CN109385008A - A kind of preparation method of high-performance polypropylene compound material - Google Patents
A kind of preparation method of high-performance polypropylene compound material Download PDFInfo
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- CN109385008A CN109385008A CN201811249114.4A CN201811249114A CN109385008A CN 109385008 A CN109385008 A CN 109385008A CN 201811249114 A CN201811249114 A CN 201811249114A CN 109385008 A CN109385008 A CN 109385008A
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Abstract
The invention discloses a kind of preparation methods of high-performance polypropylene compound material, are related to polypropylene material field, comprising the following steps: (1) preparation of graphene powder；(2) preparation of polypropylene powder；(3) graphene powder and polyacrylic dispersion mixing；(4) CO 2 supercritical infiltrates；(5) polypropylene-graphene pellet preparation；(6) preparation of polypropylene-maleic anhydride pellet；(7) preparation of high-performance polypropylene compound material；Preparation method of the present invention is infiltrated by using supercritical carbon dioxide between graphene, it is uniformly dispersed in polypropylene to improve graphene, by maleic anhydride and nucleating agent and the polyacrylic flexibility of polypropene blended improvement and compatibility, PP composite material made from blended melting has good mechanical mechanics property and thermal stability.
Description
Technical field
The present invention relates to polypropylene material fields, and in particular to a kind of preparation method of high-performance polypropylene compound material.
Background technique
Polypropylene (PP) has many advantages, such as that inexpensive, light, source is wide and processing performance is good and obtains extensive due to it
Using.But the nonpolarity due to PP, crystallinity and surface can be low, big spherocrystal easily generated, causes when cooling down in the molten state
Impact strength is low, the easy embrittlement of when low temperature, adhesiveness, antistatic property, hydrophily difference and with polar polymer, metal or inorganic fill out
The poor compatibility etc. of material, therefore limit polypropylene in the further expansion of application field, however the cheap price of polypropylene and
Ideal processing performance promotes people to pass through economical and practical method of modifying to improve its performance.
Chinese patent application file CN200510002252.9 discloses a kind of hot channel injecting formation acrylic resin
Composition and preparation method thereof.The composition includes the ethylene-propylene-diene monomer of the polypropylene homopolymer of mass parts ratio 90-98,1-5
Glue, the Powdered Rubber of Ultrafine Styrene Butadiene of 1-5, the Sorbitol Nucleator of 0.1-1,0.1-0.25 Hinered phenols primary antioxidant, 0.2-
0.5 phosphorous acid esters aid anti-oxidants, 0.1-0.2 organo-fluorine polymer rheology conditioner；Preparation method: at normal temperature will
Mixing granulator in parallel equidirectional two-screw extruder is added with feeder in above-mentioned material mixing 3-5 minutes.The composition
With high impact flexibility, tensile strength and rigidity are suitable with polypropylene base resin, and the composition processing rheological property
It is substantially better than polypropylene base resin and close other modified systems of composition ratio, melt flows orientation tendency reduces, product
Vertical and horizontal shrinking percentage difference be also significantly less than homopolypropylene and close other modified systems of composition ratio, the present invention
Composition can greatly improve the shortcomings that easy friability of polypropylene material, improve the flexibility of polypropylene material, but right
The promotion of the mechanical mechanics property of polypropylene material is not apparent.
It is multiple that Chinese patent CN105153545B discloses a kind of polypropylene/maleic anhydride inoculated polypropylene/bacteria cellulose
Condensation material, it is by weight percentage, composed of the following components: polypropylene homopolymer 85~94.5%, maleic anhydride grafting poly- third
Alkene 5% and bacteria cellulose 0.5~10%.Polypropylene homopolymer, maleic anhydride are grafted by the present invention by double screw extruder
Polypropylene is blended with bacteria cellulose, gained polypropylene/maleic anhydride inoculated polypropylene/bacteria cellulose composite material composite wood
The tensile strength of material has improvement result compared with virgin pp, polyacrylic application prospect can be improved, but there are still resistance to
Hot and not excellent enough the disadvantage that wears no resistance.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of preparation sides of high-performance polypropylene compound material
Method, preparation method of the present invention are infiltrated by using supercritical carbon dioxide between graphene, and raising graphene is in polypropylene
It is uniformly dispersed, pass through maleic anhydride and nucleating agent and it is polypropene blended improve polyacrylic flexibility and compatibility, be blended
Melting PP composite material obtained has good mechanical mechanics property and thermal stability.
