CN104387671B - A kind of preparation method of PA6/PP/ CNT High performance nanometer composite material - Google Patents
A kind of preparation method of PA6/PP/ CNT High performance nanometer composite material Download PDFInfo
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- CN104387671B CN104387671B CN201410750672.4A CN201410750672A CN104387671B CN 104387671 B CN104387671 B CN 104387671B CN 201410750672 A CN201410750672 A CN 201410750672A CN 104387671 B CN104387671 B CN 104387671B
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- 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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- 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
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- C08K2201/011—Nanostructured additives
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- 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
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Abstract
The present invention provides a kind of method of PA6/PP/ CNT High performance nanometer composite material. First passing through sol-gel process and be coated with one layer of silicon oxide in carbon nano tube surface, then recycle silicon alkane coupling agent prepares polyamide 6/polypropylene/CNT High performance nanometer composite material with melt-blending process after enveloped carbon nanometer tube is carried out surface treatment. Experiments show that, APTES (KH-550) surface treatment CNT can be effectively improved CNT dispersion in PA6/PP matrix, increase the interface cohesion between CNT and PA6/PP matrix, by adding CNT as the reinforcement of PA6/PP polymer, the mechanical property of polymer can be significantly improved.
Description
Technical field
The invention belongs to chemical industry field of compound material, the preparation method being specifically related to a kind of polyamide 6/polypropylene/CNT High performance nanometer composite material.
Background technology
Since CNT (CNTs) is found, just cause the great interest of people. CNTs has the mechanical property of excellence, excellent chemical stability and heat stability, the characteristics such as good electrical property and microwave absorption, and there is nano effect specific to unique one-dimensional nano structure, become the desirable reinforcement of polymeric material, and can give polymeric material many new functions. but the surface of CNTs can be higher, it is easy to reunite, it is made to be difficult to uniform tiny dispersion in polymeric matrix. CNTs have to combine closely with polymeric matrix as reinforcing material, and stress so just can be made to be efficiently transferred on CNTs. how dispersed CNTs strengthen the interface cohesion between CNTs and polymeric matrix, is current urgent problem. coupling agent is a kind of two kinds of materials of different nature by chemically or physically acting on a kind of auxiliary agent combined, can be widely used in the composite. the close inorganic group of coupling agent is combined with filling surface, and parent's organic group tangles with macromolecule matrix or reaction, thus playing the effect of molecular bridge. utilize the inorganic filler that this distinctive molecular bridge performance can make surface nature differ greatly compatible with macromolecular material, thus being greatly improved the physical property of composite, electrical property, hot property and optical property etc. organo silane coupling agent is to strengthen widely used coupling agent in polymer composites at filler, can be used as the surface conditioning agent of various filler or viscosifier. the scholars such as VastL it have been reported that about with silane coupler process carbon nano tube surface method (VastL, PhilippinG, DestreeA, MoreauN, FonsecaA, NagyJB, DelhalleJ, MekhalifZ.Chemicalfunctionalizationbyafluorinatedtrichlo rosilaneofmulti-walledcarbonnanotubes.Nanotechnology, 2004, 15, 781-785.), but these methods are required for first passing through chemical oxidation treatment and introduce hydroxyl in carbon nano tube surface, therefore can the structure of destroying carbon nanometer tube, thus have impact on the performance that CNT is excellent.Polypropylene is a kind of widely used big kind general-purpose plastics, has superior tensile performance and has prominent stress cracking resistance and wearability, but there is also the molding shrinkage shortcoming such as split big, fragile under low temperature. Polyamide 6 be a kind of highly polar, there is the crystalline polymer of certain reactivity, there is the characteristics such as excellent shock resistance, tension, wear-resisting and self lubricity. But water absorption is big, dimensional stability is deteriorated so that it is application is restricted. If but by blended for PP and the PA6 shortcoming overcoming single polymers. Owing to CNT specific surface is big, making a concerted effort strong with polymer scale, CNT is joined the research in single polymers by many bibliographical informations, and studying more for polymer is PP, PA6. Had evolved in recent years adopt carbon nano-tube modification PA6/PP blend, thus comprehensively blending and modifying and nano combined advantage can prepare high-performance PA6/PP based nano composite material.
