CN110511429A - A kind of conductive additive and application, conducing composite material and its preparation method and application - Google Patents

A kind of conductive additive and application, conducing composite material and its preparation method and application Download PDF

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Publication number
CN110511429A
CN110511429A CN201910755162.9A CN201910755162A CN110511429A CN 110511429 A CN110511429 A CN 110511429A CN 201910755162 A CN201910755162 A CN 201910755162A CN 110511429 A CN110511429 A CN 110511429A
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conductive
composite material
conducing composite
agent
conductive additive
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Inventor
王浩然
张敏
张新和
赵露华
王建华
高占忠
刘婷婷
任增辉
徐欢
马青喜
李金来
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New Austrian (inner Mongolia) Graphene Material Co Ltd
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New Austrian (inner Mongolia) Graphene Material Co Ltd
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Priority to CN201910755162.9A priority Critical patent/CN110511429A/en
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Abstract

The present invention discloses a kind of conductive additive and application, conductive polymer composite and its preparation method and application, it is related to high molecule nano composite material technical field, to improve the mechanical strength of conducing composite material, reduce the combustibility and melting rate of conducing composite material.The conductive additive includes at least the conductive material of micro-nano hydridization, and the micro-nano conductive material includes zero dimension conductive material, one-dimensional electric material and two-dimentional conductive material.The conducing composite material includes above-mentioned conductive additive.Conductive additive provided by the invention is in conducting polymer product.

Description

A kind of conductive additive and application, conducing composite material and its preparation method and application
Technical field
The present invention relates to high molecule nano composite material technical field more particularly to a kind of conductive additive and application, lead Composite and its preparation method and application.
Background technique
Conductivity type polymer composite is that one kind fills conductive agent macromolecule obtained in macromolecule polymeric material Conducing composite material has been carried out large-scale production.
To guarantee that conductivity type polymer composite has good electric conductivity, the high molecular polymer material to insulation is needed The a large amount of conductive material of addition in material, this also leads to being decreased obviously for the mechanical property of conductivity type polymer composite, finally Damage the service performance and application range of product made by conductivity type polymer composite.
Summary of the invention
The purpose of the present invention is to provide a kind of conductive additive and application, conducing composite material and preparation method thereof and answer With to improve the mechanical strength of conducing composite material, reduce the combustibility and melting rate of conducing composite material.
To achieve the goals above, the present invention provides a kind of conductive additive.The conductive additive is led including at least micro-nano Electric material, the micro-nano conductive material include zero dimension conductive material, one-dimensional electric material and two-dimentional conductive material.
Compared with prior art, in conductive additive provided by the invention, micro-nano conductive material include zero dimension conductive material, One-dimensional electric material and two-dimentional conductive material, so that after conductivity additive is mixed with base resin material, zero dimension conductive material, One-dimensional electric material and two-dimentional conductive material are in microcosmic upper composition " point-line-face " space conductive network structure.Also, this spy Zero dimension conductive material, one-dimensional electric material and two-dimentional conduction material in different structure (i.e. " point-line-face " space conductive network structure) Material can be complementary to one another space defect in microcosmic upper realization, so that fault of construction, so that spatial complementary effect is realized, so that microcosmic " point-line-face " space conductive network structure denser, therefore, conductive additive provided by the invention and matrix resin are mixed After conjunction, the mechanical property of matrix resin will not influence substantially, so that conducing composite material obtained relatively matrix resin Mechanical property.
Moreover, because microcosmic " point-line-face " space conductive network structure is more improved and stability is high, and have good Good heating conduction, so that it is conductive to can use microcosmic " point-line-face " space in heated or burning for conducing composite material The effective starvation of network structure enters microcosmic " point-line-face " space conductive network inside configuration space, but can will be outer Portion's heat transfer is to microcosmic " point-line-face " space conductive network inside configuration space, in conducing composite material combustion process The material of the middle inner space for promoting to be located at microcosmic " point-line-face " space conductive network structure reduces conductive multiple at charcoal The combustibility of condensation material.Simultaneously as microcosmic " point-line-face " space conductive network structure has good thermally conductive function, make It obtains and absorbs partial heat in conducing composite material combustion process and scatter and disappear away, to reduce conducing composite material combustion process Middle heat release rate peak value, and then reduce the melting rate of conducing composite material.
The present invention also provides a kind of conducing composite materials.The conducing composite material includes that matrix resin and above-mentioned conduction add Add agent.
Compared with prior art, the beneficial effect of conducing composite material provided by the invention and above-mentioned conductivity additive Beneficial effect is identical, and this will not be repeated here.
The present invention also provides a kind of preparation methods of above-mentioned conducing composite material.The preparation method of the conducing composite material Include:
Conductive additive is dispersed in matrix resin, conducing composite material is obtained, the conductive additive is above-mentioned leads Composite.
Compared with prior art, the beneficial effect of the preparation method of conducing composite material provided by the invention and above-mentioned conduction The beneficial effect of property additive is identical, and this will not be repeated here.
The present invention also provides a kind of application of above-mentioned conductive additive in conducing composite material.
Compared with prior art, the beneficial effect of application of the conductive additive provided by the invention in conducing composite material Identical as the beneficial effect of above-mentioned conductivity additive, this will not be repeated here.
The present invention also provides a kind of application of above-mentioned conducing composite material in conducting polymer product.
Compared with prior art, the beneficial effect of application of the conducing composite material provided by the invention in conducing composite material Fruit is identical as the beneficial effect of above-mentioned conductivity additive, and this will not be repeated here.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present invention, constitutes a part of the invention, this hair Bright illustrative embodiments and their description are used to explain the present invention, and are not constituted improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is the simulation drawing of " point-line-face " space conductive network structure in the embodiment of the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of conducing composite material provided in an embodiment of the present invention；
Fig. 3 is the preparation method flow chart one of conducing composite material provided in an embodiment of the present invention；
Fig. 4 is the preparation method flow chart two of conducing composite material provided in an embodiment of the present invention；
Fig. 5 is the preparation method flow chart three of conducing composite material provided in an embodiment of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
Conductivity type polymer composite is that one kind filling conductive agent in the macromolecule polymeric materials such as matrix resin is obtained The conductive polymer composites obtained, have been carried out large-scale production.
To guarantee that conductivity type polymer composite has good electric conductivity, the high molecular polymer material to insulation is needed The a large amount of conductive material of addition in material, this also leads to being decreased obviously for the mechanical property of conductivity type polymer composite, finally Damage the service performance and application range of product made by conductivity type polymer composite.
Current-conducting material generally comprises traditional material such as carbon black, carbon fiber, crystalline flake graphite, metallic particles, fiber conductive agent Material.Such as: when the metal material perishable using metallic particles etc. is as conductive agent, conductivity type polymer composite obtained Ageing-resistant performance and long-term mechanical property decline.Moreover, introducing fibrous conductive agent (such as carbon fiber) easily leads to product Conductivity type polymer composite surface generates burr, seriously affects appearance, and damages production equipment (example in process Such as: abrasion extruder screw leads to shortening for extrusion screw rod service life).In another example carbon black additive amount is excessive, it is easily reduced conduction The processing performance of type polymer composite, and carbon deposition rate is relatively high.Moreover, the import dependency degree of highly conductive carbon black is high, price Height causes the cost of material of conductivity type polymer composite higher.
Embodiment one
The embodiment of the invention provides a kind of conductive additives, include at least micro-nano conductive material, the micro-nano conduction material Material includes zero dimension conductive material (0D), one-dimensional electric material (1D) and two-dimentional conductive material (2D).It should be understood that the embodiment of the present invention The hybrid mode of the materials such as the conductive additive of offer and matrix resin is varied, and for details, reference can be made to existing conductivity type macromolecules The preparation process of composite material, is not detailed herein.