In order to achieve the above object, the present invention is achieved through the following technical solutions:
A kind of preparation method of high-performance polypropylene compound material, comprising the following steps:
(1) graphene is placed in ethanol solution, the octadecylamine for being equivalent to its weight 2-5% is added, is stirred
It after uniformly, is placed in ultrasonic wave separating apparatus after ultrasonic disperse 1 hour, filters, it is dry, it places and is ground 5-8 hours in ball mill,
Obtain graphene powder；
(2) polypropylene is placed in drying 2 hours in vacuum oven, the polypropylene after drying is put into grinder and is ground into
For micropowder, polypropylene powder is obtained；
(3) graphene powder, polypropylene powder and silane coupling agent are added in ethanol solution and are uniformly mixed, formed
After stirring 5-8 hours, after vacuum filtration pumping filter, it is dry to be placed on air blast with 800-1500 revs/min of speed for suspension
In dry case after drying 5 hours, mixed material 1 is obtained；
(4) mixed material is placed in autoclave, autoclave temp is warming up to 40 degrees Celsius, carbon dioxide is pumped into height
It presses in kettle, until for pressure to 8-12MPa, carbon dioxide starts the cycle over flowing in autoclave, in the supercritical state, infiltrates 6 hours
Afterwards, fast pressure relief is to normal pressure state；
(5) product made from step (4) is added twin-screw extrude into carry out extruding pelletization, pellet deionized water is clear
It is 12 hours dry in the baking oven of 80-90 degrees Celsius of merging after washing, obtain polypropylene-graphene pellet；
(6) after dissolving maleic anhydride than adding into acetone according to the quality of 1:3, with polypropylene, initiator and nucleating agent
It is added in high-speed mixer and is mixed 10-15 minutes under 70-90 degrees Celsius, obtain mixed material 2；
(7) mixed material 2 is added twin-screw extrude into carry out extruding pelletization, after pellet is cleaned with deionized water, set
Enter in 80-90 degrees Celsius of baking oven, it is 12 hours dry, obtain polypropylene-maleic anhydride pellet；
(8) high speed is added in polypropylene-graphene pellet, polypropylene-maleic anhydride pellet, polypropylene granules and antioxidant
In mixing machine after mixing, it is placed in double screw extruder and carries out extruding pelletization, after pellet is cleaned with deionized water, merging
In 80-90 degrees Celsius of baking oven, dry 12 hours to get the high-performance polypropylene compound material.
Preferably, the grinding in the step (1) specifically: the medium used be stainless steel ball, ratio of grinding media to material 8-20:1,
Grinder rotating speed is 200-600 revs/min.
Preferably, the mass ratio of the graphene powder in the step (3), polypropylene and silane coupling agent is 8-12:
100:3-5。
Preferably, the silane coupling agent is γ-propyl silane, vinyltriethoxysilane, vinyl
The combination of one or more of trimethoxy silane and vinyl three ('beta '-methoxy ethyoxyl) silane.
Preferably, maleic anhydride, polypropylene, initiator and the nucleating agent in the step (6) are according to mass ratio 3-7:
100:0.8-2:2-5。
Preferably, the initiator is benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, peroxidating two
One or more of isopropylbenzene and peroxidized t-butyl perbenzoate combine.
Preferably, the nucleating agent is that inorganic nucleator and organic nucleating agent are formed according to mass ratio 3:1 mixing；
The inorganic nucleator is in talcum, calcium carbonate, mica, clay, carbon nanotube and the chitosan of 600-1000 mesh
One or more of mixing compositions.
The organic nucleating agent is 1,3,2,4- bis- (two benzal of 3,4- dimethyl) sorbierite, two (to ethyl benzal) sorbs
Alcohol, two (to methyl benzal) sorbic acids, two (replacing benzal to chlorine), are in sorbierites and 4,4- (two benzal of dimethyl sulphur-based) sorbierite
One or more of combine.
Preferably, the high-performance polypropylene compound material in the step (8) includes the raw material of following parts by weight meter: poly- third
100 parts of alkene particle, polypropylene -30-60 parts of graphene pellet, 15-45 parts of polypropylene-maleic anhydride pellet and antioxidant 0.8-
1.5 part.
Preferably, the antioxidant is one of antioxidant 1076, antioxidant 1010, antioxidant 300 and irgasfos 168
Or several combinations.
Preferably, the extrusion temperature of the double screw extruder be 200-220 degrees Celsius, screw speed be 150-200 turn/
Minute.
The present invention have it is following the utility model has the advantages that
(1) preparation method of the present invention is infiltrated by using supercritical carbon dioxide between graphene, and raising graphene exists
It is uniformly dispersed in polypropylene, pass through maleic anhydride and nucleating agent and the polypropene blended polyacrylic flexibility and compatible of improving
Property, PP composite material made from blended melting has good mechanical mechanics property and thermal stability.
(2) graphene is easy to reunite in high molecular material matrix, and dispersibility is poor, directly affects the performance of material, this hair
It is bright to use zero surface tension of supercritical carbon dioxide, high diffusion coefficient and excellent surface wettability, diffuse and penetrate into graphite
Alkene piece interlayer, reduction are the molecular force between graphene layer, improve dispersibility of the graphene in polypropylene powder, improve compound
The mechanical property and thermal stability of material.
(3) using maleic anhydride and initiator and polypropene blended extruding pelletization, while by compounding work with nucleating agent
With the polypropylene-maleic anhydride composite material of preparation has good flexibility and mechanical shock resistance, improves polypropylene friability
The shortcomings that degree height and poor compatibility.
(4) present invention first carries out graphene and maleic anhydride after granulation is blended with polypropylene segment pellet respectively,
Blending granulation is carried out in polypropylene granules, carries out multiple melting extrusion granulation, the dispersibility and flexibility of pellet can be improved, together
When the unicity of component in material can be improved, help to improve the mechanical property of material.
(5) present invention will after modification polypropylene-graphene pellet, polypropylene-maleic anhydride pellet and common
Polypropylene granules blending extrusion is granulated, PP composite material obtained, has good wearability, corrosion resistance, mechanical force
It learns performance and flexibility, excellent material performance is with a wide range of applications.
Specific embodiment
Below with reference to embodiment, further description of the specific embodiments of the present invention, and following embodiment is only used for more
Technical solution of the present invention is clearly demonstrated, and not intended to limit the protection scope of the present invention.
