CN101928418A - Polyolefin/polyamide composite material and preparation method thereof - Google Patents
Polyolefin/polyamide composite material and preparation method thereof Download PDFInfo
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- CN101928418A CN101928418A CN2009100877794A CN200910087779A CN101928418A CN 101928418 A CN101928418 A CN 101928418A CN 2009100877794 A CN2009100877794 A CN 2009100877794A CN 200910087779 A CN200910087779 A CN 200910087779A CN 101928418 A CN101928418 A CN 101928418A
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- polyolefin
- polyamide
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- carbon nanotube
- polymeric amide
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Abstract
The invention provides a polyolefin/polyamide composite material, which comprises the following components blended together: polyolefin, polyamide and a carbon nano tube, wherein the carbon nano tube is a single-wall nano tube with the diameter of 0.5 to 3 nm and the length of 1 to 50 mum, or is a multi-wall nano tube with the diameter of 3 to 60 nm and the length of 5 to 50 mu m; the carbon nano tube is not subjected to carboxylation or is subjected to the carboxylation; based on 100 weight parts of a polyolefin/polyamide plastic matrix, the adding amount of the carbon nano tube is 0.01 to 10 parts; and the polyolefin/polyamide plastic matrix comprises 50 to 95 weight percent of the polyolefin, and 5 to 50 weight percent of the polyamide. A preparation method of the polyolefin/polyamide composite material can ensure that the final product has a laminated structure and has better obstruction performance.
Description
Technical field
The present invention relates to a kind of polyolefin/polyamide composite material and preparation method thereof, specifically, relate to a kind of have a laminate structure contain polyolefin/polyamide composite material of carbon nanotube and preparation method thereof.
Technical background
With the high density polyethylene(HDPE) is the maximum general-purpose plastics of the polyolefine amount of being to use of representative, is widely used in to make to produce hollow container.But polyolefine is a non-polar polymer, and solubility parameter is close with most of varsol, and is poor to the barrier of gases such as oxygen, carbonic acid gas and varsol.Therefore can not directly be used to make the container that contacts with varsol.With nylon 6 is that the polymeric amide of representative has good barrier property, but its melt strength is low, is difficult to direct blow molding.Mostly the technology that adopts is polyolefine and polymeric amide are carried out the stratiform blend at present.In order to reach ideal layered distribution structure, for the viscosity ratio and the processing units of intermingling material certain particular requirement is arranged all, and in the course of processing, often need to add compatilizer and improve interface interaction power between two components.
Chinese patent 89101562.0 (1989, E. I. Du Pont de Nemours and Co) has been mentioned the layered article of a kind of polyolefine and nylon/polyvinyl alcohol blend.It prepares the melt blended material blend of a kind of polyolefine with about 2-39% nylon/polyvinyl alcohol component, makes compatilizer with the polyolefine of alkane carboxyl substituted during blend.
Chinese patent 96117564.8 (1997, Sichuan Union University), provide a kind of irradiation compatibilizing method to prepare the high barrier high-density polyethylene material, prepare high barrier high density polyethylene(HDPE) (HDPE) material by the irradiation compatibilizing method, be characterized in being that the HDPE of 280-400mm ultraviolet irradiation and nylon 6 (PA6) are in 210-240 ℃ of following blend extrusion moulding of extruder head temperature through wavelength.Owing in the irradiation process, be introduced into polar group on the HDPE molecular chain, in the high pressure extrusion, interact with nylon 6 (PA6), PA6 is stretched along the direction of extrusion, formation is equivalent to have multilayer PA6 barrier layer in the HDPE base material.
Chinese patent 01106697.0 (2001, Chemistry and Material Science Inst., Hubei Univ.) relate to and a kind of organic solvent is had the high molecule alloy material polyethylene/nylon blend separation material of excellent barrier properties, this material is by polyethylene, nylon and the nylon grafted is ethane-ethenol copolymer commixed forms.Described material is a vessel prepd through slush molding, can form parallel to each other, overlapped lamelliform nylon discontinuous phase in its wall of container, organic solvent there is fabulous barriering effect, can be widely used in fields such as fuel tank of vehicle, pesticides packaging, paint packing, cosmetic package.
