is：
（1）By the 4,4 ' of 0.002mol-difluoro benzophenone, 0.0022mol 4,4 '-dihydroxy benzophenone, 0.0024mol
Natrium carbonicum calcinatum, 0.012mol diphenyl sulphone (DPS) are fitted into reaction vessel, are warming up to 180 DEG C in a nitrogen atmosphere, react 6 h, so
After be warming up to 300 DEG C, react 5 h, then polymer separated out in deionized water, this is washed repeatedly with ethanol and deionized water
Solid precipitates three times, then filters, and drying 24 h by gained solid in vacuum drying oven, at 120 DEG C obtains polyether-ketone；
（2）In round-bottomed flask, above-mentioned steps are sequentially added（1）13 g of g, KH-560 of g, KH-550 of gained polyether-ketone 5, oxygen
The g of graphite alkene 15, the g of dimethyl sulfoxide (DMSO) 330, after leading to 1 h of nitrogen protection, system temperature is risen to 80 DEG C, after reacting 5 hours,
Room temperature is down to, is discharged in ethanol, obtains fluffy solid, washs the fluffy solid respectively 3 times with deionized water and ethanol, most
It is dried in vacuo 24 hours at 50 DEG C afterwards, obtains the polyether-ketone modified graphene oxide.
In one embodiment, the average grain diameter of the nanometer hydroxyapatite is 200-700 nanometers；Preferably 500
Nanometer.
In one embodiment, the average grain diameter of the graphene oxide is 500-2000 nanometers；Preferably 800 receive
Rice.
The present invention also provides the preparation method of the high durable high abrasion PC materials of the modified graphene oxide, including as follows
Step：
Above-mentioned raw materials are added in the high-speed mixer that rotating speed is 900 revs/min and mixed, until because being rubbed caused by high-speed stirred
Chafing makes temperature of charge be discharged when being increased to 120 DEG C, and then mixed material is sent in cooling and stirring device, passed through under agitation
The mode of cooling jacket cooling is cooled to 50 DEG C；
Mixed material after cooling is sent in the double screw extruder for having reached design temperature, mixed material is by double spiral shells
Bar extruder is extruded as billot, and set extrusion die temperature is 230 DEG C；The billot extruded is cooled down through tank, drawn
It is granulated into pelleter and obtains the high durable high abrasion PC materials based on modified graphene oxide；
The precedence that above-mentioned double screw extruder passes through according to material is divided into 4 heating zones and extrusion die, and set is each
The heating-up temperature of heating zone is followed successively by：Temperature T1=170 DEG C~210 DEG C of first heating zone, temperature T2=210 of the second heating zone
DEG C~240 DEG C, temperature T3=240 DEG C~250 DEG C of the 3rd heating zone, temperature T4=250 DEG C~260 DEG C of the 4th heating zone.
Compared with prior art, beneficial effects of the present invention are：
ELECTRODE WITH BILAYER POLYMERIC thing coats the addition of nanometer hydroxyapatite, by the synergy of rigid polyether-ketone and flexible polyether amine,
The dispersiveness of filler is substantially increased, can greatly increase the content of filler, and improves the intensity and fire resistance of system simultaneously.
The addition of polyether-ketone modified graphene oxide can further improve the wearability of system, and coat nanometer hydroxyl with ELECTRODE WITH BILAYER POLYMERIC thing
Base apatite cooperates with, and further improves fire resistance.
Embodiment
Raw material：
Polycarbonate PC is SABIC-PC1800R.Polybutylene terephthalate (PBT) PBT resin is Du Pont LW9030FR.Nanometer
Hydroxyapatite（Average grain diameter is 500 nanometers）Purchased from Aladdin reagent.Graphene oxide（Average grain diameter is 800 nanometers）It is purchased from
Hunan richization.Other raw materials are purchased from Western Regions chemical industry.
