CN105585850B - A kind of antistatic organic silicon rubber and the preparation method and application thereof that Ag quantum dot is compound - Google Patents
A kind of antistatic organic silicon rubber and the preparation method and application thereof that Ag quantum dot is compound Download PDFInfo
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Abstract
The present invention relates to field of organic silicon, to solve the problems, such as that organic silicon rubber does not have antistatic property, the present invention provides a kind of antistatic silicone rubber and preparation method thereof, 5 ~ 65 Shore A of hardness of gained silicon rubber, 0.2 ~ 3.8 MPa of tensile strength, elongation at break 40% ~ 300% has excellent antistatic property, is applied to electronic component and encapsulates.
Description
Technical field
The present invention relates to field of organic silicon, and in particular to a kind of antistatic organic silicon rubber that Ag quantum dot is compound and its system
Preparation Method is applied to electronic component and encapsulates.
Technical background
Electrostatic is that object positive charge and negative electrical charge are unbalanced in subrange as a result, being by electronics or ion-transfer
And formed.The reason of causing electronics imbalance to be distributed is that electronics is de-orbited by external force, this external force includes various energy
(such as kinetic energy, position energy, thermal energy, chemical energy), therefore, in daily life, as contact, friction, flushing.Electrolysis, piezoelectricity, partially
Difference, sense light can all generate electrostatic.Electrostatic destroys electronic component there may be following:
1. Electrostatic Absorption dust reduces element insulating resistance (shortening the service life): in the manufacturing of semiconductor components and devices
Cheng Zhong, as largely having used utensil and material made of quartz and polymer substance, insulativity is very high, in use
Some inevitable frictions can cause its surface charge constantly to gather, and current potential is higher and higher.Due to the mechanics effect of electrostatic,
In this case, it is easy to so that the suspending dust of workplace is adsorbed in chip surface, and have can for the absorption of the dust of very little
It can influence the superperformance of semiconductor devices.
2. static discharge and dielectric breakdown, prevent damaging components from working and (destroying completely): static discharge plays discharge source
It is space charge, thus the energy stored by it is limited, therefore it is only capable of providing the partial breakdown energy of of short duration generation.Although
The energy of static discharge is smaller, but its discharge waveform is very complicated, and control is got up also more troublesome.Hitting for component is caused by electrostatic
Wear be electrostatic hazard in electronics major way, be most universal, most serious harm in electronics manufacture.
3. the heat that static discharge electric field or electric current generate keeps element injured (latent lesion).
4. the electromagnetic field magnitude that static discharge generates very big (reaching a few hectovolt/rice), frequency spectrum are extremely wide (from tens to thousands of
Million) device, is produced to electronics and interferes even damage (electromagnetic interference).
If element all destroys, it must can be noticeable and exclude in production and detection, influence smaller；If element is slight
It is impaired, it is not easy to find under proper testing.It in this case, often can be because by multi-level processing, or even when in use
It was found that being destroyed, not only check and be not easy, and it is difficult to predict will expend that how many manpower and financial resources could check out and own for its loss
Problem.If just discovering failure when in use, loss will likely be huge.
Organic silicon rubber has the performances such as excellent electrical apparatus insulation, heatproof, weather-proof, cold-resistant thermal shock, in electronic component
Occupy important place position in encapsulation, but organic silicon rubber itself does not have antistatic property.In order to expand the application field of silicon rubber, need pair
Its progress is antistatic modified.Currently, the report of antistatic silicone rubber is considerably less.The only beautiful apex material strain formula meeting in east at present
Society is gathered using organosiloxane, organic hydrogen polysiloxanes, silane coupling agent, conducting polymer and platinum catalyst with by anion
Polythiophene or derivatives thereof of conjunction method preparation is blended, and having invented a kind of antistatic silicone release coating films, (Chinese invention is special
Sharp ZL200780013037.6), product has good antistatic effect.But polythiophene or derivatives thereof preparation is complicated, leads
Electric effect is poor, and larger dosage is needed just to can get good antistatic effect；In addition, polythiophene or derivatives thereof is compatible with organosilicon
Property is poor, is easy to split-phase.
Summary of the invention
To solve the problems, such as that organic silicon rubber does not have antistatic property, the present invention provides a kind of antistatic silicone rubber
And preparation method thereof, gained silicon rubber has excellent antistatic property, is applied to electronic component and encapsulates.
The present invention is achieved by the following technical solutions: a kind of antistatic organic silicon rubber that Ag quantum dot is compound it is hard
Spend 5~65Shore A, 0.2~3.8MPa of tensile strength, elongation at break 40%~300%.
