CN110408030A - The method that a kind of ring-opening polymerisation of cyclosiloxane original position prepares high-performance conductive silicon rubber - Google Patents

The method that a kind of ring-opening polymerisation of cyclosiloxane original position prepares high-performance conductive silicon rubber Download PDF

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CN110408030A
CN110408030A CN201910742428.6A CN201910742428A CN110408030A CN 110408030 A CN110408030 A CN 110408030A CN 201910742428 A CN201910742428 A CN 201910742428A CN 110408030 A CN110408030 A CN 110408030A
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silicon rubber
cyclotetrasiloxane
tetramethyl
conductive
doping
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李志波
赵娜
时金凤
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Qingdao University of Science and Technology
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Abstract

The invention discloses the polysiloxanes that a kind of cyclosiloxane monomers in situ ring-opening polymerisation using organic phosphazene catalyst catalysis doping conductive fill particle, reinforced filling, vulcanizing agent without metallic element prepares doping conductive fill particle, and the method for preparing conductive silicon rubber nanocomposite through sulfidization molding.One kettle way preparation can be used in the silicon rubber nano composite material of this report invention, preparation method is simple and efficient, all fillers can be added before the polymerization, it is uniformly mixed with monomer, cyclosiloxane monomer in situ polymerization effect is not by fillers affect, and gained silicon rubber composite material appearance is flat and smooth, and particle filled composite is uniformly dispersed, the good mechanical property of pure sulphurated siliastic is maintained, and has both excellent electric conductivity.

Description

The method that a kind of ring-opening polymerisation of cyclosiloxane original position prepares high-performance conductive silicon rubber
Technical field
The present invention relates to the preparation methods that a kind of ring-opening polymerisation of cyclosiloxane original position prepares high-performance conductive silicon rubber, specifically It is related to the polysiloxanes using organic phosphazene catalyst catalysis cyclosiloxane original position ring-opening polymerisation preparation doping conductive fill particle, And the method for through sulfidization molding preparing high-performance conductive silicon rubber nano composite material.
Background technique
Conductive silicon rubber is composite material that is a kind of while possessing electric conductivity and mechanical performance, has good pressure drag special Property and temperature resistance characteristic.Conductive filler can not only assign conductivity of composite material, can also reduce material cost, significantly improve multiple The various performances of condensation material, keep its application range more extensive, such as the fields such as aviation, industry, the life of electrical and schedule. For conductive silicon rubber, it has the characteristic of softness haptic perception, in various sensors, machine human skin, perception The application aspects such as pressure seat have very great meaning, and its performance also with research deeply it is more and more stable, therefore It is a kind of functional material being concerned.
For conductive silicon rubber, the structure and physical characteristic of polymeric matrix itself and material internal conductive network Structure composition decides electric conductivity, mechanical performance, service life of final composite material etc..The electric conductivity of conductive silicon rubber Stability specifically include that piezoresistive characteristic, relaxation time, lag performance etc., by added filler, matrix properties and sulphur The influence of the factors such as chemical industry skill.
Traditional conductive silicon rubber is by the way that various conductive fillers, such as all kinds of metal powders, conductive black, conductive stone is added The conductive fillers such as ink, and cooperate other reinforced fillings, make composite material with superior electric conductivity and mechanical performance.Its The dispersity of middle conductive material in a polymer matrix can also generate electric conductivity and significantly affect, by taking conductive carbon black as an example, The size of carbon black particle, molecular surface structures and dispersity in rubber matrix to the percolation threshold of electric silica gel and Electric conductivity is affected.Because there are significant difference, the two in chemical structure and physical aspect for filler and matrix polymer Between binding ability it is poor, therefore, many scholars study for conducting particles in the intracorporal dispersity of base now, pass through To the surface activation process of filler grain, stable bonding state can be formed with matrix polymer, to improve conductive multiple The electric conductivity of condensation material.