Embodiment 1
By weight, by 100 parts of PC resin, 10 parts of PBT resin, ELECTRODE WITH BILAYER POLYMERIC thing 50 parts of nanometer hydroxyapatite of cladding, polyethers
10 parts of ketone modified graphene oxide, 1 part of ethylene bis stearamide, 1 part of dioctyl ester base pentaerythritol diphosphites and it is double (2,
4- di-tert-butyl-phenyls) 1 part of addition rotating speed of pentaerythritol diphosphites is mixes in 900 revs/min of high-speed mixer, directly
Temperature of charge is discharged when being increased to 120 DEG C to because of frictional heat caused by high-speed stirred, be then sent to mixed material cold
But in agitator, 50 DEG C are cooled to by way of cooling jacket cooling under agitation；
Mixed material after cooling is sent in the double screw extruder for having reached design temperature, mixed material is by double spiral shells
Bar extruder is extruded as billot, and set extrusion die temperature is 230 DEG C；The billot extruded is cooled down through tank, drawn
It is granulated into pelleter and obtains the high durable high abrasion PC materials based on modified graphene oxide；
The precedence that above-mentioned double screw extruder passes through according to material is divided into 4 heating zones and extrusion die, and set is each
The heating-up temperature of heating zone is followed successively by：Temperature T1=190 DEG C of first heating zone, temperature T2=210 DEG C of the second heating zone, the 3rd
Temperature T3=240 DEG C of heating zone, temperature T4=260 DEG C of the 4th heating zone；
The preparation method of ELECTRODE WITH BILAYER POLYMERIC thing cladding nanometer hydroxyapatite is：
（1）In reaction vessel, sequentially add 0.044 mol 1H- imidazoles -4- ethamine, 10 g epoxy resin E-44 and
The ml of DMF 300, after leading to 30 min of nitrogen protection, heat up after 100 DEG C of 5 h of reaction, it is molten to obtain sticky polyetheramine
Liquid；
（2）Into above-mentioned sticky polyether amine solution, 100 g nanometer hydroxyapatite, 2 g silane coupler KH- are added
550, under 100 DEG C, nitrogen protection, continue after stirring 2 h, by reaction solution precipitating in 2000 ml ethanol, obtain a large amount of solids
Precipitation, solid precipitation is washed repeatedly three times with ethanol and deionized water, is then filtered, by gained solid in vacuum drying oven,
24 h are dried at 50 DEG C and obtain single polymer layer cladding nanometer hydroxyapatite；
（3）By the 4,4 ' of 0.002mol-difluoro benzophenone, 0.0021mol 4,4 '-dihydroxy benzophenone, 0.0024mol
Natrium carbonicum calcinatum, 0.012mol diphenyl sulphone (DPS) are fitted into reaction vessel, are warming up to 180 DEG C in a nitrogen atmosphere, react 6 h, so
After be warming up to 300 DEG C, react 5 h, then reaction solution separated out in deionized water, washed repeatedly with ethanol and deionized water
The solid precipitates three times, then filters, and drying 24 h by gained solid in vacuum drying oven, at 120 DEG C obtains polyether-ketone；
（4）Take step（3）The g of gained polyether-ketone 10 is dissolved in 300 ml diphenyl sulphone (DPS)s, then adds step（2）Gained individual layer gathers
Compound coats the g of nanometer hydroxyapatite 100, after being warming up to 80 DEG C of 2 h of stirring, reaction solution is separated out in deionized water, used
Ethanol and deionized water wash solid precipitation three times repeatedly, then filter, by gained solid in vacuum drying oven, at 120 DEG C
Dry 24 h and obtain ELECTRODE WITH BILAYER POLYMERIC thing cladding nanometer hydroxyapatite；
The preparation method of the polyether-ketone modified graphene oxide is：
（1）By the 4,4 ' of 0.002mol-difluoro benzophenone, 0.0022mol 4,4 '-dihydroxy benzophenone, 0.0024mol
Natrium carbonicum calcinatum, 0.012mol diphenyl sulphone (DPS) are fitted into reaction vessel, are warming up to 180 DEG C in a nitrogen atmosphere, react 6 h, so
After be warming up to 300 DEG C, react 5 h, then polymer separated out in deionized water, this is washed repeatedly with ethanol and deionized water
Solid precipitates three times, then filters, and drying 24 h by gained solid in vacuum drying oven, at 120 DEG C obtains polyether-ketone；
（2）In round-bottomed flask, above-mentioned steps are sequentially added（1）13 g of g, KH-560 of g, KH-550 of gained polyether-ketone 5, oxygen
The g of graphite alkene 15, the g of dimethyl sulfoxide (DMSO) 330, after leading to 1 h of nitrogen protection, system temperature is risen to 80 DEG C, after reacting 5 hours,
Room temperature is down to, is discharged in ethanol, obtains fluffy solid, washs the fluffy solid respectively 3 times with deionized water and ethanol, most
It is dried in vacuo 24 hours at 50 DEG C afterwards, obtains the polyether-ketone modified graphene oxide.