Chinese patent 200610102138.8 (2007, Northcentral University) provides a kind of nylon/ethane-ethenol copolymer commixed type lamination barrier material and preparation method thereof, relating to a kind of macromolecular material and preparation method, specifically is a kind of nylon/ethane-ethenol copolymer commixed type lamination barrier material and preparation method thereof.Form by the following raw materials by weight percentage cooperation: nylon 65～95%, ethylene-vinyl alcohol copolymer 5～35%, and the superoxide of nylon and ethylene-vinyl alcohol copolymer gross weight 0.2～3%.
Chinese patent 200510031564.2 (2006, Hunan University) provides a kind of HDPE/PA-6 high-barrier polymer laminated blending material, and a kind of high-barrier polymer laminated blending material and complete processing thereof are provided.The characteristics of this barrier material are that its raw material proportioning components is (mass percent): high density polyethylene(HDPE) 60～88, nylon PA-630～10, compatilizer 2～10.The complete processing of this material is as follows: nylon 6 that drying is good and compatilizer and high density polyethylene(HDPE) thorough mixing 10 minutes in high-speed mixer; Extrude through the dicing machine pelletizing on the exhaust twin-screw mixer machine in the same way in the TE-35 type then and obtain stratiform blend pellet.
More than these inventions all adopted organic expanding material so that work in-process produces laminate structure.
Chinese patent 200410005224.8 (2004, Atuofeina Corp) provides a kind of polyamide/polyolefine blend that contains carbon nanotube, changing patent requires polymeric amide content to be not less than 40wt%, be the situation of polymeric amide during as body material, and this patent does not relate to the adding carbon nanotube, induces the formation laminate structure.
According to the requirement of barrier material, has only the iris action that when polyolefine and polymeric amide formation laminate structure, just can give full play to polymeric amide.Therefore how work in-process forms the key that the morphological structure of layered distribution is the preparation barrier material.
Summary of the invention
The inventor finds by great deal of experimental, in the polyamide/polyolefine blend, add small amount of carbon nanotubes, and control it and mainly be distributed in the polymeric amide, utilize the high length-diameter ratio characteristic Induced polymeric amide of carbon nanotube to form lamellated structure mutually, make this blend have good barrier, and the mechanical property of blend is constant or increase.
The purpose of this invention is to provide above-mentioned polyolefin/polyamide composite material, the following component that includes blend: polyolefine, polymeric amide, carbon nanotube, wherein said carbon nanotube are the single-walled nanotube of diameter 0.5～3nm, length 1～50um and/or many walls nanotube of diameter 3～60nm, length 5～50um; In the polyolefin/polyamide plastic substrate is 100 parts by weight, and the carbon nanotube add-on is 0.01～10 part; In the polyolefin/polyamide plastic substrate, polyolefinic amount is 65～95wt%, and the amount of polymeric amide is 5～35wt%.
Polymeric amide of the present invention is the material that nylon 6, nylon 66 or Ni Long11 etc. contain amido linkage.
Carbon nanotube of the present invention is diameter 0.5～3nm, the single-walled nanotube of length 1～50um, preferred diameter 0.8～1.6nm, the single-walled nanotube of length 5～30um; Perhaps be diameter 3～60nm, many walls nanotube of length 5～50um, preferred diameter＜8nm, many walls nanotube of length 10～30um.。
The contriver finds under study for action, if make carbon nanotube all or major part be distributed in the polymeric amide, polyolefin/polyamide/carbon nano tube compound material will be easy to form laminate structure.In order to guarantee that carbon nanotube is distributed in the polymeric amide, can adopt the carbon nanotube of carboxylated processing, because thereby it can be distributed in the polymeric amide phase region with the end group generation chemical reaction of polymeric amide, the carbon nanotube of described carboxylated processing is that carbon nanotube is refluxed more than 1 hour in boiling point in the nitration mixture of nitric acid and sulfuric acid (weight ratio 1/3), obtains with the distilled water cleaning-drying then; Carry out blend with polyolefine again after also the blend of carbon nanotube and polymeric amide elder generation can being prepared masterbatch, can guarantee that also most of carbon nanotube is distributed in the polymeric amide phase region.