The method for preparing conductive silicon rubber at present is usually the conductive silicon of this method preparation by the way of powder addition That there are elongations is low for rubber, and tearing-resistant performance is poor, and be unfavorable for environmental protection and the health of operator, complex process etc. Disadvantage.Therefore by the designing technique of Modern Composite Materials, satisfactory high-performance conductive composite material is designed, biography is overcome The shortcomings that controlling Preparation Method, is not only the important topic of field of scientific study, while also having important meaning in terms of engineer application Justice.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention One purpose is to propose a kind of using organic phosphazene catalyst catalysis cyclosiloxane original position ring-opening polymerisation without metallic element The polysiloxanes of conductive fill particle is adulterated in preparation, and the side of conductive silicon rubber nanocomposite is prepared through sulfidization molding Method.One kettle way preparation can be used in the conductive silicon rubber nanocomposite of this report invention, and preparation method is simple and efficient, all to fill out Material can be added before the polymerization, be uniformly mixed with monomer, cyclosiloxane monomer in situ polymerization effect is not by fillers affect, gained Silicon rubber composite material appearance is flat and smooth, and particle filled composite is uniformly dispersed, and maintains the good mechanics of pure sulphurated siliastic Performance, and have both excellent electric conductivity.
In the first aspect of the present invention, the invention proposes a kind of ring-opening polymerisation preparation doping conductive fill particles in situ The method of silicone premix material.According to an embodiment of the invention, this method comprises:
(a) by cyclosiloxane monomer and conductive fill particle, reinforced filling, sulfurizing agent, under nitrogen protection, it is placed in one Determine to stir evenly under the reaction condition of temperature；
(b) catalyst, initiator and anhydrous solvent are contacted, under nitrogen protection, rapidly joins the mixture in step (a) In, it is vigorously stirred；
(c) reaction a period of time, system viscosity increase at a certain temperature, form semi-solid and adulterate conductive fill particle Silicone premix material.
According to an embodiment of the invention, raw material used by this method is easy to get, preparation method is simple, and particle filled composite is poly- It is uniformly distributed in siloxanes.
In some embodiments of the invention, in step (a), the cyclosiloxane monomer is 1,3,5,7- tetramethyl cyclotetrasiloxanes Siloxanes, heptamethylcyclotetrasiloxane, tetraethyl cyclotetrasiloxane, octamethylcy-clotetrasiloxane, hexamethyl cyclotrisiloxane, 2, 4,6,8- tetramethyl -2,4,6,8- tetravinyl cyclotetrasiloxane, three silicon oxygen of 2,4,6- trimethyl -2,4,6- triethylene basic ring Alkane, octaphenylcyclotetrasiloxane, hexaphenyl cyclotrisiloxane, octaethyl cyclotetrasiloxane, 2,4,6- trimethyl -2,4,6- three (3,3,3- trifluoro propyl) cyclotrisiloxane, four silicon oxygen of 2,4,6,8- tetramethyl -2,4,6,8- four (3,3,3- trifluoro propyl) ring Alkane, 2,2,4,4- tetramethyl -6,6- diphenyl cyclotrisiloxane, 2,4,6- trimethyl -2,4,6- triphenyl cyclotrisiloxane, 2, 2,4,4,6,6- tetramethyl -8,8- diphenyl cyclotetrasiloxane, four silicon oxygen of 2,2,4,4- tetramethyl -6,6,8,8- tetraphenyl ring Alkane, 2,4,6,8- tetramethyl -2,4,6,8- tetraphenyl cyclotetrasiloxane, four cyanogen propyl ring of 1,3,5,7- tetramethyl -2,4,6,8- At least one of tetrasiloxane, four cyanogen propyl cyclotetrasiloxane of 1,3,5,7- tetraphenyl -2,4,6,8-.
In some embodiments of the invention, in step (a), the conductive fill particle is conductive black, graphene, carbon The various metal nanoparticles such as nanotube, carbon fiber, fullerene, aluminium, zinc, iron, nickel, silver, copper, silver-coated copper powder, Al contained Ni, nickel Copper-clad powder, nickel packet carbon fiber, nickel bag graphite, metallic fiber, metal sheet, doping polythiophene, Doped polypyrrole, the poly- second of doping At least one of alkynes, doping polysulfur nitride, polyaniline, polyphenylene sulfide, poly- phthalocyanine.
In some embodiments of the invention, in step (a), the quality of the conductive fill particle and cyclosiloxane monomer Than for (1~50): 100.
