CN106832582B - A kind of preparation method of high-ductility polypropylene based composites - Google Patents

A kind of preparation method of high-ductility polypropylene based composites Download PDF

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CN106832582B
CN106832582B CN201710057842.4A CN201710057842A CN106832582B CN 106832582 B CN106832582 B CN 106832582B CN 201710057842 A CN201710057842 A CN 201710057842A CN 106832582 B CN106832582 B CN 106832582B
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polypropylene
masterbatch
nucleating agent
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CN106832582A (en
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王勇
杨朝金
张楠
杨静晖
黄婷
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Southwest Jiaotong University
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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
    • C08L23/12—Polypropene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • 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
    • C08K2201/004—Additives being defined by their length
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids
    • C08L2205/242—Beta spherulite nucleating agents

Abstract

It the invention discloses a kind of preparation method of high-ductility polypropylene based composites, has main steps that polypropylene and nucleating agent by the mass ratio of 90-99:1-10, polypropylene/nucleating agent composite material is made by double screw extruder, masterbatch 1 is used as after drying；The mass ratio that ethylene propylene diene rubber and carbon nanotube are pressed to 80-95:5-20, is made ethylene propylene diene rubber/carbon nano tube compound material by double screw extruder, and masterbatch 2 is used as after drying；The mass ratio that masterbatch 1, masterbatch 2 and polypropylene, ethylene propylene diene rubber are pressed to 0.2-10:1-20:70-90:0-19, is made composite material by double screw extruder.In obtained behavior of polypropylene composites, the content of ethylene propylene diene rubber is 10-20%, and content of carbon nanotubes 0.1-3%, the content of polypropylene nucleater is 0.01-0.5%.Polypropylene Nanocomposites impact strength made from this method is high and tensile strength is preferable, and its simple process, is conducive to be mass produced.