Embodiment 1
A kind of preparation method of high-performance polypropylene compound material, comprising the following steps:
(1) graphene is placed in ethanol solution, the octadecylamine for being equivalent to its weight 2% is added, be stirred
It after even, is placed in ultrasonic wave separating apparatus after ultrasonic disperse 1 hour, filters, it is dry, it places and is ground 5 hours in ball mill, obtain stone
Black alkene powder；
(2) polypropylene is placed in drying 2 hours in vacuum oven, the polypropylene after drying is put into grinder and is ground into
For micropowder, polypropylene powder is obtained；
(3) graphene powder, polypropylene powder and silane coupling agent are added in ethanol solution and are uniformly mixed, formed
Suspension after stirring 5 hours, after vacuum filtration pumping filter, is placed in air dry oven and is done with 800 revs/min of speed
After dry 5 hours, mixed material 1 is obtained；
(4) mixed material is placed in autoclave, autoclave temp is warming up to 40 degrees Celsius, carbon dioxide is pumped into height
It presses in kettle, until for pressure to 8MPa, carbon dioxide starts the cycle over flowing in autoclave, in the supercritical state, after infiltration 6 hours,
Fast pressure relief is to normal pressure state；
(5) product made from step (4) is added twin-screw extrude into carry out extruding pelletization, extrusion temperature is taken the photograph for 215
Family name's degree, screw speed are 150 revs/min, after pellet is cleaned with deionized water, and in the baking oven of 80 degrees Celsius of merging, dry 12 is small
When, obtain polypropylene-graphene pellet；
(6) after dissolving maleic anhydride than adding into acetone according to the quality of 1:3, with polypropylene, initiator and nucleating agent
It is added in high-speed mixer and is mixed 10 minutes under 70 degrees Celsius, obtain mixed material 2；
(7) mixed material 2 is added twin-screw extrude into carry out extruding pelletization, extrusion temperature is 200 degrees Celsius, screw rod
Revolving speed is 160 revs/min, after pellet is cleaned with deionized water, 12 hours dry in the baking oven of 80 degrees Celsius of merging, is gathered
Propylene maleic anhydride pellet；
(8) high speed is added in polypropylene-graphene pellet, polypropylene-maleic anhydride pellet, polypropylene granules and antioxidant
In mixing machine after mixing, it is placed in double screw extruder and carries out extruding pelletization, extrusion temperature is 218 degrees Celsius, and screw rod turns
Speed is 185 revs/min, after pellet is cleaned with deionized water, and in the baking oven of 80 degrees Celsius of merging, dry 12 hours to get described
High-performance polypropylene compound material.
Grinding in step (1) specifically: the medium used is stainless steel ball, and ratio of grinding media to material 8:1, grinder rotating speed is
200 revs/min.
The mass ratio of graphene powder, polypropylene and silane coupling agent in step (3) is 8:100:3.
Silane coupling agent is γ-propyl silane.
Maleic anhydride, polypropylene, initiator and nucleating agent in step (6) is according to mass ratio 3:100:0.8:2.
Initiator is benzoyl peroxide.
Nucleating agent is that inorganic nucleator and organic nucleating agent are formed according to mass ratio 3:1 mixing；
Inorganic nucleator is that the talcum of 600 mesh and the calcium carbonate of 600 mesh are mixed according to mass ratio 1:1 and formed.
Organic nucleating agent is 1,3,2,4- bis- (two benzal of 3,4- dimethyl) sorbierite.
High-performance polypropylene compound material in step (8) includes the raw material of following parts by weight meter: PP GRANULES 100
Part, polypropylene -30 parts of graphene pellet, 15 parts of polypropylene-maleic anhydride pellet and 0.8 part of antioxidant.
Antioxidant is antioxidant 1076.
Embodiment 2
A kind of preparation method of high-performance polypropylene compound material, comprising the following steps:
(1) graphene is placed in ethanol solution, the octadecylamine for being equivalent to its weight 5% is added, be stirred
It after even, is placed in ultrasonic wave separating apparatus after ultrasonic disperse 1 hour, filters, it is dry, it places and is ground 8 hours in ball mill, obtain stone
Black alkene powder；
(2) polypropylene is placed in drying 2 hours in vacuum oven, the polypropylene after drying is put into grinder and is ground into
For micropowder, polypropylene powder is obtained；
(3) graphene powder, polypropylene powder and silane coupling agent are added in ethanol solution and are uniformly mixed, formed
Suspension after stirring 8 hours, after vacuum filtration pumping filter, is placed in air dry oven with 1500 revs/min of speed
After 5 hours dry, mixed material 1 is obtained；
(4) mixed material is placed in autoclave, autoclave temp is warming up to 40 degrees Celsius, carbon dioxide is pumped into height
It presses in kettle, until for pressure to 12MPa, carbon dioxide starts the cycle over flowing in autoclave, in the supercritical state, after infiltration 6 hours,
Fast pressure relief is to normal pressure state；
(5) product made from step (4) is added twin-screw extrude into carry out extruding pelletization, extrusion temperature is taken the photograph for 212
Family name's degree, screw speed are 175 revs/min, after pellet is cleaned with deionized water, and in the baking oven of 90 degrees Celsius of merging, dry 12 is small
When, obtain polypropylene-graphene pellet；
(6) after dissolving maleic anhydride than adding into acetone according to the quality of 1:3, with polypropylene, initiator and nucleating agent
It is added in high-speed mixer and is mixed 13 minutes under 85 degrees Celsius, obtain mixed material 2；
(7) mixed material 2 is added twin-screw extrude into carry out extruding pelletization, extrusion temperature is 208 degrees Celsius, screw rod
Revolving speed is 190 revs/min, after pellet is cleaned with deionized water, 12 hours dry in the baking oven of 88 degrees Celsius of merging, is gathered
Propylene maleic anhydride pellet；
(8) high speed is added in polypropylene-graphene pellet, polypropylene-maleic anhydride pellet, polypropylene granules and antioxidant
In mixing machine after mixing, it is placed in double screw extruder and carries out extruding pelletization, extrusion temperature is 220 degrees Celsius, and screw rod turns
Speed is 200 revs/min, after pellet is cleaned with deionized water, and in the baking oven of 80-90 degrees Celsius of merging, dry 12 hours to get institute
State high-performance polypropylene compound material.
