CN104774345A - Method for preparing filled conductive rubber by radiation method - Google Patents
Method for preparing filled conductive rubber by radiation method Download PDFInfo
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- CN104774345A CN104774345A CN201510204889.XA CN201510204889A CN104774345A CN 104774345 A CN104774345 A CN 104774345A CN 201510204889 A CN201510204889 A CN 201510204889A CN 104774345 A CN104774345 A CN 104774345A
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Abstract
The invention provides a method for preparing filled conductive rubber by a radiation method, relating to methods for preparing filled conductive rubber. The invention aims to solve the technical problem of poor uniformity and stability of a blending system in an emulsion blending method of the present filled conductive rubber. The method comprises the following steps: I. expanded graphite stripping; II. blending; III. electron beam radiation; IV. demulsification. The problem of poor dispersion uniformity and stability of fillers in an emulsion blending system is effectively solved by adopting the method.
Description
Technical field
The present invention relates to a kind of method preparing filled-type conductive rubber.
Background technology
The elasticity that elastomeric material has is the distinguishing feature of this kind of macromolecular material, is not only to its elastomeric demand at present, and elastomeric material functionalization is the important development direction in this field, particularly elastomeric material conducting function always.Conductive rubber is widely applied in antistatic product, electronic devices and components and electromagnetic shielding sealing article etc. are numerous.The topmost method preparing conductive rubber is at present exactly be filled in rubber by blended method by conductive filler material to form conductive network, realizes its conducting function.Filled-type conductive rubber has the features such as easy processing, cost be low relative to structural conductive rubber, and the preparation method of filled-type conductive rubber mainly contains the methods such as melt blending, emulsion blending and solution blending.The method of current technology of preparing mainly melt blending, such as Chinese patent CN103122085A and CN102911411A; The method of emulsion blending, such as Chinese patent 103289138A and 103183847A; The method of solution blending, such as Chinese patent CN102674324A and CN104130753A.The subject matter adopting melt blending to prepare matrix material is that packing specific area is comparatively large, and surface energy is higher, and this can make filler cause gathering in polymeric matrix, causes its dispersiveness poor; In addition, rubber melt viscosity is comparatively large, and mixed refining process is more difficult.Adopt the method for solution blending can solve the problem that rubber melt viscosity is comparatively large, mixed refining process is difficult, but it can cause environmental pollution, and difficult solvent recovery, preparation cost is higher.The method of emulsion blending has obvious advantage, processing is easier to, and can not pollute, although latex particle and conductive filler material co-coagulation can be made when breakdown of emulsion, the homogeneity of conductive filler material dispersion is better, but due to latex and filler interphase interaction less, reassociating between latex particle and between filler is still difficult to avoid, therefore solve emulsion blending prepare the technical bottleneck that electro-conductive material and co-mixing system homogeneity and stability problem are this area all the time.
Summary of the invention
The present invention is the technical problem of co-mixing system homogeneity and poor stability in the emulsion dispersion that will solve current filled-type conductive rubber, and provides a kind of radiation method to prepare the method for filled-type conductive rubber.
The method that a kind of radiation method of the present invention prepares filled-type conductive rubber is carried out according to the following steps:
One, expanded graphite is peeled off: with microwave oven to expanded graphite microwave radiation 30s ~ 40s, then put in water phase surfactant mixture, ultrasonic 20h ~ 24h, obtain nano graphite flakes water miscible liquid; The mass concentration of described water phase surfactant mixture is 3 ‰ ~ 5 ‰; In described nano graphite flakes water miscible liquid, the mass concentration of expanded graphite is 0.6 ‰ ~ 2 ‰;
Two, blended: nano graphite flakes water miscible liquid step one obtained joins in latax, and ultrasonic 30min ~ 40min, obtains blended liquid; Mass ratio 1:(5 ~ 200 of the solute in the expanded graphite described in step one and the latax described in step 2);
Three, electron beam irradiation: blended liquid step 2 obtained is encapsulated in polythene film bag, energy be 1.2MeV, beam intensity carries out electron beam irradiation under being 0.05mA ~ 1mA and the condition of irradiation dose at 10kGy ~ 150kGy, obtains mixed solution;
Four, breakdown of emulsion: add CaCl in the mixed solution obtained to step 3 under ultrasonic condition
2the aqueous solution, obtains throw out, then suction filtration, and be dry 3h ~ 4h under the condition of 100 DEG C in temperature, compressing tablet, obtains filled-type conductive rubber prepared by radiation method; Described CaCl
2the mass concentration of the aqueous solution is 1% ~ 1.5%; Described CaCl
2the volume ratio of the mixed solution that the aqueous solution and step 3 obtain is 1:7.5.