In some embodiments of the invention, in step (a), the reinforced filling be white carbon black and diatomite, montmorillonite, Silica flour, silicon powder, precipitated calcium carbonate, aluminium hydroxide, magnesium hydroxide, titanium dioxide, magnesium silicate, carbon black, zinc oxide, oxidation At least one of iron, titanium dioxide, zirconium silicate, calcium carbonate.
In some embodiments of the invention, in step (a), the mass ratio of the reinforced filling and cyclosiloxane monomer is (10~300): 100.
In some embodiments of the invention, in step (a), the vulcanizing agent is benzoyl peroxide, 2,4- dichloro mistake Benzoyl Oxide, peroxidized t-butyl perbenzoate, di-t-butyl peroxide, cumyl peroxide, 2,5- dimethyl -2,5- two Tert-butyl hydroperoxide hexane, the azo-compound of fatty acid, the peroxide of hydrosilyl group-containing or polymer (using platinum catalyst) At least one of.
In some embodiments of the invention, in step (a), cyclosiloxane described in the vulcanizing agent and step (a) Mass ratio is (0.1~5): 100.
In some embodiments of the invention, in step (a), the reaction temperature is 0~150 degree Celsius.
In some embodiments of the invention, in step (b), the catalyst is organic shown in formula (I) or formula (II) Phosphazene compound,
Wherein,
R1For halogen ,-NR2, or
R and R2For the C optionally replaced1-6Alkyl, the C optionally replaced1-6Naphthenic base, optionally replaces the aryl optionally replaced Benzyl, halogen or R form C with the N atom that is connected1-6Heterocyclylalkyl,
R3For the C optionally replaced1-6Alkyl, the C optionally replaced1-6Naphthenic base, the aryl optionally replaced, the benzyl optionally replaced Base or halogen,
N is integer and n >=1.
In some embodiments of the invention, in step (b), cyclosiloxane list described in the catalyst and step (a) The molar ratio of body be 1:(10~100 000).
In some embodiments of the invention, in step (b), the initiator be methanol, ethyl alcohol, isopropanol, the tert-butyl alcohol, Benzylalcohol, phenylpropanol, water, ethylene glycol, 1,2- propylene glycol, 2,3- butanediol, cyclohexanediol, glycerine, trimethylolpropane, season penta At least one of tetrol, xylitol, inositol, glucose.
In some embodiments of the invention, in step (b), the catalyst and initiator are with 1:(0.01~1000) Molar ratio carry out the reaction.
In some embodiments of the invention, in step (b), the anhydrous solvent is benzene, toluene, tetrahydrofuran, dichloro At least one of methane, dioxane, n-hexane, hexamethylene, petroleum ether, normal heptane and pentane.
In some embodiments of the invention, in step (c), the polysiloxanes is formula (III) compound represented,
Wherein,
R1And R2It is separately or concurrently hydrogen, methyl, phenyl, ethyl, trifluoro propyl or cyanogen propyl,
X, y, z are 1~100 000 integers.
In the second aspect of the present invention, the invention proposes a kind of poly- silicon oxygen by above-mentioned doping conductive fill particle in situ The method that alkane premix material prepares conductive silicon rubber nanocomposite.According to an embodiment of the invention, this method comprises:
The silicone premix material of above-mentioned doping conductive fill particle in situ is placed in mold, at a certain temperature, Heat sulfidization molding.
In some embodiments of the invention, the curing temperature be 40~200 degrees Celsius, the vulcanization time be 1~ 120 minutes.
According to an embodiment of the invention, conductive silicon rubber nanocomposite preparation method prepared by the present invention is simple, fill out It fills that particle distribution is uniform, and has both excellent elasticity and tensile property.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures Obviously and it is readily appreciated that, in which:
Fig. 1 is the photo of prepared conductive silicon rubber in the embodiment of the present invention 2.
Fig. 2 is the photo of prepared conductive silicon rubber in the embodiment of the present invention 4.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer, For can be with conventional products that are commercially available.