Grinding in step (1) specifically: the medium used is stainless steel ball, and ratio of grinding media to material 20:1, grinder rotating speed is
600 revs/min.
The mass ratio of graphene powder, polypropylene and silane coupling agent in step (3) is 12:100:5.
Silane coupling agent is vinyltriethoxysilane.
Maleic anhydride, polypropylene, initiator and nucleating agent in step (6) is according to mass ratio 7:100:2:5.
Initiator is lauroyl peroxide.
Nucleating agent is that inorganic nucleator and organic nucleating agent are formed according to mass ratio 3:1 mixing；
Inorganic nucleator is the mica of 1000 mesh.
Organic nucleating agent is two (to ethyl benzal) sorbierites.
High-performance polypropylene compound material in step (8) includes the raw material of following parts by weight meter: PP GRANULES 100
Part, polypropylene -60 parts of graphene pellet, 45 parts of polypropylene-maleic anhydride pellet and 1.5 parts of antioxidant.
Antioxidant is antioxidant 1010.
Embodiment 3
A kind of preparation method of high-performance polypropylene compound material, comprising the following steps:
(1) graphene is placed in ethanol solution, the octadecylamine for being equivalent to its weight 3.5% is added, is stirred
It after uniformly, is placed in ultrasonic wave separating apparatus after ultrasonic disperse 1 hour, filters, it is dry, it places and is ground 6.5 hours in ball mill,
Obtain graphene powder；
(2) polypropylene is placed in drying 2 hours in vacuum oven, the polypropylene after drying is put into grinder and is ground into
For micropowder, polypropylene powder is obtained；
(3) graphene powder, polypropylene powder and silane coupling agent are added in ethanol solution and are uniformly mixed, formed
Suspension after stirring 7 hours, after vacuum filtration pumping filter, is placed in air dry oven with 1200 revs/min of speed
After 5 hours dry, mixed material 1 is obtained；
(4) mixed material is placed in autoclave, autoclave temp is warming up to 40 degrees Celsius, carbon dioxide is pumped into height
It presses in kettle, until for pressure to 10MPa, carbon dioxide starts the cycle over flowing in autoclave, in the supercritical state, after infiltration 6 hours,
Fast pressure relief is to normal pressure state；
(5) product made from step (4) is added twin-screw extrude into carry out extruding pelletization, extrusion temperature is taken the photograph for 216
Family name's degree, screw speed are 168 revs/min, after pellet is cleaned with deionized water, and in the baking oven of 88 degrees Celsius of merging, dry 12 is small
When, obtain polypropylene-graphene pellet；
(6) after dissolving maleic anhydride than adding into acetone according to the quality of 1:3, with polypropylene, initiator and nucleating agent
It is added in high-speed mixer and is mixed 13 minutes under 82 degrees Celsius, obtain mixed material 2；
(7) mixed material 2 is added twin-screw extrude into carry out extruding pelletization, extrusion temperature is 210 degrees Celsius, screw rod
Revolving speed is 175 revs/min, after pellet is cleaned with deionized water, 12 hours dry in the baking oven of 87 degrees Celsius of merging, is gathered
Propylene maleic anhydride pellet；
(8) high speed is added in polypropylene-graphene pellet, polypropylene-maleic anhydride pellet, polypropylene granules and antioxidant
In mixing machine after mixing, it is placed in double screw extruder and carries out extruding pelletization, extrusion temperature is 218 degrees Celsius, and screw rod turns
Speed is 185 revs/min, after pellet is cleaned with deionized water, and in the baking oven of 86 degrees Celsius of merging, dry 12 hours to get described
High-performance polypropylene compound material.
Grinding in step (1) specifically: the medium used is stainless steel ball, and ratio of grinding media to material 15:1, grinder rotating speed is
400 revs/min.
The mass ratio of graphene powder, polypropylene and silane coupling agent in step (3) is 10:100:3.8.
Silane coupling agent is vinyltrimethoxysilane.
Maleic anhydride, polypropylene, initiator and nucleating agent in step (6) is according to mass ratio 5:100:1.5:3.2.
Initiator is di-t-butyl peroxide.
Nucleating agent is that inorganic nucleator and organic nucleating agent are formed according to mass ratio 3:1 mixing；
Inorganic nucleator is the clay of 800 mesh.
Organic nucleating agent is two (replacing benzal to chlorine) sorbierites.
