CN100386188C - Process for preparing nano composite polymer/metal powder by millstone type mechanicochemical reactor - Google Patents
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- CN100386188C CN100386188C CNB011073799A CN01107379A CN100386188C CN 100386188 C CN100386188 C CN 100386188C CN B011073799 A CNB011073799 A CN B011073799A CN 01107379 A CN01107379 A CN 01107379A CN 100386188 C CN100386188 C CN 100386188C
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Abstract
The present invention relates to a method for preparing nano composite polymer/metal powder by a millstone type mechanicochemical reactor. The method is characterized in that initial raw materials (by weight) of 5 to 300 portions of polymer particles with the particle sizes of 10 mu m-5mm, 10 to 600 portions of metal particles with the particle sizes of 1-500 mu m and 0 to 10 portions of coupling agents are added to a millstone type mechanicochemical reactor (ZL95111258.9) and are milled and pulverized, polymers form ultramicro powder with tight combination and uniform mixing, wherein the sizes of metal crystal particles are from 5 nm to 100 nm, the particle sizes of the polymers are from 1 mu m to 50 mu m, and then polymer/metal nano composite powder is obtained.
Description
The present invention relates to the method that the millstone type Mechanico-chemical reactor prepares the nano polymer/metal composite granule.
The polymer/metal composite is owing to functions such as the conduction that has processability, mechanical property and the metal material of polymer concurrently, heat conduction, magnetic, has application widely in fields such as conducting polymer composite, magnetic material, electromagnetic shielding material, low-resistance electric heating device, microwave absorbing material and sensors, and nano polymer/metal composite material has the nano effect of nano material, and possesses the nanometer enhancement effect, can effectively improve mechanics, the thermal property of composite and realize the function of nano particle, therefore cause people's extensive attention.The preparation of nano polymer/metal material in the past is to be splashed into technology by ion metal is introduced to be formed nano polymer/metal composite material (Khaibullin, R.I. in the polymeric matrix; Osin, Y.N.; Stepanov, A.L.; Khaibullisn, I.B.Nuclear Instruments ﹠amp; Methods in Physics Research; Section B:BeamInteractions with Materials and Atoms 1999; 148 (1-4): 1023-1028); or metal nano powder obtained (Gunther with the polymer melt-processed; B.H; Inter.J.Powder.Metall.; 1999,35 (7): 53-58), or have the polymer microballoon of metallic element to make metal ion become the zeroth order element to be attached to (Vizel on the polymer powder by in-situ reducing in the absorption complexing; S.Margel; S., J.Mater.Res., 1999; 14 (10): 3913-3920); there is the cost height in these methods; the shortcoming that is difficult for scale preparation is simultaneously because nano metal because the surface can be huge, is easy to mutual gathering; inaccessible nano-dispersed in polymeric matrix, and influence its performance and application.In recent years, improve the dispersiveness of nano particle, enlarging preparation amount and reducing manufacturing cost is the nanometer material science urgent problem, by descending, bulk or bulky grain material are pulverized the approach that obtains ultrafine powder, be considered to have much the method for practical significance.Wherein based on collision, distortion, the high-energy ball milling of cracked mechanism is pulverized, because it is simple to operate, but the adaptability of comminution of material is wider, be widely used in inorganic and preparation (Koch metal nano material, C.C.Nanostructured Materials, 1997,9,13), yet, because the efficient that high-energy ball milling is pulverized depends on the contact probability of ball-material, impulsive force size, amplitude and rotating speed, crushing process require ball/material than high, the pulverizing time is long, often be tens to hundreds of hour, the pulverizing of metal is easy to generate work hardening phenomenon and atomic reunion, hindered the further miniaturization of particle size; Pulverizing to polymer then often causes contrary crushing phenomenon, reach very soon and pulverize limitation, collision, frictional heating easily make the soft clayization of polymer surfaces for a long time, the fragmentation and the granular of polymer particle have been influenced, therefore, the application of high-energy ball-milling process in the preparation of preparation nano polymer/metal composite granule is subjected to bigger restriction.