Embodiment 1
Under nitrogen protection, under the conditions of 100 DEG C, the octamethylcy-clotetrasiloxane (50.0g) that 100 part of mass parts and 1 part T etram-ethyltetravinylcyclotetrasiloxane (0.5g) is uniformly mixed, and 5 parts of carbon fiber particles (2.5g), 10 parts of vapor phase method hard charcoals are added Black (5.0g), 1 part of 2,5- dimethyl -2,5- di-t-butyl hexane peroxide (0.5g) maintain high-speed stirred, and mass parts are added 0.01 part of phosphonitrile base catalyst toluene solution (catalyst concn 0.05M), polymerization reaction start, and reaction system viscosity increases rapidly Greatly, continue to be kept for 100 DEG C condition 20 minutes, obtain the silicone premix material of uniform doped carbon fibrous particle in situ.
The above-mentioned silicone premix material adulterated in situ is added in mold, is vulcanized 10 minutes, curing temperature 170 DEG C, obtain doping carbon fiber silicon rubber nano composite material in situ.The volume resistivity of the silicon rubber is 5.5 Ω cm, is stretched Intensity 3.5MPa, elongation at break 458%.
Embodiment 2
Under nitrogen protection, under the conditions of 100 DEG C, the octamethylcy-clotetrasiloxane (50.0g) that 100 part of mass parts and 1 part T etram-ethyltetravinylcyclotetrasiloxane (0.5g) is uniformly mixed, and 10 parts of conductive black nano particles (5.0g), 20 parts of gas are added Phase method white carbon black (10.0g), 1 part of 2,5- dimethyl -2,5- di-t-butyl hexane peroxide (0.5g) maintain high-speed stirred, add Enter 0.01 part of mass parts of phosphonitrile base catalyst toluene solution (catalyst concn 0.05M), polymerization reaction starts, and reaction system is viscous Degree increases rapidly, and continues to be kept for 100 DEG C condition 20 minutes, and the polysiloxanes for obtaining uniform doping conductive black particle in situ is pre- Mixed material.
The above-mentioned silicone premix material adulterated in situ is added in mold, is vulcanized 10 minutes, curing temperature 170 DEG C, obtain doping conductive black silicon rubber nano composite material in situ.The volume resistivity of the conductive silicon rubber is 4.5 Ω Cm, tensile strength 3.9MPa, elongation at break 315%.
Embodiment 3
Under nitrogen protection, under the conditions of 60 DEG C, the octamethylcy-clotetrasiloxane (50.0g) that 100 part of mass parts, the four of 1 part Methyl cyclotetrasiloxane (0.5g) and 1 part of t etram-ethyltetravinylcyclotetrasiloxane (0.5g) are uniformly mixed, and are added 10 parts and are led Electric carbon black nano particle (5.0g), 20 parts of fume colloidal silicas (10.0g), 0.01 part of Karstedt catalyst (platinum-siloxanes network Close object, Pt content 5000ppm) (5.0mg), high-speed stirred is maintained, it is molten that 0.01 part of mass parts of phosphonitrile base catalyst toluene is added Liquid (catalyst concn 0.05M), polymerization reaction start, and reaction system viscosity increases rapidly, and continue to be kept for 60 DEG C condition 30 minutes, Obtain the silicone premix material of uniform doping conductive black nanoparticle in situ.
The above-mentioned silicone premix material adulterated in situ is added in mold, vulcanization 8 hours, 80 DEG C of curing temperature, Obtain doping conductive black nanometer silicon rubber nano composite material in situ.The volume resistivity of the conductive silicon rubber is 5.4 Ω Cm, tensile strength 5.1MPa, elongation at break 434%.
Embodiment 4
Under nitrogen protection, under the conditions of 60 DEG C, the octamethylcy-clotetrasiloxane (50.0g) that 100 part of mass parts, the four of 1 part Methyl cyclotetrasiloxane (0.5g) and 1 part of t etram-ethyltetravinylcyclotetrasiloxane (0.5g) are uniformly mixed, and 20 parts of warps are added The modified carbon nanotube (10.0g) in silane coupling agent surface, (platinum-silicone complex, Pt contain 0.01 part of Karstedt catalyst Measure 5000ppm) (5.0mg), high-speed stirred is maintained, 0.01 part of mass parts of phosphonitrile base catalyst toluene solution (catalyst is added Concentration 0.05M), polymerization reaction starts, and reaction system viscosity increases rapidly, and continues to be kept for 60 DEG C condition 30 minutes, obtain uniformly Doped carbon nanometer pipe in situ silicone premix material.