Micro-nano conductive material refers at the size at least one direction in the conductive material of 1~1000 micron-scale.On Zero dimension conductive material is stated microcosmic upper for micro-or nano size chondritic.One-dimensional electric material microcosmic upper presentation it is linear, it is rodlike, Strip is band-like, their cross section is micro-or nano size interface.For two-dimentional conductive material in microcosmic upper presentation sheet, lamella is micro- The lamella of nano-scale.Based on this, zero dimension conductive material, one-dimensional electric material and two-dimentional conductive material can obtain zero dimension conduction material Material, one-dimensional electric material and two-dimentional conductive material can mutually make up spatial defects on microcosmic, so that conductive additive After mixing with materials such as matrix resins, conducing composite material obtained has good mechanical property.Such as: one-dimensional electric material Material can make up generated bedding void in two-dimentional conductive material banking process, and zero dimension conductive material can make up one-dimensional electric Gap caused by material stacking, two-dimentional conductive material accumulation institute.So that zero dimension conductive material, one-dimensional electric material and two dimension are led " point-line-face " space conductive network structure that electric material is constituted on microcosmic is closer, there's almost no gap.
Fig. 1 shows in the embodiment of the present invention simulation drawing of " point-line-face " space conductive network structure.It can from Fig. 1 Out: zero dimension conductive material 0D, one-dimensional electric material 1D and two dimension conductive material 2D fill banking process each other on microcosmic and are produced Raw gap, so that " point-line-face " that zero dimension conductive material 0D, one-dimensional electric material 1D and two dimension conductive material 2D are constituted Space conductive network structure is closer, and then the effect for being advantageously implemented blocking oxygen, promoting heat transfer.Below to from three sides It is described in detail in face of " point-line-face " space conductive network structure.
In a first aspect, micro-nano conductive material includes zero dimension conductive material, one-dimensional electric material and two-dimentional conductive material, so that After conductivity additive is mixed with base resin material, zero dimension conductive material, one-dimensional electric material and two-dimentional conductive material are micro- " point-line-face " space conductive network structure is constituted in sight.Also, the zero dimension being somebody's turn to do in " point-line-face " space conductive network structure Conductive material, one-dimensional electric material and two-dimentional conductive material can be complementary to one another space defect in microcosmic upper realization, so that structure Defect, so that realize spatial complementary effect, so that microcosmic " point-line-face " space conductive network structure denser, therefore, After conductive additive provided in an embodiment of the present invention is mixed with matrix resin, the mechanical property of matrix resin will not influence substantially, So that the mechanical property of conducing composite material obtained relatively matrix resin.Zero dimension conductive material, one-dimensional electric material " point-line-face " network is formed by while enhancing the mechanical property of conducing composite material with two-dimentional conductive material, " point- The three-dimensional netted microstructure of line-face " facilitate micro-nano synergistic effect enhancing, it is therefore prevented that in conducing composite material certain point in response to The phenomenon that power is concentrated and is broken.It finds after tested, conductive additive provided in an embodiment of the present invention is applied to conductive compound In material, using the test of GB/T 1040.3-2006 plastic tensile performance, the tensile strength of testing conductive composite material is 16MPa-23MPa, elongation at break 450%-600%.Using GB/T 13525-1992 plastic tensile impact property experimental test The impact strength of conducing composite material is 20KJ/m2-30KJ/m2。
Second aspect since microcosmic " point-line-face " space conductive network structure is more perfect and stability is high, but has There is good heating conduction, so that conducing composite material can use microcosmic " point-line-face " space in heated or burning The effective starvation of conductive network structure enters microcosmic " point-line-face " space conductive network inside configuration space, but can Outside heat is transferred to microcosmic " point-line-face " space conductive network inside configuration space, to burn in conducing composite material Promote the material for being located at the inner space of microcosmic " point-line-face " space conductive network structure at charcoal in the process, and then reduces and lead The combustibility of composite.In other words, zero dimension conductive material, one-dimensional electric material and two-dimentional conductive material are constituted micro- Conductive material of receiving has the function of being catalyzed and promote into charcoal to matrix resin.
The third aspect, since microcosmic " point-line-face " space conductive network structure has good thermally conductive function, so that Partial heat is absorbed in conducing composite material combustion process and is scattered and disappeared away, to reduce in conducing composite material combustion process Heat release rate peak value, and then reduce the melting rate of conducing composite material, so as to improve matrix resin close to ignition temperature When melting behaviour, and then reduce the mass loss speed of conducing composite material in combustion.Tests prove that: 210 DEG C oxidation induction time be greater than or equal to 30min, use (ISO 3915:1981) EN ISO 11357-6-2013 plastics- The-the 6 part of differential scanning calorimetry (DSC): the measurement (isothermal OIT) of oxidation induction time and oxidation induction temperature (dynamic OIT) (ISO 11357-6:2008).
In some embodiments, in order to improve electric conductivity, above-mentioned zero dimension conductive material includes carbon black, in Carbon Cluster At least one, but it is not limited only to this.Carbon Cluster can be C60, C70 etc..Above-mentioned one-dimensional electric material includes nano wire, receives At least one of rice stick, nanotube, but it is not limited only to this.Above-mentioned two dimension conductive material includes graphene, but is not limited only to this.This When, the resistance of the conducing composite material containing conductive additive is 102Ω-105Ω, resistance measurement are public using ISO 3915:1981 The measurement standard for the plastics conductive plastic resistance opened.
Above-mentioned graphene and carbon nanotube have high conductive capability, excellent mechanical strength and high surface living Property, good application prospect has been shown in conducting function field of compound material.Wherein,
Graphene is by carbon atom with sp2The two-dimensional material of the monoatomic layer thickness of hybridized orbit composition, single-layer graphene Resistivity be only 10-6Ω cm, while there is good flexibility, rigidity and thermal conductivity, conducting function can assigned Meanwhile improving the mechanical property and heat dissipation performance of polymer composite.Carbon nanotube is current civilian most commonly used function Carbon nanomaterial.When being used alone or be used in mixed way graphene and carbon nanotube, the cost of raw material is all higher, is unfavorable for extensive Popularization and application.
In order to reduce cost, above-mentioned zero dimension conductive material is carbon black, so that in carbon black, nano wire, nanometer rods, nanotube extremely A kind of few and graphene constitutes " point-line-face " space conductive network structure.When conductive additive provided in an embodiment of the present invention It, can be in the addition for reducing at least one of nano wire, nanometer rods, nanotube and graphene when applied to conducing composite material While amount, carbon black can guarantee the mechanical property of conducing composite material to a certain extent, and reduce conducing composite material can Combustion property and melting rate, therefore, in conductive additive provided in an embodiment of the present invention, zero dimension conductive material is carbon black, one-dimensional to lead Electric material is at least one of nano wire, nanometer rods, nanotube, when two-dimentional conductive material includes graphene, can effectively dropped While inexpensive, when guaranteeing that conductive additive is applied to conducing composite material, the electric conductivity of conductive additive, to avoid list Solely when addition carbon black, conducing composite material poor in processability caused by carbon black adding too much, bad dispersibility, carbon deposition rate is high to be asked Topic.
Moreover, conductive additive provided in an embodiment of the present invention contains the high nano wire of conductive capability, nanometer rods, nanometer At least one of pipe and graphene, so that the conductive capability of conductive additive is higher than the conventional conductive agents such as common carbon black, therefore, For the conducing composite material of same conductive capability, conductive additive provided in an embodiment of the present invention is in composite conducting material In content be less than content of the conventional conductive agent in composite conducting material.In other words, conductive addition provided by the invention In the case that additive amount of the agent in conducing composite material is fewer, it is ensured that conducing composite material has good electric conductivity Under the premise of energy, the preparation cost of conducing composite material is reduced, and reduces conducing composite material during the preparation process because of carbon black Dust pollution caused by additive amount is excessive.