Description

A kind of preparation method of high-ductility polypropylene based composites
Technical field
The invention belongs to field of high polymer material processing, more particular to a kind of preparation of high-ductility polypropylene composite material Method.
Background technique
Polypropylene is one of five big general-purpose plastics, and since its raw material sources is abundant, simple production process is easily processed into Type, product excellent combination property, do not absorb water and it is resistant to chemical etching, density is small, heat-resist, electrical insulating property is excellent, cheap, Its product is nontoxic, tasteless, can be widely applied to the fields such as household supplies, food packaging and medical instrument.Although having numerous excellent Different performance, but there is also some shortcomingss for polypropylene, wherein most prominent disadvantage is exactly, notch punching very sensitive to notch Hit intensity is low, and especially the brittleness under low temperature or high strain rate is obvious, this greatly limits application.Therefore, polypropylene Toughening modifying be always study a hot spot.
Polypropylene toughening mainly uses two methods of chemical modification and physical modification at present.The former is by being copolymerized, connecing The methods of branch or crosslinking can reach modified purpose, but usually process is complicated, higher cost.The latter includes using polypropylene as base Plasticizer, elastomer, toughness high polymer, inorganic filler, nucleating agent etc. is added in body, and since method is simple and easy, cost is relatively low, So using relatively broad.
For plasticizer, elastomer and toughness high polymer, toughening effect is played to polypropylene, the amount being usually added into Big, generally in 20wt% or more, while after these modified materials are added in large quantities, polyacrylic intensity be will be greatly reduced.And For the inorganic fillers such as such as montmorillonite, carbon black, carbon nanotube, although their addition can improve the machine of composite material Tool performance, hot property and electric property etc., but the dispersity of filler, and compatibility between matrix are affected, Simultaneously to the raising limitation of toughness.
Isotactic polypropylene is that a kind of crystalline polymer, crystal structure and pattern have large effect to its performance.It is poly- For propylene crystal there are many crystal form, that of greatest concern is α and beta crystal, the former due to high stability so more universal, but due to Crystal structure is finer and close and causes polypropylene impact flexibility lower；The latter needs using addition β type nucleating agent, shearing force, temperature The degree any special measures such as gradient can just obtain, but the loose structure of β crystal can be improved polyacrylic toughness, so using nucleating agent β type nucleating agent can generally be used by carrying out toughening modifying.
It is limited using the toughening effect for adding single filler or Nucleating Agent on Pp, and be individually added into plasticizer, Although elastomer or toughness high polymer have preferable toughening effect, but will cause the strength of materials simultaneously and decline to a great extent, so mesh A small amount of plasticizer, elastomer or toughness height can be added using multicomponent material and polypropene blended in preceding major part method for toughening After polymers, filler or nucleating agent are added, to reach preferable coordination plasticizing effect, while will not be lost excessive strong Degree.Having result of study to show to add a small amount of β type nucleating agent and nano silica in polypropylene/elastomer blend can be with Improve the intensity, modulus and toughness of co-mixing system simultaneously, achievees the purpose that activeness and quietness simultaneously, be detailed in, Wu Lili, β is nucleated Agent and the composite modified PP/POE composite material research of nanosized SiO_2, plastic additive, the 3rd phase: 34-39,2010.
Despite the use of the method that multiple material is blended carries out toughening modifying to polypropylene, but it is most of be both needed to using More elastomer or toughness high polymer, causes the intensity of basis material itself to decline, while the nucleating agent being added mostly uses β Type nucleating agent, induction polypropylene matrix generate more loose beta crystal, can be only achieved toughening purpose.And in low content bullet Property body or toughness high polymer under, about α type Nucleating Agent on Pp toughening effect influence research it is less.
Summary of the invention
The purpose of the present invention is proposing a kind of preparation method of high-ductility polypropylene based composites, low dosage is added in this method Rubber, Polypropylene Nanocomposites impact strength obtained is high and tensile strength is preferable, and its simple process, is conducive to big Large-scale production.
A kind of preparation method of high-ductility polypropylene based composites of the invention, key step are as follows:
1) mass ratio that polypropylene and nucleating agent are pressed to 90-99:1-10, by double screw extruder be made polypropylene/at Core agent composite material is used as masterbatch 1 after drying；Extrusion temperature is 180-230 DEG C, revolving speed 100-250rpm；
2) mass ratio that ethylene propylene diene rubber and carbon nanotube are pressed to 80-95:5-20, is made three by double screw extruder First EP rubbers/carbon nano tube compound material is used as masterbatch 2 after drying；Extrusion temperature is 180-230 DEG C, revolving speed 100- 250rpm；
3) masterbatch 1, masterbatch 2 and polypropylene, ethylene propylene diene rubber are pressed to the mass ratio of 0.2-10:1-20:70-90:0-19, Composite material is made by double screw extruder；Temperature when extrusion is 180-230 DEG C, revolving speed 100-250rpm.