The present invention further provides the preparation method of said polyolefins/polyamide compoiste material.
The preparation method of polyolefin/polyamide composite material of the present invention comprises: earlier described polymeric amide and carbon nanotube are pressed described set of dispense than melt blending, extrude pelletizing; The pellet that obtains again with polyolefine in described ratio melt blending.
If add the carbon nanotube of carboxylated processing, preparation method of the present invention can also for, comprising: will include described polymeric amide, polyolefine and compare melt blending by described set of dispense through the carbon nanotube of carboxylated processing.
Adopt melt-mixing method to prepare in the polyolefin/polyamide composite material process of the present invention, the blending temperature of material is the processing temperature of polyolefin/polyamide composite material, selects not only guaranteeing the complete fusion of matrix Co-polypropylene but also can not make in the scope of its decomposition.
Employed melt blending equipment is the general blending equipment in the rubber and plastic processing industry in preparation method of the present invention, can be twin screw extruder, single screw extrusion machine, mill or Banbury mixer etc.
Operating procedure is simple and reliable in the preparation process of the present invention, and cost is lower.The polyolefin/polyamide composite material particle of gained can utilize injection or conventional moulding means such as extrude and prepare shapes such as pipe, kettle, jar and bottle.This method can make the finished product present laminate structure to possess better barrier property.
Description of drawings
Fig. 1 is that the matrix material of Comparative Examples 1 uses section photo after the SEM scanning electron microscope direct viewing etching
Fig. 2 is that the matrix material of embodiment 1 uses section photo after the SEM scanning electron microscope direct viewing etching
Fig. 3 is that the matrix material of Comparative Examples 2 uses section photo after the SEM scanning electron microscope direct viewing etching
Fig. 4 is that the matrix material of embodiment 2 uses section photo after the SEM scanning electron microscope direct viewing etching
Fig. 5 is that the matrix material of Comparative Examples 3 uses section photo after the SEM scanning electron microscope direct viewing etching
Fig. 6 is that the matrix material of embodiment 3 uses section photo after the SEM scanning electron microscope direct viewing etching
Embodiment
The invention will be further described below in conjunction with specific embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Testing method:
1, tensile strength: ASTM D 638
2, modulus in flexure: ASTM D 790
3, IZOD notched Izod impact strength: ASTM 256
4, heat-drawn wire: ASTM 148
5, oxygen permeability: on film health OX-TRANModel2/21 oxygen flow instrument (OTR oxygen transmission rate tester), carry out, this instrument adopts method of coulometric analysis (isopiestic method), uses high precision coulomb electric charge transmitter to detect the oxygen transmission rate of polymer barrier material and package.High precision coulomb electric charge transmitter is a kind of stable absolute value transducer, and smooth film is clipped in the testing chamber, and it is clean to utilize oxygen-free carrier gas that remnant oxygen is purged.Carrier gas is transported on the transmitter continuously, until steady state, thereby determines zero point.With testing chamber outside 99.9% the oxygen feeding, the oxygen from film permeation to inboard testing chamber is delivered to transmitter by carrier gas, draws the OTR oxygen transmission rate of film sample then, and the barrier of the low more expression material of OTR oxygen transmission rate is good more.