The above-mentioned silicone premix material adulterated in situ is added in mold, vulcanization 8 hours, 80 DEG C of curing temperature, Obtain doped carbon nanometer pipe silicon rubber nano composite material in situ.The volume resistivity of the conductive silicon rubber is 0.5 Ω cm, is drawn Stretch intensity 7.3MPa, elongation at break 552%.
Embodiment 5
Under nitrogen protection, under the conditions of 100 DEG C, the octamethylcy-clotetrasiloxane (50.0g) that 100 part of mass parts and 1 part T etram-ethyltetravinylcyclotetrasiloxane (0.5g) is uniformly mixed, and 3 parts of silver nano-grains (1.5g), 50 parts of vapor phase method hard charcoals are added Black (25.0g), 1 part of 2,5- dimethyl -2,5- di-t-butyl hexane peroxide (0.5g) maintain high-speed stirred, and mass parts are added 0.01 part of phosphonitrile base catalyst toluene solution (catalyst concn 0.05M), polymerization reaction start, and reaction system viscosity increases rapidly Greatly, continue to be kept for 100 DEG C condition 20 minutes, obtain the silicone premix material of uniform doping silver nano-grain in situ.
The above-mentioned silicone premix material adulterated in situ is added in mold, is vulcanized 10 minutes, curing temperature 170 DEG C, obtain doping silver nano-grain silicon rubber nano composite material in situ.The volume resistivity of the conductive silicon rubber is 5.1 Ω Cm, tensile strength 6.5MPa, elongation at break 447%.
Embodiment 6
Under nitrogen protection, under the conditions of 100 DEG C, the octamethylcy-clotetrasiloxane (50.0g) that 100 part of mass parts and 1 part T etram-ethyltetravinylcyclotetrasiloxane (0.5g) is uniformly mixed, and 20 parts of nickel bag graphites modified through silane coupling agent surface are added (10.0g), 20 parts of fume colloidal silicas (10.0g), 1 part of di-t-butyl peroxide (0.5g) maintain high-speed stirred, and quality is added The phosphonitrile base catalyst toluene solution (catalyst concn 0.05M) of 0.01 part of part, polymerization reaction start, and reaction system viscosity is rapid Increase, continue to be kept for 100 DEG C condition 20 minutes, obtains the polysiloxanes premix of uniform doping nickel bag graphite nanoparticle in situ Material.
The above-mentioned silicone premix material adulterated in situ is added in mold, is vulcanized 10 minutes, curing temperature 170 DEG C, obtain doping nickel bag graphite silicon rubber nano composite material in situ.The volume resistivity of the conductive silicon rubber is 1.5 Ω Cm, tensile strength 5.3MPa, elongation at break 471%.
Embodiment 7
Under nitrogen protection, under the conditions of 100 DEG C, the octamethylcy-clotetrasiloxane (50.0g) that 100 part of mass parts, 10 parts Octaphenylcyclotetrasiloxane and 1 part of t etram-ethyltetravinylcyclotetrasiloxane (0.5g) are uniformly mixed, and 10 parts of conductive charcoals are added Black (5.0g), 20 parts of fume colloidal silicas (10.0g), 1 part of 2,5- dimethyl -2,5- di-t-butyl hexane peroxide (0.5g), High-speed stirred is maintained, 0.01 part of mass parts of phosphonitrile base catalyst toluene solution (catalyst concn 0.05M), polymerization reaction is added Start, reaction system viscosity increases rapidly, and continues to be kept for 100 DEG C condition 20 minutes, obtains uniform doping conductive black in situ The silicone premix material of particle.
The above-mentioned silicone premix material adulterated in situ is added in mold, is vulcanized 10 minutes, curing temperature 170 DEG C, obtain doping conductive black silicon rubber nano composite material in situ.The volume resistivity of the conductive silicon rubber is 5.5 Ω Cm, tensile strength 5.3MPa, elongation at break 465%.
