CN106188614A - CNT SiO2the preparation method of composite - Google Patents

CNT SiO2the preparation method of composite Download PDF

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Publication number
CN106188614A
CN106188614A CN201610543033.XA CN201610543033A CN106188614A CN 106188614 A CN106188614 A CN 106188614A CN 201610543033 A CN201610543033 A CN 201610543033A CN 106188614 A CN106188614 A CN 106188614A
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sio
cnt
composite
preparation
carbon source
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CN106188614B (en
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赵海静
李红
董明
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Sayfo (Xuzhou) Co., nano science and technology
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Suzhou Saifu Debei Trade Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention belongs to field of material technology, the invention discloses a kind of CNT SiO2The preparation method of composite, it comprises the steps: carbon source, organosilicon source, catalyst are mixed into liquid according to a certain ratio, is added by liquid in high-temperature nuclei stove and carry out high-temperature gasification pyrolysis, grow into CNT SiO2 composite under protective atmosphere.Present invention achieves SiO2Form the most compound of nanoscale with CNT, make new material have SiO concurrently2With the advantage of carbon nano-tube material, improve SiO2With rubber sympathy, it is achieved that CNT and SiO2And be used in rubber and be uniformly distributed.

Description

CNT-SiO2The preparation method of composite
Technical field
The invention belongs to field of material technology, be specifically related to CNT-SiO2The synthetic method of composite.
Background technology
Along with the reinforcement of environmental consciousness, " the green that resistance to rolling is little, anti-slippery good, oil consumption is low in preparation, waste gas discharge is few Tire " increasingly it is subject to people's attention.Green tire formula can utilize SiO2Alternative carbon black improves the anti-slippery of tire Can, reduce resistance to rolling.SiO2Non-conductive, weak heat-dissipating, causes the conduction of tire to reduce with heat conductivity；SiO2Blind date with rubber Property poor, need the consumption carrying out processing or increase coupling agent before using, thus cause long processing time, energy consumption big, thus impact wheel The bulk strength of tire and serviceability.
CNT has the heat conduction of excellence, conduction, machinery enhancing performance, with SiO2It is used in conjunction with, SiO can be made up2Self Deficiency in terms of conduction, heat conduction.But, CNT and SiO2Particle diameter is little, surface can greatly, easily reunite, it is difficult in rubber-based Body is formed and is uniformly distributed, become the stress concentration point in material, reduce intensity and the serviceability of material.Improve SiO2With rubber The sympathy of glue, realize CNT and SiO2And be used in rubber and be uniformly distributed, it is key and the difficult point improving tyre performance. To this end, the present invention comes therefrom.
Summary of the invention
The present invention solves above-mentioned technical problem, it is provided that a kind of CNT-SiO2The synthetic method of composite, both SiO can be improved2With the sympathy of rubber, also solve the problem that CNT and SiO2And it is used in difficult equally distributed problem in rubber, To the CNT-SiO that is uniformly combined of nanoscale2Material, improves bulk strength and the serviceability of tire.
A first aspect of the present invention provides a kind of CNT-SiO2The synthetic method of composite, it includes walking as follows Rapid:
(1) carbon source, organosilicon source, catalyst are the most uniformly mixed,
(2) aforementioned mixed uniformly raw material addition high-temperature nuclei stove will carry out high-temperature gasification pyrolysis under protective atmosphere, Grow into CNT-SiO2Composite.
Preferably technical scheme, described carbon source is organic carbon source, and its molecular formula is CxHyOz, wherein 20 >=x >=1, y >=0, z >=0, include but not limited to methanol, ethanol, benzene.
Preferably technical scheme, organosilicon source molecular formula is mSiO2NC pH, wherein 10 >=m >=1,20 >=n ＞ 0, p ＞ 0, including positive silicate class, silanol.
Preferably technical scheme, described catalyst is selected from ferrocene, nickel acetylacetonate, cobalt naphthenate, cobaltous octadecanate, diformazan One or more in base sulfoxide, diphenyl sulfide, thiophene.
Preferably technical scheme, in described raw material, the mol ratio of C Yu Si is 1:1-100, preferably 1:10-50.
Preferably technical scheme, the SiO in the composite obtained2Diameter at 50-100nm, and surface length has carbon to receive Mitron.
Preferably technical scheme, obtains the CNT in composite and includes two kinds: a. and SiO2Symbiosis CNT Diameter at 20-100nm, length is in 1-30 μm；B. SiO it is grown in2The diameter of surface carbon nanotube exists in 5-30nm, length 10-1000nm。