With nylon 6 (Yueyang Ba Ling petrochemical industry, YH600) and carbon nanotube (MWNT) (epoch nanometer company of middle section, M1 type multi-walled carbon nano-tubes, external diameter:＜8nm, internal diameter: 2-5nm, length: 10-30um) high-speed mixing is even, in twin screw extruder, melt extrude cooling and dicing.Forcing machine heating zone temperature is respectively 220～250 ℃; The pellet of gained and high density polyethylene(HDPE) (HDPE) (Sinopec is raised sub-petrochemical industry branch office, and the trade mark is 5000S) are melt extruded cooling and dicing in proportion in twin screw extruder.Then with the gained pellet in 260 ℃ of injection moldings, and the preparation standard batten carries out the test of correlated performance on request.The gained pellet at the film that is molded under 240 ℃ about thickness 15 μ m, is used for the barrier property test.Concrete prescription sees Table 1, and wherein each component concentration is all with listed as parts by weight.Results of property such as table 1
Comparative Examples 1～3:
Except that do not add carbon nanotube and the difference of specifically filling a prescription, all the other conditions are all identical with previous embodiment.Concrete prescription sees Table 1, and wherein each component concentration is all in weight part.Results of property is as shown in table 1.
Table 1 comparative example and Example formulations and performance
By table 1 and accompanying drawing 1～6 as seen, do not add carbon nanotube, what matrix material presented is island structure, and after the adding small amount of carbon nanotubes, matrix material presents laminate structure, its barrier property is greatly improved, and its modulus in flexure and heat-drawn wire also increase simultaneously, and other performances do not descend.
Claims (7)
1. polyolefin/polyamide composite material, the following component that includes blend: polyolefine, polymeric amide, carbon nanotube, wherein said carbon nanotube are the single-walled nanotube of diameter 0.5～3nm, length 1～50um and/or many walls nanotube of diameter 3～60nm, length 5～50um; In the polyolefin/polyamide plastic substrate is 100 parts by weight, and the carbon nanotube add-on is 0.01～10 part; In the polyolefin/polyamide plastic substrate, polyolefinic amount is 65～95wt%, and the amount of polymeric amide is 5～35wt%.
2. polyolefin/polyamide composite material according to claim 1, wherein in the polyolefin/polyamide plastic substrate, polyolefinic amount is 60～95wt%, the amount of polymeric amide is 10～35wt%
3. polyolefin/polyamide composite material according to claim 1 is 100 weight parts in the polyolefin/polyamide plastic substrate wherein, and carbon nanotube is 0.05～0.1 part.
4. polyolefin/polyamide composite material according to claim 1, wherein said carbon nanotube for for diameter be 0.8～1.6nm, length be 5～30um single-walled nanotube and or diameter be that 30～50nm, length are many walls nanotube of 10～20um.
5. polyolefin/polyamide composite material according to claim 1, wherein said carbon nanotube was handled through carboxylated.
6. the preparation method of polyolefin/polyamide composite material as claimed in claim 1 comprises: earlier described polymeric amide and carbon nanotube are pressed described set of dispense than melt blending, extrude pelletizing; The pellet that obtains again with polyolefine in described ratio melt blending;
7. the preparation method of polyolefin/polyamide composite material as claimed in claim 5 comprises: will include described polymeric amide, polyolefine and compare melt blending through the carbon nanotube of carboxylated processing by described set of dispense.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038201A (en) * | 2015-06-10 | 2015-11-11 | 苏州宏恒化工有限公司 | Environment-friendly polyethylene/polyamide laminated barrier material and preparation method thereof |
| CN113121901A (en) * | 2021-03-11 | 2021-07-16 | 深圳烯湾科技有限公司 | Composite resin material for pressure gas storage container and preparation method thereof |
-
2009
- 2009-06-26 CN CN2009100877794A patent/CN101928418A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038201A (en) * | 2015-06-10 | 2015-11-11 | 苏州宏恒化工有限公司 | Environment-friendly polyethylene/polyamide laminated barrier material and preparation method thereof |
| CN113121901A (en) * | 2021-03-11 | 2021-07-16 | 深圳烯湾科技有限公司 | Composite resin material for pressure gas storage container and preparation method thereof |
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Open date: 20101229 |