Embodiment 8
Under nitrogen protection, under the conditions of 100 DEG C, the octamethylcy-clotetrasiloxane (50.0g) that 100 part of mass parts and 2 parts T etram-ethyltetravinylcyclotetrasiloxane (1.0g) is uniformly mixed, and 20 parts of conductive black nano particles (10.0g), 20 parts of gas are added Phase method white carbon black (10.0g), 1 part of 2,5- dimethyl -2,5- di-t-butyl hexane peroxide (0.5g) maintain high-speed stirred, add Enter 0.01 part of mass parts of phosphonitrile base catalyst toluene solution (catalyst concn 0.05M), polymerization reaction starts, and reaction system is viscous Degree increases rapidly, and continues to be kept for 100 DEG C condition 20 minutes, obtains the poly- silicon oxygen of uniform doping conductive black nanoparticle in situ Alkane premixes material.
The above-mentioned silicone premix material adulterated in situ is added in mold, is vulcanized 10 minutes, curing temperature 170 DEG C, obtain doping conductive black silicon rubber nano composite material in situ.The volume resistivity of the conductive silicon rubber is 0.3 Ω Cm, tensile strength 6.1MPa, elongation at break 384%.
Embodiment 9
Under nitrogen protection, under the conditions of 100 DEG C, the octamethylcy-clotetrasiloxane (50.0g) that 100 part of mass parts and 2 parts T etram-ethyltetravinylcyclotetrasiloxane (1.0g) is uniformly mixed, and 20 parts of conductive polyanilines (10.0g), 20 parts of vapor phase methods are added White carbon black (10.0g), 1 part of 2,5- dimethyl -2,5- di-t-butyl hexane peroxide (0.5g) maintain high-speed stirred, and matter is added The phosphonitrile base catalyst toluene solution (catalyst concn 0.05M) of 0.01 part of part of amount, polymerization reaction start, and reaction system viscosity is fast Speed increases, and continues to be kept for 100 DEG C condition 20 minutes, obtains the silicone premix material of uniform doped polyaniline in situ.
The above-mentioned silicone premix material adulterated in situ is added in mold, is vulcanized 10 minutes, curing temperature 170 DEG C, obtain doping conductive black silicon rubber nano composite material in situ.The volume resistivity of the conductive silicon rubber is 280 Ω Cm, tensile strength 5.8MPa, elongation at break 360%.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned Embodiment is changed, modifies, replacement and variant.

Claims (9)

1. it is a kind of original position ring-opening polymerisation preparation doping conductive fill particle silicone premix material method it is characterized in that, Include:
(a) by cyclosiloxane monomer and conductive fill particle, reinforced filling, sulfurizing agent, under nitrogen protection, it is placed in certain temperature It is stirred evenly under the reaction condition of degree；
(b) catalyst, initiator and anhydrous solvent are contacted, under nitrogen protection, are rapidly joined in the mixture in step (a), It is vigorously stirred；
(c) reaction a period of time, system viscosity increase at a certain temperature, form the poly- of semi-solid doping conductive fill particle Silicone premix material.
2. the method according to claim 1, wherein the cyclosiloxane monomer is 1,3,5,7- in step (a) Tetramethyl-ring tetrasiloxane, heptamethylcyclotetrasiloxane, tetraethyl cyclotetrasiloxane, octamethylcy-clotetrasiloxane, pregnancy basic ring Trisiloxanes, 2,4,6,8- tetramethyl -2,4,6,8- tetravinyl cyclotetrasiloxane, 2,4,6- trimethyl -2,4,6- triethylene Basic ring trisiloxanes, octaphenylcyclotetrasiloxane, hexaphenyl cyclotrisiloxane, octaethyl cyclotetrasiloxane, 2,4,6- trimethyl- 2,4,6- tri- (3,3,3- trifluoro propyl) cyclotrisiloxane, 2,4,6,8- tetramethyl -2,4,6,8- four (3,3,3- trifluoro propyl) Cyclotetrasiloxane, 2,2,4,4- tetramethyl -6,6- diphenyl cyclotrisiloxane, 2,4,6- trimethyl -2,4,6- triphen basic ring three Siloxanes, 2,2,4,4,6,6- tetramethyl -8,8- diphenyl cyclotetrasiloxane, 2,2,4,4- tetramethyl -6,6,8,8- tetraphenyl Cyclotetrasiloxane, 2,4,6,8- tetramethyl -2,4,6,8- tetraphenyl cyclotetrasiloxane, 1,3,5,7- tetramethyl -2,4,6,8- four At least one of cyanogen propyl cyclotetrasiloxane, four cyanogen propyl cyclotetrasiloxane of 1,3,5,7- tetraphenyl -2,4,6,8-.