Illustratively, the mass ratio of above-mentioned zero dimension conductive material, one-dimensional electric material and two-dimentional conductive material is (0.1- 1): (0.1-6): (0.1-5) can also in the light of actual conditions set mass ratio certainly.Such as: when zero dimension conductive material is carbon black When, micro-nano conductive material is based on one-dimensional electric material and two-dimentional conductive material, and auxiliary carbon black makes up space defect, and raising is led The electric conductivity of electric additive.
Illustratively, above-mentioned one-dimensional electric material is carbon nanotube, and the major diameter ratio of the carbon nanotube is greater than 1000, and carbon is received The diameter of mitron is 2nm-30nm, and the powder conductivity rate of carbon nanotube is greater than or equal to 3000S/m.
Above-mentioned two dimension conductive material is graphene.The lamella of graphene is 2 layers -10 layers, and the maximum single layer of graphene is radial Length is 20 μm, the powder conductivity rate 10 of graphene2S/m-106S/m。
In some embodiments, above-mentioned conductive additive further includes fire retardant, to increase the anti-flammability of conducing composite material Energy.Meanwhile above-mentioned micro-nano conductive material can reduce the combustibility of conducing composite material, make micro-nano conductive material as synergist The flame retardant property of fire retardant is strengthened, so that the anti-flammability of conducing composite material is further increased, therefore, for same resistance For the conducing composite material for firing performance, when conductivity additive provided in an embodiment of the present invention is applied to conducing composite material, The amount of fire retardant contained therein is less than the amount of the fire retardant contained by existing conducing composite material, and therefore, the present invention is real The flame retardant agent content for applying the conductive additive of example offer is fewer, but still is able to reach excellent flame retardant property.This is significantly Fire-retardant cost is reduced, and reduces conducing composite material during the preparation process because of the excessive caused dust of fire retardant additive amount Pollution problem.
Existing conducing composite material on the market is limited by flame-retarded technology and market, and fire retardant contained therein is generally Cheap halogenated flame retardant, but it can release highly acid gas and dense smoke in combustion, pollute environment, endanger people Body health, is gradually substituted by halogen-free flame retardants.In existing halogen-free flame retardants, metal oxide, metal hydroxides, phosphorus Nitrogen system, nitrogen system, silicon systems, phosphorus system and expansion type flame retardant are usually used in the flame-retardant modified of the high molecular materials such as matrix resin.
It is shown according to research, when a kind of fire retardant be used alone being applied to conducing composite material, conducing composite material Flame retardant property be not achieved high fire-retardance requirement.Part hydroxide flame retardant non-refractory, can decompose during melt-processed Water is generated, the flame retardant property of words hydroxide flame retardant is broken, while influencing the appearance of product；And nitrogenated flame retardant, the resistance of phosphorus nitrogen system It is poor, poor at charcoal effect to fire big agent additive amount, poor processability, material mechanical performance, is often used in compounding with antimony system flame-retardant system, at This is higher.
Organic expander type fire retardant is a kind of using substances such as ammonium polyphosphate, ammonium phosphate, polyphosphate, sulfuric acid as sour member, Using pentaerythrite, dipentaerythritol, ethylene glycol, can the substances such as swollen graphite as carbon source, with objects such as melamine, urea, dicyandiamides Matter is the flame-retardant system of nitrogen source.The flame-retardant system has high flame retardant, without molten drop behavior, to long-time or repeated exposure in fire There are fabulous repellence and environmental protection in flame.But flame-retardant system formula is complicated, gives full play to the association between fire retardant Most important with effect, a certain component slightly changes the anti-flammability that can influence system.Through experimental studies have found that, this is fire-retardant System is easy to generate stomata in the material, material appearance is caused to become in polythene material in application, after melting mixing process The disadvantages of difference, there is also additive amounts for the system greatly, poor processability, higher cost.
Phosphorus flame retardant is a kind of current the most widely used flame-retardant system, because of its good flame resistance, low toxin And it is industrially used on a large scale.Red phosphorus forms the derivative of phosphoric acid in burning, in the PO radical-scavenging flame of generation Hydroperoxyl radical and hydroxyl radical free radical, play fire-retardant effect.But it has been investigated that: when phosphorus flame retardant is used alone, The anti-flammability of high density polyethylene (HDPE) can just be made by needing to add the phosphorus flame retardant that mass percent is 8% in conducing composite material Reach UL94V0 grades, moreover, red phosphorus higher cost, high additive amount increases the cost of material of material, influences pushing away extensively for product Wide and application.Therefore, loading of the red phosphorus in composite conducting material is big, it is caused to divide in the high molecular materials such as matrix resin It dissipates poor, influences the mechanical property of product, and higher cost.
From the foregoing, it will be observed that reducing the use of fire retardant while in order to guarantee that conducing composite material has good flame-retardance energy Amount, the fire retardant contained by conductive additive provided in an embodiment of the present invention is phosphorus system compound flame retardant, to reduce fire retardant pair Harm caused by environment and health.In other words, when fire retardant is phosphorus system compound flame retardant, phosphorus system is multiple in other words for fire retardant It should include phosphorus flame retardant and non-phosphorus flame retardant with fire retardant.Certain non-phosphorus flame retardant should be non-phosphorus system's halogen-free flameproof Agent.
Above-mentioned non-phosphorus flame retardant includes at least one of silicon-series five-retardant, hydroxide flame retardant, melamine, but not It is only limitted to this.Above-mentioned phosphorus flame retardant includes at least one of ammonium polyphosphate, polyphosphate, red phosphorus, ammonium phosphate, but is not only limited In can also be set according to actual conditions.
Wherein, silicon-series five-retardant includes at least one of alumina silicate, magnesium silicate, silica.Hydroxide flame retardant packet Include at least one of calcium hydroxide, magnesium hydroxide, aluminium hydroxide.
When the melamine that above-mentioned non-phosphorus flame retardant contains, if phosphorus flame retardant include ammonium polyphosphate, polyphosphate, At least one of ammonium phosphate, zero dimension conductive material include at least one of carbon black, Carbon Cluster, and one-dimensional electric material includes receiving At least one of rice noodles, nanometer rods, nanotube, when two-dimentional conductive material includes graphene, poly- phosphorus included by phosphorus flame retardant At least one of sour ammonium, polyphosphate, ammonium phosphate can be used as acid source, zero dimension conductive material, one-dimensional electric material and two dimension and leads Electric material may be constructed the flame-retardant system of organic expander type fire retardant as carbon source as carbon source, melamine, to give full play to Flame retardant property, so that anti-flammability is V0 grades.
In some embodiments, above-mentioned conductive additive further includes dispersing agent, flow ability modifying agent, surface modifier and processing Auxiliary agent.When conductive additive is applied to conducing composite material, dispersing agent can guarantee that micro-nano conductive material fills in matrix resin Micro-nano conductive material can be improved in the contact performance of matrix resin in the dispersion divided, flow ability modifying agent, and surface modifier can have The contact performance of effect enhancing fire retardant and matrix resin.And the weatherability of conducing composite material then can be improved in processing aid.
It, can be according to the actual situation as the type of above-mentioned dispersing agent, flow ability modifying agent, surface modifier and processing aid Selection.Such as:
Above-mentioned dispersing agent includes at least one of polyethylene wax, paraffin, OP wax.Above-mentioned flow ability modifying agent include paraffin oil, At least one of dimethicone.Above-mentioned surface modifier includes chromium complex coupling agent, silane coupling agent, titanate esters coupling At least one of agent, aluminate coupling agent, magnesium class coupling agent, tin class coupling agent.
Chromium complex coupling agent includes complex compound (Volan U.S. DuPont), the anti-butylene two of methacrylate-chromic chloride Nitric acid chromium complex B-301 (U.S. DuPont).
Silane coupling agent may include silane resin acceptor kh-550, silane coupling agent KH-78, in silane coupling agent 702 extremely Few one kind.
Titanate coupling agent includes titanate coupling agent YB-201 (Dongguan City mountain one is plasticized Co., Ltd), titanate esters coupling At least one of agent TMC-130 (Anhui Tianzhang City green chemical industry auxiliary agent long production).