A second aspect of the present invention provides a kind of CNT-SiO2 composite, and it prepares by the following method: (1) carbon source, organosilicon source, catalyst are the most uniformly mixed,
(2) aforementioned mixed uniformly raw material addition high-temperature nuclei stove will carry out high-temperature gasification pyrolysis under protective atmosphere, Grow into CNT-SiO2 composite.
A third aspect of the present invention provides aforesaid CNT-SiO2Composite is for manufacturing the use of rubber tyre On the way.
The present invention provides a kind of CNT-SiO2The synthetic method of composite:
1) by carbon source (CxHyOz), wherein 20 >=x >=1, y >=0, z >=0, organosilicon source (mSiO2NC pH), 10 >=m >=1,20 >=n ＞ 0, the raw material such as p ＞ 0, catalyst adds in high temperature (700-1400 DEG C) synthetic furnace according to a certain ratio；
2) organosilicon source and carbon source generate free carbon, hydrogen and SiO in high temperature action gasified, pyrolysis2Nano-particle；Urge Agent pyrolysis, reduction generate metal simple-substance and S simple substance；
3) partial catalyst metal simple-substance is deposited on SiO2Particle surface, it is formed in situ CNT；Partial catalyst gold Belong to simple substance to be individually present, generate alone CNT；
4) in synthetic furnace, each material is fluidized state, forms the SiO that Si/C ratio is controlled2Equal with carbon nanotube yardstick The composite of even mixing.
Present invention achieves SiO2Form the most compound of nanoscale with CNT, make new material have SiO concurrently2With carbon The advantage of nano-tube material, improves SiO2With rubber sympathy, it is achieved that CNT and SiO2And be used in rubber and uniformly divide Cloth, thus improve the overall mechanical property of tire, conduction and heat dispersion, wet-sliding resistant performance, reduce tire drag.
Compared with prior art, the method have the advantages that: 1) present invention firstly provides, utilize high temperature pyrolytic cracking (HTP) direct growth to receive CNT-the SiO that metrical scale is uniformly combined2Material；2) product has SiO concurrently2Advantage with carbon nano-tube material；3) in product SiO2It is that nanoscale uniformly mixes with CNT.
Accompanying drawing explanation
Fig. 1 is the SEM photograph of the CNT low amplification of-SiO2 composite that the embodiment of the present invention 1 prepares.
Fig. 2 is the SEM photograph of the CNT-SiO2 composite high-amplification-factor that the embodiment of the present invention 1 prepares.
Fig. 3 is that CNT-SiO2 composite scattered SEM in NBR that the embodiment of the present invention 1 prepares shines Sheet.
Detailed description of the invention
Below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiments are for illustrating The present invention and be not limited to limit the scope of the present invention.The implementation condition used in embodiment can be done according to the condition of concrete producer Adjusting further, not marked implementation condition is usually the condition in normal experiment.
Embodiment 1
Ethanol the most in molar ratio: tetraethyl orthosilicate: ferrocene: thiophene=50:200:2:1 is by raw material mix homogeneously, shape Become mixing liquid A, stand-by；
2. synthetic furnace is warming up to 1050 DEG C, under protective atmosphere, carries mixing liquid A with effusion meter in synthetic furnace, its In, the transporting velocity of mixing liquid A is 100mL/min, and mixing liquid A forms CNT-SiO after pyrolytic is polymerized2 Composite.
Utilize the scanning electron microscope CNT-SiO to preparation2Composite is analyzed, and obtains SEM photograph, As shown in Figure 1 and Figure 2.Spherical SiO as seen from Figure 12Dispersed with CNT.Spherical SiO2Diameter at 50-100nm Between, with SiO2The diameter of the CNT of symbiosis at about 80nm, a length of 5～20 μm.Fig. 2 is Fig. 1 partial enlargement photo, spherical Material is SiO2, SiO2Surface length has CNT, SiO2Surface carbon tube diameters is longer than 100nm in about 10nm, length.
By CNT-SiO2Composite joins in NBR, and its distribution photo in NBR is as shown in Figure 3.Carbon is received Mitron and SiO2It is uniformly dispersed in NBR.Mechanics Performance Testing finds, uses CNT-SiO2 composite in NBR Breaking strength reaches 36MPa, than directly use CNT and SiO2Time (breaking strength is 29MPa) improve 20%.
Embodiment 2
Butyl silicate the most in molar ratio: ferrocene: thiophene=100:2:1, by raw material mix homogeneously, forms mixed liquor Body B, stand-by；
2. synthetic furnace is warming up to 900 DEG C, under protective atmosphere, carries mixing liquid B with effusion meter in synthetic furnace, its In, the transporting velocity of mixing liquid B is 60mL/min, and mixing liquid A forms CNT-SiO after pyrolytic is polymerized2Multiple Condensation material.
Examples detailed above, only for technology design and the feature of the explanation present invention, its object is to allow the person skilled in the art be Will appreciate that present disclosure and implement according to this, can not limit the scope of the invention with this.All according to present invention essence God's equivalent transformation of being done of essence or modification, all should contain within protection scope of the present invention.