The melt-blending process such as Lan Hao has prepared PP/PPR/PA6 composite, atactic copolymerized polypropene (PPR), polyamide 6 (PA6) and the bulking agent impact (Lan Hao on PP/PPR/PA6 composite materials property and fatigue performance is have studied by mechanical property, fatigue property test and scanning electron microscope (SEM), Wang Baoxu, Yin Yunshan, Qin Lijie. strengthen research and the application of PP/PPR/PA6 composite. plastics science and technology, 2014,03,42,70-76.). HaiyanMa etc. are prepared for PP/PA6/PP-g-PAH composite (HaiyanMa, ZhaofengLiu, JunZhang, HaijunMa.Polypropylene/polyamide6/polypropylene-g-maleic anhydrideblendingmonofilaments:effectsofquenchtemperatur e.JournalofPolymerResearch, 2011,06,18,1941-1946.).
Summary of the invention
The preparation method that the purpose of the present invention is to propose to a kind of polyamide 6/polypropylene/CNT High performance nanometer composite material, by adding CNT as the reinforcement of PA6/PP polymer, can significantly improve the mechanical property of polymer.
For achieving the above object, the technical solution used in the present invention is: the preparation method of a kind of PA6/PP/ CNT High performance nanometer composite material, comprises the following steps:
1) first process CNT with dodecylbenzene sodium sulfonate and obtain the CNT that surfactant processes, being coated with one layer silicon oxide by sol-gel process in carbon nano tube surface with tetraethyl orthosilicate again and obtain tetraethyl orthosilicate and the CNT mixed liquor of silicon oxide cladding, mixed liquor obtains the CNT of pure silicon oxide cladding after hydrolysis, concentration;
2) obtain mixed liquor after the silicon oxide enveloped carbon nanometer tube prepared in step 1) being carried out surface treatment with silane resin acceptor kh-550, scrubbed, dry, grind after obtain the CNT (f-CNTs) of silane coupler process;
3) first by polypropylene (PP), polyamide 6 (PA6), polypropylene grafted maleic anhydride (PP-g-MAH) and step 2) in the CNT that processes of the silane coupler for preparing be placed in vacuum drying oven dry, being then placed in torque rheometer by above-mentioned dried each raw material mixing melt blending obtains polyamide 6/polypropylene/CNT High performance nanometer composite material.
In step (3), the mass ratio of the CNT that described polypropylene, polyamide 6, polypropylene grafted maleic anhydride and silane coupler process is 70:30:5:1.
The present invention also provides for polyamide 6/polypropylene/CNT High performance nanometer composite material prepared by a kind of said method.
The major advantage of the present invention;
(1) preparation method of the present invention first passes through sol-gel process at one layer of silicon oxide of CNTs Surface coating, and then recycle silicon alkane coupling agent is to the CNTs method carrying out surface treatment. With other method processing CNTs surface with silane coupler reported, this method introduces hydroxyl without first pass through chemical oxidation treatment in carbon nano tube surface, from without the structure destroying CNTs.
(2) quantity of carbon nano tube surface oxy radical can be added with the CNT of silane coupler process silicon oxide cladding, more graft site is provided for other materials of carbon nano tube surface grafting, improve the percent grafting of carbon nano tube compound material, make the performance of composite obtain bigger lifting.
(3) the preparation method preparation technology of the present invention is simple, and equipment requirements is simple, it is not necessary to large-scale high price apparatus, under usual terms all can volume production, preparation technology is safe efficient, economical.
(4) polyamide 6/polypropylene/CNT High performance nanometer composite material prepared by the preparation method of the present invention is owing to having high hot strength and bending strength, can be widely applied in actual production, produce the plastic of high intensity, the demand of people can be better met.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the CNT (b) of pure nano-carbon tube (a) and silicon oxide cladding;
Fig. 2 be silicon oxide cladding CNT (a) and CNT 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 CNT of silicon oxide cladding;
Fig. 7 is the transmission electron microscope photo of the CNT that silane coupler processes;
Fig. 8 is PP/PA6/5M/1C(70/30/5/1) transmission electron microscope photo.