The present invention by expansible black lead after microwave treatment, join in water phase surfactant mixture and infiltrate, obtain peeling off the graphite flake water miscible liquid for nanoscale after supersound process, and joined in rubber latex liquid, electron beam radiation treatment is used again, the conductive rubber finally utilizing electrolyte solution breakdown of emulsion to obtain latex particle and nano graphite flakes to mix alternately after ultrasonic disperse process.
In the present invention, because electron beam irradiation makes the degree of crosslinking of latex particle increase, latex particle is assembled tendency and is reduced, and thus, particle keeps the ability of its intrinsic form to improve; Simultaneously, under x ray irradiation x condition, latex particle surface is not only made to produce active centre, also the nano graphite flakes of suspended state is made to produce active centre (and the sp2 of graphite also can make active centre more stable) on the surface, thus make latex particle and nano graphite flakes form bonding, therefore, can obtain after breakdown of emulsion finely divided, have and interact and orderly floss, it is obtained conductive rubber after suction filtration, drying and compressing tablet again, effectively solves the problem of fillers dispersed homogeneity and poor stability in emulsion blending system.
Conductive filler material of the present invention is utilize expansible black lead after adding thermal expansion by the ultrasonic nano graphite flakes peeling off preparation, this conductive rubber is that part stripping nano graphite flake is dispersed in and obtains orderly distribution in rubber matrix and by radiation treatment and formed interacting, and becomes the network structure that latex particle is wrapped in nano graphite flakes.
Latax of the present invention all can directly bought on the market, and every money latax all has the to one's name distinctive trade mark, and the mass concentration of the latax that each trade mark is corresponding is fixing.
Accompanying drawing explanation
Fig. 1 is thermogravimetric curve figure, and curve 1 is filled-type conductive rubber prepared by test one, and curve 2 is filled-type conductive rubber prepared by radiation method that test two obtains;
Fig. 2 is absorbance curve figure, curve 1 is in test three be the absorbance curve recorded after FM301 carboxy nitrile rubber latax is diluted to 280 times to the trade mark, curve 2 is that blended liquid that test one step 2 obtains carries out diluting and makes the wherein trade mark be the absorbance curve recorded after the mass concentration of FM301 carboxy nitrile rubber latax is diluted to 280 times, and curve 3 is that mixed solution that test two step 3 obtains carries out diluting and makes the wherein trade mark be the absorbance curve recorded after the mass concentration of FM301 carboxy nitrile rubber latax dilutes 280 times;
Fig. 3 is electron beam irradiation amount-volume specific resistance graph of a relation, curve 1 is the curve of conductive rubber matching of test one, test two, test 11, test 12, test 13, test 14 and test 15 preparation, the curve of the gum material matching that curve 2 be test five, prepared by test four, test six, test seven, test eight, test nine and test ten.
Embodiment
Embodiment one: present embodiment is a kind of method that radiation method prepares filled-type conductive rubber, specifically carries out according to the following steps:
One, expanded graphite is peeled off: with microwave oven to expanded graphite microwave radiation 30s ~ 40s, then put in water phase surfactant mixture, ultrasonic 20h ~ 24h, obtain nano graphite flakes water miscible liquid; The mass concentration of described water phase surfactant mixture is 3 ‰ ~ 5 ‰; In described nano graphite flakes water miscible liquid, the mass concentration of expanded graphite is 0.6 ‰ ~ 2 ‰;
Two, blended: nano graphite flakes water miscible liquid step one obtained joins in latax, and ultrasonic 30min ~ 40min, obtains blended liquid; Mass ratio 1:(5 ~ 200 of the solute in the expanded graphite described in step one and the latax described in step 2);
Three, electron beam irradiation: blended liquid step 2 obtained is encapsulated in polythene film bag, energy be 1.2MeV, beam intensity carries out electron beam irradiation under being 0.05mA ~ 1mA and the condition of irradiation dose at 10kGy ~ 150kGy, obtains mixed solution;
Four, breakdown of emulsion: add CaCl in the mixed solution obtained to step 3 under ultrasonic condition
2the aqueous solution, obtains throw out, then suction filtration, and be dry 3h ~ 4h under the condition of 100 DEG C in temperature, compressing tablet, obtains filled-type conductive rubber prepared by radiation method; Described CaCl
2the mass concentration of the aqueous solution is 1% ~ 1.5%; Described CaCl
2the volume ratio of the mixed solution that the aqueous solution and step 3 obtain is 1:7.5.
