CN108276682A - A kind of high fluidity polypropylene composite material with high strength and toughness and preparation method thereof - Google Patents
A kind of high fluidity polypropylene composite material with high strength and toughness and preparation method thereof Download PDFInfo
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- CN108276682A CN108276682A CN201711434297.2A CN201711434297A CN108276682A CN 108276682 A CN108276682 A CN 108276682A CN 201711434297 A CN201711434297 A CN 201711434297A CN 108276682 A CN108276682 A CN 108276682A
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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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a kind of high flowing polypropylene composite material with high strength and toughness, are made of the raw material of following weight percent meter:69 97wt% of polypropylene;1 20wt% of inorganic nano-filler;1 30wt% of hyper-branched polymer;0.1 1wt% of antioxidant.Compared to conventional linear toughener, hyper-branched polymer is in space spherical structure, with smaller hydrodynamic radius, show significant lubricity low melt viscosity characteristic, the fluidity of molten of the polyolefine materials such as PP can be substantially improved while promoting material impact intensity, there is better dispersion performance to inorganic nano-particle, reach enhancing effect of the inorganic nano-particle to material to further improve, so this product is especially excellent in inorganic nano enhancing system performance.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to one kind being based on polyacrylic modified material.The material
At least it is grouped as by following three kinds of groups:Macromolecule matrix, inorganic nano-particle, hyper-branched polymer, can also contain and other groups
Point.The characteristics of modified material, is there is higher intensity and toughness simultaneously, while also having high fluidity.
Background technology
In all plastics, polyacrylic cost is minimum, and density is minimum, and processing and forming is also easiest to, therefore polypropylene is vapour
The most high molecular material of automobile-used amount.While polypropylene material provides a large amount of high-quality low-cost materials for auto industry, automobile
Light-weighted development also also puts forward higher requirements parts with pp material performance.In the premise for not reducing product standard
Lower realize is thinned, and achievees the purpose that automotive light weight technology.But the design that is thinning of auto parts and components is not simply to promote material
Rigidity realize the reduction of product thickness, weight, and should be ensure thin-wall part have good shock resistance,
Under the premise of dimensional stability, improve the rigidity and processing fluidity of material as far as possible so that the molding cycle of product shorten and
Has good shape support effect, to meet the light-weight design requirement of automobile, this just proposes polypropylene material high
Requirement.
People have carried out extensive work and have carried out toughening modifying research to PP.The various thermoplastic elastic bodies of generally use
It is blended with PP, forms the blend of impact strength and excellent in low temperature toughness, such as polypropylene/thermoplastic elastomer (TPE) (PP/POE)
Extensive use is obtained, but the mechanical strength of PP and rigidity have larger reduction and loss.It is widely used various inorganic at present
Filler (calcium carbonate, talcum powder, mica and wollastonite etc.) is filled, reinforcement, to improve the dimensional stability, heat-resisting of material
Property, rigidity, while reducing material cost.Common thermoplastic elastomer (TPE) and inorganic filler is added simultaneously in PP systems, although
Intensity and toughness can be improved simultaneously, but the amplitude that the two improves simultaneously is little, and mobility substantially reduces.
Invention content
In view of the deficiencies of the prior art, technical problem to be solved by the invention is to provide a kind of high fluidity high-strength and high ductilities
PP composite material and preparation method thereof, its main feature is that inorganic nano-particle and hyper-branched polymer is selected to cooperate with activeness and quietness
Polypropylene, while mobility is improved.
To achieve the above object, the present invention uses following technical scheme:
A kind of high flowing polypropylene composite material with high strength and toughness, is made of the raw material of following weight percent meter:
Polypropylene 69-97wt%;
Inorganic nano-filler 1-20wt%;
Hyper-branched polymer 1-30wt%;
Antioxidant 0.1-1wt%.
Preferably,
A kind of high flowing polypropylene composite material with high strength and toughness, is made of the raw material of following weight percent meter:
Polypropylene 84.6.%, inorganic nano-filler 5%, hyper-branched polymer 10%, irgasfos 168 0.4%.
In above-mentioned PP composite material system,
The inorganic nano-filler is acicular wollastonite, the talcum powder of sheet, mica powder or montmorillonite;Or it is received for carbon
Mitron, graphene oxide etc..