The objective of the invention is provides a kind of millstone type Mechanico-chemical reactor to prepare the method for nano polymer/metal composite granule at the deficiencies in the prior art, be characterized in utilizing millstone type Mechanico-chemical reactor (Chinese patent ZL95111258.9), in operation process, material is applied powerful pressure, shear stress and circumference stress, produce high crush efficiency and excellent mixed function, make copolymer and metallic particles by rub, shear, break, power is chimeric and process such as power diffusion obtains the good nano polymer/metal composite granule of dispersion stabilization.
The objective of the invention is to be implemented by following technical measures, wherein said raw material umber is parts by weight except that specified otherwise.
The millstone type Mechanico-chemical reactor prepares the method for nano polymer/metal composite granule, is characterized in recipe ingredient being:
5～300 parts of polymer beads
10～600 parts of metallic particles
0～10 part of coupling agent
Wherein the particle diameter of polymer beads is 10 μ m～5mm, and the particle diameter of metallic particles is 1～500 μ m, according to its particle size difference, adopts different precomminution and mixed method:
A. the particle size range when polymer is 10 μ m～0.5mm, when the particle size range of metal is 1～75 μ m, material added in the high speed agitator mix, send into the millstone type Mechanico-chemical reactor then and mill and pulverize 20～60 times, promptly obtain the nano polymer/metal composite granule;
B. working as the metal particle size range is 75 μ m～500 μ m, when polymer particle diameter scope is 0.5mm～5mm, need with the two respectively in the millstone type Mechanico-chemical reactor pre-grinding be crushed to below the 75 μ m and below the 0.5mm, in high speed agitator, mix then with coupling agent, mill at the millstone type Mechanico-chemical reactor and to pulverize 20～60 times, promptly obtain the nano polymer/metal composite granule
Polymer is a polyethylene, polypropylene, Merlon, polymethyl methacrylate, polyester, polyacrylate, polyimides, phenolic resins, melmac, polyamide, polystyrene, polyvinyl chloride, epoxy resin, polyvinyl acetate, polytetrafluoroethylene (PTFE), neoprene, Vingon, polyformaldehyde, polyethylene glycol oxide, polyvinyl alcohol, polybutadiene, polyisobutene, polymethylpentene and/or poly-(acrylonitrile-butadiene-styrene (ABS)), poly-(styrene-butadiene), poly-copolymers such as (ethylene-propylenes) is at least a.
Metal is that iron, cobalt, nickel, aluminium, lead, zinc, copper, chromium, zirconium, magnesium, manganese, molybdenum, strontium, antimony, tungsten, tin and rare-earth elements of lanthanum, cerium, praseodymium, neodymium, europium and/or dysprosium are at least a.
Coupling agent is C
12～C
18Higher fatty acids, silane coupler, titanate coupling agent and/or aluminate coupling agent are at least a, and to be these auxiliary agents do not have a negative impact to the realization and the obtaining of excellent results of the present invention of the object of the invention its precondition.
The nano polymer/metal composite granule of the present invention's preparation, through ESEM (Fig. 1, Fig. 2 and Fig. 3) and transmission electron microscope (Fig. 4) test, Fig. 1 pulverizes the ESEM pattern of preceding iron particle for pan-milling, Fig. 2 pulverizes the ESEM pattern of iron after 15 times for pan-milling, Fig. 3 pulverizes the ESEM pattern of iron particle after 25 times for pan-milling, and Fig. 4 is the transmission electron microscope pattern of iron micro mist after the pan-milling pulverizing 30 times.Transmission electron microscope (TEM) result shows that the part iron particle is of a size of 10～90nm (as shown in Figure 4); Fig. 5 is the relation that polypropylene/iron composite powder system is equipped with x-ray diffraction pattern and pan-milling number of times in the process, 1 is polypropylene (before milling) among the figure, 2 are polypropylene/iron mixture (before milling), 3 are polypropylene/iron mixed powder (milling 11 times), 4 are polypropylene/iron mixed powder (milling 13 times), 5 are polypropylene/iron mixed powder (milling 15 times), 6 are polypropylene/iron mixed powder (milling 17 times), 7 are polypropylene/iron mixed powder (milling 19 times), and 8 are polypropylene/iron mixed powder (milling 25 times).Calculating shows that the crystallite dimension of metal in the composite granule that obtains is 20～90nm (seeing Fig. 6～7 for details), and composite granule is of a size of 1～50 μ m (seeing Fig. 8 for details).