High-performance polypropylene compound material in step (8) includes the raw material of following parts by weight meter: PP GRANULES 100
Part, polypropylene -50 parts of graphene pellet, 30 parts of polypropylene-maleic anhydride pellet and 1.2 parts of antioxidant.
Antioxidant is antioxidant 300.
Embodiment 4
A kind of preparation method of high-performance polypropylene compound material, comprising the following steps:
(1) graphene is placed in ethanol solution, the octadecylamine for being equivalent to its weight 4.8% is added, is stirred
It after uniformly, is placed in ultrasonic wave separating apparatus after ultrasonic disperse 1 hour, filters, it is dry, it places and is ground 7.5 hours in ball mill,
Obtain graphene powder；
(2) polypropylene is placed in drying 2 hours in vacuum oven, the polypropylene after drying is put into grinder and is ground into
For micropowder, polypropylene powder is obtained；
(3) graphene powder, polypropylene powder and silane coupling agent are added in ethanol solution and are uniformly mixed, formed
Suspension after stirring 7.5 hours, after vacuum filtration pumping filter, is placed on air dry oven with 1400 revs/min of speed
After middle drying 5 hours, mixed material 1 is obtained；
(4) mixed material is placed in autoclave, autoclave temp is warming up to 40 degrees Celsius, carbon dioxide is pumped into height
It presses in kettle, until for pressure to 11MPa, carbon dioxide starts the cycle over flowing in autoclave, in the supercritical state, after infiltration 6 hours,
Fast pressure relief is to normal pressure state；
(5) product made from step (4) is added twin-screw extrude into carry out extruding pelletization, extrusion temperature is taken the photograph for 220
Family name's degree, screw speed are 180 revs/min, after pellet is cleaned with deionized water, and in the baking oven of 87 degrees Celsius of merging, dry 12 is small
When, obtain polypropylene-graphene pellet；
(6) after dissolving maleic anhydride than adding into acetone according to the quality of 1:3, with polypropylene, initiator and nucleating agent
It is added in high-speed mixer and is mixed 13 minutes under 85 degrees Celsius, obtain mixed material 2；
(7) mixed material 2 is added twin-screw extrude into carry out extruding pelletization, extrusion temperature is 215 degrees Celsius, screw rod
Revolving speed is 190 revs/min, after pellet is cleaned with deionized water, 12 hours dry in the baking oven of 84 degrees Celsius of merging, is gathered
Propylene maleic anhydride pellet；
(8) high speed is added in polypropylene-graphene pellet, polypropylene-maleic anhydride pellet, polypropylene granules and antioxidant
In mixing machine after mixing, it is placed in double screw extruder and carries out extruding pelletization, extrusion temperature is 213 degrees Celsius, and screw rod turns
Speed is 160 revs/min, after pellet is cleaned with deionized water, and in the baking oven of 90 degrees Celsius of merging, dry 12 hours to get described
High-performance polypropylene compound material.
Grinding in step (1) specifically: the medium used is stainless steel ball, and ratio of grinding media to material 17:1, grinder rotating speed is
500 revs/min.
The mass ratio of graphene powder, polypropylene and silane coupling agent in step (3) is 10:100:4.2.
Silane coupling agent is vinyl three ('beta '-methoxy ethyoxyl) silane.
Maleic anhydride, polypropylene, initiator and nucleating agent in step (6) is according to mass ratio 6.4:100:1.8:4.5.
Initiator is cumyl peroxide.
Nucleating agent is that inorganic nucleator and organic nucleating agent are formed according to mass ratio 3:1 mixing；
Inorganic nucleator is 1000 mesh carbon nanotubes.
Organic nucleating agent is two (replacing benzal to chlorine) sorbierites.
High-performance polypropylene compound material in step (8) includes the raw material of following parts by weight meter: PP GRANULES 100
Part, polypropylene -48 parts of graphene pellet, 28 parts of polypropylene-maleic anhydride pellet and 1.1 parts of antioxidant.
Antioxidant is irgasfos 168.
Embodiment 5
A kind of preparation method of high-performance polypropylene compound material, comprising the following steps:
(1) graphene is placed in ethanol solution, the octadecylamine for being equivalent to its weight 3.8% is added, is stirred
It after uniformly, is placed in ultrasonic wave separating apparatus after ultrasonic disperse 1 hour, filters, it is dry, it places and is ground 7.2 hours in ball mill,
Obtain graphene powder；
(2) polypropylene is placed in drying 2 hours in vacuum oven, the polypropylene after drying is put into grinder and is ground into
For micropowder, polypropylene powder is obtained；
(3) graphene powder, polypropylene powder and silane coupling agent are added in ethanol solution and are uniformly mixed, formed
Suspension after stirring 6.5 hours, after vacuum filtration pumping filter, is placed on air dry oven with 1300 revs/min of speed
After middle drying 5 hours, mixed material 1 is obtained；
(4) mixed material is placed in autoclave, autoclave temp is warming up to 40 degrees Celsius, carbon dioxide is pumped into height
It presses in kettle, until for pressure to 10MPa, carbon dioxide starts the cycle over flowing in autoclave, in the supercritical state, after infiltration 6 hours,
Fast pressure relief is to normal pressure state；
(5) product made from step (4) is added twin-screw extrude into carry out extruding pelletization, extrusion temperature is taken the photograph for 210
Family name's degree, screw speed are 185 revs/min, after pellet is cleaned with deionized water, and in the baking oven of 87 degrees Celsius of merging, dry 12 is small
When, obtain polypropylene-graphene pellet；
(6) after dissolving maleic anhydride than adding into acetone according to the quality of 1:3, with polypropylene, initiator and nucleating agent
It is added in high-speed mixer and is mixed 13 minutes under 82 degrees Celsius, obtain mixed material 2；
(7) mixed material 2 is added twin-screw extrude into carry out extruding pelletization, extrusion temperature is 220 degrees Celsius, screw rod
Revolving speed is 170 revs/min, after pellet is cleaned with deionized water, 12 hours dry in the baking oven of 84 degrees Celsius of merging, is gathered
Propylene maleic anhydride pellet；
(8) high speed is added in polypropylene-graphene pellet, polypropylene-maleic anhydride pellet, polypropylene granules and antioxidant
In mixing machine after mixing, it is placed in double screw extruder and carries out extruding pelletization, extrusion temperature is 208 degrees Celsius, and screw rod turns
Speed is 180 revs/min, after pellet is cleaned with deionized water, and in the baking oven of 87 degrees Celsius of merging, dry 12 hours to get described
High-performance polypropylene compound material.
