CN102453356A - Manufacturing method of nano carbon black through in-situ polyethylene grafting - Google Patents
Manufacturing method of nano carbon black through in-situ polyethylene grafting Download PDFInfo
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- CN102453356A CN102453356A CN2010105161779A CN201010516177A CN102453356A CN 102453356 A CN102453356 A CN 102453356A CN 2010105161779 A CN2010105161779 A CN 2010105161779A CN 201010516177 A CN201010516177 A CN 201010516177A CN 102453356 A CN102453356 A CN 102453356A
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Abstract
The invention relates to a manufacturing method of nano carbon black through in-situ polyethylene grafting, belonging to the technical field of polyolefin modification. Nano carbon black and polyethylene capable of degrading to produce active free radicals are mixed in a mechanical shear force field, and the nano carbon black is prepared directly through grafting reaction at the temperature above the melting point of the polyethylene for production of the active free radicals. The prepared nano carbon black has good dispersibility and compatibility. When the nano carbon black is filled into a polyethylene matrix, a high-performance polyethylene product can be prepared. The process of the preparation method of the nano carbon black is simple, no solvents are needed, the cost is low, and no pollution can be caused. Moreover, high-volume continuous production can be realized, and the grafted nano carbon black can be applied to production of high-performance polyethylene composite materials such as high-grade polyethylene pipes and the like.
Description
Technical field
The present invention relates to a kind of method of manufacture of nano carbon black of Vilaterm situ-formed graft, belong to polyolefin modified technical field.
Background technology
Polyolefine is that present range of application is the widest, the maximum family macromolecule material of output, annual more than 2,000 ten thousand tons of half dependence on import of market of China's polyolefine, and the hundreds billion of units of the direct products output value are first with non-resultant product output value many trillion.The annual import polyolefin products of China need spend tens billion of U.S. dollar exchanges; Wherein be mainly high-performance poly alkene PP Pipe Compound; The still complete dependence on import of high-grade PE100 level polyethylene pipe material like present China pressure-bearing gas pipe and water pipe market in urgent need (demand surpasses more than 1,000,000 tons); Even China also faces the severe challenge from Middle East Ultra Low Cost product at the general purpose polyolefin product scope; In order to break external technical monopoly and blockade on new techniques in the high-performance polyolefin field, exploitation " high-performance poly alkene technology " is the only way of China's polyolefin industry development.
But since Vilaterm synthetic with the course of processing in residual minim transition metal and initiator residue (containing a small amount of carbonyl, hydrogen peroxide group etc.) in the body; Ability strong absorption UV-light; Cause the reaction of Vilaterm photooxidation droping, thereby damage poly intensity and toughness.At present mainly suppress or slow down poly photo-oxidative degradation through adding photostabilizer (UV light absorber, quencher, radical scavenger and photomask agent), the protection macromolecular material is avoided ultraviolet ray and is destroyed, thus the work-ing life of raising macromolecular material.And mostly these photostabilizers are organic cpds, and it decomposes easily, and spinoff is bigger.Along with the development of nanotechnology, inorganic nano photostabilizers such as nano-ZnO, nano TiO 2, nano carbon black are paid close attention to because of its higher chemistry and thermostability have caused Chinese scholars widely.And along with the nanometer of matrix material to the propelling of nanometer level and numerous traditional micron order rigid particles; Be that matrix, inorganic nano-particle are the mechanical property that the coordination plasticizing enhancement techniques of disperse phase has obviously improved matrix material with the polymer, become one of focus of current polyolefine high performance research.
Summary of the invention
The object of the present invention is to provide a kind of method of manufacture of nano carbon black of Vilaterm situ-formed graft; The nano carbon black that makes has dispersiveness and consistency preferably; Be filled in the Vilaterm matrix and can obtain high performance polyethylene products; And the preparation method not only technology simple, need not solvent, cost is low, pollution-free, can also continuous production in enormous quantities.
The method of manufacture of the nano carbon black of Vilaterm situ-formed graft of the present invention; It is characterized in that under the mechanical shearing force field nano carbon black (can directly buy) and the Vilaterm that produces living radical of degrading mixes; Under the temperature that can produce more than the poly fusing point of living radical, directly carry out making behind the graft reaction.
