CN104387671A - Preparation method of PA6 (polyamide 6)/PP (polypropylene)/carbon nano tube high-performance nano composite material - Google Patents
Preparation method of PA6 (polyamide 6)/PP (polypropylene)/carbon nano tube high-performance nano composite material Download PDFInfo
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- CN104387671A CN104387671A CN201410750672.4A CN201410750672A CN104387671A CN 104387671 A CN104387671 A CN 104387671A CN 201410750672 A CN201410750672 A CN 201410750672A CN 104387671 A CN104387671 A CN 104387671A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention provides a preparation method of a PA6 (polyamide 6)/PP (polypropylene)/carbon nano tube high-performance nano composite material. The preparation method comprises the following steps: firstly, coating the surface of a carbon nano tube with a layer of silicon oxide by virtue of a sol-gel method; then, performing surface treatment on a coated carbon nano tube by using a silane coupling agent, and then preparing the PA6/PP/carbon nano tube high-performance nano composite material by adopting a melt blending method. According to the experiments, a 3-amino propyl triethoxy silane (KH-550) surface treatment carbon nano tube can be used for effectively improving the dispersion of the carbon nano tube in PA6/PP matrix and increasing the interface bonding between the carbon nano tube and the PA6/PP base body. By adding the carbon nano tube as a reinforcer of the PA6/PP polymer, the mechanical performance of the polymer can be obviously improved.
Description
Technical field
The invention belongs to chemical industry field of compound material, be specifically related to a kind of preparation method of polyamide 6/polypropylene/carbon nanotube High performance nanometer composite material.
Background technology
Since carbon nanotube (CNTs) is found, just cause the great interest of people.CNTs has excellent mechanical property, excellent chemical stability and thermostability, the characteristics such as good electrical property and microwave absorbing, and there is nano effect specific to unique one dimension Nano structure, become the reinforcement that polymer materials is desirable, and can give polymer materials many new functions.But the surface energy of CNTs is higher, easily reunites, it is made to be difficult to realize even tiny dispersion in polymeric matrix.CNTs must will combine closely with polymeric matrix as strongthener, and stress so just can be made effectively to be delivered on CNTs.How dispersed CNTs the interface cohesion strengthened between CNTs and polymeric matrix is current urgent problem.Coupling agent is a kind of a kind of auxiliary agent that two kinds of materials of different nature can be combined by chemistry or physical action, is widely used in the composite.The close inorganic group of coupling agent is combined with filling surface, and close organic group and macromolecule matrix tangle or react, thus play the effect of molecular bridge.The mineral filler utilizing this distinctive molecular bridge performance that surface properties can be made to differ greatly is compatible with macromolecular material, thus greatly improves the physicals of matrix material, electrical property, thermal characteristics and optical property etc.Organo silane coupling agent strengthens widely used coupling agent in polymer composites at filler, can be used as surface treatment agent or the tackifier of various filler.The scholars such as Vast L have reported about method (the Vast L by silane coupling agent process carbon nano tube surface, Philippin G, Destree A, Moreau N, Fonseca A, Nagy J B, Delhalle J, Mekhalif Z. Chemical functionalization by a fluorinated trichlorosilane of multi-walled carbon nanotubes. Nanotechnology, 2004, 15, 781-785.), but these methods all need first to introduce hydroxyl by chemical oxidation treatment in carbon nano tube surface, therefore can the structure of destroying carbon nanometer tube, thus have impact on the excellent performance of carbon nanotube.Polypropylene is a kind of widely used large kind general-purpose plastics, has superior tensile performance and has outstanding stress cracking resistance and wear resistance, but also there is large, the fragile under low temperature shortcoming such as to split of molding shrinkage.Polyamide 6 is a kind of strong polarity, has the crystalline polymer of certain reactive behavior, has the characteristics such as excellent shock resistance, tension, wear-resisting and self lubricity.But water-absorbent is large, dimensional stability is deteriorated, and makes it apply and is restricted.If but by blended for PP and the PA6 shortcoming overcoming single polymers.Because carbon nanotube specific surface is large, make a concerted effort strong with polymer scale, carbon nanotube is joined the research in single polymers by many bibliographical informations, and that for polymkeric substance, research is more is PP, PA6.Developed in recent years and adopted carbon nano-tube modification PA6/PP blend, comprehensively blending and modifying and nano combined advantage can prepare high-performance PA6/PP based nano composite material thus.