Aluminate coupling agent includes aluminate coupling agent LS-62 (Anhui Tianzhang City green chemical industry auxiliary agent long production), aluminic acid At least one of ester coupling agent LS-821 (Wuhan is far at Sai Chuan Science and Technology Ltd.).
Magnesium class coupling agent is dimerization di (isooctyl) phosphate magnesium stearate (Foshan South Sea the Changjiang river plastics Co., Ltd), dimerization phosphorus At least one of sour di-isooctyl magnesium stearate (south big -821).
Above-mentioned processing aid includes Hinered phenols antioxidant, alkyl polyphenol kind antioxidant, hindered amine light stabilizer, phosphorous Acid esters kind antioxidant, thio rouge, haloflex, acrylic resin, ethylene-vinyl acetate copolymer, in fluorine-containing auxiliary agent extremely Few one kind.Wherein,
Hinered phenols antioxidant includes at least one of 2,8- di-tert-butyl-4-methy phenol, antioxidant lU1U.Hindered amine Class light stabilizer includes benzoic acid (2,2,6,6- tetramethyl -4- hydroxy piperidine) ester, bis- (2,2,6, the 6- tetramethyl -4- of decanedioic acid Hydroxy piperidine) ester, at least one of nitrogen base three [acetic acid (2,2,6,6- tetramethyl -4- hydroxy piperidine) ester].Phosphorous acid esters are anti- Oxygen agent includes at least one of antioxidant 618, antioxidant 852.Thio rouge includes thio-2 acid laurel alcohol ester, thio-2 acid At least one of octadecanol ester.Acrylic resin include thermoplastic acrylic resin, in thermosetting acrylic resin at least It is a kind of.Fluorine-containing auxiliary agent includes:
Fluorine-containing auxiliary agent includes fluorine-containing processing aid FX 5920A (U.S. 3M production), the fluorine-containing 5911 (U.S. processing aid FX At least one of 3M production).
In order to enable conductive additive provided by the invention gives full play to its performance in matrix resin, the micro-nano conduction material Material, fire retardant, dispersing agent, flow ability modifying agent, surface modifier and processing aid mass ratio be (1-9): (4-9): (2-10): (0.5-8): (0.1-3): (0.1-3).
Embodiment two
The embodiment of the invention provides a kind of application of conductive additive in conducing composite material.It is of the invention based on this Embodiment additionally provides a kind of conducing composite material.The conducing composite material includes matrix resin and above-mentioned conductive additive, with Realize above-mentioned conductive additive beneficial effect achieved.
Illustratively, Fig. 2 shows the scanning electron microscope (SEM) photographs of conducing composite material provided in an embodiment of the present invention.In Fig. 2 Plates are as the graphene of two-dimentional conductive material, and filamentous is nanotube, and blocks is carbon black.As seen from Figure 2, stone Black alkene, nanotube and carbon black interact with each other, to make up generated gap during material stacking, so that constituted " point-line-face " space conductive network structure is closer.The scanning electron microscope (SEM) photograph of conducing composite material illustrated in fig. 2 also confirms that The accuracy of the simulation drawing of " point-line-face " space conductive network structure shown in figure 1.
It should be understood that the mass ratio of matrix resin and micro-nano conductive material is (61-84): (1-9), it can also be according to practical feelings Condition adjustment.At this point, the sheet resistance of conducing composite material provided in an embodiment of the present invention is 102Ω-105Ω, anti-flammability V0 Grade, tensile strength 16MPa-23MPa, elongation at break 450%-600%, impact strength 20KJ/m2-30KJ/m2, In 210 DEG C of oxidation induction time is greater than or equal to 30min.It can be seen that conducing composite material tool provided in an embodiment of the present invention There are good mechanical property and electric conductivity, can be applicable to the application in conducting polymer product, therefore, the embodiment of the present invention is also Provide a kind of application of conducing composite material in conducting polymer product.
Above-mentioned matrix resin includes low density polyethylene (LDPE), linear low density polyethylene, high density polyethylene (HDPE), super high molecular weight Polyethylene, polystyrene, random polypropylene, isotactic polypropylene, polycarbonate, parylene's glycol ester, nylon 6, Buddhist nun At least one of dragon 66.Wherein,
Low density polyethylene (LDPE) (Low Density Polyethylene, be abbreviated as LDPE) is also known as high pressure polyethylene, is one Kind plastic material, it is suitble to the various moulding process of thermoplastic molding's processing, and molding processibility is good, and relative density is in 0.910- 0.925, design feature non-linear hour, molecular weight is generally in 100000-50000.
High density polyethylene (HDPE) (High Density Polyethylene, be abbreviated as HDPE) is also known as low pressure polyethylene, is one Kind crystallinity is high, non-polar plane is in a degree of translucent.The density of HDPE is in 0.940~0.976g/cm3In range； Crystallinity is 80%~90%, and softening point is 125~135 DEG C, using temperature up to 100 DEG C；120~160 DEG C of fusion temperature, weight Average molecular weight is 5000-500000.
Linear low density polyethylene (Linear low density polyethylene, be abbreviated as LLDPE) be it is nontoxic, Tasteless, odorless milky white granules, density are 0.918~0.935g/cm3.It is compared with LDPE, softening temperature with higher And melting temperature, have the advantages that intensity is big, good toughness, rigidity is big, heat-resisting, cold resistance is good, also there is good environmental stress resistance Cracking behavior, the performances such as impact resistant strength, tear-resistant intensity, and can acid and alkali resistance, organic solvent etc. and be widely used in industry, agricultural, The fields such as medicine, health and daily necessities.
(ultra-high molecular weight polyethylene, is abbreviated as ultra-high molecular weight polyethylene UHMWPE) be 1,000,000 or more molecular weight polyethylene.85 DEG C of heat distortion temperature (0.46MPa), 130~136 DEG C of fusing point) it is one The thermoplastic engineering plastic with Good All-around Property of kind linear structure.In the world earliest by U.S. AlliedChemical public affairs It takes charge of and realizes industrialization in nineteen fifty-seven, hereafter Hoechst company, Germany, Hercules company, the U.S., Mitsui petrochemistry are public Department etc. also puts into industrialized production.
Embodiment three
The embodiment of the invention also provides a kind of preparation methods of conducing composite material.The preparation side of the conducing composite material Method includes:
Conductive additive is dispersed in matrix resin, conducing composite material is obtained, which is embodiment one The conducing composite material of description, so that the preparation method of conducing composite material provided in an embodiment of the present invention can reach above-mentioned conduction The beneficial effect of additive.
In some embodiments, in the prior art, when the one-dimensional electric material contained by above-mentioned conductive additive includes receiving At least one of rice noodles, nanometer rods, nanotube, when above-mentioned two dimension conductive material includes graphene, one-dimensional electric material and graphite The large specific surface area of alkene leads to the electric conductivity office of be processed into conduct piece so that being easy to reunite when processing conducing composite material Portion is uneven, limits it in the application of the higher-end businesses such as accurate device.
In a kind of example, as shown in figure 3, above-mentioned be dispersed in conductive additive in matrix resin, obtain conductive compound Material includes:
Step S100A: being mixed and heated to mixing temperature for micro-nano conductive material, matrix resin and flow ability modifying agent, obtains Conductive filler；Flow ability modifying agent can reduce the air gap between matrix resin and micro-nano conductive material at this time, to increase base The contact performance of body resin and micro-nano conductive material.Micro-nano conductive material, matrix resin and flow ability modifying agent are to stir at low speed Mode is heated to mixing temperature.The speed stirred at low speed may be set according to actual conditions, such as: in 50r/min~150r/min Speed under stir.
Step S200A: at a temperature of mixing, by conductive filler, dispersing agent, surface modifier, fire retardant and processing aid It is uniformly mixed, obtains conducing composite material semi-finished product.Due to mixing the fusion temperature that temperature is dispersing agent, dispersing agent exists Can adequately be melted at a temperature of the mixing, such dispersing agent can to greatest extent with conductive filler, surface modifier, resistance Agent and processing aid contact are fired, so that under the action of the dispersing agent of fusing, conductive filler, surface modifier, fire retardant and is added Work auxiliary agent adequately contacts.