3. the method according to claim 1, wherein the conductive fill particle is conductive charcoal in step (a) The various metal nanoparticles such as black, graphene, carbon nanotube, carbon fiber, fullerene, aluminium, zinc, iron, nickel, silver, copper, wicker copper Powder, Al contained Ni, nickel coated copper powder, nickel packet carbon fiber, nickel bag graphite, metallic fiber, metal sheet, doping polythiophene, doping are poly- At least one of conducting polymers such as pyrroles, doped polyacetylene, doping polysulfur nitride, polyaniline, polyphenylene sulfide, poly- phthalocyanine.
4. the method according to claim 1, wherein the reinforced filling is white carbon black and diatom in step (a) Soil, silica flour, silicon powder, precipitated calcium carbonate, aluminium hydroxide, magnesium hydroxide, titanium dioxide, magnesium silicate, carbon black, zinc oxide, oxygen Change at least one of iron, titanium dioxide, zirconium silicate, calcium carbonate, the vulcanizing agent is benzoyl peroxide, 2,4- dichloro peroxide Change benzoyl, peroxidized t-butyl perbenzoate, di-t-butyl peroxide, cumyl peroxide, two uncle of 2,5- dimethyl -2,5- In butyl peroxy hexane, the azo-compound of fatty acid, the peroxide of hydrosilyl group-containing or polymer (using platinum catalyst) At least one of, the conductive fill particle, reinforced filling, vulcanizing agent and cyclosiloxane monomer mass ratio be (1~50): (10~300): (0.1~5): 100, the reaction temperature is 0~150 degree Celsius.
5. according to the method described in claim 2, it is characterized in that, the catalyst is formula (I) or formula (II) in step (b) Shown in organic phosphazene compound,
Wherein,
R1For halogen ,-NR2, or
R and R2For the C optionally replaced1-6Alkyl, the C optionally replaced1-6Naphthenic base, the aryl optionally replaced, the benzyl optionally replaced Base, halogen or R form C with the N atom being connected1-6Heterocyclylalkyl,
R3For the C optionally replaced1-6Alkyl, the C optionally replaced1-6Naphthenic base, the aryl optionally replaced, the benzyl optionally replaced, or Person's halogen,
N be integer and n >=1,
The molar ratio of cyclosiloxane monomer described in the catalyst and step (a) be 1:(10~100 000).
6. according to the method described in claim 2, it is characterized in that, the initiator is methanol, ethyl alcohol, isopropyl in step (b) Alcohol, the tert-butyl alcohol, benzylalcohol, phenylpropanol, water, ethylene glycol, 1,2- propylene glycol, 2,3- butanediol, cyclohexanediol, glycerine, three hydroxyl first At least one of base propane, pentaerythrite, xylitol, inositol, glucose, the catalyst and initiator are with 1:(0.01 ~1000) molar ratio carries out the reaction.
7. according to the method described in claim 2, it is characterized in that, the anhydrous solvent is benzene, toluene, tetrahydro in step (b) At least one of furans, methylene chloride, dioxane, n-hexane, hexamethylene, petroleum ether, normal heptane and pentane.
8. the method according to claim 1, wherein the polysiloxanes is shown in formula (III) in step (c) Compound,
Wherein,
R1And R2It is separately or concurrently hydrogen, methyl, phenyl, ethyl, trifluoro propyl or cyanogen propyl,
X, y, z are 1~100 000 integers.
9. it is nano combined that a kind of silicone premix material by above-mentioned doping conductive fill particle in situ prepares conductive silicon rubber The method of material, which is characterized in that the compound being prepared using any one of claim 1~8 the method is as in situ The silicone premix material for adulterating conductive fill particle, is placed in mold, at a certain temperature, heats sulfidization molding, described Curing temperature is 40~200 degrees Celsius, and the vulcanization time is 1~120 minute.
CN201910742428.6A 2019-08-13 2019-08-13 The method that a kind of ring-opening polymerisation of cyclosiloxane original position prepares high-performance conductive silicon rubber Pending CN110408030A (en)

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