Further, the grain size of the inorganic nano-filler is between 10~500nm.
The hyper-branched polymer is dendroid dispersibility toughener.
For the polypropylene under 230 DEG C, the test condition of 2.16kg, the copolymerization that melt index is 30-120g/10min is poly-
Propylene.
The antioxidant includes primary antioxidant and auxiliary anti-oxidant;Wherein, primary antioxidant 3,5- di-t-butyl -4- hydroxyl benzyls
Base diethyl phosphate (3114), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (1010), thio two
One or more of propionic acid octadecyl ester (DSTP);The auxiliary anti-oxidant is diphosphorous acid pentaerythrite distearyl alcohol ester
(618) or three (2,4- di-tert-butyl-phenyls) phosphite esters (168).
The preparation method of above-mentioned high flowing polypropylene composite material with high strength and toughness, its step are as follows:
(1) polypropylene, hyper-branched polymer and antioxidant first are weighed by following parts by weight, be uniformly mixed, it is former to obtain mixing
Material, then weighs inorganic nano-particle again;
(2) it after drying above-mentioned mixed raw material, is placed in the main feeding bin of meshing co rotating twin screw extrusion, through feeding spiral shell
Bar is added in the machine barrel of extruder, inorganic nano-particle is added to from melt zone charge door in extruder, extruder screw
A diameter of 35mm, draw ratio L/D are 40, and each zone temperature that main barrel is exported from charge door to head is set as:190℃、200
DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, engine speed be 250 revs/min, through melting extrusion, cooling, granulation, baking
PP composite material is made in dry-cure.
The beneficial effects of the invention are as follows:Hyper-branched polymer has excellent toughening effect, and can significantly improve PP's
Melt flowability is the characteristic brought by its special dendritic structure.There is long-chain-segment flexible in dendritic structure,
Molecule interchain plays the role of a kind of connection, cushioning effect, enable system when being impacted from absorb energy, shock absorbing,
Crazing is reduced because stress develops into the chance of crackle, to improve the impact strength of system;And dendritic structure surface is big
The long flexible chain section of amount is in space three-dimensional extended position, and space three is more readily formed by the interaction of strand in system
Reticular structure is tieed up, impact force of the external force to system is further buffered, to further promote toughening effect.In addition, compared to biography
It unites linear toughener, hyper-branched polymer is in space spherical structure, has smaller hydrodynamic radius, shows significantly to moisten
Slip low melt viscosity characteristic can substantially improve the melt flows of the polyolefine materials such as PP while promoting material impact intensity
Property, there is better dispersion performance to inorganic nano-particle, reach increasing of the inorganic nano-particle to material to further improve
Potent fruit, so this product is especially excellent in inorganic nano enhancing system performance.
Specific implementation mode
The present invention can be further elucidated above by the acquisition of following preferred embodiment, but these embodiments are merely to illustrate,
The scope of the present invention is not made and defining.
In the composite-material formula of embodiment and comparative example, polypropylene used is the copolymer polypropylene that SK Chemical provides,
Trade names are 3800;Inorganic nano-filler by Zhejiang Feng Hong companies offer organic modified nano montmorillonite, trade names
For DK4, grain size 3.5nm;Hyper-branched polymer is provided by Weihai Chen Yuan companies, trade names CYD-6100;Common inorganic
Filler chooses the talcum powder of 3000 mesh, and grain size is between 5 microns;Antioxidant is provided by BASF AG and ICE companies of Britain, commodity
The trade mark is Irganox 168 and Negonox DSTP.
Embodiment 1
First polypropylene 96.6%, hyper-branched polymer 1%, irgasfos 168 0.3%, antioxidant are weighed by following parts by weight
DSTP 0.1%, which is put into, mixes 3~5min in high-speed mixer.It is to be mixed uniformly after, mixture is placed in intermeshing co-rotating twin-screw
It in the main feeding bin of extruder, is added in the machine barrel of extruder through feed screw, weighs 2% organic modification montmonrillonite from molten
Melt a section charge door to be added in extruder, extruder screw a diameter of 35mm, draw ratio L/D is 40, main barrel from charge door to
Each zone temperature of head outlet is set as:190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, engine speed
It is 250 revs/min, through melting extrusion, cooling, granulation, drying and processing, PP composite material is made.