In order to further increase being uniformly mixed for conductive filler, dispersing agent, surface modifier, fire retardant and processing aid Property, as shown in figure 4, conductive filler, dispersing agent, surface modifier, fire retardant and processing aid are mixed equal at a temperature of mixing Even, obtaining conducing composite material semi-finished product includes:
Step S210A: at a temperature of mixing, conductive filler, dispersing agent and surface modifier being mixed, until dispersing agent is molten Change, obtains hybrid conductive agent.In this process, under the action of the dispersing agent of fusing, surface modifier can be filled out with conduction Material comes into full contact with.The mixing speed of conductive filler, dispersing agent and surface modifier may be set according to actual conditions.Such as: when leading When the mixing speed of electric filler, dispersing agent and surface modifier is high speed, mixing speed is 400r/min~500r/min.
Step S220A: at a temperature of mixing, hybrid conductive agent, fire retardant and processing aid being uniformly mixed, and obtained conductive Composite semi-finished products.In this process, the flow ability modifying agent contained by hybrid conductive agent and surface modifier can make Fire retardant is preferably contacted with matrix resin, to guarantee that fire retardant can be preferably dispersed in matrix resin.
Step S300A: conducing composite material semi-finished product being melted, and extruding pelletization, obtains conducing composite material.One As melting operation carried out using kneading machine, kneading machine can be convertible mixer, continuous internal mixer, one in open mill Kind.Extrusion operation is generally carried out using extruder, extruder can be single screw extrusion machine, parallel double-screw extruder, taper One of double screw extruder, three-screw extruder.
It should be understood that above-mentioned mixing temperature, melting temperature and extruding pelletization temperature are then set according to actual conditions.Such as: on Stating and mixing temperature is 50 DEG C -180 DEG C, and the temperature melted is 150 DEG C -270 DEG C, and the temperature of extruding pelletization is 150 DEG C -270 ℃.The mixing temperature maintained time is mixing time, which is set according to actual conditions, such as 20s-360s.Melting Time 3-25min.The revolving speed of kneading machine used in melting is defined as engine speed.Engine speed is 50r/min-500r/ min。
In another example, as shown in figure 5, conductive additive is dispersed in matrix resin, conductive composite wood is obtained Material includes:
Step S100B: micro-nano conductive material, flow ability modifying agent, surface modifier are dispersed in dispersion solvent, mixed Close solution；Ultrasonic vibration is carried out to mixed solution at 20 DEG C -50 DEG C, dispersing agent then is added to mixed solution, is pre-processed Liquid one；Dispersion solvent is varied, such as: the volume ratio of the mixed solvent of dimethylbenzene and ethyl alcohol, dimethylbenzene and ethyl alcohol can be (2 ~5): 1, but it is not limited only to this.As for the ultrasonic vibration time, then concrete condition decision is regarded.Such as: the ultrasonic vibration time is 4h- 20h, with guarantee flow ability modifying agent, surface modifier can adequately with micro-nano conductive material contacts.
Step S200B: matrix resin, dispersing agent, fire retardant and processing aid are uniformly mixed, and obtain mixture；40 15min-30min is mixed in mixture and pretreatment fluid one by DEG C -60 DEG C, obtains pretreatment fluid two.Due in step S100B Flow ability modifying agent, surface modifier can adequately with micro-nano conductive material contacts, therefore, when mixture be added pretreatment fluid For the moment, the matrix resin contained by mixture, fire retardant and processing aid can be mixed well with pretreatment fluid one.
Step S300B: the dispersion solvent that pretreatment fluid two is contained removes, and obtains pretreatment material；Remove dispersion solvent Method is varied, such as vacuum drying or normal pressure drying.
Step S400B: extruding pelletization is expected into pretreatment, obtains conducing composite material.Equipment used in extruding pelletization and Temperature can refer to above.
It can be seen from upper two kinds of examples in the preparation method of conducing composite material provided in an embodiment of the present invention, it will lead The specific embodiment that electric additive is dispersed in matrix resin improves, and each component can be effectively ensured can be evenly dispersed In matrix resin, it is seen then that the preparation method of conducing composite material provided in an embodiment of the present invention can guarantee conductive composite wood Contained each component is uniformly mixed in material, is alleviated and is added using nanotube, graphene as conductive material in matrix resin When caused conductive material disperse problem of non-uniform, and then it is conductive not to avoid prepared conducting polymer product from part occur Equal problem.Meanwhile the preparation method of conducing composite material provided in an embodiment of the present invention also simplifies technical process, shortens Production time, to guarantee conducing composite material production efficiency with higher, so that conducing composite material can realize industry metaplasia It produces.
Example IV
The embodiment of the invention provides a kind of preparation methods of conducing composite material.The preparation method of the conducing composite material Include:
Step 1: micro-nano conductive material, flow ability modifying agent, matrix resin are put into the mixing in high mixer with 50r/min Speed is warming up to 120 DEG C in mixing, in 120 DEG C of mixing 60s, obtains conductive filler.Micro-nano conductive material includes that mass ratio is Carbon black, carbon nanotube (trade mark ENN-CMw11, Xin Ao graphene Technology Co., Ltd.) and the graphene (trade mark of 0.4:2:0.1 ENN-HEC-2L, Xin Ao graphene Technology Co., Ltd.).Flow ability modifying agent is paraffin oil, and matrix resin is high density polyethylene (HDPE). The mass ratio of micro-nano conductive material, flow ability modifying agent and matrix resin is 1.5:2:84.
Step 2: addition dispersing agent and surfactant continues to mix 180s into high mixer, dispersing agent melts at this time；So Phosphorus system compound flame retardant and processing aid is added thereto afterwards and stirring 120s is continuesd to mix with the revolving speed of 450r/min, is led Composite semi-finished product.The matter of micro-nano conductive material, dispersing agent, surfactant, phosphorus system compound flame retardant and processing aid Amount is than being 1.5:2:1.5:8:1.5.Wherein, phosphorus system compound flame retardant includes the red phosphorus, magnesium silicate and alumina silicate of 5:2:1, dispersion Agent is ethylene waxes, and surfactant is the complex compound of methacrylate-chromic chloride, processing aid 2,8- di-t-butyl -4- methyl Phenol.
Step 3: mixed material is placed in convertible mixer, under the revolving speed of 300r/min, melted in 180 DEG C 5min is mixed, is directly placed into single screw extrusion machine after mixing in 180 DEG C of extruding pelletizations, it is conductive high that highly effective flame-retardant can be obtained Molecular composite material.
Embodiment five
The embodiment of the invention provides a kind of preparation methods of conducing composite material.The preparation method of the conducing composite material Include:
Step 1: micro-nano conductive material, flow ability modifying agent, matrix resin are put into the mixing in high mixer with 150r/min Speed is warming up to 50 DEG C in mixing, in 50 DEG C of mixing 60s, obtains conductive filler.Micro-nano conductive material includes that mass ratio is Carbon black, carbon nanotube (trade mark ENN-CMw11, Xin Ao graphene Technology Co., Ltd.) and the graphene (trade mark of 0.4:0.1:5 ENN-HEC-2L, Xin Ao graphene Technology Co., Ltd.).Flow ability modifying agent is dimethicone, and matrix resin is poly- for low-density Ethylene.The mass ratio of micro-nano conductive material, flow ability modifying agent and matrix resin is 9:8:61.