The melt-blending process such as Lan Hao has prepared PP/PPR/PA6 matrix material, atactic copolymerized polypropene (PPR), polyamide 6 (PA6) and the expanding material impact (Lan Hao on PP/PPR/PA6 composite materials property and fatigue performance is have studied by mechanical property, fatigue property test and scanning electronic microscope (SEM), Wang Baoxu, Yin Yunshan, Qin Lijie. strengthen the Study and appliance of PP/PPR/PA6 matrix material. plastics science and technology, 2014,03,42,70-76.).Haiyan Ma etc. has prepared PP/PA6/PP-g-PAH matrix material (Haiyan Ma, Zhaofeng Liu, Jun Zhang, Haijun Ma. Polypropylene/polyamide 6/polypropylene-g-maleic anhydride blending monofilaments:effects of quench temperature. Journal of Polymer Research, 2011,06,18,1941-1946.).
Summary of the invention
The object of the invention is the preparation method proposing a kind of polyamide 6/polypropylene/carbon nanotube High performance nanometer composite material, by adding the reinforcement of carbon nanotube as PA6/PP polymkeric substance, the mechanical property of polymkeric substance can be significantly improved.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of PA6/PP/ carbon nanotube High performance nanometer composite material, comprises the following steps:
1) carbon nanotube of tensio-active agent process is first obtained with Sodium dodecylbenzene sulfonate process carbon nanotube, obtain tetraethoxy and silicon oxide coated carbon nanotube mixed solution by sol-gel method at carbon nano tube surface coated one deck silicon oxide with tetraethoxy again, mixed solution through hydrolysis, concentrated after obtain the coated carbon nanotube of pure silicon oxide;
2) obtain mixed solution after surface treatment being carried out to silicon oxide enveloped carbon nanometer tube obtained in step 1) with silane resin acceptor kh-550, after washing, drying, grinding, obtain the carbon nanotube (f-CNTs) of silane coupling agent process;
3) first by polypropylene (PP), polyamide 6 (PA6), polypropylene grafted maleic anhydride (PP-g-MAH) and step 2) in the carbon nanotube of obtained silane coupling agent process to be placed in vacuum drying oven dry, then above-mentioned dried each raw material mixing is placed in torque rheometer melt blending and obtains polyamide 6/polypropylene/carbon nanotube High performance nanometer composite material.
In step (3), the mass ratio of the carbon nanotube of described polypropylene, polyamide 6, polypropylene grafted maleic anhydride and silane coupling agent process is 70:30:5:1.
Polyamide 6/polypropylene/carbon nanotube High performance nanometer composite material that the present invention also provides a kind of aforesaid method to prepare.
Major advantage of the present invention;
(1) preparation method of the present invention first by sol-gel method at CNTs Surface coating one deck silicon oxide, and then with silane coupling agent, surface-treated method is carried out to CNTs.The method with silane coupling agent process CNTs surface reported with other, this method does not need first to introduce hydroxyl by chemical oxidation treatment in carbon nano tube surface, thus does not destroy the structure of CNTs.
(2) quantity of carbon nano tube surface oxy radical can be added with the carbon nanotube that silane coupling agent process silicon oxide is coated, for other materials of carbon nano tube surface grafting provide more graft site, improve the percentage of grafting of carbon nano tube compound material, make the performance of matrix material obtain larger lifting.
(3) preparation method preparation technology of the present invention is simple, and equipment requirements is simple, does not need large-scale high price apparatus, all can volume production under usual terms, and preparation technology is safe, efficient, economical.
(4) polyamide 6/polypropylene/carbon nanotube High performance nanometer composite material of preparing of preparation method of the present invention is owing to having high tensile strength and flexural strength, can be widely applied in actual production, produce the plastics of high strength, the demand of people can better be met.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of pure nano-carbon tube (a) and the coated carbon nanotube (b) of silicon oxide;
Fig. 2 is the coated carbon nanotube (a) of silicon oxide and carbon nanotube graft-polyamide 6(b) infrared spectrogram;
Fig. 3 is PP/PA6(70/30) stereoscan photograph;
Fig. 4 is PP/PA6/5M/1C(70/30/5/1) stereoscan photograph;
Fig. 5 is the transmission electron microscope photo of pure nano-carbon tube;
Fig. 6 is the transmission electron microscope photo of the coated carbon nanotube of silicon oxide;
Fig. 7 is the transmission electron microscope photo of the carbon nanotube of silane coupling agent process;
Fig. 8 is PP/PA6/5M/1C(70/30/5/1) transmission electron microscope photo.