Embodiment 2
By weight, by 100 parts of PC resin, 20 parts of PBT resin, ELECTRODE WITH BILAYER POLYMERIC thing 60 parts of nanometer hydroxyapatite of cladding, silane
20 parts of modified graphene oxide, 3 parts of ethylene bis stearamide, 2 parts of dioctyl ester base pentaerythritol diphosphites and double (2,4-
Di-tert-butyl-phenyl) 2 parts of pentaerythritol diphosphites add in the high-speed mixer that rotating speeds are 900 revs/min and mix, until
Because frictional heat caused by high-speed stirred makes temperature of charge be discharged when being increased to 120 DEG C, mixed material is then sent to cooling
In agitator, 50 DEG C are cooled to by way of cooling jacket cooling under agitation；
Mixed material after cooling is sent in the double screw extruder for having reached design temperature, mixed material is by double spiral shells
Bar extruder is extruded as billot, and set extrusion die temperature is 230 DEG C；The billot extruded is cooled down through tank, drawn
It is granulated into pelleter and obtains the high durable high abrasion PC materials based on modified graphene oxide；
The precedence that above-mentioned double screw extruder passes through according to material is divided into 4 heating zones and extrusion die, and set is each
The heating-up temperature of heating zone is followed successively by：Temperature T1=190 DEG C of first heating zone, temperature T2=210 DEG C of the second heating zone, the 3rd
Temperature T3=240 DEG C of heating zone, temperature T4=260 DEG C of the 4th heating zone；
The preparation method of ELECTRODE WITH BILAYER POLYMERIC thing cladding nanometer hydroxyapatite is：
（1）In reaction vessel, sequentially add 0.044 mol 1H- imidazoles -4- ethamine, 10 g epoxy resin E-44 and
The ml of DMF 300, after leading to 30 min of nitrogen protection, heat up after 100 DEG C of 5 h of reaction, it is molten to obtain sticky polyetheramine
Liquid；
（2）Into above-mentioned sticky polyether amine solution, 100 g nanometer hydroxyapatite, 2 g silane coupler KH- are added
550, under 100 DEG C, nitrogen protection, continue after stirring 2 h, by reaction solution precipitating in 2000 ml ethanol, obtain a large amount of solids
Precipitation, solid precipitation is washed repeatedly three times with ethanol and deionized water, is then filtered, by gained solid in vacuum drying oven,
24 h are dried at 50 DEG C and obtain single polymer layer cladding nanometer hydroxyapatite；
（3）By the 4,4 ' of 0.002mol-difluoro benzophenone, 0.0021mol 4,4 '-dihydroxy benzophenone, 0.0024mol
Natrium carbonicum calcinatum, 0.012mol diphenyl sulphone (DPS) are fitted into reaction vessel, are warming up to 180 DEG C in a nitrogen atmosphere, react 6 h, so
After be warming up to 300 DEG C, react 5 h, then reaction solution separated out in deionized water, washed repeatedly with ethanol and deionized water
The solid precipitates three times, then filters, and drying 24 h by gained solid in vacuum drying oven, at 120 DEG C obtains polyether-ketone；
（4）Take step（3）The g of gained polyether-ketone 10 is dissolved in 300 ml diphenyl sulphone (DPS)s, then adds step（2）Gained individual layer gathers
Compound coats the g of nanometer hydroxyapatite 100, after being warming up to 80 DEG C of 2 h of stirring, reaction solution is separated out in deionized water, used
Ethanol and deionized water wash solid precipitation three times repeatedly, then filter, by gained solid in vacuum drying oven, at 120 DEG C
Dry 24 h and obtain ELECTRODE WITH BILAYER POLYMERIC thing cladding nanometer hydroxyapatite；
The preparation method of the polyether-ketone modified graphene oxide is：
（1）By the 4,4 ' of 0.002mol-difluoro benzophenone, 0.0022mol 4,4 '-dihydroxy benzophenone, 0.0024mol
Natrium carbonicum calcinatum, 0.012mol diphenyl sulphone (DPS) are fitted into reaction vessel, are warming up to 180 DEG C in a nitrogen atmosphere, react 6 h, so
After be warming up to 300 DEG C, react 5 h, then polymer separated out in deionized water, this is washed repeatedly with ethanol and deionized water
Solid precipitates three times, then filters, and drying 24 h by gained solid in vacuum drying oven, at 120 DEG C obtains polyether-ketone；
（2）In round-bottomed flask, above-mentioned steps are sequentially added（1）13 g of g, KH-560 of g, KH-550 of gained polyether-ketone 5, oxygen
The g of graphite alkene 15, the g of dimethyl sulfoxide (DMSO) 330, after leading to 1 h of nitrogen protection, system temperature is risen to 80 DEG C, after reacting 5 hours,
Room temperature is down to, is discharged in ethanol, obtains fluffy solid, washs the fluffy solid respectively 3 times with deionized water and ethanol, most
It is dried in vacuo 24 hours at 50 DEG C afterwards, obtains the polyether-ketone modified graphene oxide.
