CN106543627A - A kind of high-temperature resistance plastice lubricating additive and preparation method thereof - Google Patents
A kind of high-temperature resistance plastice lubricating additive and preparation method thereof Download PDFInfo
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- CN106543627A CN106543627A CN201610904613.7A CN201610904613A CN106543627A CN 106543627 A CN106543627 A CN 106543627A CN 201610904613 A CN201610904613 A CN 201610904613A CN 106543627 A CN106543627 A CN 106543627A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The present invention relates to plastic processing additive agent field, and in particular to a kind of high-temperature resistance plastice lubricating additive and preparation method thereof.By making Calcium Carbonate nodularization and activating to spraying formula jet mill, the further preparation method Jing after polyester liquid grinding using conventional masterbatch prepares high-temperature resistance plastice lubricant under conditions of polyphosphazene polymer alkene is carrier.The high-temperature resistance plastice lubricant makes calcium carbonate surface firmly be connected with polyester by polyester liquid grinding by Calcium Carbonate nodularization so as to have good greasy property, and the processing compatibility is good, effectively prevents Calcium Carbonate exposed.Particularly preparation process need not add the auxiliary agent of the easily vaporization at high temperature such as low molecule coupling agent, wax, with good heat-resisting quantity, can replace the lubricants such as paraffin, Tissuemat E stearic acid, fat acid calcium, zinc stearate, magnesium stearate, white oil is used for the processing of plastics.
Description
Technical field
The present invention relates to plastic processing additive agent field, and in particular to a kind of high-temperature resistance plastice lubricating additive and its preparation
Method.
Background technology
With synthesis of polymer material and the technological progress of processing, plastics obtain extensive, deep application in every profession and trade.It is special
It is not significantly to have expanded plastics by the modified various functions such as plastics high tenacity, high intensity, high flame retardant, high permeability resistance that give
Application and range of application.For example make plastics that there is high-ductility by composite glass fiber, carbon fiber, boron fibre, whisker etc.
Property and intensity；The intensity of plastics is improved further by increasing molecular weight, crosslinking；Plastics are lifted by adding flame-retardant master batch
Anti-flammability so as to deeply apply in fields such as building materials, electrical equipment；The permeability resistance of plastics is made further to increase by composite nano materials
By force.Be modified the inexpensive product for having derived stone paper, stone plastics etc. with inorganic particle as material of main part even with depth,
The application for making plastics is no longer the plastics of traditional sense.
As the core of plastics is thermoplasticity processing, above-mentioned all kinds of modified problems faceds are in modifying process and modified
Processability problems.Known, the processing of plastics needs good mobility, but using fiber, fire retardant, nano-powder,
During the filler modified plastics of all kinds of inorganic particles, its processing fluidity can be remarkably decreased.Despite the use of many technological means are modified,
But still existing defects.Typical technological means have：Improve processing temperature.Temperature is low, and viscosity of plastic melts is big, flow difficulties, into
Type is poor, and elasticity is big, is raised by temperature so that intermolecular, and the motion of molecule interchain is accelerated, so that plastic molecules
Winding between chain is reduced, the distance between molecule increase, so as to cause viscosity to reduce.But on the one hand high temperature process is lost energy
Amount, on the other hand can also cause decomposition, cause molecular weight to reduce, and intensity is damaged；Increase shearing force.By increase shear strength and
Shear rate, reduces the viscosity of plastics, but due to having small sky between the molecule inside plastic melt, between strand
Between, too high shearing force can cause the distance between macromole to reduce, and not only cause excessive power attenuation and excessive equipment
Abrasion, can also cause product internal stress unstable, it is difficult to processing precise product；The lubricants such as low molecular weight additives such as paraffin.
Lubrication is played between plastics macromolecular chain by low molecule lubricant thus reduces melt viscosity, at present mostly by using
The low molecule such as paraffin lubricant is lifting the processability of plastics.Particularly used in existing plastics, substantial amounts of all kinds of fillings are female
Material, needs to add more lubricants to ensure processing fluidity therewith.But the addition of lubricant have impact on plastic molecules simultaneously
Between connection, cause product strength to reduce.More seriously, under the conditions of high temperature process, the volatile drop of low molecule lubricant
Solution, causes the deterioration of product, such as thin film cavity occur, and the defects such as bubble occurs in moulding.
According to above-mentioned, it is existing reduce viscosity improve plastic processing mobility technological means plastics performance is present it is larger
Negative effect, it is difficult to meet the process requirements that plastics develop to Composite, functionalization.Such as some special applications such as 3D printing,
Higher shearing is difficult to set up at present, is relied only on high temperature to lift processing fluidity, is not only caused plastic degradation to decompose, and make
Product intensity declines obvious.