Wherein:
Nano carbon black is 1000～1: 10 with the poly mass ratio that produces living radical of degrading.
Nano carbon black with the poly reaction conditions that produces living radical of degrading is: temperature: 120～350 ℃; Reaction times: 10～60min; The rotor speed of the used whipping device in mechanical shear stress field: 30～150rpm.
Nano carbon black need be handled at 110～130 ℃ of following vacuum-drying 10～14h, and can degrade the Vilaterm that produces living radical need be better at 60～90 ℃ of following vacuum-drying 2～6h treatment effects.
The Vilaterm that can degraded produces living radical has linear low density polyethylene, high density polyethylene(HDPE), two or more poly arbitrary proportion compounds arbitrarily.
In the reaction, forming the whipping device that uses in the mechanical shearing field of force has Haake torque rheometer, mill machine, single screw extrusion machine, twin screw extruder, Planetary Screw Extruder, conical screw extruder, continuous mixer, Banbury mixer, Z-shaped kneader or other any commercially available mixing equipment that can produce the mechanical shear stress effect etc.
Adopt traditional banburying method to prepare engrafted nanometer carbon black composite polyethylene material, concrete operations are following: the engrafted nanometer carbon black and the matrix polyethylene mixture that will comprise 0.01～100wt% nano carbon black place the HAAKE torque rheometer to react.TR: 120～350 ℃; Reaction times: 10～60min; Rotor speed: 30～150rpm.
Under hot mechanical effect; Nano carbon black is dispersed into state of aggregation or primary partical from the coacervate state; The Vilaterm degraded produces macromolecular radical, and the free polymer readical of generation is caught by the nano carbon black surface, thereby obtains polymer in situ grafted nano carbon black; Its dispersiveness and consistency in the Vilaterm matrix is improved; And improve the mechanical property, electric property, optical property etc. of the various composite polyethylene materials contain nano carbon black, thus can be when improving the Vilaterm uvioresistant performance, do not damage even improve its physical and mechanical properties.
The present invention has following beneficial effect:
The present invention can produce in the mixing equipment of powerful shearing force, to the Vilaterm that can fragment into living radical with have the nano carbon black blend of living radical and carry out situ-formed graft, thereby obtain Vilaterm situ-formed graft nano carbon black.The nano carbon black that makes has dispersiveness and consistency preferably, is filled in the Vilaterm matrix and can obtains high performance polyethylene products.The preparation method of this nano carbon black not only technology simple, need not solvent, cost is low, pollution-free, but also continuous production in enormous quantities.
The engrafted nanometer carbon black that makes is applied to produce high-performance polyethylene matrix material such as high-grade polyvinyl piping materials etc.
Description of drawings
Fig. 1-1, be untreated and through the TG graphic representation of the SC-3 of hot mechanical effect degraded.
Fig. 1-2, be untreated and through the DTG graphic representation of the SC-3 of hot mechanical effect degraded.
The infrared spectrum of Fig. 2, former nano carbon black and engrafted nanometer carbon black.
The TGA graphic representation of Fig. 3, former nano carbon black and engrafted nanometer carbon black.
The TEM photo of Fig. 4-1, former nano carbon black.
The TEM photo of Fig. 4-2, engrafted nanometer carbon black.
Fig. 5-1, Fig. 5-2, Fig. 5-3, Fig. 5-4, Fig. 5-5, Fig. 5-6, former nano carbon black and engrafted nanometer carbon black be dispersive SEM photo in DBGB2480H.
The ultraviolet absorption curve figure of Fig. 6-1, DBGB2480H engrafted nanometer carbon black.
The ultraviolet absorption curve figure of Fig. 6-2, DBGB2480H matrix material.
Embodiment
Below in conjunction with embodiment the present invention is described further.
Use poly engrafted nanometer carbon black: nano carbon black 160g, high density polyethylene(HDPE) SC-332g.
With nano carbon black and Vilaterm in the HAAKE torque rheometer in 140 ℃ of following blend, screw speed is 100rpm, the blend time is 15min, makes Vilaterm SC-3 situ-formed graft nano carbon black with this understanding.