The preparation process explanation crushing mechanism of milling of the present invention with polypropylene/iron composite nano-powder.Experimental result shows: metallic particles stands processes such as calendering, crackle produces and break and forms ultrafine powder in the pan-milling process, when PP GRANULES and iron powder are milled altogether, polypropylene particles is through by compression and shear action, priority cracks, forms laminar structured, and metal dust is entrenched in polypropylene surface and forms the top layer; Under mill complex stress field action, fragment further stands repeatedly calendering and cracked, and grain refine forms polypropylene/iron composite nano-powder.The X-ray diffraction analysis result of Fig. 5 shows, when metallic iron and polypropylene are milled altogether, the diffracted intensity of (110) crystal face of iron increases with grinding times and descends, and half-peak breadth increases with grinding times, proves that the crystallite dimension of iron reduces with the grinding times increase; Fig. 6 shows, when metallic iron and polypropylene were milled altogether, the crystallite dimension of iron reached 22nm after milling for 25 times; And when iron is milled separately its size reduce generally only in μ m level, be difficult to obtain nano level iron micro mist (see figure 7), illustrate that polymer has good grinding aid effect to metal.Transmission electron microscope pattern result of study (see figure 8) shows that iron is scattered in the polypropylene with nano shape in polypropylene/iron composite powder body.Explanation thus, the millstone type Mechanico-chemical reactor can be used to prepare the nano polymer/metal composite granule.
The nano polymer/metal powder of the present invention preparation can make an addition to other or with making the nano polymer/metal composite material with certain outward appearance, mechanical strength in the base polymer by hot-forming, powder injection or as masterbatch; Or directly by electrostatic spraying, hot dipping burst, method such as fluid bed is attached on other base material, forms the nano polymer/metal composite material coating.Material of being made by the nano polymer/metal composite granule of the present invention preparation or coating can be applicable to conduction, heat conduction, electrostatic screen, magnetic recording, antistatic, sound insulation and noise reducing, low-resistance electrical heating, microwave absorption and senser element and fields such as powder injection and powder extrusion molding.
The present invention has following advantage:
1, the present invention utilizes millstone type Mechanico-chemical reactor particular structure and material is applied powerful shear stress, and crushing medium (mill) closely contacts with crushed material, the crush efficiency height; Can realize the miniaturization and compoundization of polymer and metal simultaneously, form composite nano-powder.
2, overcome because the agglomeration traits that the huge surface of metal nanoparticle can produce has solved the dispersion of metal nano, stable and compound problem.
3, this method prepares the nano polymer/metal composite granule under solid conditions, need not heating or deep cooling, have energy-conservation, technology is simple, easy to operate, low cost of manufacture, can realize that scale produces continuously; It is a kind of eco-friendly method for preparing ultrafine powder.
4, realize the compound of metal-powder and polymer under high tenor, when having overcome high tenor, the polymer/metal compound system is big because of melt viscosity, can not melt extrude the problem of processing with melt injection.
5, can be used for the ultramicro grinding of multiple polymers and metal material and compound.
Embodiment
By the following examples the present invention is specifically described.It must be noted that following embodiment only is applicable to can not be interpreted as limiting the scope of the invention to further specifying that the present invention carries out.The engineers and technicians in this field can do some nonessential improvement and adjustment to the present invention according to the invention described above content.