The content of the invention
In order to improve plastic processing mobility and avoid Strong shear and high temperature process from causing the decay of plastics performance, the present invention
Propose a kind of high-temperature resistance plastice lubricating additive.The lubricating additive is with calcium carbonate particle as material of main part, by carbonic acid
Calcium inorganic particulate nodularization, further wraps thermoplastic resin in spherical calcium carbonate surface of inorganic particles and obtains.During for plastics, tool
There are good lubrication property and dispersing characteristic, effectively prevent the thermal degradation of plastics.Further provide for preparing high-temperature resistance plastice profit
The method of sliding additive.
The technical solution adopted in the present invention is：
A kind of preparation method of high-temperature resistance plastice lubricating additive, is characterized in that preparation method is carried out as follows：
1）Micron order calcium carbonate inorganic particle is sent into spraying in formula jet mill, to spray by two nozzles respectively with acid solution
Formula jet mill arranges two nozzles, crushes nozzle for one and sprays into micron order calcium carbonate inorganic particle with the pressure of 1-2MPa
Acid solution is sprayed into pulverizing chamber with the pressure of 0.5-1MPa by pulverizing chamber, a feed introduction, and the straying quatity of acid solution is forming acid environment
, micron order calcium carbonate inorganic particle produce the indoor collision in the form of jet is crushed the impact force of high intensity, shearing force,
Frictional force, in high velocity air during repeated stock, cutting rubbing, rotation, the corner angle of micron order calcium carbonate inorganic particle
The spherical calcium carbonate inorganic particulate of activation is gradually passivated and is ultimately formed under acid environment and rotary collision effect；Wherein, powder
Broken chamber interior walls are ultra hard ceramic；
2）By step 1）The spherical calcium carbonate inorganic particle 80-95 weight portions of activation for obtaining are with a small amount of polyester liquid in grinder
In be ground, then mix homogeneously with the polyolefin of 15-20 weight portions, be placed in screw extruder, mixing extrusion is simultaneously made
Grain, obtains a kind of high-temperature resistance plastice lubricating additive；Wherein described polyester liquid is polyethylene terephthalate, gathers to benzene
Dioctyl phthalate fourth diester, the xylene solution of polyarylate.
Above-mentioned preparation method the 1st）The described acid solution of step is the dilute hydrochloric acid or dilute sulfuric acid that concentration is 2-4mol/L.
Above-mentioned preparation method the 2nd）The described polyolefin of step is polyethylene, polypropylene, polyvinyl acetate, polystyrene, poly-
At least one in vinyl chloride.
Above-mentioned preparation method the 2nd）The described screw extruder of step is adopted and includes spiral shell that is currently reported and/or using
Bar extruder carries out extruding pelletization, and preferred parallel dual-screw extruding machine, screw slenderness ratio are more than 35:1.
The invention under acid environment auxiliary, by spraying formula jet mill, to be passivated Calcium Carbonate corner angle final
Nodularization is simultaneously activated, and the further preparation method that conventional masterbatch is utilized Jing after polyester liquid grinding is carrier in polyphosphazene polymer alkene
Under the conditions of prepare high-temperature resistance plastice lubricant.The high-temperature resistance plastice lubricant passes through Calcium Carbonate nodularization so as to have good profit
Slip energy, makes calcium carbonate surface firmly be connected with polyester by polyester liquid grinding, and the processing compatibility is good, effectively prevents carbonic acid
Calcium is exposed.Particularly preparation process need not add the auxiliary agent of the easily vaporization at high temperature such as low molecule coupling agent, wax, with good resistance to
High temperatures, can replace the lubricants such as paraffin, Tissuemat E stearic acid, fat acid calcium, zinc stearate, magnesium stearate, white oil is used for
The processing of plastics.
A kind of high-temperature resistance plastice lubricating additive, it is characterized in that by above-mentioned preparation method be prepared with heat-resisting quantity
The plastics lubricating additive of energy.
Typically applying for one is：During 3D printing ABS, due to lacking shearing, it usually needs improve processing temperature to realize
Good flowing, but low-molecular-weight lubricant therein is extremely easy in decomposition under the high temperature conditions, volatilizees, and not only causes lacking for product
Fall into, and working environment because it is substantial amounts of volatilization become severe, have impact on its normal use.The high temperature resistant modeling that the present invention is obtained
Material lubricating additive is used for the 3D printing of ABS, is obviously improved its high temperature process mobility, and without volatilizing, substantially improves
Working environment, improves quality of item.