Step 2: addition dispersing agent and surfactant continues to mix 120s into high mixer, dispersing agent melts at this time；So Phosphorus system compound flame retardant and processing aid is added thereto afterwards and stirring 100s is continuesd to mix with the revolving speed of 500r/min, is led Composite semi-finished product.The matter of micro-nano conductive material, dispersing agent, surfactant, phosphorus system compound flame retardant and processing aid Amount is than being 9:10:2.1:7:2.9.Wherein, phosphorus system compound flame retardant includes the polyphosphate and melamine of 1:2, and dispersing agent is Mass ratio is the paraffin and OP wax of 2:1, and surfactant is the silane resin acceptor kh-550 and silane coupling agent that mass ratio is 4:3 702, processing aid is benzoic acid (2,2,6, the 6- tetramethyl -4- hydroxy piperidine) ester and antioxidant lU1U that mass ratio is 2:1.
Step 3: mixed material is placed in convertible mixer, under the revolving speed of 350r/min, melted in 150 DEG C 25min is mixed, is directly placed into single screw extrusion machine after mixing in 150 DEG C of extruding pelletizations, highly effective flame-retardant conduction can be obtained Polymer composite.
Embodiment six
The embodiment of the invention provides a kind of preparation methods of conducing composite material.The preparation method of the conducing composite material Include:
Step 1: micro-nano conductive material, flow ability modifying agent, matrix resin are put into the mixing in high mixer with 150r/min Speed is warming up to 180 DEG C in mixing, in 180 DEG C of mixing 20s, obtains conductive filler.Micro-nano conductive material includes that mass ratio is Carbon black, carbon nanotube (trade mark ENN-CMw11, Xin Ao graphene Technology Co., Ltd.) and the graphene (trade mark of 0.1:0.5:2 ENN-HEC-2L, Xin Ao graphene Technology Co., Ltd.).Matrix resin includes the linear low density polyethylene that mass ratio is 3:1 And ultra-high molecular weight polyethylene.Flow ability modifying agent includes the paraffin oil and dimethicone that mass ratio is 1:1.Micro-nano conduction material The mass ratio of material, flow ability modifying agent and matrix resin is 5:3:76.6.
Step 2: addition dispersing agent and surfactant continues to mix 120s into high mixer, dispersing agent melts at this time；So Phosphorus system compound flame retardant and processing aid is added thereto afterwards and stirring 200s is continuesd to mix with the revolving speed of 400r/min, is led Composite semi-finished product.The matter of micro-nano conductive material, dispersing agent, surfactant, phosphorus system compound flame retardant and processing aid Amount is than being 5:3:2.4:9:1.Wherein, phosphorus system compound flame retardant includes ammonium polyphosphate, ammonium phosphate and the calcium hydroxide of 1:2:1, point Powder is OP wax, and surfactant includes that the aluminate coupling agent LS-62 that mass ratio is 1:3 and dimerization di (isooctyl) phosphate are stearic Sour magnesium, processing aid are fluorine-containing processing aid FX 5911.
Step 3: mixed material is placed in convertible mixer, under the revolving speed of 450r/min, melted in 250 DEG C 3min is mixed, is directly placed into single screw extrusion machine after mixing in 250 DEG C of extruding pelletizations, it is conductive high that highly effective flame-retardant can be obtained Molecular composite material.
Embodiment seven
The embodiment of the invention provides a kind of preparation methods of conducing composite material.The preparation method of the conducing composite material Include:
Step 1: micro-nano conductive material, flow ability modifying agent, matrix resin are put into the mixing in high mixer with 100r/min Speed is warming up to 170 DEG C in mixing, in 170 DEG C of mixing 20s, obtains conductive filler.Micro-nano conductive material includes that mass ratio is Carbon black, carbon nanotube (trade mark ENN-CMw11, Xin Ao graphene Technology Co., Ltd.) and the graphene (trade mark ENN- of 1:6:3 HEC-2L, Xin Ao graphene Technology Co., Ltd.).Matrix resin includes the random polypropylene and polycarbonate that mass ratio is 2:1. Flow ability modifying agent is paraffin oil.The mass ratio of micro-nano conductive material, flow ability modifying agent and matrix resin is 1:0.5:75.5.
Step 2: addition dispersing agent and surfactant continues to mix 180s into high mixer, dispersing agent melts at this time；So Phosphorus system compound flame retardant and processing aid is added thereto afterwards and stirring 120s is continuesd to mix with the revolving speed of 400r/min, is led Composite semi-finished product.The matter of micro-nano conductive material, dispersing agent, surfactant, phosphorus system compound flame retardant and processing aid Amount is than being 1:4:3:4:3.Wherein, phosphorus system compound flame retardant includes ammonium polyphosphate, ammonium phosphate and the calcium hydroxide of 1:2:1, dispersion Agent is polyethylene wax, and surfactant includes that the aluminate coupling agent LS-62 that mass ratio is 1:3 and dimerization di (isooctyl) phosphate are hard Fatty acid magnesium, processing aid are fluorine-containing processing aid FX 5911.
Step 3: mixed material is placed in convertible mixer, under the revolving speed of 450r/min, melted in 200 DEG C 10min is mixed, is directly placed into single screw extrusion machine after mixing in 200 DEG C of extruding pelletizations, highly effective flame-retardant conduction can be obtained Polymer composite.
Embodiment eight
The embodiment of the invention provides a kind of preparation methods of conducing composite material.The preparation method of the conducing composite material Include:
Step 1: micro-nano conductive material, flow ability modifying agent, surface modifier are dispersed in dispersion solvent, and at 20 DEG C Ultrasonic vibration 20h obtains mixed solution.Dispersion solvent is the dimethylbenzene and ethyl alcohol that mass ratio is 2:1.Micro-nano conductive material, stream The mass ratio 5:4:2 of dynamic modifying agent, surface modifier.Micro-nano conductive material includes that mass ratio is the carbon black of 0.6:3:2, carbon nanometer Stick and graphene (trade mark ENN-HEC-2L, Xin Ao graphene Technology Co., Ltd.).Flow ability modifying agent is dimethicone, surface Modifying agent includes the titanate coupling agent TMC-130 and aluminate coupling agent LS-821 that mass ratio is 2:1.
Step 2: matrix resin, phosphorus system compound flame retardant, dispersing agent, processing aid are uniformly mixed, mixture is obtained. 30min is mixed in mixture and pretreatment fluid one at 40 DEG C, obtains pretreatment fluid two.Matrix resin, fire retardant and processing The mass ratio of auxiliary agent is 70:9:7:3.Matrix resin includes parylene's glycol ester that mass ratio is 1:1.Phosphorus system compounding Fire retardant includes red phosphorus, silica, the aluminium hydroxide that mass ratio is 2:0.5:1.Processing aid includes that mass ratio is the anti-of 2:1 Oxygen agent 618 and thermoplastic acrylic resin.Dispersing agent is paraffin.
Step 3: removing the dispersion solvent that pretreatment fluid two contains by the way of normal pressure drying.It will pretreatment at 270 DEG C Material extruding pelletization in single screw extrusion machine, obtains conducing composite material.
Embodiment nine
The embodiment of the invention provides a kind of preparation methods of conducing composite material.The preparation method of the conducing composite material Include:
Step 1: micro-nano conductive material, flow ability modifying agent, surface modifier are dispersed in dispersion solvent, and at 50 DEG C Ultrasonic vibration 4h obtains mixed solution.Dispersion solvent is the dimethylbenzene and ethyl alcohol that mass ratio is 4:1.Micro-nano conductive material, flowing The mass ratio 3:4:1 of modifying agent, surface modifier.Micro-nano conductive material includes carbon black, the carbon nano rod that mass ratio is 0.6:3:2 With graphene (trade mark ENN-HEC-2L, Xin Ao graphene Technology Co., Ltd.).Flow ability modifying agent is dimethicone, and surface changes Property agent be dimerization di (isooctyl) phosphate magnesium stearate.