The preparation method is following steps:
(1) it prepares Ag quantum dot: the aqueous solution of borohydride salts being added dropwise into the silver soluble saline solution of stirring, at room temperature
Be protected from light after being stirred to react 0.2-24h, centrifugation obtains solid, several times with ethyl alcohol and water washing, after preferably washing 3~4 times
Vacuum is protected from light drying under 0.06~0.09MPa, obtains silver-colored quantum dot；Silver soluble saline solution is selected from AgF, AgNO3And AgClO4
The mixture of one or more of aqueous solution；Borohydride salts are selected from the mixed of one or both of sodium borohydride, potassium borohydride
Close object.Preferably, silver soluble saline solution is selected from AgNO3、AgClO4One or both of aqueous solution；Borohydride salts choosing
From one or both of sodium borohydride, potassium borohydride, usage amount is the amount of silver salt substance in silver soluble saline solution
0.01%~0.1%.(2) it is organic that the compound antistatic of Ag quantum dot is prepared after mixing liquid silastic with Ag quantum dot
Silicon rubber.0.1%~15%, the Ag quantum dot and liquid silastic that Ag quantum dot usage amount is liquid silastic quality are through three rollers
Machine or ball mill are uniformly mixed, through room temperature at 0.06~0.09Mpa of vacuum degree 5~30min of deaeration, curing temperature is 20~
Sulfidization molding at 150 DEG C obtains the compound antistatic organic silicon rubber of Ag quantum dot.
Liquid silastic is selected from one of add-on type silicon liquid body rubber or condensed type silicon rubber.Add-on type liquid silicon rubber
It is mixed by vinyl silicone oil, containing hydrogen silicone oil, reinforced filling, platinum complex catalyst；Condensed type liquid silastic is by hydroxyl
Silicone oil, silane coupling agent, reinforced filling, condensed type catalyst are mixed.
Reinforced filling is selected from one or both of fume colloidal silica, precipitated silica, and usage amount is silicone oil quality
2%~55%.Middle silicone oil is made of vinyl silicone oil, containing hydrogen silicone oil；Silicone oil is hydroxy silicon oil in condensed type liquid silastic.
Add-on type liquid silicon rubber medium vinyl silicone molecule structural formula is Me2ViSiO(Me2SiO)a(R1R2SiO)bSiViMe2, R in formula1、R2It is respectively and independently selected from one of methyl, phenyl, but R1With R2It is not simultaneously methyl, a is 5~4000
Positive integer, b be 0 or 0~1000 positive integer, 0≤b/ (a+b)≤0.99；Containing hydrogen silicone oil molecular structure is Me2R3SiO
(Me2SiO)c(MeHSiO)d(R4R5SiO)eSiR3Me2, R in formula3It is a kind of in Me, H, R4、R5It is respectively and independently selected from methyl, benzene
One of base, but R4And R5Not simultaneously be methyl, c be 4~900 positive integer, d be 4~600 positive integer, e be 0 or 0~
900 positive integer, 0≤e/ (c+d+e)≤0.99.The usage amount of containing hydrogen silicone oil and vinyl silicone oil is silicon hydrogen and silico ethylene base
Molar ratio is 0.7~2: 1, preferably 0.9~1.8: 1.
Platinum complex catalyst is selected from H2PtCl6Aqueous isopropanol, H2PtCl6Tetrahydrofuran solution, Pt (PPh3)4、
Platinum complex, the dicyclopentadiene dichloro that platinum complex, the diethyl phthalate of methyl vinyl silicone coordination are coordinated
Change one or more of platinum, platinum complex of dichloro bis- (triphenylphosphines), the usage amount of platinum complex catalyst is to make platinum
Belong to the 1~150ppm, preferably 1~30ppm that element quality is add-on type liquid silicon rubber quality.
Hydroxy silicon oil molecular structural formula is OHMe in condensed type liquid silastic2SiO(Me2SiO)a(R1R2SiO)bSiMe2OH, R in formula1、R2It is respectively and independently selected from one of methyl, phenyl, but R1With R2It is not simultaneously methyl, a is 5~4000
Positive integer, b be 0 or 0~1000 positive integer, 0≤b/ (a+b)≤0.99；Silane coupling agent is selected from ethyl orthosilicate, positive silicon
It is sour methyl esters, trimethoxy silane (including methyltrimethoxysilane, phenyltrimethoxysila,e), triethoxysilane, three different
Npropoxysilane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane (KH-560), γ-(methacryloxypropyl) propyl three
Methoxy silane (KH-570), n- octyl trimethoxy silane, n- octyltri-ethoxysilane, in n- propyl-triethoxysilicane
One or several kinds, usage amount is the 0.05%~3% of condensed type liquid silastic quality, and it is sub- that curing catalysts are selected from octanoic acid
Tin, dibutyl tin dilaurate, diisobutyl tin laurate, tetrabutyl titanate, tetrabutyl titanate acetylacetone chelate in
One or more, usage amount be condensed type liquid silica gel quality 0.005%~0.1%.