For the grafting nano carbon black is characterized; Need unreacted Vilaterm in the system be removed; Method obtained below pure engrafted nanometer carbon black adopted: the nano carbon black of above-mentioned gained and poly reactant are dissolved in the YLENE; In under 130～140 ℃ at least stirring and refluxing place supercentrifuge (Beijing Medical Centrifugal Machine Factory) sedimentation to topple over upper solution after 20 minutes dispersion liquid after 72 hours; Settled nano carbon black is scattered in the YLENE once more, carries out spinning again until in upper solution, can not detecting Vilaterm.The nano carbon black of extracting is carried out following rerum natura sign.
Can see that from Fig. 1 Vilaterm SC-3 is after the hot mechanical effect of HAAKE torque rheometer, thermogravimetric curve is to the skew of low temperature direction, and heat decomposition temperature has descended about 13 ℃.Degraded has taken place in this explanation Vilaterm SC-3 in the HAAKE torque rheometer.Simultaneously, experiment shows that after the hot mechanical effect through the HAAKE torque rheometer, the melting index of SC-3 can rise to 0.81g/10min (5kg, 190 ℃) from 0.30g/10min, and this has proved that also degraded has taken place SC-3.
Can see that from Fig. 2 Vilaterm SC-3 successfully is grafted to the nano carbon black surface.According to the TGA curve of Fig. 3 nano carbon black and engrafted nanometer carbon black, can calculate percentage of grafting is 10.1wt%.
Get not engrafted nanometer carbon black and engrafted nanometer carbon black respectively and put into beaker for 1 part, add 100 parts of YLENE, place ultrasonic cleaner (the letter instrument company in Shanghai), ultra-sonic dispersion 20min, controlled temperature is 130～140 ℃, makes the nano carbon black dispersion liquid.On copper mesh, vacuum-drying 24h places on the transmission electron microscope and observes with dispersant liquid drop.As can be seen from Figure 4 grafted occasion not, nano carbon black exists with the coacervate form, on the contrary through graft modification, aggregate form or the primary partical form of nano carbon black about with 100nm exists, and realized the object of the invention.
Use poly engrafted nanometer carbon black: nano carbon black 160g, high density polyethylene pipe material DBGB2480H 32g.
With nano carbon black and Vilaterm in the HAAKE torque rheometer in 140 ℃ of following blend, screw speed is 100rpm, the blend time is 15min, makes Vilaterm DBGB2480H situ-formed graft nano carbon black with this understanding.
For the grafting nano carbon black is characterized; Need unreacted Vilaterm in the system be removed; Method obtained below pure engrafted nanometer carbon black adopted: the nano carbon black of above-mentioned gained and poly reactant are dissolved in the YLENE; In under 130～140 ℃ at least stirring and refluxing place supercentrifuge (Beijing Medical Centrifugal Machine Factory) sedimentation to topple over upper solution after 20 minutes dispersion liquid after 72 hours; Settled nano carbon black is scattered in the YLENE once more, carries out spinning again until in upper solution, can not detecting Vilaterm.
Get not engrafted nanometer carbon black and engrafted nanometer carbon black respectively and put into beaker for 1 part, add 100 parts of YLENE, place ultrasonic cleaner (the letter instrument company in Shanghai), ultra-sonic dispersion 20min, controlled temperature is 130～140 ℃, makes the nano carbon black dispersion liquid.On copper mesh, vacuum-drying 24h places on the transmission electron microscope and observes with dispersant liquid drop; Can find out not grafted occasion; Nano carbon black exists with the coacervate form, otherwise, through graft modification; Aggregate form or the primary partical form of nano carbon black about with 100nm exists, and realized the object of the invention.
Use poly engrafted nanometer carbon black: nano carbon black 160g, linear low density polyethylene 704232g.
With nano carbon black and Vilaterm in the HAAKE torque rheometer in 140 ℃ of following blend, screw speed is 100rpm, the blend time is 15min, makes Vilaterm 7042 situ-formed graft nano carbon blacks with this understanding.