Step 2: matrix resin, phosphorus system compound flame retardant, dispersing agent, processing aid are uniformly mixed, mixture is obtained. 15min is mixed in mixture and pretreatment fluid one at 60 DEG C, obtains pretreatment fluid two.Matrix resin, fire retardant and processing The mass ratio of auxiliary agent is 75:7:10:3.Matrix resin is polystyrene.Phosphorus system compound flame retardant includes that mass ratio is the red of 2:1 Phosphorus and melamine.Processing aid includes the thio-2 acid laurel alcohol ester and fluorine-containing processing aid FX that mass ratio is 2:1 5920A.Dispersing agent is OP wax.
Step 3: removing the dispersion solvent that pretreatment fluid two contains by the way of normal pressure drying.It will pretreatment at 250 DEG C Material extruding pelletization in single screw extrusion machine, obtains conducing composite material.
Embodiment ten
The embodiment of the invention provides a kind of preparation methods of conducing composite material.The preparation method of the conducing composite material Include:
Step 1: micro-nano conductive material, flow ability modifying agent, surface modifier are dispersed in dispersion solvent, and at 35 DEG C Ultrasonic vibration 12h obtains mixed solution.Dispersion solvent is the dimethylbenzene and ethyl alcohol that mass ratio is 2:1.Micro-nano conductive material, stream The mass ratio 5:4:2 of dynamic modifying agent, surface modifier.Micro-nano conductive material includes that mass ratio is the carbon black of 0.6:3:2, carbon nanometer Stick and graphene (trade mark ENN-HEC-2L, Xin Ao graphene Technology Co., Ltd.).Flow ability modifying agent is dimethicone, surface Modifying agent includes the titanate coupling agent TMC-130 and aluminate coupling agent LS-821 that mass ratio is 2:1.
Step 2: matrix resin, phosphorus system compound flame retardant, dispersing agent, processing aid are uniformly mixed, mixture is obtained. 20min is mixed in mixture and pretreatment fluid one at 50 DEG C, obtains pretreatment fluid two.Matrix resin, fire retardant and processing The mass ratio of auxiliary agent is 68:9:10:3.Matrix resin includes parylene's glycol ester that mass ratio is 1:1.Phosphorus system is multiple It include red phosphorus, silica, the aluminium hydroxide that mass ratio is 2:0.5:1 with fire retardant.Processing aid includes that mass ratio is 2；1 Antioxidant 618 and thermoplastic acrylic resin.Dispersing agent is paraffin.
Step 3: removing the dispersion solvent that pretreatment fluid two contains by the way of normal pressure drying.It will pretreatment at 270 DEG C Material extruding pelletization in single screw extrusion machine, obtains conducing composite material.
Comparative example one
The embodiment of the invention provides a kind of preparation methods of conducing composite material.The preparation method of the conducing composite material Include:
It is mixed step 1: carbon black, flow ability modifying agent, matrix resin are put into high mixer with the mixing velocity side of 50r/min Material side is warming up to 120 DEG C, in 120 DEG C of mixing 60s, obtains conductive filler.Flow ability modifying agent is paraffin oil, and matrix resin is highly dense Spend polyethylene.The mass ratio of carbon black, flow ability modifying agent and matrix resin is 1.5:2:84.
Step 2: addition dispersing agent and surfactant continues to mix 180s into high mixer, dispersing agent melts at this time；So Red phosphorus and processing aid is added thereto afterwards and stirring 120s is continuesd to mix with the revolving speed of 450r/min, obtains conducing composite material Semi-finished product.Carbon black, dispersing agent, surfactant, red phosphorus and processing aid mass ratio be 1.5:2:1.5:8:1.5.Wherein, divide Powder is ethylene waxes, and surfactant is the complex compound of methacrylate-chromic chloride, processing aid 2,8- di-t-butyl -4- first Base phenol.
Step 3: mixed material is placed in convertible mixer, under the revolving speed of 300r/min, melted in 180 DEG C 5min is mixed, is directly placed into single screw extrusion machine after mixing in 180 DEG C of extruding pelletizations, conducing composite material can be obtained.
Comparative example two
This comparative example provides a kind of preparation method of conducing composite material.The preparation method packet of the conducing composite material It includes:
It is mixed step 1: carbon black, flow ability modifying agent, matrix resin are put into high mixer with the mixing velocity side of 150r/min Material side is warming up to 180 DEG C, in 180 DEG C of mixing 20s, obtains conductive filler.Matrix resin includes that mass ratio is the linear low close of 3:1 Spend polyethylene and ultra-high molecular weight polyethylene.Flow ability modifying agent includes the paraffin oil and dimethicone that mass ratio is 1:1.Micro-nano The mass ratio of conductive material, flow ability modifying agent and matrix resin is 5:3:76.6.
Step 2: addition dispersing agent and surfactant continues to mix 120s into high mixer, dispersing agent melts at this time；So Ammonium polyphosphate and processing aid is added thereto afterwards and stirring 200s is continuesd to mix with the revolving speed of 400r/min, obtains conductive compound Material semi-finished product.Carbon black, dispersing agent, surfactant, ammonium polyphosphate and processing aid mass ratio be 5:3:2.4:9:1.Its In, dispersing agent is OP wax, and surfactant includes that the aluminate coupling agent LS-62 that mass ratio is 1:3 and dimerization di(2-ethylhexyl)phosphate are different pungent Ester magnesium stearate, processing aid are fluorine-containing processing aid FX 5911.
Step 3: mixed material is placed in convertible mixer, under the revolving speed of 450r/min, melted in 250 DEG C 3min is mixed, is directly placed into single screw extrusion machine after mixing in 250 DEG C of extruding pelletizations, obtains conducing composite material.
It is right in order to verify the mechanical property and flame retardant property of conducing composite material prepared by above-described embodiment and comparative example Conducing composite material is tested as follows:
By conducing composite material with the mold tabletting with a thickness of 2mm and 4mm, the equipment that tabletting uses is hydraulic press, pressure Power is greater than 15MPa, and the time is greater than 20min, and the sample of extrusion is used for the standard jig of testing conductive and anti-flammability.Wherein, it uses The impact batten standard module and tensile bars standard module of national standard, which extrude, stretches and impacts batten；Alternatively, directly poly- Ethylene PP Pipe Compound is put into injection molding machine, is molded by the stretching to comply with the national standard requirements and impact batten with standard injection mold tool.
Testing standard is as follows:
Tensile strength testing standard: the test of GB/T 1040.3-2006 plastic tensile performance.
Impact strength testing standard: GB/T 13525-1992 plastic tensile impact property test method.
Sheet resistance testing standard: the measurement of SFS-EN ISO 3915-1999 plastics conductive plastic resistance.
Oxidation induction time and temperature test standard: (ISO 3915:1981) EN ISO 11357-6-2013 plastics-poor Show scanning-the 6 part calorimetric (DSC): the measurement (isothermal OIT) of oxidation induction time and oxidation induction temperature (dynamic OIT) (ISO 11357-6:2008).
The mechanical property and flame test result of 1 conducing composite material of table
As can be seen from Table 1: relatively existing conducing composite material, conducing composite material prepared by the embodiment of the present invention exist Oxidation induction time is long, conductivity is relatively good, and has preferable elongation at break and impact strength, so that same Under the premise of the conductive agent of additive amount, fire retardant, there is better mechanical property and flame retardant property.
Specifically, micro-nano conductive material and comparative example one that conducing composite material prepared by the embodiment of the present invention four contains The ratio for the carbon black that prepared conducing composite material contains is consistent, the tool of conducing composite material prepared by the embodiment of the present invention four There is better electric conductivity.The phosphorus system compound flame retardant and comparative example that conducing composite material prepared by the embodiment of the present invention six contains It is provided in an embodiment of the present invention conductive multiple under flame retardant agent content unanimous circumstances contained by conducing composite material prepared by two Condensation material has better anti-flammability.Based on this, if in the case where same conductivity, conduction provided in an embodiment of the present invention Composite material can reach existing conducing composite material in carbon black in the case where micro-nano conductive material and less fire retardant additive amount With mechanical property and flame retardant property of the fire retardant additive amount in the case where relatively high, carbon black in the prior art and fire retardant are alleviated In the case that additive amount is relatively high, conducing composite material poor in processability, bad dispersibility, the high problem of carbon deposition rate.