Properties of product are tested:
Melt flow rate (MFR) is tested;By ISO1133-1 standard testings, test condition is 230 DEG C, 2.26Kg.Tensile property:
It is carried out by ISO527-2 standards, test rate 5mm/min.Bending property:It is carried out by IS178 standards, span 64mm, test
Speed is 2mm/min.Impact property:It is carried out on impact tester for simple supported beam by ISO179-1 standards, batten notch is A types.
Concrete outcome is shown in Table 1.
Embodiment 2
First polypropylene 94.6%, hyper-branched polymer 3%, irgasfos 168 0.3%, antioxidant are weighed by following parts by weight
DSTP 0.1%, which is put into, mixes 3~5min in high-speed mixer.It is to be mixed uniformly after, mixture is placed in intermeshing co-rotating twin-screw
It in the main feeding bin of extruder, is added in the machine barrel of extruder through feed screw, weighs 2% organic modification montmonrillonite from molten
Melt a section charge door to be added in extruder, extruder screw a diameter of 35mm, draw ratio L/D is 40, main barrel from charge door to
Each zone temperature of head outlet is set as:190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, engine speed
It is 250 revs/min, through melting extrusion, cooling, granulation, drying and processing, PP composite material is made.
Properties of product are tested:
Melt flow rate (MFR) is tested;By ISO1133-1 standard testings, test condition is 230 DEG C, 2.26Kg.Tensile property:
It is carried out by ISO527-2 standards, test rate 5mm/min.Bending property:It is carried out by IS178 standards, span 64mm, test
Speed is 2mm/min.Impact property:It is carried out on impact tester for simple supported beam by ISO179-1 standards, batten notch is A types.
Concrete outcome is shown in Table 1.
Embodiment 3
First polypropylene 89.6.%, hyper-branched polymer 5%, irgasfos 168 0.3%, antioxygen are weighed by following parts by weight
Agent DSTP 0.1%, which is put into, mixes 3~5min in high-speed mixer.It is to be mixed uniformly after, mixture is placed in engagement double spiral shells in the same direction
In the main feeding bin of bar extruder, be added in the machine barrel of extruder through feed screw, weigh 5% organic modification montmonrillonite from
Melt zone charge door is added in extruder, extruder screw a diameter of 35mm, and draw ratio L/D is 40, and main barrel is from charge door
Each zone temperature exported to head is set as:190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, host turns
Speed is 250 revs/min, and through melting extrusion, cooling, granulation, drying and processing, PP composite material is made.
Properties of product are tested:
Melt flow rate (MFR) is tested;By ISO1133-1 standard testings, test condition is 230 DEG C, 2.26Kg.Tensile property:
It is carried out by ISO527-2 standards, test rate 5mm/min.Bending property:It is carried out by IS178 standards, span 64mm, test
Speed is 2mm/min.Impact property:It is carried out on impact tester for simple supported beam by ISO179-1 standards, batten notch is A types.
Concrete outcome is shown in Table 1.
Embodiment 4
First polypropylene 84.6.%, hyper-branched polymer 10%, irgasfos 168 0.3%, antioxygen are weighed by following parts by weight
Agent DSTP 0.1%, which is put into, mixes 3~5min in high-speed mixer.It is to be mixed uniformly after, mixture is placed in engagement double spiral shells in the same direction
In the main feeding bin of bar extruder, be added in the machine barrel of extruder through feed screw, weigh 5% organic modification montmonrillonite from
Melt zone charge door is added in extruder, extruder screw a diameter of 35mm, and draw ratio L/D is 40, and main barrel is from charge door
Each zone temperature exported to head is set as:190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, host turns
Speed is 250 revs/min, and through melting extrusion, cooling, granulation, drying and processing, PP composite material is made.
Embodiment 5
First polypropylene 74.6.%, hyper-branched polymer 20%, irgasfos 168 0.3%, antioxygen are weighed by following parts by weight
Agent DSTP 0.1%, which is put into, mixes 3~5min in high-speed mixer.It is to be mixed uniformly after, mixture is placed in engagement double spiral shells in the same direction
In the main feeding bin of bar extruder, be added in the machine barrel of extruder through feed screw, weigh 5% organic modification montmonrillonite from
Melt zone charge door is added in extruder, extruder screw a diameter of 35mm, and draw ratio L/D is 40, and main barrel is from charge door
Each zone temperature exported to head is set as:190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, host turns
Speed is 250 revs/min, and through melting extrusion, cooling, granulation, drying and processing, PP composite material is made.
