CN106188614B - CNT SiO2The preparation method of composite - Google Patents

CNT SiO2The preparation method of composite Download PDF

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Publication number
CN106188614B
CN106188614B CN201610543033.XA CN201610543033A CN106188614B CN 106188614 B CN106188614 B CN 106188614B CN 201610543033 A CN201610543033 A CN 201610543033A CN 106188614 B CN106188614 B CN 106188614B
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cnt
sio
composite
rubber
diameter
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CN106188614A (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, and the invention discloses a kind of CNT SiO2The preparation method of composite, it comprises the following steps：Carbon source, organic silicon source, catalyst are mixed into liquid according to a certain ratio, liquid is added under protective atmosphere high-temperature gasification pyrolysis is carried out in high―temperature nuclei stove, grow into CNT SiO2 composites.The present invention realizes SiO2The uniform compound of nanoscale is formed with CNT, new material is had SiO concurrently2The advantages of with carbon nano-tube material, improve SiO2With rubber sympathy, CNT and SiO are realized2And it is uniformly distributed in rubber.

Description

CNT-SiO2The preparation method of composite
Technical field
The invention belongs to field of material technology, and in particular to CNT-SiO2The synthetic method of composite.
Background technology
With the reinforcement of environmental consciousness, " the green that rolling resistance is small, anti-slippery is good, oil consumption is low, waste gas discharge is few is prepared Tire " is increasingly valued by people.SiO can be utilized in green tire formula2Alternative carbon black improves the anti-slippery of tire Can, reduce rolling resistance.SiO2Non-conductive, weak heat-dissipating, the conduction and thermal conductivity for causing tire reduce；SiO2With the blind date of rubber Property it is poor, need to be handled or increased the dosage of coupling agent before use, so as to cause long processing time, energy consumption big, thus influence wheel The bulk strength and performance of tire.
CNT has excellent heat conduction, conduction, machinery enhancing performance, with SiO2It is used in conjunction with, SiO can be made up2Itself Deficiency in terms of conductive, heat conduction.But CNT and SiO2Particle diameter is small, surface energy is big, easily reunites, it is difficult in rubber-based Formed and be uniformly distributed in body, turned into the stress concentration point in material, reduce the intensity and performance of material.Improve SiO2With rubber The sympathy of glue, realize CNT and SiO2And be uniformly distributed in rubber, it is the key and difficult point for improving tyre performance. Therefore, the present invention comes therefrom.
The content of the invention
The present invention is in order to solve the above technical problems, provide a kind of CNT-SiO2The synthetic method of composite, both SiO can be improved2With the sympathy of rubber, CNT and SiO are also solved the problem that2And the problem of difficulty is uniformly distributed in rubber is used in, obtain The uniform compound CNT-SiO of nanoscale arrived2Material, improve the bulk strength and performance of tire.
The first aspect of the present invention provides a kind of CNT-SiO2The synthetic method of composite, it includes following step Suddenly：
(1) carbon source, organic silicon source, catalyst are uniformly mixed according to a certain ratio,
(2) foregoing mixed uniformly raw material is added under protective atmosphere and high-temperature gasification pyrolysis is carried out in high―temperature nuclei stove, Grow into CNT-SiO2Composite.
Preferable technical scheme, the carbon source are organic carbon source, and its molecular formula is CxHyOz, wherein 20 >=x >=1, y >=0, z >=0, including but not limited to methanol, ethanol, benzene.
Preferable technical scheme, organic silicon source molecular formula are mSiO2NCpH, wherein 10 >=m >=1,20 >=n ＞ 0, p ＞ 0, including positive silicate class, silanol.
Preferable technical scheme, the catalyst are selected from ferrocene, nickel acetylacetonate, cobalt naphthenate, cobaltous octadecanate, diformazan One or more in base sulfoxide, diphenyl sulfide, thiophene.
Preferable technical scheme, C and Si mol ratio is 1 in the raw material：1-100, preferably 1:10-50.
Preferable technical scheme, the SiO in obtained composite2Diameter in 50-100nm, and surface is received with carbon Mitron.
Preferable technical scheme, the CNT obtained in composite include two kinds：A. with SiO2Symbiosis CNT Diameter in 20-100nm, length is at 1-30 μm；B. it is grown in SiO2The diameter of surface CNT exists in 5-30nm, length 10-1000nm。
The second aspect of the present invention provides a kind of CNT-SiO2 composites, and it is prepared by the following method： (1) carbon source, organic silicon source, catalyst are uniformly mixed according to a certain ratio,
(2) foregoing mixed uniformly raw material is added under protective atmosphere and high-temperature gasification pyrolysis is carried out in high―temperature nuclei stove, Grow into CNT-SiO2 composites.
The third aspect of the present invention provides foregoing CNT-SiO2Composite is used for the use for manufacturing 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, organic silicon source (mSiO2NCpH), 10 >=m >=1,20 >=n ＞ 0, the raw material such as p ＞ 0, catalyst add in high temperature (700-1400 DEG C) synthetic furnace according to a certain ratio；
2) organic silicon source and carbon source gasify under high temperature action, are pyrolyzed generation free carbon, hydrogen and SiO2Nano particle；Urge Agent pyrolysis, reduction generation 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 Category simple substance is individually present, and generates CNT alone；
4) each material is in fluidized state in synthetic furnace, forms the controllable SiO of Si/C ratios2It is equal with carbon nanotube yardstick The composite of even mixing.
The present invention realizes SiO2The uniform compound of nanoscale is formed with CNT, new material is had SiO concurrently2With carbon The advantages of nano-tube material, improve SiO2With rubber sympathy, CNT and SiO are realized2And uniformly divide in rubber Cloth, so as to improve the overall mechanical properties of tire, conductive 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 received using high temperature pyrolytic cracking (HTP) direct growth The uniform compound CNT-SiO of metrical scale2Material；2) product has SiO concurrently2The advantages of with carbon nano-tube material；3) in product SiO2It is that nanoscale uniformly mixes with CNT.
Brief description of the drawings
Fig. 1 is the SEM photograph for the low multiplication factor of CNT-SiO2 composites that the embodiment of the present invention 1 is prepared.
Fig. 2 is the SEM photograph for the CNT-SiO2 composite high-amplification-factors that the embodiment of the present invention 1 is prepared.
Fig. 3 is that the SEM that the CNT-SiO2 composites that the embodiment of the present invention 1 is prepared disperse in NBR shines Piece.
Embodiment
Such scheme is described further below in conjunction with specific embodiment.It should be understood that these embodiments are to be used to illustrate 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 specific producer Further adjustment, unreceipted implementation condition is usually the condition in normal experiment.
Embodiment 1
1. ethanol in molar ratio：Tetraethyl orthosilicate：Ferrocene：Thiophene=50:200:2:1 is well mixed raw material, shape It is stand-by into mixing liquid A；
2. synthetic furnace is warming up to 1050 DEG C, under protective atmosphere, mixing liquid A is conveyed into synthetic furnace with flowmeter, its In, mixing liquid A transporting velocity is 100mL/min, and mixing liquid A forms CNT-SiO after pyrolytic polymerize2 Composite.
CNT-SiO using SEM to preparation2Composite is analyzed, and obtains SEM photograph, As shown in Figure 1 and Figure 2.Spherical SiO as seen from Figure 12It is dispersed with CNT.Spherical SiO2Diameter in 50-100nm Between, with SiO2For the CNT of symbiosis diameter in 80nm or so, length is 5~20 μm.Fig. 2 is Fig. 1 partial enlargement photos, spherical Material is SiO2, SiO2Surface is with CNT, SiO2Surface carbon nanotube diameter is longer than 100nm in 10nm or so, length.
By CNT-SiO2Composite is added 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 is found, CNT-SiO2 composites are used in NBR Breaking strength reaches 36MPa, than directly using CNT and SiO2When (breaking strength 29MPa) improve 20%.
Embodiment 2
1. butyl silicate in molar ratio：Ferrocene：Thiophene=100:2:1 is well mixed raw material, forms mixed liquor Body B, it is stand-by；
2. synthetic furnace is warming up to 900 DEG C, under protective atmosphere, mixing liquid B is conveyed into synthetic furnace with flowmeter, its In, mixing liquid B transporting velocity is 60mL/min, and mixing liquid A forms CNT-SiO after pyrolytic polymerize2It is multiple Condensation material.
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow the person skilled in the art to be Present disclosure can be understood and implemented according to this, it is not intended to limit the scope of the present invention.It is all smart according to the present invention The equivalent transformation or modification that refreshing essence is done, should all be included within the scope of the present invention.