Embodiment two: present embodiment and embodiment one unlike: in the water phase surfactant mixture described in step one, tensio-active agent is the mixture of one or more in Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, polysorbate60 and tween 80.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment two unlike: the power of the microwave oven described in step one is 900W.Other is identical with embodiment two.
Embodiment four: present embodiment and embodiment two unlike: the latax described in step 2 is the mixture of one or more in caoutchouc latex liquid, styrene-butadiene rubber(SBR) latax, cis-1,4-polybutadiene rubber latax, acrylic elastomer latax, chloroprene rubber latax, paracril latax and carboxy nitrile rubber latax.Other is identical with embodiment two.
Embodiment five: present embodiment and embodiment one unlike: in step 3, the blended liquid that step 2 obtains is encapsulated in polythene film bag, energy be 1.2MeV, beam intensity carries out electron beam irradiation under being 0.2mA ~ 0.6mA and the condition of irradiation dose at 70kGy ~ 100kGy, obtains mixed solution.Other is identical with embodiment one.
Adopt following verification experimental verification effect of the present invention:
Test one: this test is simultaneous test, specifically carries out according to the following steps:
One, expanded graphite is peeled off: with microwave oven to expanded graphite microwave radiation 35s, then put in water phase surfactant mixture, ultrasonic 24h, obtain nano graphite flakes water miscible liquid; The mass concentration of described water phase surfactant mixture is 3.5 ‰; In described nano graphite flakes water miscible liquid, the mass concentration of expanded graphite is 0.7 ‰;
Two, blended: nano graphite flakes water miscible liquid step one obtained joins in latax, and ultrasonic 30min, obtains blended liquid; The mass ratio 1:100 of the solute in the expanded graphite described in step one and the latax described in step 2;
Three, breakdown of emulsion: add CaCl in the blended liquid obtained to step 2 under ultrasonic condition
2the aqueous solution, obtains throw out, then suction filtration, and be dry 3h under the condition of 100 DEG C in temperature, compressing tablet, obtains filled-type conductive rubber; Described CaCl
2the mass concentration of the aqueous solution is 1%; Described CaCl
2the volume ratio of the mixed solution that the aqueous solution and step 3 obtain is 1:7.5.
The model of the expanded graphite described in step one is 8099300; In water phase surfactant mixture described in step one, tensio-active agent is Sodium dodecylbenzene sulfonate; The power of the microwave oven described in step one is 900W; Latax described in step 2 is the trade mark is FM301 carboxy nitrile rubber latax.
Test two: this test is a kind of method that radiation method prepares filled-type conductive rubber, specifically carries out according to the following steps:
One, expanded graphite is peeled off: with microwave oven to expanded graphite microwave radiation 35s, then put in water phase surfactant mixture, ultrasonic 24h, obtain nano graphite flakes water miscible liquid; The mass concentration of described water phase surfactant mixture is 3.5 ‰; In described nano graphite flakes water miscible liquid, the mass concentration of expanded graphite is 0.7 ‰;
Two, blended: nano graphite flakes water miscible liquid step one obtained joins in latax, and ultrasonic 30min, obtains blended liquid; The mass ratio 1:100 of the solute in the expanded graphite described in step one and the latax described in step 2;
Three, electron beam irradiation: blended liquid step 2 obtained is encapsulated in polythene film bag, energy be 1.2MeV, beam intensity carries out electron beam irradiation under being 0.25mA and the condition of irradiation dose at 50kGy, obtains mixed solution;
Four, breakdown of emulsion: add CaCl in the mixed solution obtained to step 3 under ultrasonic condition
2the aqueous solution, obtains throw out, then suction filtration, and be dry 3h under the condition of 100 DEG C in temperature, compressing tablet, obtains filled-type conductive rubber prepared by radiation method; Described CaCl
2the mass concentration of the aqueous solution is 1%; Described CaCl
2the volume ratio of the mixed solution that the aqueous solution and step 3 obtain is 1:7.5;
In water phase surfactant mixture described in step one, tensio-active agent is Sodium dodecylbenzene sulfonate; The power of the microwave oven described in step one is 900W; Latax described in step 2 is the trade mark is FM301 carboxy nitrile rubber latax.