Properties of product are tested:
Melt flow rate (MFR) is tested;By ISO1133-1 standard testings, test condition is 230 DEG C, 2.26Kg.Tensile property:
It is carried out by ISO527-2 standards, test rate 5mm/min.Bending property:It is carried out by IS178 standards, span 64mm, test
Speed is 2mm/min.Impact property:It is carried out on impact tester for simple supported beam by ISO179-1 standards, batten notch is A types.
Concrete outcome is shown in Table 1.
Comparative example 1
First polypropylene 94.6.%, 3000 mesh talcum powder 5%, irgasfos 168 0.3%, antioxygen are weighed by following parts by weight
Agent DSTP 0.1%, which is put into, mixes 3~5min in high-speed mixer.It is to be mixed uniformly after, mixture is placed in engagement double spiral shells in the same direction
In the main feeding bin of bar extruder, it is added in the machine barrel of extruder through feed screw.The a diameter of 35mm of extruder screw, major diameter
It is 40 than L/D, each zone temperature that main barrel is exported from charge door to head is set as:190℃、200℃、200℃、200℃、
200 DEG C, 210 DEG C, 210 DEG C, engine speed is 250 revs/min, through melting extrusion, cooling, granulation, drying and processing, is made poly- third
Alkene composite material.
Properties of product are tested:
Melt flow rate (MFR) is tested;By ISO1133-1 standard testings, test condition is 230 DEG C, 2.26Kg.Tensile property:
It is carried out by ISO527-2 standards, test rate 5mm/min.Bending property:It is carried out by IS178 standards, span 64mm, test
Speed is 2mm/min.Impact property:It is carried out on impact tester for simple supported beam by ISO179-1 standards, batten notch is A types.
Concrete outcome is shown in Table 1.
Comparative example 2
Polypropylene 99.6.%, irgasfos 168 0.3% first are weighed by following parts by weight, antioxidant DSTP 0.1% is put into
3~5min is mixed in high-speed mixer.It is to be mixed uniformly after, mixture is placed in the main feeding of meshing co rotating twin screw extrusion
In storehouse, it is added in the machine barrel of extruder through feed screw.Extruder screw a diameter of 35mm, draw ratio L/D are 40, main barrel
Each zone temperature exported from charge door to head is set as:190℃、200℃、200℃、200℃、200℃、210℃、210
DEG C, engine speed is 250 revs/min, and through melting extrusion, cooling, granulation, drying and processing, PP composite material is made.
Properties of product are tested:
Melt flow rate (MFR) is tested;By ISO1133-1 standard testings, test condition is 230 DEG C, 2.26Kg.Tensile property:
It is carried out by ISO527-2 standards, test rate 5mm/min.Bending property:It is carried out by IS178 standards, span 64mm, test
Speed is 2mm/min.Impact property:It is carried out on impact tester for simple supported beam by ISO179-1 standards, batten notch is A types.
Concrete outcome is shown in Table 1.
1 PP composite material physical property of table:
From the point of view of the performance test of each embodiment and comparative example shown in table 1, using heretofore described inorganic nano
Enhancing and hyper-branched polymer toughening compound system, more conventional Talc, have in terms of the rigidity of material after the property and
It is obviously improved effect, and bending modulus is promoted to from 1400~1600MPa in the interval range of 2600~2900MPa, this
It is that material copes with the prerequisite for being thinning design;Furthermore melting means is only 16 or so in common fillers filling, material flow
Dynamic property is limited, and the mold briquetting pressure for being thinning design is very big, it is desirable that material has a preferable mobile performance, and each embodiment
In material MFR be held in 20~40g/10min or so, reach as high as 35g/10min, be fully able to meet ultra-thin product
Briquetting pressure demand shortens the machine-shaping period.It is noted that although bending property, mobile performance are significantly carried
Height, while impact property is also significantly increased, up to 36.8kJ/m2Between, it is sufficient to cope with every finished parts of thin-gage goods
Test, makes it have good performance.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, all answer by the change or replacement that can be readily occurred in
Cover within the scope of the present invention.Therefore, the protection domain that protection scope of the present invention should be defined with claim
Subject to.