Detailed description of the invention
Embodiment 1:
1) sol-gel process cladding silicon oxide: in the beaker of 500mL, adds the 2.0g CNT dried and 200mL dodecyl sodium sulfate content is the aqueous solution of 0.5wt%, disperses 2h with 80kHz ultrasound wave. Gained solution, after Bu Shi Suction filtration device sucking filtration, with deionized water wash three times, removes the unnecessary uncoated dodecyl sodium sulfate in carbon nano tube surface, obtains the CNT that surfactant processes. Under hyperacoustic effect, the CNT that surfactant processes 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 CNT is joined in the mixed solution (weight proportion of tetraethyl orthosilicate, deionized water and dehydrated alcohol is 2:1:4) of tetraethyl orthosilicate, deionized water and dehydrated alcohol. The mixed solution supersound process 2h that will obtain, makes CNT be dispersed in solution, prevents solution point phase simultaneously. Then, mixed solution is mechanical agitation 24h at room temperature, makes tetraethyl orthosilicate be fully hydrolyzed and concentrates, thus forming silicon oxide cladding in carbon nano tube surface. After hydrolysis terminates, after washing three times with dehydrated alcohol centrifugation, obtain the CNT (Si-CNTs) of silicon oxide cladding, productivity 85%��95%;
2) silane coupler surface treatment: the silicon enveloped carbon nanometer tube of 1.0g is dispersed in the dehydrated alcohol of 1L with ultrasound wave.The silane resin acceptor kh-550 of 1.0g is added dropwise in solution, 75oStirring reaction 5h under C. After reaction terminates, with Bu Shi Suction filtration device sucking filtration, then with absolute ethanol washing five times, 60oAfter C vacuum drying 2d, grind and obtain the CNT (f-CNTs) that silane coupler processes, productivity 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 prepare silane coupler process CNT be placed in 80oDry 8h in C vacuum drying oven. The preparation method of PA6/PP/CNTs composite is to be pre-mixed uniformly by a certain percentage by above-mentioned dried each raw material, then melt blending in Germany's HaakeRC90 torque rheometer. Blending temperature is 190oC, rotating speed is 50rpm, and the blended time is 10min.
Embodiment 2:
The mass ratio of PP, PA6 is 70:30, and other conditions, with embodiment 1, are designated as PP/PA6, experiments show that, the hot strength of PP/PA6 is 31.06MPa, and bending strength is 50.02MPa.
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, experiments show that, the hot strength of PP/PA6/5M is 38.89MPa, and bending 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, experiments show that, the hot strength of PP/PA6/5M/1C is 56.76MPa, and bending strength is 86.32MPa.
Claims (2)
1. the preparation method of a PA6/PP/ CNT High performance nanometer composite material, it is characterised in that comprise the following steps:
1) first process CNT with dodecylbenzene sodium sulfonate and obtain the CNT that surfactant processes, being coated with one layer silicon oxide by sol-gel process in carbon nano tube surface with tetraethyl orthosilicate again and obtain tetraethyl orthosilicate and the CNT mixed liquor of silicon oxide cladding, mixed liquor obtains the CNT of pure silicon oxide cladding after hydrolysis, concentration;
2) obtain mixed liquor after the silicon oxide enveloped carbon nanometer tube prepared in step 1) being carried out surface treatment with silane resin acceptor kh-550, scrubbed, dry, grind after obtain the CNT (f-CNTs) of silane coupler process;
3) first by polypropylene, polyamide 6, polypropylene grafted maleic anhydride and step 2) in the CNT that processes of the silane coupler for preparing be placed in vacuum drying oven dry, being then placed in torque rheometer by above-mentioned dried each raw material mixing melt blending obtains polyamide 6/polypropylene/CNT High performance nanometer composite material;
In step 3), the mass ratio of the CNT that described polypropylene, polyamide 6, polypropylene grafted maleic anhydride and silane coupler process is 70:30:5:1.
2. the PP/PA6/ CNT High performance nanometer composite material that prepared by the method for claim 1.
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| 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 |
| CN105694442A (en) * | 2016-01-27 | 2016-06-22 | 苏州翠南电子科技有限公司 | Preparation method of 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 |
| CN111393744B (en) * | 2020-03-26 | 2023-06-23 | 南京京锦元科技实业有限公司 | TPE material with antibacterial conductivity 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 |
| 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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