1. with polyethylene powder (particle size range 21.5～82.7 μ m) 60g, nickel powder (particle size range 35～60 μ m) 300g, stearic acid 1.5g, place high-speed stirring mixer to mix (model: GH-10DY, Beijing plastics machinery factory), incorporation time 30 minutes, wherein every stirring stopped three minutes in 5 minutes, to prevent that frictional heating from making polymer softening, adhesion.Feed recirculated water at millstone type Mechanico-chemical reactor static cutting disk lateral surface cavity, 15～20 ℃ of water temperatures start the millstone type Mechanico-chemical reactor, 40～50 rev/mins of control rotating speeds.By charge door, add by the polyethylene powder, the mixture that nickel powder and stearic acid are formed, the pulverizing of milling, control charging rate and speed of grinding plate make the time of staying of material in mill between 20～40 seconds.Mixture after last time pulverizing is carried out pan-milling once more, collect the fine powder that obtains, mill to death 40 times promptly obtains polyethylene/nickel composite nano-powder.X-ray diffraction test and transmission electron microscope analysis show that the crystallite dimension of nickel is 30～50nm in polyethylene/nickle composite powder, and the average grain diameter that the laser particle size distribution instrument records composite granule is 18.5 μ m, and particle size distribution range is 6.8～41.2 μ m.
2. (particle size range 3～5mm) is milled 3～5 times at the millstone type Mechanico-chemical reactor, makes its shaped flatization and forms the fragment that specific surface increases with PP GRANULES.With above-mentioned polypropylene fragment 200g that obtains and metallic iron (particle size range 18.5～28.1 μ m) 45g, place high-speed stirring mixer to mix (model: GH-10DY, Beijing plastics machinery factory), incorporation time 45 minutes, wherein every stirring stopped three minutes in 5 minutes, to prevent that frictional heating from making polymer softening, adhesion.Feed recirculated water at millstone type Mechanico-chemical reactor static cutting disk lateral surface cavity, 15～20 ℃ of water temperatures start the millstone type Mechanico-chemical reactor, 35～45 rev/mins of control rotating speeds.By charge door, add the mixture of forming by polypropylene fragment, iron powder, the pulverizing of milling, control charging rate and speed of grinding plate make the time of staying of material in mill between 20～40 seconds.With the mixture mill to death after last time pulverizing 30 times, promptly obtain polypropylene/iron composite nano-powder.X-ray diffraction test and transmission electron microscope analysis show that the crystallite dimension of nickel is 28-62nm in polypropylene/iron composite powder body, and the average grain diameter that the laser particle size distribution instrument records composite granule is 6.5 μ m, and particle size distribution range is 1.2～35.8 μ m.
3. the iron granule that with the grain size scope is 150.2～230.5 μ m (average grain diameter 198.7 μ m) is milled 5～10 times at the millstone type Mechanico-chemical reactor, makes its shaped flatization and forms the powder that specific surface increases.Get the above-mentioned iron powder 25g that obtains, with polymethyl methacrylate powder (particle size range 0.18～0.32mm, average grain diameter 0.25mm) 200g, titanate coupling agent 4.8g places high-speed stirring mixer to mix (model: GH-10DY, Beijing's plastics machinery factory), incorporation time 15 minutes, wherein every stirring stopped three minutes in 5 minutes, made polymer softening to prevent frictional heating, adhesion.Feed recirculated water at millstone type Mechanico-chemical reactor static cutting disk lateral surface cavity, 20～25 ℃ of water temperatures start the millstone type Mechanico-chemical reactor, 25～30 rev/mins of control rotating speeds.By charge door, add the mixture of forming by polymethyl methacrylate powder, titanate coupling agent and iron powder, the pulverizing of milling, control charging rate and speed of grinding plate make the time of staying of material in mill between 20～40 seconds.Mixture after last time pulverizing is milled once more, collect the fine powder that obtains, mill to death 45 times promptly obtains polymethyl methacrylate/iron composite nano-powder.X-ray diffraction test and transmission electron microscope analysis show that the crystallite dimension of iron is 23-42nm in polymethyl methacrylate/iron composite powder body, and the average grain diameter that the laser particle size distribution instrument records composite granule is 31.7 μ m, and particle size distribution range is 15.8～48.5 μ m.