Claims (9)
1. a kind of high flowing polypropylene composite material with high strength and toughness, it is characterised in that:By the raw material group of following weight percent meter
At:
Polypropylene 69-97wt%;
Inorganic nano-filler 1-20wt%;
Hyper-branched polymer 1-30wt%;
Antioxidant 0.1-1wt%.
2. a kind of high flowing polypropylene composite material with high strength and toughness according to claim 1, it is characterised in that:By following heavy
Measure the raw material composition of percentages:
Polypropylene 84.6.%, inorganic nano-filler 5%, hyper-branched polymer 10%, antioxidant 0.4%.
3. a kind of high flowing polypropylene composite material with high strength and toughness according to claim 1 or 2, it is characterised in that:It is described
Inorganic nano-filler be acicular wollastonite, the talcum powder of sheet, mica powder or montmorillonite.
4. a kind of high flowing polypropylene composite material with high strength and toughness according to claim 1 or 2, it is characterised in that:It is described
Inorganic nano-filler is carbon nanotube or graphene oxide.
5. a kind of high flowing polypropylene composite material with high strength and toughness according to claim 1 or 2, it is characterised in that:It is described
The grain size of inorganic nano-filler is between 10~500nm.
6. a kind of high flowing polypropylene composite material with high strength and toughness according to claim 1 or 2, it is characterised in that:It is described
Hyper-branched polymer is dendroid dispersibility toughener.
7. a kind of high flowing polypropylene composite material with high strength and toughness according to claim 1 or 2, it is characterised in that:It is described
For polypropylene under 230 DEG C, the test condition of 2.16kg, melt index is the copolymer polypropylene of 30-120g/10min.
8. a kind of high flowing polypropylene composite material with high strength and toughness according to claim 1 or 2, it is characterised in that:It is described
Antioxidant include primary antioxidant and auxiliary anti-oxidant;Wherein, primary antioxidant 3,5- di-tert-butyl-4-hydroxyl benzyl p diethylaminobenzoic acids
Ester (3114), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (1010), thio-2 acid octadecyl ester
One or more of (DSTP);The auxiliary anti-oxidant is diphosphorous acid pentaerythrite distearyl alcohol ester (618) or three (2,4-
Di-tert-butyl-phenyl) phosphite ester (168).
9. the preparation method of one of the arbitrary high flowing polypropylene composite material with high strength and toughness of claim 1-8, feature exist
In:Its step are as follows:
(1) polypropylene, hyper-branched polymer and antioxidant first are weighed by following parts by weight, is uniformly mixed, obtains mixed raw material, so
Weigh inorganic nano-particle again afterwards;
(2) after drying above-mentioned mixed raw material, be placed in the main feeding bin of meshing co rotating twin screw extrusion, through feed screw plus
Enter into the machine barrel of extruder, inorganic nano-particle is added to from melt zone charge door in extruder, extruder screw diameter
For 35mm, draw ratio L/D is 40, and each zone temperature that main barrel is exported from charge door to head is set as:190℃、200℃、
200 DEG C, 200 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, engine speed is 250 revs/min, through melting extrusion, cooling, granulation, drying
PP composite material is made in processing.
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CN109370041A (en) * | 2018-08-09 | 2019-02-22 | 河南工程学院 | A kind of polypropylene modified material and preparation method thereof having both good rigidity and high elongation at tear |
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CN114685095A (en) * | 2020-12-25 | 2022-07-01 | 比亚迪股份有限公司 | Organic-inorganic composite material and preparation method and application thereof |
CN114685095B (en) * | 2020-12-25 | 2023-07-11 | 比亚迪股份有限公司 | Organic-inorganic composite material and preparation method and application thereof |
WO2022242298A1 (en) * | 2021-05-18 | 2022-11-24 | 金发科技股份有限公司 | Glass-fiber-reinforced polypropylene composition, preparation method therefor and use thereof |
CN114133664A (en) * | 2021-12-07 | 2022-03-04 | 西华大学 | Superfine slag micro powder filled polypropylene-based automobile special material and preparation method thereof |
CN114409999A (en) * | 2021-12-31 | 2022-04-29 | 金发科技股份有限公司 | Polypropylene composition and preparation method thereof |
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