In a kind of preparation method of high-ductility polypropylene based composites of the invention, the polypropylene is isotactic poly- third Alkene.
In a kind of preparation method of high-ductility polypropylene based composites of the invention, the carbon nanotube is that diameter is 5- 200nm, the single-walled carbon nanotube or multi-walled carbon nanotube that length is 100nm-50 μm.
In a kind of preparation method of high-ductility polypropylene based composites of the invention, the nucleating agent is polypropylene α type Nucleating agent: adipic acid, sodium benzoate, talcum powder, sodium cinnamate, p-tert-butyl benzoic acid hydroxy Al, dibenzal sorbitol, (1, 3:2,4- bis- is to two benzal of methyl) sorbierite, two (3,4- dimethyl, two benzal) sorbierites, phosphoric acid 2 or 2- methene-(4,6- bis- Tert-butyl-phenyl) sodium.
In a kind of preparation method of high-ductility polypropylene based composites of the invention, the nucleating agent is β type nucleating agent, Such as: aryl amide compound, aromatic amine compound, dicyclohexyl terephthalamide, pimelic acid aluminium or calcium pimelate.
Compared with prior art, the beneficial effects of the present invention are:
The toughness of rubber is fine, and polypropylene toughening, which is generally needed to be added larger amount of rubber just, apparent toughening effect, But the intensity and modulus of rubber itself is lower, and the intensity and modulus that will lead to entire behavior of polypropylene composites when additional amount is more is anxious Play decline.The present invention is reaching preferable toughening with carbon nanotube, nucleating agent coordination plasticizing polypropylene using a small amount of rubber While effect, the intensity and modulus of composite material can also be avoided to be greatly reduced；
Carbon nanotube is distributed on the interface of rubber phase region the inside or rubber and polypropylene matrix, substantially through whole A rubber phase region increases by two alternate interaction forces, and when composite material is by external force, carbon nanotube can promote to answer Power enables stress field to be superimposed in the transmitting of material internal, improves the mechanical property of material；
The addition of nucleating agent can refine polyacrylic crystalline size, and lesser crystal grain is conducive to improve polyacrylic impact Toughness, can together with rubber, carbon nanotube coordination plasticizing polypropylene.
It is demonstrated experimentally that behavior of polypropylene composites produced by the present invention, when ethylene propylene diene rubber content is 15%, carbon nanometer When pipe content is 1%, nucleation agent content is 0.2%, it is virgin pp that the notch impact strength of composite material, which is 51.2kJ/m2, More than 13 times, be Pp/epdm (85/15) blend more than 3 times, be a kind of high-ductility polypropylene base composite wood Material.
Specific embodiment
The present invention is described in further details With reference to embodiment.
Embodiment 1
1) mass ratio that isotactic polypropylene and nucleating agent are pressed to 95:5, is made polypropylene/nucleation by double screw extruder Agent composite material is used as masterbatch 1 after drying；Extrusion temperature is 200 DEG C, revolving speed 150rpm；
2) mass ratio that ethylene propylene diene rubber and carbon nanotube are pressed to 90:10, is made ternary second by double screw extruder Third rubber/carbon nano tube compound material is used as masterbatch 2 after drying；Extrusion temperature is 190 DEG C, revolving speed 150rpm；
The mass ratio that masterbatch 1, masterbatch 2 and polypropylene, ethylene propylene diene rubber are pressed to 4:10:81:6, passes through twin-screw extrusion Mechanism obtains composite material；Temperature when extrusion is 200 DEG C, revolving speed 150rpm.Carbon nanotube used in it is that diameter is 50nm, the acidification multi-walled carbon nanotube that length is 10-20 μm, nucleating agent are (3, the 4- dimethyl dibenzyls of polypropylene α type nucleating agent two Fork) sorbierite (commercially available DMDBS).
Comparative example 1:
The mass ratio that isotactic polypropylene, ethylene propylene diene rubber are pressed to 85:15, is made composite wood by double screw extruder Material, extrusion temperature are 200 DEG C, revolving speed 150rpm.Polypropylene used in it is isotactic polypropylene.
Comparative example 2:
The mass ratio that polypropylene and nucleating agent are pressed to 95:5, it is compound to be made polypropylene/nucleating agent by double screw extruder Material is used as masterbatch after drying；Extrusion temperature is 200 DEG C, revolving speed 150rpm；
The mass ratio that masterbatch and polypropylene, ethylene propylene diene rubber are pressed to 4:81:10, is made compound by double screw extruder Material；Temperature when extrusion is 200 DEG C, revolving speed 150rpm.Nucleating agent used in it is polypropylene α type nucleating agent DMDBS.
Comparative example 3:
The mass ratio that ethylene propylene diene rubber and carbon nanotube are pressed to 90:10, is made EPDM by double screw extruder Rubber/carbon nano tube compound material is used as masterbatch after drying；Extrusion temperature is 190 DEG C, revolving speed 150rpm；
The mass ratio that masterbatch and isotactic polypropylene, ethylene propylene diene rubber are pressed to 10:85:6, is made by double screw extruder Composite material；Temperature when extrusion is 200 DEG C, revolving speed 150rpm.Carbon nanotube used in it is that diameter is 50nm, length For 10-20 μm of acidification multi-walled carbon nanotube.
The notch impact strength of the above made sample is as shown in table 1.
As it can be seen from table 1 carbon nanotube and polypropylene α type nucleating agent can coordination plasticizing behavior of polypropylene composites, Notch impact strength can reach 51.2MPa, belong to high-ductility polypropylene based composites.