Comparative example 1
By weight, by 100 parts of PC resin, 20 parts of PBT resin, ELECTRODE WITH BILAYER POLYMERIC thing 60 parts of nanometer hydroxyapatite of cladding, ethylene
3 parts of bis-stearamides, 2 parts of dioctyl ester base pentaerythritol diphosphites and double (2,4- di-tert-butyl-phenyl) pentaerythrites two
2 parts of phosphite ester is added in the high-speed mixer that rotating speed is 900 revs/min and mixed, until because of friction caused by high-speed stirred
Heat makes temperature of charge be discharged when being increased to 120 DEG C, then mixed material is sent in cooling and stirring device, under agitation by cold
The mode of water leg cooling is cooled to 50 DEG C；
Mixed material after cooling is sent in the double screw extruder for having reached design temperature, mixed material is by double spiral shells
Bar extruder is extruded as billot, and set extrusion die temperature is 230 DEG C；The billot extruded is cooled down through tank, drawn
It is granulated into pelleter and obtains the high durable high abrasion PC materials based on modified graphene oxide；
The precedence that above-mentioned double screw extruder passes through according to material is divided into 4 heating zones and extrusion die, and set is each
The heating-up temperature of heating zone is followed successively by：Temperature T1=190 DEG C of first heating zone, temperature T2=210 DEG C of the second heating zone, the 3rd
Temperature T3=240 DEG C of heating zone, temperature T4=260 DEG C of the 4th heating zone；
The preparation method of ELECTRODE WITH BILAYER POLYMERIC thing cladding nanometer hydroxyapatite is：
（1）In reaction vessel, sequentially add 0.044 mol 1H- imidazoles -4- ethamine, 10 g epoxy resin E-44 and
The ml of DMF 300, after leading to 30 min of nitrogen protection, heat up after 100 DEG C of 5 h of reaction, it is molten to obtain sticky polyetheramine
Liquid；
（2）Into above-mentioned sticky polyether amine solution, 100 g nanometer hydroxyapatite, 2 g silane coupler KH- are added
550, under 100 DEG C, nitrogen protection, continue after stirring 2 h, by reaction solution precipitating in 2000 ml ethanol, obtain a large amount of solids
Precipitation, solid precipitation is washed repeatedly three times with ethanol and deionized water, is then filtered, by gained solid in vacuum drying oven,
24 h are dried at 50 DEG C and obtain single polymer layer cladding nanometer hydroxyapatite；
（3）By the 4,4 ' of 0.002mol-difluoro benzophenone, 0.0021mol 4,4 '-dihydroxy benzophenone, 0.0024mol
Natrium carbonicum calcinatum, 0.012mol diphenyl sulphone (DPS) are fitted into reaction vessel, are warming up to 180 DEG C in a nitrogen atmosphere, react 6 h, so
After be warming up to 300 DEG C, react 5 h, then reaction solution separated out in deionized water, washed repeatedly with ethanol and deionized water
The solid precipitates three times, then filters, and drying 24 h by gained solid in vacuum drying oven, at 120 DEG C obtains polyether-ketone；
（4）Take step（3）The g of gained polyether-ketone 10 is dissolved in 300 ml diphenyl sulphone (DPS)s, then adds step（2）Gained individual layer gathers
Compound coats the g of nanometer hydroxyapatite 100, after being warming up to 80 DEG C of 2 h of stirring, reaction solution is separated out in deionized water, used
Ethanol and deionized water wash solid precipitation three times repeatedly, then filter, by gained solid in vacuum drying oven, at 120 DEG C
Dry 24 h and obtain ELECTRODE WITH BILAYER POLYMERIC thing cladding nanometer hydroxyapatite.