4. (ABS resin, particle diameter 2～4mm) is milled 4 times at the millstone type Mechanico-chemical reactor, makes its shaped flatization and forms the fragment that specific surface increases will to gather (acrylonitrile-butadiene-styrene (ABS)) copolymer.With ABS resin fragment 350g and metallic zinc (particle size range 23～50 μ m) 120g that obtains, and silane coupler 1.8g places high-speed stirring mixer to mix (model: GH-10DY, Beijing plastics machinery factory), incorporation time 30 minutes, every stirring stopped three minutes in 5 minutes, to prevent that frictional heating from making polymer softening, adhesion.Feed recirculated water at millstone type Mechanico-chemical reactor static cutting disk lateral surface cavity, 18～23 ℃ of water temperatures start the millstone type Mechanico-chemical reactor, 40～50 rev/mins of control rotating speeds.Add the mixture of being made up of ABS resin fragment, metallic zinc and silane coupler by charge door, carry out pan-milling and pulverize, control charging rate and speed of grinding plate make the time of staying of material in mill between 20～40 seconds.With the powder mill to death that obtains 45 times, promptly obtain ABS resin/zinc composite nano-powder.X-ray diffraction test and transmission electron microscope analysis show that the crystallite dimension of zinc is 18～22nm in ABS resin/zinc composite granule, and the average grain diameter that the laser particle size distribution instrument records composite granule is 11.3 μ m, and particle size distribution range is 4.7～21.4 μ m.Show the composite nano-powder that can be used to prepare copolymer and metal formation by method provided by the invention.
5. the manufacture method of the polynary composite granule formed of polypropylene, polyethylene, copper and aluminium
(1) (particle diameter 3～5mm) is milled 3～5 times at the millstone type Mechanico-chemical reactor, makes its shaped flatization and forms the fragment that specific surface increases with PP GRANULES.Getting 200g polypropylene fragment and ultra-high molecular weight polyethylene powder (average grain diameter 120 μ m) 60g mixes at high-speed stirring mixer.Mill 10 times at the millstone type Mechanico-chemical reactor then, obtaining average grain diameter is the mixed with polymers powder of 200 μ m.
(2) metallic copper particle (average grain diameter 200 μ m) 100g is milled 5 times at the millstone type Mechanico-chemical reactor, make its shaped flatization and form the powder that specific surface increases, other gets metallic aluminium powder (average grain diameter 50 μ m) 100g and mixes at high-speed stirring mixer.Obtain the metal mixed powder.
(3) will mix at high-speed stirring mixer by step (1) mixed with polymers powder that obtains and the metal mixed powder that obtains by step (2), incorporation time 20 minutes, wherein every stirring stopped three minutes in 5 minutes, made polymer softening to prevent frictional heating, adhesion.Feed recirculated water at millstone type Mechanico-chemical reactor static cutting disk lateral surface cavity, 20～25 ℃ of water temperatures start the millstone type Mechanico-chemical reactor, 35～45 rev/mins of control rotating speeds.The mixed powder that adding is made up of polypropylene, ultra-high molecular weight polyethylene, metallic copper and metallic aluminium carries out pan-milling and pulverizes, and control charging rate and speed of grinding plate make the time of staying of material in mill between 20～40 seconds.Mixture after last time pulverizing is put into pan-milling once more, collect the fine powder that obtains, mill to death 50 times, the average grain diameter that the laser particle size distribution instrument records composite granule is 5.1 μ m, particle size distribution range is 0.8～12.7 μ m, in the X-ray diffraction test shows composite granule, the average grain size of copper is 18.2nm, and the average grain size of aluminium is 20.8nm.Explanation can be used to prepare the composite nano-powder of multicomponent polymeric and multicomponent metal formation by method provided by the invention.