In order to lift the processing flowability of plastics, generally using addition low molecular lubricant such as paraffin, Tissuemat E
Stearic acid, fat acid calcium, zinc stearate, magnesium stearate, white oil etc. are increasing mobility.However, the use shadow of low molecule lubricant
The connection between plastic molecules is rung, has caused product strength to reduce, and the volatile degraded of low molecule lubricant under the high temperature conditions, make
Into the deterioration of product, a serious defect is to cause thin film cavity occur, and bubble etc. occurs in moulding.High temperature resistant modeling of the present invention
Material lubricating additive is effectively prevent using low-molecular-weight lubricant.
Compared with prior art, the characteristics of present invention is prominent and beneficial effect are：
1st, the preparation method of a kind of high-temperature resistance plastice lubricating additive of the invention, under acid environment auxiliary, by spraying formula air-flow
Pulverizer makes Calcium Carbonate nodularization and activates, it is ensured that the good sliding of lubricant.
2nd, the preparation method of a kind of high-temperature resistance plastice lubricating additive of the invention, grinds the carbonic acid of nodularization by polyester liquid
Calcium, makes calcium carbonate surface firmly be connected with polyester, and the processing compatibility is good, effectively prevents Calcium Carbonate exposed, it is to avoid using low point
Son amount coupling agent.
3rd, a kind of high-temperature resistance plastice lubricating additive of the invention, with good greasy property and resistance to elevated temperatures, can be with
Replacing the lubricants such as paraffin, Tissuemat E stearic acid, fat acid calcium, zinc stearate, magnesium stearate, white oil is used for the processing of plastics.
The negative effect brought using low-molecular-weight lubricant will be prevented effectively from.
4th, the present invention plants the preparation method of high-temperature resistance plastice lubricating additive, and simple production process is controllable, production cost compared with
It is low, it is adapted to large-scale production, with huge market using value.
Specific embodiment
Detailed description below, is described in further detail again to the above of the present invention.But this should not be managed
Solve the scope for above-mentioned theme of the invention and be only limitted to Examples below.Without departing from the idea case in the present invention described above, root
The various replacements made according to ordinary skill knowledge and customary means or change, all should be included within the scope of the invention.
Embodiment 1
1）Dilute sulfuric acid by commercially available 1250 mesh ground calcium carbonate with concentration for 2mol/L is sent into spraying formula by two nozzles respectively
In jet mill, two nozzles are set to spraying formula jet mill, one is crushed nozzle with the constant pressure of 1MPa by carbonic acid
Calcium inorganic particulate sprays into pulverizing chamber, and acid solution is sprayed into pulverizing chamber with the pressure of 0.5MPa by a feed introduction, and the penetrating of acid solution makes
The acid environment of pulverizing chamber formation acid mist, the 2% of the calcium carbonate quantity weight of the consumption of acid solution, calcium carbonate inorganic particle is in pulverizing chamber
The impact force of the interior collision generation high intensity in the form of jet, shearing force, frictional force, repeated stock, cutting in high velocity air
During friction, rotation, the corner angle of micron order calcium carbonate inorganic particle are gradually blunt under acid environment and rotary collision effect
Change and ultimately form the spherical calcium carbonate inorganic particulate of activation；Wherein, it is ultra hard ceramic to crush chamber interior walls；
2）By step 1）Spherical 80 weight portion of calcium carbonate inorganic particle of activation for obtaining and the diformazan of polybutylene terephthalate
Benzole soln is ground in grinder, is then filtered dry, and is mixed homogeneously with the polypropylene of 20 weight portions, is placed in screw slenderness ratio big
In 35:1 parallel dual-screw extruding machine, mixing extrusion pelletize, obtain a kind of high-temperature resistance plastice lubricating additive.
Embodiment 1 is obtained into high-temperature resistance plastice lubricating additive ABS is made an addition to 5% ratio, prepare 3D printing special
ABS material bar, is obviously improved its high temperature process mobility, and without volatilizing, substantially improves working environment, improve product matter
Amount.