Comparative example 2
By weight, by 100 parts of PC resin, 20 parts of PBT resin, silane-modified 20 parts of graphene oxide, ethylene bis stearamide 3
Part, 2 parts of dioctyl ester base pentaerythritol diphosphites and double 2 parts of (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites
Add in the high-speed mixer that rotating speed is 900 revs/min and mix, until because frictional heat caused by high-speed stirred makes temperature of charge
It is increased to discharge at 120 DEG C, then mixed material is sent in cooling and stirring device, is cooled down under agitation by cooling jacket
Mode is cooled to 50 DEG C；
Mixed material after cooling is sent in the double screw extruder for having reached design temperature, mixed material is by double spiral shells
Bar extruder is extruded as billot, and set extrusion die temperature is 230 DEG C；The billot extruded is cooled down through tank, drawn
It is granulated into pelleter and obtains the high durable high abrasion PC materials based on modified graphene oxide；
The precedence that above-mentioned double screw extruder passes through according to material is divided into 4 heating zones and extrusion die, and set is each
The heating-up temperature of heating zone is followed successively by：Temperature T1=190 DEG C of first heating zone, temperature T2=210 DEG C of the second heating zone, the 3rd
Temperature T3=240 DEG C of heating zone, temperature T4=260 DEG C of the 4th heating zone；
The preparation method of the polyether-ketone modified graphene oxide is：
（1）By the 4,4 ' of 0.002mol-difluoro benzophenone, 0.0022mol 4,4 '-dihydroxy benzophenone, 0.0024mol
Natrium carbonicum calcinatum, 0.012mol diphenyl sulphone (DPS) are fitted into reaction vessel, are warming up to 180 DEG C in a nitrogen atmosphere, react 6 h, so
After be warming up to 300 DEG C, react 5 h, then polymer separated out in deionized water, this is washed repeatedly with ethanol and deionized water
Solid precipitates three times, then filters, and drying 24 h by gained solid in vacuum drying oven, at 120 DEG C obtains polyether-ketone；
（2）In round-bottomed flask, above-mentioned steps are sequentially added（1）13 g of g, KH-560 of g, KH-550 of gained polyether-ketone 5, oxygen
The g of graphite alkene 15, the g of dimethyl sulfoxide (DMSO) 330, after leading to 1 h of nitrogen protection, system temperature is risen to 80 DEG C, after reacting 5 hours,
Room temperature is down to, is discharged in ethanol, obtains fluffy solid, washs the fluffy solid respectively 3 times with deionized water and ethanol, most
It is dried in vacuo 24 hours at 50 DEG C afterwards, obtains the polyether-ketone modified graphene oxide.
Comparative example 3
By weight, it is 100 parts of PC resin, 20 parts of PBT resin, 3 parts of ethylene bis stearamide, dioctyl ester base pentaerythrite two is sub-
It is 900 revs/min that 2 parts of 2 parts of phosphate and double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites, which add rotating speed,
Mixed in high-speed mixer, until because frictional heat caused by high-speed stirred makes temperature of charge be discharged when being increased to 120 DEG C, then
Mixed material is sent in cooling and stirring device, is cooled to 50 DEG C by way of cooling jacket cooling under agitation；
Mixed material after cooling is sent in the double screw extruder for having reached design temperature, mixed material is by double spiral shells
Bar extruder is extruded as billot, and set extrusion die temperature is 230 DEG C；The billot extruded is cooled down through tank, drawn
It is granulated into pelleter and obtains the high durable high abrasion PC materials based on modified graphene oxide；
The precedence that above-mentioned double screw extruder passes through according to material is divided into 4 heating zones and extrusion die, and set is each
The heating-up temperature of heating zone is followed successively by：Temperature T1=190 DEG C of first heating zone, temperature T2=210 DEG C of the second heating zone, the 3rd
Temperature T3=240 DEG C of heating zone, temperature T4=260 DEG C of the 4th heating zone；
Test condition
Mechanical strength is tested according to GB/T1040-1992.
Oxygen index (OI) is tested according to GB/T2460-1993.
Friction loss rate is tested：Use fretting wear rate (mg/ of the MPV-20B types friction wear testing machine to made sample
H) tested, experimental condition：Velocity of rotation 400r/min, run time 60min, load 300N, dry friction.
Test result is shown in Table 1.