Grinding in step (1) specifically: the medium used is stainless steel ball, and ratio of grinding media to material 16:1, grinder rotating speed is
500 revs/min.
The mass ratio of graphene powder, polypropylene and silane coupling agent in step (3) is 10:100:4.5.
Silane coupling agent is γ-propyl silane.
Maleic anhydride, polypropylene, initiator and nucleating agent in step (6) is according to mass ratio 5.2:100:1.5:3.6.
Initiator is peroxidized t-butyl perbenzoate.
Nucleating agent is that inorganic nucleator and organic nucleating agent are formed according to mass ratio 3:1 mixing；
Inorganic nucleator is the chitosan of 800 mesh.
Organic nucleating agent is 4,4- (two benzal of dimethyl sulphur-based) sorbierite.
High-performance polypropylene compound material in step (8) includes the raw material of following parts by weight meter: PP GRANULES 100
Part, polypropylene -45 parts of graphene pellet, 45 parts of polypropylene-maleic anhydride pellet and 1.3 parts of antioxidant.
Antioxidant is antioxidant 1076.
Comparative example 1: plain polypropylene material
Comparative example 2: being not added with polypropylene-graphene pellet, remaining preparation method and raw material are same as Example 1；
Comparative example 3: being not added with polypropylene-maleic anhydride pellet, remaining preparation method and raw material are same as Example 1；
Comparative example 4: being not added with nucleating agent, remaining preparation method and embodiment 1 are identical；
Graphene and polypropene blended melting extrusion: being directly granulated by comparative example 5, and uses material quantity and 1 phase of embodiment
Together, polypropylene-graphene pellet is prepared, remaining preparation method and raw material are same as Example 1；
By the plain polypropylene material of high-performance polypropylene compound material made from embodiment 1-5 and comparative example 1 and right
PP composite material made from ratio 2-5, is tested for the property, as a result such as the following table 1:
There are upper 1 data of table, analyzed as follows:
(1) data of comparative example 1 and comparative example 1 can be seen that high-performance polypropylene composite wood made from embodiment 1
Expect that the tensile strength than the plain polypropylene material of comparative example 1 improves 84.0%, bending strength improves 149.8%, notch
Impact strength reduces 69.5%, and thermal decomposition temperature improves 20.4%, illustrates that high-performance polypropylene produced by the present invention is compound
Material has and is obviously improved on the mechanical mechanics property and thermal stability of material.
(2) data of comparative example 1 and comparative example 2 can be seen that high-performance polypropylene composite wood made from embodiment 1
Expect that the tensile strength than PP composite material made from comparative example 2 improves 44.3%, bending strength improves 68.2%, lacks
Mouth impact strength reduces 57.0%, and thermal decomposition temperature improves 16.8%, it can be seen that in polypropylene material from analysis data
Graphene is added in material, improves significantly to the mechanical property and thermal stability of material.
(3) comparative example 1 and comparative example 3, high-performance polypropylene compound material made from embodiment 1 are made than comparative example 3
The tensile strength of the PP composite material obtained improves 48.7%, and bending strength improves 50.0%, notch impact strength drop
Low 51.1%, thermal decomposition temperature improves 10.0%, illustrates the synthesis of the addition material of polypropylene-maleic anhydride composite granule
Performance boost has important influence.
(4) comparative example 1 and comparative example 4, high-performance polypropylene compound material made from embodiment 1 are made than comparative example 4
The tensile strength of the PP composite material obtained improves 16.1%, and bending strength improves 19.8, and notch impact strength reduces
20.1%, thermal decomposition temperature improves 4.5%, illustrate mechanical property and thermal stability of the addition to composite material of nucleating agent
There is improvement result.
(5) comparative example 1 and comparative example 5, high-performance polypropylene compound material made from embodiment 1 are made than comparative example 5
The tensile strength of the PP composite material obtained improves 32.8%, and bending strength improves 44.9%, notch impact strength drop
Low 33.3%, thermal decomposition temperature improves 14.9%, and comparative example is compared in the carry out CO 2 supercritical infiltration in embodiment 1
It is directly blended using graphene in 5, mechanical property and thermal stability tool are significantly improved.Illustrate the stone that the present invention uses
Black alkene and polyacrylic mixed method are obviously improved the comprehensive performance of material.