The tensile strength of the above made sample is as shown in table 1.As can be seen from the table, the tensile strength of comparative example one is 26.4MPa, it is more somewhat reduced than the tensile strength of virgin pp, but amplitude and little is reduced, the tensile strength of embodiment 1 is 27.3MPa, there are also some increase, illustrates that carbon nanotube and nucleating agent are poly- in coordination plasticizing on the basis of keeping tensile strength While propylene based composites, polyacrylic intensity can be preferably kept.The polypropylene-base nanometer as made from this method Composite impact intensity is high and tensile strength is preferable.
Embodiment 2:
The mass ratio that polypropylene and nucleating agent are pressed to 99:1, it is compound to be made polypropylene/nucleating agent by double screw extruder Material is used as masterbatch 1 after drying；Extrusion temperature is 180 DEG C, revolving speed 100rpm；
The mass ratio that ethylene propylene diene rubber and carbon nanotube are pressed to 95:5, is made ethylene-propylene-diene monomer by double screw extruder Glue/carbon nano tube compound material is used as masterbatch 2 after drying；Extrusion temperature is 180 DEG C, revolving speed 100rpm；
The mass ratio that masterbatch 1, masterbatch 2 and polypropylene, ethylene propylene diene rubber are pressed to 10:1:70:19, passes through twin-screw extrusion Mechanism obtains composite material；Temperature when extrusion is 180 DEG C, revolving speed 100rpm.
Wherein polypropylene is isotactic polypropylene, and carbon nanotube is that diameter is 5nm, and length is the single-walled carbon nanotube of 10nm, Nucleating agent is polypropylene beta type nucleating agent (TMB-5) aromatic amine compound.
Embodiment 3:
The mass ratio that polypropylene and nucleating agent are pressed to 90:10, it is compound to be made polypropylene/nucleating agent by double screw extruder Material is used as masterbatch 1 after drying；Extrusion temperature is 230 DEG C, revolving speed 250rpm；
The mass ratio that ethylene propylene diene rubber and carbon nanotube are pressed to 80:20, is made EPDM by double screw extruder Rubber/carbon nano tube compound material is used as masterbatch 2 after drying；Extrusion temperature is 230 DEG C, revolving speed 250rpm；
The mass ratio that masterbatch 1, masterbatch 2 and polypropylene are pressed to 0.2:20:80, is made composite wood by double screw extruder Material；Temperature when extrusion is 230 DEG C, revolving speed 250rpm.
Wherein polypropylene is isotactic polypropylene, and carbon nanotube is that diameter is 200nm, the multi-wall carbon nano-tube that length is 50 μm Pipe, nucleating agent are polypropylene α type nucleating agent sodium benzoate.
Embodiment 4:
The mass ratio that polypropylene and nucleating agent are pressed to 93:7, it is compound to be made polypropylene/nucleating agent by double screw extruder Material is used as masterbatch 1 after drying；Extrusion temperature is 210 DEG C, revolving speed 200rpm；
The mass ratio that ethylene propylene diene rubber and carbon nanotube are pressed to 85:15, is made EPDM by double screw extruder Rubber/carbon nano tube compound material is used as masterbatch 2 after drying；Extrusion temperature is 200 DEG C, revolving speed 220rpm；
The mass ratio that masterbatch 1, masterbatch 2 and polypropylene, ethylene propylene diene rubber are pressed to 0.2:1:90:9, passes through twin-screw extrusion Mechanism obtains composite material；Temperature when extrusion is 210 DEG C, revolving speed 220rpm.
Wherein polypropylene is isotactic polypropylene, and carbon nanotube is diameter for 50nm, the single-walled carbon nanotube that length is 1 μm, Nucleating agent is polypropylene beta type nucleating agent CHB-5 aryl amide compound.
Embodiment 5:
The mass ratio that polypropylene and nucleating agent are pressed to 97:3, it is compound to be made polypropylene/nucleating agent by double screw extruder Material is used as masterbatch 1 after drying；Extrusion temperature is 220 DEG C, revolving speed 160rpm；
The mass ratio that ethylene propylene diene rubber and carbon nanotube are pressed to 85:15, is made EPDM by double screw extruder Rubber/carbon nano tube compound material is used as masterbatch 2 after drying；Extrusion temperature is 210 DEG C, revolving speed 180rpm；
The mass ratio that masterbatch 1, masterbatch 2 and polypropylene, ethylene propylene diene rubber are pressed to 3:20:74:3, passes through twin-screw extrusion Mechanism obtains composite material；Temperature when extrusion is 220 DEG C, revolving speed 190rpm.
Wherein polypropylene is isotactic polypropylene, and carbon nanotube is that diameter is 100nm, the multi-wall carbon nano-tube that length is 20 μm Pipe, nucleating agent are organic phosphate (NA-11).
Embodiment 6:
The mass ratio that polypropylene and nucleating agent are pressed to 95:5, it is compound to be made polypropylene/nucleating agent by double screw extruder Material is used as masterbatch 1 after drying；Extrusion temperature is 200 DEG C, revolving speed 120rpm；
The mass ratio that ethylene propylene diene rubber and carbon nanotube are pressed to 90:10, is made EPDM by double screw extruder Rubber/carbon nano tube compound material is used as masterbatch 2 after drying；Extrusion temperature is 180 DEG C, revolving speed 140rpm；
The mass ratio that masterbatch 1, masterbatch 2 and polypropylene, ethylene propylene diene rubber are pressed to 7:10:72:11, passes through twin-screw extrusion Mechanism obtains composite material；Temperature when extrusion is 230 DEG C, revolving speed 250rpm.
Wherein polypropylene is isotactic polypropylene, and carbon nanotube is that diameter is 150nm, the single that length is 40 μm Pipe, nucleating agent are polypropylene beta type nucleating agent calcium pimelate.Table 1
Table 2