Table 1
Claims (10)
1. the high durable high abrasion PC materials based on modified graphene oxide, it is characterised in that by weight, its preparing raw material
For：
100 parts of PC resin, PBT resin 10-30 parts, ELECTRODE WITH BILAYER POLYMERIC thing cladding nanometer hydroxyapatite 50-80 parts, polyether-ketone are modified
Graphene oxide 10-30 parts, ethylene bis stearamide 1-5 parts, dioctyl ester base pentaerythritol diphosphites 1-3 parts and double
(2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites 1-3 parts.
2. the high durable high abrasion PC materials according to claim 1 based on modified graphene oxide, it is characterised in that press
Parts by weight meter, its preparing raw material are：
100 parts of PC resin, 20 parts of PBT resin, ELECTRODE WITH BILAYER POLYMERIC thing 60 parts of nanometer hydroxyapatite of cladding, silane-modified graphite oxide
20 parts of alkene, 3 parts of ethylene bis stearamide, 2 parts of dioctyl ester base pentaerythritol diphosphites and double (2,4- di-tert-butyls
Base) 2 parts of pentaerythritol diphosphites.
3. the high durable high abrasion PC materials according to claim 1 based on modified graphene oxide, it is characterised in that institute
The outer layer for stating ELECTRODE WITH BILAYER POLYMERIC thing is rigid polyether-ketone, and internal layer is flexible polyether amine.
4. the high durable high abrasion PC materials based on modified graphene oxide according to claim any one of 1-3, it is special
Sign is that the preparation method of the ELECTRODE WITH BILAYER POLYMERIC thing cladding nanometer hydroxyapatite is：
（1）In reaction vessel, sequentially add 0.044 mol 1H- imidazoles -4- ethamine, 10 g epoxy resin E-44 and
The ml of DMF 300, after leading to 30 min of nitrogen protection, heat up after 100 DEG C of 5 h of reaction, it is molten to obtain sticky polyetheramine
Liquid；
（2）Into above-mentioned sticky polyether amine solution, 100 g nanometer hydroxyapatite, 2 g silane coupler KH- are added
550, under 100 DEG C, nitrogen protection, continue after stirring 2 h, by reaction solution precipitating in 2000 ml ethanol, obtain a large amount of solids
Precipitation, solid precipitation is washed repeatedly three times with ethanol and deionized water, is then filtered, by gained solid in vacuum drying oven,
24 h are dried at 50 DEG C and obtain single polymer layer cladding nanometer hydroxyapatite；
（3）By the 4,4 ' of 0.002mol-difluoro benzophenone, 0.0021mol 4,4 '-dihydroxy benzophenone, 0.0024mol
Natrium carbonicum calcinatum, 0.012mol diphenyl sulphone (DPS) are fitted into reaction vessel, are warming up to 180 DEG C in a nitrogen atmosphere, react 6 h, so
After be warming up to 300 DEG C, react 5 h, then reaction solution separated out in deionized water, washed repeatedly with ethanol and deionized water
The solid precipitates three times, then filters, and drying 24 h by gained solid in vacuum drying oven, at 120 DEG C obtains polyether-ketone；
（4）Take step（3）The g of gained polyether-ketone 10 is dissolved in 300 ml diphenyl sulphone (DPS)s, then adds step（2）Gained individual layer gathers
Compound coats the g of nanometer hydroxyapatite 100, after being warming up to 80 DEG C of 2 h of stirring, reaction solution is separated out in deionized water, used
Ethanol and deionized water wash solid precipitation three times repeatedly, then filter, by gained solid in vacuum drying oven, at 120 DEG C
Dry 24 h and obtain ELECTRODE WITH BILAYER POLYMERIC thing cladding nanometer hydroxyapatite.
5. the high durable high abrasion PC materials based on modified graphene oxide according to claim any one of 1-3, it is special
Sign is that the preparation method of the polyether-ketone modified graphene oxide is：
（1）By the 4,4 ' of 0.002mol-difluoro benzophenone, 0.0022mol 4,4 '-dihydroxy benzophenone, 0.0024mol
Natrium carbonicum calcinatum, 0.012mol diphenyl sulphone (DPS) are fitted into reaction vessel, are warming up to 180 DEG C in a nitrogen atmosphere, react 6 h, so
After be warming up to 300 DEG C, react 5 h, then polymer separated out in deionized water, this is washed repeatedly with ethanol and deionized water
Solid precipitates three times, then filters, and drying 24 h by gained solid in vacuum drying oven, at 120 DEG C obtains polyether-ketone；
（2）In round-bottomed flask, above-mentioned steps are sequentially added（1）13 g of g, KH-560 of g, KH-550 of gained polyether-ketone 5, oxygen
The g of graphite alkene 15, the g of dimethyl sulfoxide (DMSO) 330, after leading to 1 h of nitrogen protection, system temperature is risen to 80 DEG C, after reacting 5 hours,
Room temperature is down to, is discharged in ethanol, obtains fluffy solid, washs the fluffy solid respectively 3 times with deionized water and ethanol, most
It is dried in vacuo 24 hours at 50 DEG C afterwards, obtains the polyether-ketone modified graphene oxide.