In conclusion the invention has the following advantages that
(1) preparation method of the present invention is infiltrated by using supercritical carbon dioxide between graphene, and raising graphene exists
It is uniformly dispersed in polypropylene, pass through maleic anhydride and nucleating agent and the polypropene blended polyacrylic flexibility and compatible of improving
Property, PP composite material made from blended melting has good mechanical mechanics property and thermal stability.
(2) graphene is easy to reunite in high molecular material matrix, and dispersibility is poor, directly affects the performance of material, this hair
It is bright to use zero surface tension of supercritical carbon dioxide, high diffusion coefficient and excellent surface wettability, diffuse and penetrate into graphite
Alkene piece interlayer, reduction are the molecular force between graphene layer, improve dispersibility of the graphene in polypropylene powder, improve compound
The mechanical property and thermal stability of material.
(3) using maleic anhydride and initiator and polypropene blended extruding pelletization, while by compounding work with nucleating agent
With the polypropylene-maleic anhydride composite material of preparation has good flexibility and mechanical shock resistance, improves polypropylene friability
The shortcomings that degree height and poor compatibility.
(4) present invention first carries out graphene and maleic anhydride after granulation is blended with polypropylene segment pellet respectively,
Blending granulation is carried out in polypropylene granules, carries out multiple melting extrusion granulation, the dispersibility and flexibility of pellet can be improved, together
When the unicity of component in material can be improved, help to improve the mechanical property of material.
(5) present invention will after modification polypropylene-graphene pellet, polypropylene-maleic anhydride pellet and common
Polypropylene granules blending extrusion is granulated, PP composite material obtained, has good wearability, corrosion resistance, mechanical force
It learns performance and flexibility, excellent material performance is with a wide range of applications.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features.It is all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of high-performance polypropylene compound material, which comprises the following steps:
(1) graphene is placed in ethanol solution, the octadecylamine for being equivalent to its weight 2-5% is added, is uniformly mixed
Afterwards, it is placed in ultrasonic wave separating apparatus after ultrasonic disperse 1 hour, filters, it is dry, it places and is ground 5-8 hours in ball mill, obtain stone
Black alkene powder；
(2) polypropylene is placed in drying 2 hours in vacuum oven, the polypropylene after drying, which is put into grinder grinding, becomes micro-
Powder obtains polypropylene powder；
(3) graphene powder, polypropylene powder and silane coupling agent are added in ethanol solution and are uniformly mixed, formed and suspended
Liquid after stirring 5-8 hours, after vacuum filtration pumping filter, is placed on air dry oven with 800-1500 revs/min of speed
After middle drying 5 hours, mixed material 1 is obtained；
(4) mixed material is placed in autoclave, autoclave temp is warming up to 40 degrees Celsius, carbon dioxide is pumped into autoclave
It is interior, until for pressure to 8-12MPa, carbon dioxide starts the cycle over flowing in autoclave, in the supercritical state, after infiltration 6 hours, fastly
Speed, which is unloaded, is depressed into normal pressure state；
(5) product made from step (4) is added twin-screw extrude into carry out extruding pelletization, pellet is cleaned with deionized water
Afterwards, it is placed in 80-90 degrees Celsius of baking oven, it is 12 hours dry, obtain polypropylene-graphene pellet；
(6) it after dissolving maleic anhydride than adding into acetone according to the quality of 1:3, is added with polypropylene, initiator and nucleating agent
It is mixed 10-15 minutes under 70-90 degrees Celsius in high-speed mixer, obtains mixed material 2；
(7) mixed material 2 is added twin-screw extrude into carry out extruding pelletization, after pellet is cleaned with deionized water, is placed in 80-
It is 12 hours dry in 90 degrees Celsius of baking oven, obtain polypropylene-maleic anhydride pellet；
(8) mixed at high speed is added in polypropylene-graphene pellet, polypropylene-maleic anhydride pellet, polypropylene granules and antioxidant
In machine after mixing, it is placed in double screw extruder and carries out extruding pelletization, after pellet is cleaned with deionized water, be placed in 80-90
Degree Celsius baking oven in, dry 12 hours to get the high-performance polypropylene compound material.
2. the preparation method of high-performance polypropylene compound material according to claim 1, which is characterized in that the step
(1) grinding in specifically: the medium used be stainless steel ball, ratio of grinding media to material 8-20:1, grinder rotating speed be 200-600 turn/
Minute.
3. the preparation method of high-performance polypropylene compound material according to claim 1, which is characterized in that the step
(3) mass ratio of graphene powder, polypropylene and silane coupling agent in is 8-12:100:3-5.
4. the preparation method of high-performance polypropylene compound material according to claim 3, which is characterized in that the silane is even
Connection agent is γ-propyl silane, three (β-of vinyltriethoxysilane, vinyltrimethoxysilane and vinyl
Methoxy ethoxy) one or more of silane combination.
5. the preparation method of high-performance polypropylene compound material according to claim 1, which is characterized in that the step
(6) maleic anhydride, polypropylene, initiator and nucleating agent in are according to mass ratio 3-7:100:0.8-2:2-5.
6. the preparation method of high-performance polypropylene compound material according to claim 5, which is characterized in that the initiator
For benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, cumyl peroxide and peroxidized t-butyl perbenzoate
One or more of combine.
7. the preparation method of high-performance polypropylene compound material according to claim 5, which is characterized in that the nucleating agent
It mixes and forms according to mass ratio 3:1 for inorganic nucleator and organic nucleating agent；
The inorganic nucleator is one in talcum, calcium carbonate, mica, clay, carbon nanotube and the chitosan of 600-1000 mesh
Kind or several mixing composition.