Me is methyl in structure above, and Vi is vinyl, and OH is hydroxyl, and room temperature is 25 DEG C.
The compound antistatic organic silicon rubber of Ag quantum dot of the present invention has outside excellent antistatic property, also has
The performances such as good heatproof, weather-proof, cold-resistant thermal shock, ultraviolet light resistant are applied in electronic component encapsulation.
Compared with prior art, the beneficial effects of the present invention are:
(1) not only have outside excellent antistatic property, but also there is good heatproof, weather-proof, cold-resistant thermal shock, resistance to purple
The performances such as external radiation；
(2) preparation method is simple.
Specific embodiment
The present invention is further illustrated by following embodiment, but embodiment is not limiting the scope of the invention,
It is raw materials used commercially available in embodiment.
Embodiment 1
1) AgNO of 600g 0.1mol/L is added into the clean 1000ml there-necked flask with masking foil shading3Aqueous solution, room
The sodium borohydride aqueous solution of 50g 0.01mol/L is added dropwise under gentle agitation in 30min, continues to react at room temperature 2h after being added dropwise,
By system sedimentation, centrifugation, solid is obtained；Baking is protected from light after obtained solid is washed 3 times with dehydrated alcohol at vacuum degree 0.06Mpa
It is dry, obtain silver-colored quantum dot 5.832g.
2) 296g D4 is added into 500ml clean there-necked flask, moisture is removed at 0.096MPa/35~40 DEG C, then
1.86g vinyl double seal head and 5.92g tetramethylammonium hydroxide silicon alkoxide is added and then heats to 135 in 100 DEG C of polymerization 5h
Then decomposition catalyst about 3h between~140 DEG C takes off low molecular compound at 0.096MPa/180 DEG C, obtains 258g vinyl
Silicone oil Me2ViSiO(Me2SiO)400SiViMe2(contents of ethylene 6.6 × 10-5mol/g)；Add in the there-necked flask clean to 500ml
Enter 296g D4, moisture is removed at -0.096MPa/35~40 DEG C, 4.2g D is then added4 H, 1.34g hydrogeneous double seal head and 15g
Then large aperture cation exchange resin is filtered in 70 DEG C of polymerization 5h, clear liquid is taken off at 0.096MPa/180 DEG C degraded
Object is closed, 245g containing hydrogen silicone oil Me is obtained2HSiO(Me2SiO)400(MeHSiO)7SiHMe2(silicon hydrogen content 3.0 × 10-4mol/g)；
3) gained vinyl silicone oil 30g, containing hydrogen silicone oil 10g (silicon hydrogen and silicon second in take the silver-colored quantum dot 0.3g of gained in 1), 2)
Alkenyl molar ratio 1.52: 1) 5g fume colloidal silica, the H of 0.030g (about 8ppm) are added,2PtCl6Aqueous isopropanol, mixing
Uniformly after, through deaeration 15min under vacuum degree 0.06Mpa, vulcanize 2h at 100 DEG C, obtain a kind of Ag quantum dot it is compound prevent it is quiet
Electric organic silicon rubber 1.
A kind of resulting 1 electrical conductivity of antistatic organic silicon rubber that Ag quantum dot is compound of embodiment 1 measures 1.7 × 10-11
Ω m, hardness 5ShoreA, tensile strength 1.5MPa, tensile elongation 250%.
Embodiment 2
The silver-colored quantum dot 0.8g of gained, vinyl silicone oil Me in Example 12ViSiO(Me2SiO)400SMMe232.3g and containing
Hydrogen silicone oil Me2HSiO(Me2SiO)400(MeHSiO)7SiHMe23.33g (silicon hydrogen and silico ethylene base molar ratio 0.7: 1), is added 10g
The dicyclopentadiene platinous chloride of fume colloidal silica, 2g precipitated silica and 0.043g (about 15ppm), after mixing,
Through deaeration 30min under vacuum degree 0.09Mpa, vulcanize 2h at 120 DEG C, obtains a kind of antistatic organosilicon that Ag quantum dot is compound
Rubber 2.
A kind of resulting 2 electrical conductivity of antistatic organic silicon rubber that Ag quantum dot is compound of embodiment 2 measures 1.0 × 10-10
Ω m, hardness are 48shore component A, tensile strength 2.65MPa, elongation 220%.