6. the high durable high abrasion PC materials according to claim 4 based on modified graphene oxide, it is characterised in that institute
The average grain diameter for stating nanometer hydroxyapatite is 200-700 nanometers.
7. the high durable high abrasion PC materials according to claim 6 based on modified graphene oxide, it is characterised in that institute
The average grain diameter for stating nanometer hydroxyapatite is 500 nanometers.
8. the high durable high abrasion PC materials according to claim 5 based on modified graphene oxide, it is characterised in that institute
The average grain diameter for stating graphene oxide is 500-2000 nanometers.
9. the high durable high abrasion PC materials according to claim 8 based on modified graphene oxide, it is characterised in that institute
The average grain diameter for stating graphene oxide is 800 nanometers.
10. the preparation method of the high durable high abrasion PC materials based on modified graphene oxide, it is characterised in that including following step
Suddenly：
Any one of claim 1-9 raw material is added in the high-speed mixer that rotating speed is 900 revs/min and mixed, until because of height
Frictional heat caused by speed stirring makes temperature of charge be discharged when being increased to 120 DEG C, and mixed material then is sent into cooling and stirring
In device, 50 DEG C are cooled to by way of cooling jacket cooling under agitation；
Mixed material after cooling is sent in the double screw extruder for having reached design temperature, mixed material is by double spiral shells
Bar extruder is extruded as billot, and set extrusion die temperature is 230 DEG C；The billot extruded is cooled down through tank, drawn
It is granulated into pelleter and obtains the high durable high abrasion PC materials based on modified graphene oxide；
The precedence that above-mentioned double screw extruder passes through according to material is divided into 4 heating zones and extrusion die, and set is each
The heating-up temperature of heating zone is followed successively by：Temperature T1=170 DEG C~210 DEG C of first heating zone, temperature T2=210 of the second heating zone
DEG C~240 DEG C, temperature T3=240 DEG C~250 DEG C of the 3rd heating zone, temperature T4=250 DEG C~260 DEG C of the 4th heating zone.
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Cited By (1)
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|---|---|---|---|---|
| CN109810488A (en) * | 2019-01-25 | 2019-05-28 | 厦门美佳美新材料科技有限公司 | High heat resistance graphene oxide modified polycarbonate plastic pellet and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424720A (en) * | 2011-11-25 | 2012-04-25 | 深圳市科聚新材料有限公司 | Conduction-enhanced PC (Polycarbonate)/PBT (Polybutylece Terephthalate) composite material and preparation method thereof |
| CN106751676A (en) * | 2016-12-23 | 2017-05-31 | 东莞市奥能工程塑料有限公司 | A kind of antistatic alloy of high intensity and preparation method thereof |
| CN107312298A (en) * | 2017-06-29 | 2017-11-03 | 江南石墨烯研究院 | A kind of flame retardant type polycarbonate composite material and preparation method thereof |
-
2018
- 2018-01-08 CN CN201810014800.7A patent/CN107880520A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424720A (en) * | 2011-11-25 | 2012-04-25 | 深圳市科聚新材料有限公司 | Conduction-enhanced PC (Polycarbonate)/PBT (Polybutylece Terephthalate) composite material and preparation method thereof |
| CN106751676A (en) * | 2016-12-23 | 2017-05-31 | 东莞市奥能工程塑料有限公司 | A kind of antistatic alloy of high intensity and preparation method thereof |
| CN107312298A (en) * | 2017-06-29 | 2017-11-03 | 江南石墨烯研究院 | A kind of flame retardant type polycarbonate composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 廖建国等: "硅烷偶联剂对纳米羟基磷灰石表面改性的研究", 《无机材料学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109810488A (en) * | 2019-01-25 | 2019-05-28 | 厦门美佳美新材料科技有限公司 | High heat resistance graphene oxide modified polycarbonate plastic pellet and preparation method thereof |
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