For the grafting nano carbon black is characterized; Need unreacted Vilaterm in the system be removed; Method obtained below pure engrafted nanometer carbon black adopted: the nano carbon black of above-mentioned gained and poly reactant are dissolved in the YLENE; In under 130～140 ℃ at least stirring and refluxing place supercentrifuge (Beijing Medical Centrifugal Machine Factory) sedimentation to topple over upper solution after 20 minutes dispersion liquid after 72 hours; Settled nano carbon black is scattered in the YLENE once more, carries out spinning again until in upper solution, can not detecting Vilaterm.
Get not engrafted nanometer carbon black and engrafted nanometer carbon black respectively and put into beaker for 1 part, add 100 parts of YLENE, place ultrasonic cleaner (the letter instrument company in Shanghai), ultra-sonic dispersion 20min, controlled temperature is 130～140 ℃, makes the nano carbon black dispersion liquid.On copper mesh, vacuum-drying 24h places on the transmission electron microscope and observes with dispersant liquid drop; Can find out not grafted occasion; Nano carbon black exists with the coacervate form, otherwise, through graft modification; Aggregate form or the primary partical form of nano carbon black about with 100nm exists, and realized the object of the invention.
Embodiment 4
Get the SC-3 engrafted nanometer carbon black among the embodiment 1; Adopt traditional banburying method to prepare engrafted nanometer carbon black composite polyethylene material; Concrete operations are following: will comprise 1,2.5,5; The Vilaterm of 10wt% nano carbon black and engrafted nanometer carbon black mixture place the HAAKE torque rheometer, react 15min down in 180 ℃.Rotor speed 60rpm.
Can see that from Fig. 5 the dispersiveness of degrading polyethylene SC-3 situ-formed graft nano carbon black in polyethylene pipe material DBGB2480H greatly improved, in nano carbon black content 1～10wt% scope, very be evenly dispersed in the PE matrix.
Degrading polyethylene SC-3 situ-formed graft nano carbon black improves significantly to the uvioresistant performance tool of polyethylene pipe material DBGB2480H, and its intensity and toughness also increase shown in table 1 and table 2 simultaneously.
The strength property (1.0wt%) of table 1, SC-3 engrafted nanometer carbon black/material DBGB2480H matrix material
The elongation at break of table 2, SC-3 engrafted nanometer carbon black/DBGB2480H matrix material
Get the DBGB2480H engrafted nanometer carbon black among the embodiment 2; Adopt traditional banburying method to prepare engrafted nanometer carbon black composite polyethylene material; Concrete operations are following: will comprise 1,2.5,5; The Vilaterm of 10wt% nano carbon black and engrafted nanometer carbon black mixture place the HAAKE torque rheometer, react 15min down in 180 ℃.Rotor speed 60rpm.
The dispersiveness of degrading polyethylene DBGB2480H situ-formed graft nano carbon black in polyethylene pipe material DBGB2480H greatly improved, and in nano carbon black content 1～10wt% scope, also very is evenly dispersed in the PE matrix.
By visible among Fig. 6, degrading polyethylene DBGB2480H situ-formed graft nano carbon black improves significantly to the uvioresistant performance tool of polyethylene pipe material DGBG2480H, and its intensity and toughness also increase shown in table 3 and table 4 simultaneously.
Table 3, DBGB2480H engrafted nanometer carbon black/DBGB2480H composite material strength performance table (1.0wt%)
The elongation at break of table 4, SC-3 engrafted nanometer carbon black/DBGB2480H matrix material
Embodiment 6
Batching: nano carbon black 500g, high density polyethylene(HDPE) SC-332g, linear low density polyethylene 704260g.
Nano carbon black is handled at 130 ℃ of following vacuum-drying 13h, and high density polyethylene(HDPE) SC-3, linear low density polyethylene are handled at 80 ℃ of following vacuum-drying 5h.
Temperature of reaction: 300 ℃; Reaction times: 40min; The rotor speed of whipping device: 100rpm.
Other is with embodiment 1
Embodiment 7
Batching: nano carbon black 320g, high density polyethylene(HDPE) SC-350g, linear low density polyethylene 30g.
Nano carbon black is handled at 120 ℃ of following vacuum-drying 11h, and high density polyethylene(HDPE) SC-3, linear low density polyethylene are handled at 70 ℃ of following vacuum-drying 3h.