Embodiment
Embodiment 1:
1) the coated silicon oxide of sol-gel method: in the beaker of 500 mL, adds the aqueous solution that the carbon nanotube of 2.0 g dryings and 200 mL sodium laurylsulfonate content are 0.5 wt%, disperses 2 h by 80 kHz ultrasonic wave.Gained solution, after Bu Shi Suction filtration device suction filtration, with deionized water wash three times, is removed the unnecessary sodium laurylsulfonate not being coated on carbon nano tube surface, is obtained the carbon nanotube of tensio-active agent process.Under hyperacoustic effect, the carbon nanotube of tensio-active agent process is re-dispersed in deionized water, obtains homodisperse carbon nano-tube aqueous solutions.According to the volume proportion of 5:1, the aqueous solution of carbon nanotube is joined in the mixing solutions (weight proportion of tetraethoxy, deionized water and dehydrated alcohol is 2:1:4) of tetraethoxy, deionized water and dehydrated alcohol.By mixing solutions supersound process 2 h obtained, make even carbon nanotube be dispersed in solution, prevent solution phase-splitting simultaneously.Then, mixing solutions is mechanical stirring 24 h at room temperature, makes tetraethoxy fully be hydrolyzed and concentrate, thus it is coated to form silicon oxide in carbon nano tube surface.After hydrolysis terminates, obtain the coated carbon nanotube of silicon oxide (Si-CNTs) after washing three times with dehydrated alcohol centrifugation, productive rate 85% ~ 95%;
2) silane coupling agent surface treatment: be dispersed in the dehydrated alcohol of 1 L with the silicon enveloped carbon nanometer tube of ultrasonic wave by 1.0 g.The silane resin acceptor kh-550 of 1.0 g is dropwise joined in solution, 75
ostirring reaction 5 h under C.After reaction terminates, with Bu Shi Suction filtration device suction filtration, then use absolute ethanol washing five times, 60
oafter C vacuum-drying 2 d, grinding obtains the carbon nanotube (f-CNTs) of silane coupling agent process, productive rate 90% ~ 95%;
3) melt-blending process prepares carbon nano tube compound material: before blended, by PP, PA6, polypropylene grafted maleic anhydride (PP-g-MAH) and step 2) in the carbon nanotube of obtained silane coupling agent process be placed in 80
odry 8 h in C vacuum drying oven.Above-mentioned dried each raw material is pre-mixed evenly by the preparation method of PA6/PP/CNTs matrix material by a certain percentage, then melt blending in German Haake RC90 torque rheometer.Blending temperature is 190
oc, rotating speed is 50 rpm, and the blended time is 10 min.
Embodiment 2:
The mass ratio of PP, PA6 is 70:30, and other conditions, with embodiment 1, are designated as PP/PA6, and experiment shows, the tensile strength of PP/PA6 is 31.06MPa, and flexural strength is 50.02 MPa.
Embodiment 3:
The mass ratio of PP, PA6, PP-g-MAH is 70:30:5, and other conditions, with embodiment 1, are designated as PP/PA6/5M, and experiment shows, the tensile strength of PP/PA6/5M is 38.89MPa, and flexural strength is 54.42MPa.
Embodiment 4:
The mass ratio of PP, PA6, PP-g-MAH, f-CNTs is 70:30:5:1, and other conditions, with embodiment 1, are designated as PP/PA6/5M/1C, and experiment shows, the tensile strength of PP/PA6/5M/1C is 56.76MPa, and flexural strength is 86.32MPa.
Claims (3)
1. a preparation method for PA6/PP/ carbon nanotube High performance nanometer composite material, is characterized in that, comprises the following steps:
1) carbon nanotube of tensio-active agent process is first obtained with Sodium dodecylbenzene sulfonate process carbon nanotube, obtain tetraethoxy and silicon oxide coated carbon nanotube mixed solution by sol-gel method at carbon nano tube surface coated one deck silicon oxide with tetraethoxy again, mixed solution through hydrolysis, concentrated after obtain the coated carbon nanotube of pure silicon oxide;
2) obtain mixed solution after surface treatment being carried out to silicon oxide enveloped carbon nanometer tube obtained in step 1) with silane resin acceptor kh-550, after washing, drying, grinding, obtain the carbon nanotube (f-CNTs) of silane coupling agent process;
3) first by polypropylene, polyamide 6, polypropylene grafted maleic anhydride and step 2) in the carbon nanotube of obtained silane coupling agent process to be placed in vacuum drying oven dry, then above-mentioned dried each raw material mixing is placed in torque rheometer melt blending and obtains polyamide 6/polypropylene/carbon nanotube High performance nanometer composite material.