Claims (9)

1. a CNT-SiO2The preparation method of composite, it comprises the steps:
(1) carbon source, organosilicon source, catalyst are the most uniformly mixed,
(2) aforementioned mixed uniformly raw material addition high-temperature nuclei stove will carry out high-temperature gasification pyrolysis under protective atmosphere, growth Become CNT-SiO2Composite.
Preparation method the most according to claim 1, it is characterised in that described carbon source is organic carbon source, its molecular formula is CxHyOz, Wherein 20 >=x >=1, y >=0, z >=0.
Preparation method the most according to claim 1, it is characterised in that described organosilicon source molecular formula is mSiO2NC pH, its In 10 >=m >=1,20 >=n ＞ 0, p ＞ 0.
Preparation method the most according to claim 1, it is characterised in that described catalyst is selected from ferrocene, nickel acetylacetonate, cycloalkanes One or more in acid cobalt, cobaltous octadecanate, dimethyl sulfoxide, diphenyl sulfide, thiophene.
Preparation method the most according to claim 1, it is characterised in that in described raw material, the mol ratio of C Yu Si is 1:1-100.
Preparation method the most according to claim 1, it is characterised in that the CNT-SiO obtained2SiO in composite2's Diameter is at 50-100nm, and surface length has CNT.
Preparation method the most according to claim 1, it is characterised in that obtain the CNT in composite and include two kinds: a. With SiO2The diameter of symbiosis CNT is at 20-100nm, and length is in 1-30 μm；B. SiO it is grown in2The diameter of surface carbon nanotube At 5-30nm, length is at 10-1000nm.
8. a CNT-SiO2Composite, it is characterised in that it prepares by the following method:
(1) carbon source, organosilicon source, catalyst are the most uniformly mixed,
(2) aforementioned mixed uniformly raw material addition high-temperature nuclei stove will carry out high-temperature gasification pyrolysis under protective atmosphere, growth Become CNT-SiO2Composite.
9. CNT-SiO as claimed in claim 82Composite is used for manufacturing rubber tyre.
CN201610543033.XA 2016-07-12 2016-07-12 CNT SiO2The preparation method of composite Active CN106188614B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114906826A (en) * 2022-05-10 2022-08-16 广东工业大学 In-situ synthesis method of nano AlN and carbon nano tube composite material, synthesized composite material and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020025374A1 (en) * 2000-08-23 2002-02-28 Lee Yun Hi Parallel and selective growth method of carbon nanotube on the substrates for electronic-spintronic device applications
CN101525135A (en) * 2009-04-10 2009-09-09 山东大学 Method for inducing and synthesizing carborundum or carborundum nano tube by low-temperature auxiliary reaction
CN102101919A (en) * 2009-12-21 2011-06-22 固特异轮胎和橡胶公司 Tire with a component containing carbon nanotubes
CN102881872A (en) * 2012-09-11 2013-01-16 天津大学 Method for synthesizing silicon oxide/carbon nanotube membranous lithium ion battery anode material by one step by utilizing chemical vapor deposition method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020025374A1 (en) * 2000-08-23 2002-02-28 Lee Yun Hi Parallel and selective growth method of carbon nanotube on the substrates for electronic-spintronic device applications
CN101525135A (en) * 2009-04-10 2009-09-09 山东大学 Method for inducing and synthesizing carborundum or carborundum nano tube by low-temperature auxiliary reaction
CN102101919A (en) * 2009-12-21 2011-06-22 固特异轮胎和橡胶公司 Tire with a component containing carbon nanotubes
CN102881872A (en) * 2012-09-11 2013-01-16 天津大学 Method for synthesizing silicon oxide/carbon nanotube membranous lithium ion battery anode material by one step by utilizing chemical vapor deposition method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114906826A (en) * 2022-05-10 2022-08-16 广东工业大学 In-situ synthesis method of nano AlN and carbon nano tube composite material, synthesized composite material and application

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