The organic nucleating agent be 1,3,2,4- bis- (two benzal of 3,4- dimethyl) sorbierite, two (to ethyl benzal) sorbierites,
One in two (to methyl benzal) sorbic acids, two (replacing benzal to chlorine) sorbierites and 4,4- (two benzal of dimethyl sulphur-based) sorbierite
Kind or several combinations.
8. the preparation method of high-performance polypropylene compound material according to claim 1, which is characterized in that the step
(8) high-performance polypropylene compound material in includes the raw material of following parts by weight meter: 100 parts of PP GRANULES, polypropylene-graphite
30-60 parts of alkene pellet, 15-45 parts of polypropylene-maleic anhydride pellet and 0.8-1.5 parts of antioxidant.
9. the preparation method of high-performance polypropylene compound material according to claim 8, which is characterized in that the antioxidant
For the combination of one or more of antioxidant 1076, antioxidant 1010, antioxidant 300 and irgasfos 168.
10. the preparation method of high-performance polypropylene compound material according to claim 1, which is characterized in that double spiral shells
The extrusion temperature of bar extruder is 200-220 degrees Celsius, and screw speed is 150-200 revs/min.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111073145A (en) * | 2019-12-26 | 2020-04-28 | 苏州润佳高分子材料有限公司 | Fabric-touch-like polypropylene composite material for automobile |
| CN111168873A (en) * | 2019-12-30 | 2020-05-19 | 郎溪佳联新材料有限公司 | Polypropylene/polycarbonate/polyvinyl chloride alloy plastic and preparation method thereof |
| CN111420466A (en) * | 2020-04-27 | 2020-07-17 | 常州美洛医疗科技有限公司 | Graphene polypropylene electret air filtration antibacterial fiber and preparation method thereof |
| CN111607298A (en) * | 2020-06-18 | 2020-09-01 | 广州鸿为新材料科技有限公司 | Preparation method of spherical polypropylene powder coating |
| CN111761751A (en) * | 2020-07-07 | 2020-10-13 | 陕西延长石油（集团）有限责任公司 | Preparation method and application of carbon-containing polyolefin master batch |
| CN112064338A (en) * | 2020-08-18 | 2020-12-11 | 上海利物盛纳米科技有限公司 | Method for preparing graphene modified polypropylene fibers by supercritical fluid method |
| CN113429677A (en) * | 2021-07-21 | 2021-09-24 | 沈阳化工大学 | Preparation method of polypropylene-based thermoplastic elastomer composite material |
| CN115322483A (en) * | 2022-08-23 | 2022-11-11 | 江西沪昌电缆有限公司 | Polypropylene-based cable insulating material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151695A (en) * | 2014-05-07 | 2014-11-19 | 武汉金牛经济发展有限公司 | Preparation method of polypropylene composite pipes modified by using graphene |
-
2018
- 2018-10-25 CN CN201811249114.4A patent/CN109385008A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151695A (en) * | 2014-05-07 | 2014-11-19 | 武汉金牛经济发展有限公司 | Preparation method of polypropylene composite pipes modified by using graphene |
Non-Patent Citations (4)
| Title |
|---|
| 刘西文: "《塑料配混工[中、高级]培训教程》", 31 January 2007, 文化发展出版社 * |
| 姜行伟 等: "超临界CO2液相插层法制备PP/石墨烯复合材料", 《工程塑料应用》 * |
| 王文广 等: "《聚合物改性原理》", 31 March 2018, 中国轻工业出版社 * |
| 程军 等: "《通用塑料手册》", 31 May 2007, 国防工业出版社 * |
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| CN111073145A (en) * | 2019-12-26 | 2020-04-28 | 苏州润佳高分子材料有限公司 | Fabric-touch-like polypropylene composite material for automobile |
| CN111168873A (en) * | 2019-12-30 | 2020-05-19 | 郎溪佳联新材料有限公司 | Polypropylene/polycarbonate/polyvinyl chloride alloy plastic and preparation method thereof |
| CN111420466A (en) * | 2020-04-27 | 2020-07-17 | 常州美洛医疗科技有限公司 | Graphene polypropylene electret air filtration antibacterial fiber and preparation method thereof |
| CN111607298A (en) * | 2020-06-18 | 2020-09-01 | 广州鸿为新材料科技有限公司 | Preparation method of spherical polypropylene powder coating |
| CN111761751A (en) * | 2020-07-07 | 2020-10-13 | 陕西延长石油（集团）有限责任公司 | Preparation method and application of carbon-containing polyolefin master batch |
| CN112064338A (en) * | 2020-08-18 | 2020-12-11 | 上海利物盛纳米科技有限公司 | Method for preparing graphene modified polypropylene fibers by supercritical fluid method |
| CN113429677A (en) * | 2021-07-21 | 2021-09-24 | 沈阳化工大学 | Preparation method of polypropylene-based thermoplastic elastomer composite material |
| CN115322483A (en) * | 2022-08-23 | 2022-11-11 | 江西沪昌电缆有限公司 | Polypropylene-based cable insulating material and preparation method thereof |
| CN115322483B (en) * | 2022-08-23 | 2024-04-16 | 山西又川新材料科技有限公司 | Polypropylene-based cable insulation material and preparation method thereof |
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Application publication date: 20190226 |