Claims (4)
1. the millstone type Mechanico-chemical reactor prepares the method for nano polymer/metal composite granule, it is characterized in that the recipe ingredient (by weight) of initiation material is:
5～300 parts of polymer beads
10～600 parts of metallic particles
0～10 part of coupling agent
Wherein the particle diameter of polymer beads is 10 μ m～5mm, and the particle diameter of metallic particles is 1～500 μ m, and according to its particle size difference, the precomminution and the mixed method of employing are as follows
A. the particle size range when polymer is 10 μ m～0.5mm, when the particle size range of metal is 1～75 μ m, raw material added in the high speed agitator mixes, send into the millstone type Mechanico-chemical reactor then and mill and pulverize 20～60 times, promptly obtain the nano polymer/metal composite granule
B. working as the metal particle size range is 75 μ m～500 μ m, when polymer particle diameter scope is 0.5mm～5mm, need with the two respectively in the millstone type Mechanico-chemical reactor pre-grinding be crushed to below the 75 μ m and below the 0.5mm, in high speed agitator, mix then with coupling agent, mill at the millstone type Mechanico-chemical reactor and to pulverize 20～60 times, promptly obtain the nano polymer/metal composite granule.
2. prepare the method for nano polymer/metal composite granule according to claims 1 described millstone type Mechanico-chemical reactor, it is characterized in that described polymer is a polyethylene, polypropylene, Merlon, polymethyl methacrylate, polyester, polyacrylate, polyimides, phenolic resins, melmac, polyamide, polystyrene, polyvinyl chloride, epoxy resin, polyvinyl acetate, polytetrafluoroethylene (PTFE), neoprene, Vingon, polyformaldehyde, polyethylene glycol oxide, polyvinyl alcohol, polybutadiene, polyisobutene, polymethylpentene, poly-(acrylonitrile-butadiene-styrene (ABS)), poly-(styrene-butadiene) and/or poly-(ethylene-propylene) copolymer are at least a.
3. prepare the method for nano polymer/metal composite granule according to claims 1 described millstone type Mechanico-chemical reactor, it is characterized in that described metal is that iron, cobalt, nickel, aluminium, lead, zinc, copper, chromium, zirconium, magnesium, manganese, molybdenum, strontium, antimony, tungsten, tin and rare-earth elements of lanthanum, cerium, praseodymium, neodymium, europium and/or dysprosium are at least a.
4. prepare the method for nano polymer/metal composite granule according to claims 1 described millstone type Mechanico-chemical reactor, it is characterized in that described coupling agent is C
12～C
18Higher fatty acids, silane coupler, titanate coupling agent and/or aluminate coupling agent are at least a.
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| CN100509881C (en) * | 2006-09-11 | 2009-07-08 | 四川大学 | Method for improving processing capability of metallocene polyethylene |
| CN103792227B (en) * | 2014-01-22 | 2017-02-15 | 北京联合大学生物化学工程学院 | Nano composite oxide sensitive material for formaldehyde and benzene |
| CN106832905A (en) * | 2017-02-28 | 2017-06-13 | 四川大学 | Polymer matrix micro-/ nano composite material powder and preparation method thereof |
| CN110642295B (en) * | 2019-10-25 | 2021-08-03 | 四川大学 | Molybdenum disulfide nanosheet layer stripping preparation method based on solid-phase mechanochemical reactor |
| CN111533978A (en) * | 2020-05-26 | 2020-08-14 | 四川大学 | High-value composite material for automobile broken residues and preparation method thereof |
| US20230312841A1 (en) | 2020-08-31 | 2023-10-05 | SETUP Performance SAS | Powder composition for additive process and printed parts thereof |
| CN112940342B (en) * | 2021-02-24 | 2022-08-12 | 四川大学 | Method for preparing open-cell ZIF-8/polymer composite foam material by utilizing solid-phase shearing and grinding technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1130545A (en) * | 1995-03-06 | 1996-09-11 | 四川联合大学 | Mechanico-chemical reactor |
| CN1266760A (en) * | 2000-04-17 | 2000-09-20 | 薛峻峰 | Process for preparing nm-class Ti-base metal powder and its special grinding apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1130545A (en) * | 1995-03-06 | 1996-09-11 | 四川联合大学 | Mechanico-chemical reactor |
| CN1266760A (en) * | 2000-04-17 | 2000-09-20 | 薛峻峰 | Process for preparing nm-class Ti-base metal powder and its special grinding apparatus |
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