Fig. 1 is thermogravimetric curve figure, curve 1 is filled-type conductive rubber prepared by test one, curve 2 is filled-type conductive rubber prepared by radiation method that test two obtains, as can be seen from the figure the conductive rubber thermostability testing irradiation 50kGy electron beam in two improves, the temperature of weightless 5% improves 8 DEG C, improves 4.5 DEG C when weightless 10%.
Test three: being under the condition of 480nm at wavelength, is carry out absorbancy test after FM301 carboxy nitrile rubber latax dilutes 280 times to the trade mark; The blended liquid that test one step 2 obtains is carried out diluting and makes the wherein trade mark be that the mass concentration of solute in FM301 carboxy nitrile rubber latax dilutes 280 times, then carry out absorbancy test; Test mixed solution that two step 3 obtain to carry out diluting and make the wherein trade mark be that the mass concentration of solute in FM301 carboxy nitrile rubber latax dilutes 280 times, then carry out absorbancy test.
Fig. 2 is absorbance curve figure, curve 1 is in test three be the absorbance curve recorded after FM301 carboxy nitrile rubber latax is diluted to 280 times to the trade mark, curve 2 is that blended liquid that test one step 2 obtains carries out diluting and makes the wherein trade mark be the absorbance curve recorded after the mass concentration of solute in FM301 carboxy nitrile rubber latax dilutes 280 times, curve 3 is that mixed solution that test two step 3 obtains carries out diluting and makes the wherein trade mark be the absorbance curve recorded after the mass concentration of solute in FM301 carboxy nitrile rubber latax dilutes 280 times, as can be seen from the figure the stability of pure latex is the highest, add its bad stability after graphite, after by blended liquid irradiation 50kGy electron beam, latex system stability is the poorest, illustrate that irradiation can make the Interaction enhanced between latex particle and graphite and jointly settle down, therefore absorbancy is minimum, Interaction enhanced between latex particle and graphite can make the stability of final finished conductive rubber strengthen.
Test four: this test is simultaneous test, specifically carries out according to the following steps:
One, electron beam irradiation: latax is encapsulated in polythene film bag, energy be 1.2MeV, beam intensity carries out electron beam irradiation under being 0.25mA and the condition of irradiation dose at 10kGy, obtains mixed solution;
Two, breakdown of emulsion: add CaCl in the mixed solution obtained to step one under ultrasonic condition
2the aqueous solution, obtains throw out, then suction filtration, and be dry 3h under the condition of 100 DEG C in temperature, compressing tablet, obtains gum material; Described CaCl
2the mass concentration of the aqueous solution is 1%; Described CaCl
2the volume ratio of the mixed solution that the aqueous solution and step one obtain is 1:7.5.
Latax described in step one is the trade mark is FM301 carboxy nitrile rubber latax.
Test five: this test is simultaneous test, specifically carries out according to the following steps:
One, breakdown of emulsion: add CaCl under ultrasonic condition in latax
2the aqueous solution, obtains throw out, then suction filtration, and be dry 3h under the condition of 100 DEG C in temperature, compressing tablet, obtains gum material; Described CaCl
2the mass concentration of the aqueous solution is 1%; Described CaCl
2the volume ratio of the aqueous solution and latax is 1:7.5; Latax described in step one is the trade mark is FM301 carboxy nitrile rubber latax.
Test six: this test be simultaneous test, this test and to test four unlike the irradiation dose of step one be 30kGy, other is identical with testing four.
Test seven: this test be simultaneous test, this test and to test four unlike the irradiation dose of step one be 50kGy, other is identical with testing four.
Test eight: this test be simultaneous test, this test and to test four unlike the irradiation dose of step one be 70kGy, other is identical with testing four.
Test nine: this test be simultaneous test, this test and to test four unlike the irradiation dose of step one be 100kGy, other is identical with testing four.
Test ten: this test be simultaneous test, this test and to test four unlike the irradiation dose of step one be 150kGy, other is identical with testing four.
Test 11: this test is for simultaneous test, and this test and test two are 10kGy unlike the irradiation dose of step one, and other is identical with testing four.
Test 12: this test is for simultaneous test, and this test and test two are 30kGy unlike the irradiation dose of step one, and other is identical with testing four.
Test 13: this test is for simultaneous test, and this test and test two are 70kGy unlike the irradiation dose of step one, and other is identical with testing four.