It should be noted that raw material kind used in the preparation method of conducing composite material provided in an embodiment of the present invention Class can adjust according to the actual situation, and above-described embodiment four to embodiment ten, which is only exemplary, to be listed several, not represent this Other components disclosed in inventive embodiments one, embodiment two are not available.
In addition, graphene involved in the embodiment of the present invention four to embodiment ten, carbon nanotube meet: the length of carbon nanotube Diameter ratio is greater than 1000, and the diameter of carbon nanotube is 2nm-30nm, and the powder conductivity rate of carbon nanotube is greater than or equal to 3000S/ m.The lamella of graphene is 2 layers -10 layers, and the maximum single layer radical length of graphene is 20 μm, the powder conductivity rate of graphene 102S/m-106S/m.On this basis, the mechanical property and resistance of conducing composite material prepared by example IV to embodiment ten Combustion performance test meets content shown in table 1.
In the description of above embodiment, particular features, structures, materials, or characteristics can be at any one or more It can be combined in any suitable manner in a embodiment or example.
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, can easily think of the change or the replacement, and should all contain Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.

Claims (19)

1. a kind of conductive additive, which is characterized in that include at least micro-nano hydridization conductive material, the micro-nano conductive material includes Zero dimension conductive material, one-dimensional electric material and two-dimentional conductive material.
2. conductive additive according to claim 1, which is characterized in that the zero dimension conductive material includes carbon black, carbon original At least one of sub- cluster, the one-dimensional electric material include at least one of nano wire, nanometer rods, nanotube, and described two Tieing up conductive material includes graphene.
3. conductive additive according to claim 1, which is characterized in that the one-dimensional electric material is carbon nanotube；Institute The major diameter ratio for stating carbon nanotube is greater than 1000, and the diameter of the carbon nanotube is 2nm-30nm, the powder of the carbon nanotube Conductivity is greater than or equal to 3000S/m；And/or
The two dimension conductive material is graphene, and the lamella of the graphene is 2 layers -10 layers, the maximum single layer of the graphene Radical length is 20 μm, the powder conductivity rate 10 of the graphene2S/m-106S/m。
4. conductive additive according to claim 1, which is characterized in that the zero dimension conductive material, the one-dimensional electric The mass ratio of material and the two-dimentional conductive material is (0.1-1): (0.1-6): (0.1-5).
5. conductive additive according to any one of claims 1 to 4, which is characterized in that the conductive additive further includes Fire retardant.
6. conductive additive according to claim 5, which is characterized in that the fire retardant includes phosphorus flame retardant and non-phosphorus Flame retardant.
7. conductive additive according to claim 6, which is characterized in that the phosphorus flame retardant includes ammonium polyphosphate, gathers At least one of phosphate, red phosphorus, ammonium phosphate；And/or
The non-phosphorus flame retardant includes at least one of silicon-series five-retardant, hydroxide flame retardant, melamine.
8. conductive additive according to claim 5, which is characterized in that the conductive additive further includes dispersing agent, stream Dynamic modifying agent, surface modifier and processing aid；The micro-nano conductive material, the fire retardant, the dispersing agent, the flowing The mass ratio of modifying agent, the surface modifier and the processing aid is (1-9): (4-9): (2-10): (0.5-8): (0.1- 3): (0.1-3).
9. conductive additive according to claim 8, which is characterized in that
The dispersing agent includes at least one of polyethylene wax, paraffin, OP wax；
The flow ability modifying agent includes at least one of paraffin oil, dimethicone；
The surface modifier includes chromium complex coupling agent, silane coupling agent, titanate coupling agent, aluminate coupling agent, magnesium At least one of class coupling agent, tin class coupling agent；
The processing aid includes Hinered phenols antioxidant, alkyl polyphenol kind antioxidant, hindered amine light stabilizer, phosphite ester Kind antioxidant, thio rouge, haloflex, acrylic resin, ethylene-vinyl acetate copolymer, in fluorine-containing auxiliary agent at least It is a kind of.
10. a kind of conducing composite material, which is characterized in that add including any one of matrix resin and claim 1~9 conduction Add agent.
11. conducing composite material according to claim 10, which is characterized in that described matrix resin and micro-nano conductive material Mass ratio be (61-84): (1-9).
12. conducing composite material according to claim 10, which is characterized in that the sheet resistance of the conducing composite material It is 102Ω-105Ω, anti-flammability are V0 grades, tensile strength 16MPa-23MPa, elongation at break 450%-600%, shock resistance Intensity is 20KJ/m2-30KJ/m2, it is greater than or equal to 30min in 210 DEG C of oxidation induction times.
13. 0~12 described in any item conducing composite materials according to claim 1, which is characterized in that described matrix resin includes Low density polyethylene (LDPE), linear low density polyethylene, high density polyethylene (HDPE), ultra-high molecular weight polyethylene, polystyrene, random poly- third At least one of alkene, isotactic polypropylene, polycarbonate, parylene's glycol ester, nylon 6, nylon66 fiber.
14. a kind of preparation method of any one of claim 10~13 conducing composite material characterized by comprising
Conductive additive is dispersed in matrix resin, obtain conducing composite material, the conductive additive be claim 1~ Any one of 9 conducing composite materials.
15. the preparation method of conducing composite material according to claim 14, which is characterized in that the conductive additive is The conductive additive of claim 8 or 9, it is described that conductive additive is dispersed in matrix resin, obtain conducing composite material Include:
Micro-nano conductive material, matrix resin and flow ability modifying agent are mixed and heated to mixing temperature, obtain conductive filler；
At a temperature of the mixing, conductive filler, dispersing agent, surface modifier, fire retardant and processing aid are uniformly mixed, obtained Obtain conducing composite material semi-finished product；
The conducing composite material semi-finished product are melted, and extruding pelletization, obtains conducing composite material.
16. the preparation method of conducing composite material according to claim 15, which is characterized in that the mixing temperature is point The fusion temperature of powder, the mixing temperature are 50 DEG C -180 DEG C, and the temperature melted is 150 DEG C -270 DEG C, extruding pelletization Temperature be 150 DEG C -270 DEG C；And/or
It is described at a temperature of the mixing, the conductive filler, dispersing agent, surface modifier, fire retardant and processing aid are mixed It closes uniformly, obtaining conducing composite material semi-finished product includes:
At a temperature of the mixing, the conductive filler, dispersing agent and surface modifier are mixed, until dispersing agent fusing, obtained Obtain hybrid conductive agent；
At a temperature of the mixing, the hybrid conductive agent, fire retardant and processing aid are uniformly mixed, obtain conductive composite wood Expect semi-finished product.
17. the preparation method of conducing composite material according to claim 14, which is characterized in that the conductive additive is The conductive additive of claim 8 or 9, it is described that conductive additive is dispersed in matrix resin, obtain conducing composite material Include:
Micro-nano conductive material, flow ability modifying agent, surface modifier are dispersed in dispersion solvent, mixed solution is obtained；20 DEG C- 50 DEG C carry out ultrasonic vibration to mixed solution, and dispersing agent then is added to mixed solution, obtain pretreatment fluid one；
Matrix resin, fire retardant, dispersing agent and processing aid are uniformly mixed, mixture is obtained；
Mixture is uniformly mixed with pretreatment fluid at 40 DEG C -60 DEG C, obtains pretreatment fluid two；
The dispersion solvent that the pretreatment fluid two is contained removes, and obtains pretreatment material；
Extruding pelletization is expected into the pretreatment, obtains conducing composite material.
18. a kind of application of any one of claim 1~9 conductive additive in conducing composite material.
19. a kind of application of any one of claim 10~13 conducing composite material in conducting polymer product.
CN201910755162.9A 2019-08-15 2019-08-15 A kind of conductive additive and application, conducing composite material and its preparation method and application Pending CN110511429A (en)

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Application publication date: 20191129