Embodiment 2
1）Dilute hydrochloric acid by commercially available 3000 mesh precipitated calcium carbonate with concentration for 3mol/L is sent into spraying formula by two nozzles respectively
In jet mill, two nozzles are set to spraying formula jet mill, one is crushed nozzle with the constant pressure of 2MPa by carbonic acid
Calcium inorganic particulate sprays into pulverizing chamber, and acid solution is sprayed into pulverizing chamber with the pressure of 1MPa by a feed introduction, and the penetrating of acid solution makes powder
The acid environment of broken room formation acid mist, the 1% of the calcium carbonate quantity weight of the consumption of acid solution, calcium carbonate inorganic particle is crushing indoor
The impact force of collision generation high intensity, shearing force, frictional force in the form of jet, repeated stock, cutting in high velocity air are rubbed
During wiping, rotation, the corner angle of micron order calcium carbonate inorganic particle are gradually passivated under acid environment and rotary collision effect
And ultimately form the spherical calcium carbonate inorganic particulate of activation；Wherein, it is ultra hard ceramic to crush chamber interior walls；
2）By step 1）What is obtained activates the xylene solution of spherical 95 weight portion of calcium carbonate inorganic particle and a small amount of polyarylate
It is ground in grinder, then mixs homogeneously with the polrvinyl chloride of 15 weight portions, be placed in single screw extrusion equipment, kneads
Extrusion pelletize, obtain a kind of high-temperature resistance plastice lubricating additive.
Embodiment 2 is obtained into the processing that high-temperature resistance plastice lubricating additive makes an addition to polyvinyl-chloride plate material with 5% ratio,
It is obviously improved its high temperature process mobility, just face causes polrvinyl chloride degraded, lubricant to separate out using low molecule lubricant
Defect.
Embodiment 3
1）Dilute sulfuric acid by commercially available 800 mesh ground calcium carbonate with concentration for 4mol/L is sent into spraying formula gas by two nozzles respectively
In stream pulverizer, two nozzles are set to spraying formula jet mill, one is crushed nozzle with the constant pressure of 1.5MPa by carbonic acid
Calcium inorganic particulate sprays into pulverizing chamber, and acid solution is sprayed into pulverizing chamber with the pressure of 0.5MPa by a feed introduction, and the penetrating of acid solution makes
The acid environment of pulverizing chamber formation acid mist, the 3% of the calcium carbonate quantity weight of the consumption of acid solution, calcium carbonate inorganic particle is in pulverizing chamber
The impact force of the interior collision generation high intensity in the form of jet, shearing force, frictional force, repeated stock, cutting in high velocity air
During friction, rotation, the corner angle of micron order calcium carbonate inorganic particle are gradually blunt under acid environment and rotary collision effect
Change and ultimately form the spherical calcium carbonate inorganic particulate of activation；Wherein, it is ultra hard ceramic to crush chamber interior walls；
2）By step 1）Spherical 80 weight portion of calcium carbonate inorganic particle of activation for obtaining is with a small amount of polyester liquid in grinder
It is ground, then mixs homogeneously with the polyethylene of 20 weight portions, be placed in conical screw extrusion equipment, mixing extrusion is simultaneously made
Grain, obtains a kind of high-temperature resistance plastice lubricating additive.
Embodiment 4
1）Dilute sulfuric acid by commercially available 1250 mesh ground calcium carbonate with concentration for 2mol/L is sent into spraying formula by two nozzles respectively
In jet mill, two nozzles are set to spraying formula jet mill, one is crushed nozzle with the constant pressure of 1MPa by carbonic acid
Calcium inorganic particulate sprays into pulverizing chamber, and acid solution is sprayed into pulverizing chamber with the pressure of 0.5MPa by a feed introduction, and the penetrating of acid solution makes
The acid environment of pulverizing chamber formation acid mist, the 2% of the calcium carbonate quantity weight of the consumption of acid solution, calcium carbonate inorganic particle is in pulverizing chamber
The impact force of the interior collision generation high intensity in the form of jet, shearing force, frictional force, repeated stock, cutting in high velocity air
During friction, rotation, the corner angle of micron order calcium carbonate inorganic particle are gradually blunt under acid environment and rotary collision effect
Change and ultimately form the spherical calcium carbonate inorganic particulate of activation；Wherein, it is ultra hard ceramic to crush chamber interior walls；
2）By step 1）Spherical 95 weight portion of calcium carbonate inorganic particle of activation for obtaining and the diformazan of polybutylene terephthalate
Benzole soln is ground in grinder, is then filtered dry and is mixed homogeneously with the polyvinyl acetate of 15 weight portions, is placed in twin screw and is squeezed
Go out in equipment, mixing extrusion simultaneously pelletize obtains a kind of high-temperature resistance plastice lubricating additive.