Test 14: this test is for simultaneous test, and this test and test two are 100kGy unlike the irradiation dose of step one, and other is identical with testing four.
Test 15: this test is for simultaneous test, and this test and test two are 150kGy unlike the irradiation dose of step one, and other is identical with testing four.
Fig. 3 is electron beam irradiation amount-volume specific resistance graph of a relation, curve 1 is test one, test two, test 11, test 12, test 13, test the curve of the conductive rubber matching that 14 prepare with test 15, curve 2 is test five, test four, test six, test seven, test eight, the curve of the gum material matching of test nine and test ten preparation, as can be seen from the figure, irradiation just can cause the change of the volume specific resistance that gum material is less, and matrix material its volume specific resistance when not having electron beam irradiation adding expanded graphite reduces 1 order of magnitude, illustrate that it has defined certain conductive path, but the volume specific resistance of matrix material obtains and significantly improves after electron beam irradiation, improve nearly 4 orders of magnitude, illustrate that graphite flake obtains further finely divided and is uniformly distributed in co-mixing system, the volume specific resistance of matrix material is just caused to improve.
Claims (5)
1. radiation method prepares a method for filled-type conductive rubber, it is characterized in that the method that radiation method prepares filled-type conductive rubber is carried out according to the following steps:
One, expanded graphite is peeled off: with microwave oven to expanded graphite microwave radiation 30s ~ 40s, then put in water phase surfactant mixture, ultrasonic 20h ~ 24h, obtain nano graphite flakes water miscible liquid; The mass concentration of described water phase surfactant mixture is 3 ‰ ~ 5 ‰; In described nano graphite flakes water miscible liquid, the mass concentration of expanded graphite is 0.6 ‰ ~ 2 ‰;
Two, blended: nano graphite flakes water miscible liquid step one obtained joins in latax, and ultrasonic 30min ~ 40min, obtains blended liquid; Mass ratio 1:(5 ~ 200 of the solute in the expanded graphite described in step one and the latax described in step 2);
Three, electron beam irradiation: blended liquid step 2 obtained is encapsulated in polythene film bag, energy be 1.2MeV, beam intensity carries out electron beam irradiation under being 0.05mA ~ 1mA and the condition of irradiation dose at 10kGy ~ 150kGy, obtains mixed solution;
Four, breakdown of emulsion: add CaCl in the mixed solution obtained to step 3 under ultrasonic condition
2the aqueous solution, obtains throw out, then suction filtration, and be dry 3h ~ 4h under the condition of 100 DEG C in temperature, compressing tablet, obtains filled-type conductive rubber prepared by radiation method; Described CaCl
2the mass concentration of the aqueous solution is 1% ~ 1.5%; Described CaCl
2the volume ratio of the mixed solution that the aqueous solution and step 3 obtain is 1:7.5.
2. a kind of radiation method according to claim 1 prepares the method for filled-type conductive rubber, it is characterized in that in the water phase surfactant mixture described in step one, tensio-active agent is the mixture of one or more in Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, polysorbate60 and tween 80.
3. a kind of radiation method according to claim 1 prepares the method for filled-type conductive rubber, it is characterized in that the power of the microwave oven described in step one is 900W.
4. a kind of radiation method according to claim 1 prepares the method for filled-type conductive rubber, and the latax that it is characterized in that described in step 2 is the mixture of one or more in caoutchouc latex liquid, styrene-butadiene rubber(SBR) latax, cis-1,4-polybutadiene rubber latax, acrylic elastomer latax, chloroprene rubber latax, paracril latax and carboxy nitrile rubber latax.
5. a kind of radiation method according to claim 1 prepares the method for filled-type conductive rubber, it is characterized in that in step 3, the blended liquid that step 2 obtains being encapsulated in polythene film bag, energy be 1.2MeV, beam intensity carries out electron beam irradiation under being 0.2mA ~ 0.6mA and the condition of irradiation dose at 70kGy ~ 100kGy, obtains mixed solution.
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| WO2014093139A1 (en) * | 2012-12-14 | 2014-06-19 | 3M Innovative Properties Company | Method of polymerizing ethylenically-unsaturated materials using ionizing radiation |
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| CN101463149A (en) * | 2007-12-19 | 2009-06-24 | 北京化工大学 | Preparation of wear resistant rubber composite material |
| CN101445646A (en) * | 2008-12-11 | 2009-06-03 | 上海交通大学 | Preparation method of polymeric based carbon nano tube composite material in the technical field of nano-materials |
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