Temperature of reaction: 240 ℃; Reaction times: 30min; The rotor speed of whipping device: 90rpm.
Other is with embodiment 1
Embodiment 8
Batching: nano carbon black 800g, linear low density polyethylene 80g.
Nano carbon black is handled at 115 ℃ of following vacuum-drying 13h, and linear low density polyethylene is handled at 80 ℃ of following vacuum-drying 5h.
Temperature of reaction: 180 ℃; Reaction times: 50min; The rotor speed of whipping device: 120rpm.
Other is with embodiment 1
Claims (5)
1. the method for manufacture of the nano carbon black of a Vilaterm situ-formed graft; It is characterized in that under the mechanical shearing force field, the nano carbon black and the Vilaterm that produces living radical of degrading being mixed; Under the temperature that can produce more than the poly fusing point of living radical, directly carry out making behind the graft reaction.
2. the method for manufacture of the nano carbon black of Vilaterm situ-formed graft according to claim 1 is characterized in that the nano carbon black and the poly mass ratio that produces living radical of degrading are 1000～1: 10.
3. the method for manufacture of the nano carbon black of Vilaterm situ-formed graft according to claim 2 is characterized in that the nano carbon black and the poly reaction conditions that produces living radical of degrading are: temperature: 120～350 ℃; Reaction times: 10～60min; The rotor speed of the used whipping device in mechanical shear stress field: 30～150rpm.
4. the method for manufacture of the nano carbon black of Vilaterm situ-formed graft according to claim 3; It is characterized in that nano carbon black need be 110～130 ℃ of following vacuum-drying 10～14h processing, the Vilaterm that produces living radical of degrading need be handled at 60～90 ℃ of following vacuum-drying 2～6h.
5. according to the method for manufacture of the nano carbon black of claim 1,2,3 or 4 described Vilaterm situ-formed grafts, the Vilaterm that produces living radical of it is characterized in that degrading has linear low density polyethylene, high density polyethylene(HDPE), two or more poly arbitrary proportion compounds arbitrarily.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106750536A (en) * | 2016-07-17 | 2017-05-31 | 佛山瑞箭体育器材有限公司 | A kind of manufacture method of nano carbon black |
| CN107234789A (en) * | 2017-07-20 | 2017-10-10 | 安徽杰蓝特新材料有限公司 | A kind of polymolecularity HDPE water-feeding pipes forming methods |
| CN111484676A (en) * | 2020-06-13 | 2020-08-04 | 厦门毅兴行塑胶原料有限公司 | Toughness-improved polypropylene and preparation method thereof |
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| CN1781999A (en) * | 2004-09-28 | 2006-06-07 | 华东理工大学 | Nano carbon black with in-situ grafted organic compound and its producing method |
| CN1789302A (en) * | 2005-12-28 | 2006-06-21 | 华东理工大学 | In-situ grafted black carbon, its preparation method and reinforced rubber containing the same |
| CN101649080A (en) * | 2009-09-17 | 2010-02-17 | 成都清洋宝柏包装有限公司 | Preparation method of polyolefin materials for package |
| CN101824126A (en) * | 2010-05-07 | 2010-09-08 | 华东理工大学 | Hydrophilic carbon black |
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Patent Citations (5)
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| CN1154378A (en) * | 1996-03-12 | 1997-07-16 | 青岛化工学院 | method for lowering formation temp. of processing chlorinated polyvinyl-chloride |
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| CN1789302A (en) * | 2005-12-28 | 2006-06-21 | 华东理工大学 | In-situ grafted black carbon, its preparation method and reinforced rubber containing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106750536A (en) * | 2016-07-17 | 2017-05-31 | 佛山瑞箭体育器材有限公司 | A kind of manufacture method of nano carbon black |
| CN107234789A (en) * | 2017-07-20 | 2017-10-10 | 安徽杰蓝特新材料有限公司 | A kind of polymolecularity HDPE water-feeding pipes forming methods |
| CN111484676A (en) * | 2020-06-13 | 2020-08-04 | 厦门毅兴行塑胶原料有限公司 | Toughness-improved polypropylene and preparation method thereof |
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Application publication date: 20120516 |