Claims (4)

  1. A kind of 1. CNT-SiO2The synthetic method of composite, it comprises the following steps：
    (1) ethanol in molar ratio：Tetraethyl orthosilicate：Ferrocene：Thiophene=50:200:2:1 is well mixed raw material, is formed mixed Liquid A is closed, it is stand-by；
    (2) synthetic furnace is warming up to 1050 DEG C, and under protective atmosphere, mixing liquid A is conveyed into synthetic furnace with flowmeter, wherein, Mixing liquid A transporting velocity is 100mL/min, and mixing liquid A forms CNT-SiO after pyrolytic polymerize2It is compound Material.
  2. 2. synthetic method according to claim 1, it is characterised in that obtained CNT-SiO2SiO in composite2's Diameter is in 50-100nm, and surface is with CNT.
  3. 3. synthetic method according to claim 1, it is characterised in that the CNT obtained in composite includes two kinds：a. With SiO2The diameter of symbiosis CNT is in 20-100nm, and length is at 1-30 μm；B. it is grown in SiO2The diameter of surface CNT In 5-30nm, length is in 10-1000nm.
  4. 4. CNT-the SiO that the method as described in claim 1 is prepared2Composite is used to manufacture rubber tyre.
CN201610543033.XA 2016-07-12 2016-07-12 CNT SiO2The preparation method of composite Active CN106188614B (en)

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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

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Address after: 221000 South Side of No.4 Road, Yangtun Town Industrial Park, Peixian County, Xuzhou City, Jiangsu Province

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Patentee before: SUZHOU SAIFU DEBEI TRADE CO., LTD.