Claims (3)

1. a kind of preparation method of high-ductility polypropylene based composites, key step are as follows:
1) mass ratio that polypropylene and nucleating agent are pressed to 90-99:1-10, is made polypropylene/nucleating agent by double screw extruder Composite material is used as masterbatch 1 after drying；Extrusion temperature is 180-230 DEG C, revolving speed 100-250rpm；
2) mass ratio that ethylene propylene diene rubber and carbon nanotube are pressed to 80-95:5-20, is made ternary second by double screw extruder Third rubber/carbon nano tube compound material is used as masterbatch 2 after drying；Extrusion temperature is 180-230 DEG C, revolving speed 100-250rpm；
3) mass ratio that masterbatch 1, masterbatch 2 and polypropylene, ethylene propylene diene rubber are pressed to 0.2-10:1-20:70-90:0-19, passes through Composite material is made in double screw extruder；Temperature when extrusion is 180-230 DEG C, revolving speed 100-250rpm.
2. a kind of preparation method of high-ductility polypropylene based composites described in accordance with the claim 1, which is characterized in that described Polypropylene is isotactic polypropylene.
3. a kind of preparation method of high-ductility polypropylene based composites described in accordance with the claim 1, it is characterised in that: described Carbon nanotube is that diameter is 5-200nm, the single-walled carbon nanotube or multi-walled carbon nanotube that length is 100nm-50 μm.
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CN110343332A (en) * 2019-07-11 2019-10-18 西北工业大学 A kind of high-toughness polypropylene/elastic composite and preparation method
CN111763372A (en) * 2020-06-10 2020-10-13 杭州联通管业有限公司 Reinforced modified polypropylene power tube and preparation method thereof
CN115851150A (en) * 2021-09-26 2023-03-28 大正新型材料(肇庆)有限公司 High-toughness polypropylene decorative film and preparation method and application thereof

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CN103897329A (en) * 2012-12-27 2014-07-02 第一毛织株式会社 Thermoplastic Resin Composition with Anti-Dripping Properties
CN105482244A (en) * 2014-10-11 2016-04-13 中国石油化工股份有限公司 Carbon nano-tube/polymer composite material and preparation method thereof
CN105623097A (en) * 2016-03-02 2016-06-01 北京航天试验技术研究所 Nanometer-material-compounded long-glass-fiber-reinforced polypropylene material and preparing method thereof

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Publication number Priority date Publication date Assignee Title
CN103897329A (en) * 2012-12-27 2014-07-02 第一毛织株式会社 Thermoplastic Resin Composition with Anti-Dripping Properties
CN105482244A (en) * 2014-10-11 2016-04-13 中国石油化工股份有限公司 Carbon nano-tube/polymer composite material and preparation method thereof
CN105623097A (en) * 2016-03-02 2016-06-01 北京航天试验技术研究所 Nanometer-material-compounded long-glass-fiber-reinforced polypropylene material and preparing method thereof

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