2. the preparation method of a kind of PA6/PP/ carbon nanotube High performance nanometer composite material according to claim 1, it is characterized in that, in step (3), the mass ratio of the carbon nanotube of described polypropylene, polyamide 6, polypropylene grafted maleic anhydride and silane coupling agent process is 70:30:5:1.
3. the PP/PA6/ carbon nanotube High performance nanometer composite material prepared of a method as claimed in claim 1 or 2.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009629A (en) * | 2015-09-22 | 2016-10-12 | 洛阳新巨能高热技术有限公司 | Carbon nanotube/polyamide composite material and preparation method thereof |
| CN106700249A (en) * | 2016-12-06 | 2017-05-24 | 东莞职业技术学院 | Carbon nanotube modified polypropylene composite material and preparation method thereof |
| WO2017128834A1 (en) * | 2016-01-27 | 2017-08-03 | 苏州翠南电子科技有限公司 | Preparation method for high-temperature-resisting and high-conductivity conductive plastic |
| CN108440752A (en) * | 2018-03-12 | 2018-08-24 | 中国石油大学(华东) | A kind of conjugation fire-retardant nylon material and preparation method thereof |
| CN109873148A (en) * | 2019-03-06 | 2019-06-11 | 昆明理工大学 | The preparation method of the modified nickelic ternary lithium battery composite positive pole of conducting polymer base |
| CN111393744A (en) * | 2020-03-26 | 2020-07-10 | 南京京锦元科技实业有限公司 | TPE material with antibacterial conductivity and preparation method thereof |
| CN112625437A (en) * | 2020-12-16 | 2021-04-09 | 湖北洋田塑料制品有限公司 | Nylon 66 thermoplastic elastomer material and preparation method thereof |
| CN112744818A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Carbon-silicon oxide compound and preparation method thereof |
| CN114907687A (en) * | 2022-05-27 | 2022-08-16 | 福州大学 | Silicon dioxide coated carbon nanotube reinforced nylon 12 composite material for MJR3D printing and preparation method and application thereof |
| CN115058114A (en) * | 2022-05-21 | 2022-09-16 | 江苏瑞美福新材料有限公司 | Process for manufacturing high-strength polyamide 6 |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009629A (en) * | 2015-09-22 | 2016-10-12 | 洛阳新巨能高热技术有限公司 | Carbon nanotube/polyamide composite material and preparation method thereof |
| WO2017128834A1 (en) * | 2016-01-27 | 2017-08-03 | 苏州翠南电子科技有限公司 | Preparation method for high-temperature-resisting and high-conductivity conductive plastic |
| CN106700249A (en) * | 2016-12-06 | 2017-05-24 | 东莞职业技术学院 | Carbon nanotube modified polypropylene composite material and preparation method thereof |
| CN108440752A (en) * | 2018-03-12 | 2018-08-24 | 中国石油大学(华东) | A kind of conjugation fire-retardant nylon material and preparation method thereof |
| CN109873148A (en) * | 2019-03-06 | 2019-06-11 | 昆明理工大学 | The preparation method of the modified nickelic ternary lithium battery composite positive pole of conducting polymer base |
| CN112744818B (en) * | 2019-10-30 | 2022-08-12 | 中国石油化工股份有限公司 | Carbon-silicon oxide compound and preparation method thereof |
| CN112744818A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Carbon-silicon oxide compound and preparation method thereof |
| CN111393744A (en) * | 2020-03-26 | 2020-07-10 | 南京京锦元科技实业有限公司 | TPE material with antibacterial conductivity and preparation method thereof |
| CN112625437A (en) * | 2020-12-16 | 2021-04-09 | 湖北洋田塑料制品有限公司 | Nylon 66 thermoplastic elastomer material and preparation method thereof |
| CN112625437B (en) * | 2020-12-16 | 2023-08-25 | 湖北洋田塑料制品有限公司 | Nylon 66 thermoplastic elastomer material and preparation method thereof |
| CN115058114A (en) * | 2022-05-21 | 2022-09-16 | 江苏瑞美福新材料有限公司 | Process for manufacturing high-strength polyamide 6 |
| CN114907687A (en) * | 2022-05-27 | 2022-08-16 | 福州大学 | Silicon dioxide coated carbon nanotube reinforced nylon 12 composite material for MJR3D printing and preparation method and application thereof |
| CN114907687B (en) * | 2022-05-27 | 2023-03-31 | 福州大学 | Silicon dioxide coated carbon nanotube reinforced nylon 12 composite material for MJR3D printing and preparation method and application thereof |
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