Claims (6)
1. a kind of preparation method of high-temperature resistance plastice lubricating additive, is characterized in that preparation method is carried out as follows：
1）Micron order calcium carbonate inorganic particle is sent into spraying in formula jet mill, to spray by two nozzles respectively with acid solution
Formula jet mill arranges two nozzles, crushes nozzle for one and sprays into micron order calcium carbonate inorganic particle with the pressure of 1-2MPa
Acid solution is sprayed into pulverizing chamber with the pressure of 0.5-1MPa by pulverizing chamber, another feed introduction, and the straying quatity of acid solution is forming sour ring
The impact force of the indoor collision generation high intensity in the form of jet, shearing are being crushed in border, micron order calcium carbonate inorganic particle
Power, frictional force, in high velocity air during repeated stock, cutting rubbing, rotation, micron order calcium carbonate inorganic particle
Corner angle are gradually passivated and ultimately form the spherical calcium carbonate inorganic particulate of activation under acid environment and rotary collision effect；Its
In, crushing chamber interior walls are ultra hard ceramic；
2）By step 1）The spherical calcium carbonate inorganic particle 80-95 weight portions of activation for obtaining are with a small amount of polyester liquid in grinder
In be ground, then mix homogeneously with the polyolefin of 15-20 weight portions, be placed in screw extruder, mixing extrusion is simultaneously made
Grain, obtains a kind of high-temperature resistance plastice lubricating additive；Wherein described polyester liquid is polyethylene terephthalate, gathers to benzene
Dioctyl phthalate fourth diester, the xylene solution of polyarylate.
2. a kind of preparation method of high-temperature resistance plastice lubricating additive according to claim 1, it is characterised in that：Preparation method
1st）The described acid solution of step is the dilute hydrochloric acid or dilute sulfuric acid that concentration is 2-4mol/L.
3. a kind of preparation method of high-temperature resistance plastice lubricating additive according to claim 1, it is characterised in that：Preparation method
2nd）Described polyolefin is walked at least one in polyethylene, polypropylene, polyvinyl acetate, polystyrene, polrvinyl chloride.
4. a kind of preparation method of high-temperature resistance plastice lubricating additive according to claim 1, it is characterised in that：Preparation method
2nd）The described screw extruder of step using include it is currently reported and/or using screw extruder carry out extrusion and make
Grain.
5. a kind of preparation method of high-temperature resistance plastice lubricating additive according to claim 1, it is characterised in that：Preparation method
2nd）The described screw extruder of step is parallel dual-screw extruding machine, and screw slenderness ratio is more than 35:1.
6. a kind of high-temperature resistance plastice lubricating additive, it is characterized in that the preparation method by described in any one of claim 1-5 prepare and
The plastics lubricating additive with heat-resisting quantity for obtaining.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60168719A (en) * | 1984-02-13 | 1985-09-02 | Toyobo Co Ltd | Production of easily slidable polyester |
| JPS62232431A (en) * | 1986-04-02 | 1987-10-12 | Toray Ind Inc | Production of polyester |
| CN1178543A (en) * | 1996-02-26 | 1998-04-08 | 赫希斯特人造丝公司 | Thermoplastic polymer composition with improved wear properties |
| CN102701174A (en) * | 2012-05-11 | 2012-10-03 | 上海大学 | Superfine processing and grain diameter control method of powder materials |
| CN105540574A (en) * | 2016-01-28 | 2016-05-04 | 成都新柯力化工科技有限公司 | Method for preparing graphene micro-sheets by using counter-jet jet mill |
| CN105802168A (en) * | 2016-05-23 | 2016-07-27 | 江西省萍乡市轩品塑胶制品有限公司 | Biodegradable nanometer filling function master batch and preparation method and application thereof |
-
2016
- 2016-10-18 CN CN201610904613.7A patent/CN106543627B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60168719A (en) * | 1984-02-13 | 1985-09-02 | Toyobo Co Ltd | Production of easily slidable polyester |
| JPS62232431A (en) * | 1986-04-02 | 1987-10-12 | Toray Ind Inc | Production of polyester |
| CN1178543A (en) * | 1996-02-26 | 1998-04-08 | 赫希斯特人造丝公司 | Thermoplastic polymer composition with improved wear properties |
| CN102701174A (en) * | 2012-05-11 | 2012-10-03 | 上海大学 | Superfine processing and grain diameter control method of powder materials |
| CN105540574A (en) * | 2016-01-28 | 2016-05-04 | 成都新柯力化工科技有限公司 | Method for preparing graphene micro-sheets by using counter-jet jet mill |
| CN105802168A (en) * | 2016-05-23 | 2016-07-27 | 江西省萍乡市轩品塑胶制品有限公司 | Biodegradable nanometer filling function master batch and preparation method and application thereof |
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