Embodiment 3
The silver-colored quantum dot 1.2g of gained, vinyl silicone oil Me in Example 12ViSiO(Me2SiO)400SiViMe222.7g and
Containing hydrogen silicone oil Me2HSiO(Me2SiO)400(MeHSiO)7SiHMe210g (silicon hydrogen and silico ethylene base molar ratio 2: 1), is added 10g
The platinum complex of the methyl vinyl silicone coordination of fume colloidal silica, 2g precipitated silica and 0.043g (about 15ppm),
After mixing, through deaeration 5min under vacuum degree 0.07Mpa, vulcanize 2h at 140 DEG C, obtain a kind of compound anti-of Ag quantum dot
Electrostatic organic silicon rubber 3.
A kind of resulting 3 electrical conductivity of antistatic organic silicon rubber that Ag quantum dot is compound of embodiment 3 measures 1.0 × 10-9
Ω m, hardness are 48shore A, tensile strength 2.30MPa, elongation 200%.
Embodiment 4
The silver-colored quantum dot 1.8g of gained, vinyl silicone oil Me in Example 12ViSiO(Me2SiO)400SiViMe215.1g and
Containing hydrogen silicone oil Me2HSiO(Me2SiO)400(MeHSiO)7SiHMe23.33g (silicon hydrogen and silico ethylene base molar ratio 1: 1), is added 5g
The platinum complexing of the diethyl phthalate coordination of fume colloidal silica, 10g precipitated silica and 0.043g (about 15ppm)
Object through deaeration 20min under vacuum degree 0.08Mpa, vulcanizes 2h at 130 DEG C after mixing, and it is compound to obtain a kind of Ag quantum dot
Antistatic organic silicon rubber 4.
A kind of 4 electrical conductivity of antistatic organic silicon rubber silicon rubber that Ag quantum dot is compound that embodiment 4 obtains measures 1.0
×10-8Ω m, hardness 58shoreA, tensile strength 1.5MPa, elongation 85%.
Embodiment 5
1) AgClO of 500g 0.1mol/L is added into the clean 1000ml there-necked flask with masking foil shading4Aqueous solution,
The potassium borohydride aqueous solution of 35g 0.01mol/L is added dropwise under the gentle agitation of room in 30min, continues to react at room temperature after being added dropwise
System sedimentation, centrifugation are obtained solid by 0.2h；It is kept away under vacuum degree 0.09Mpa after obtained solid is washed 3 times with dehydrated alcohol
Light drying obtains silver-colored quantum dot 4.6510g.
2) 296g D4,136g aminomethyl phenyl cyclotrisiloxane, in 0.096MPa/ are added into 500ml clean there-necked flask
Moisture is removed at 35~40 DEG C, 1.86g vinyl double seal head and 8.64g tetramethylammonium hydroxide silicon alkoxide is then added, 90
DEG C polymerization 8h, then heat to decomposition catalyst about 3h between 135~140 DEG C, low point then taken off at 0.096MPa/180 DEG C
Sub- compound obtains 294g methyl phenyl vinyl silicone oil Me2ViSiO(Me2SiO)400(MePhSiO)100SiViMe2(vinyl
Content 4.54 × 10-5mol/g)；；296g D4 and 136g aminomethyl phenyl mixing ring silicon oxygen are added in the there-necked flask clean to 500ml
Alkane removes moisture at -0.096MPa/35~40 DEG C, and 8.4g D is then added4 H, 1.34g hydrogeneous double seal head and the large aperture 15g
Then cation exchange resin is filtered in 70 DEG C of polymerization 5h, clear liquid is taken off low molecular compound at 0.096MPa/180 DEG C,
Obtain 312 g methyl and phenyl hydrogen-containing silicon oil Me2HSiO(Me2SiO)400(MePhSiO)100(MeHSiO)14SiHMe2(silicon hydrogen content
3.64×10-4mol/g)；
3) gained methyl phenyl vinyl silicone oil 20g and aminomethyl phenyl are hydrogeneous in take the silver-colored quantum dot 0.3g of gained in 1), 2)
Each 5g of silicone oil (silicon hydrogen and silico ethylene base molar ratio 1: 1), is added 10g precipitated silica, the H of 0.060g (about 16ppm)2PtCl6
Tetrahydrofuran solution through deaeration 10min under vacuum degree 0.09Mpa, vulcanize 4h after mixing at 150 DEG C, obtain one kind
The compound antistatic organic silicon rubber 5 of Ag quantum dot.
A kind of 55 electrical conductivity of antistatic organic silicon rubber that Ag quantum dot is compound of gained of embodiment measures 1.5 × 10-11
Ω m, hardness 12ShoreA, tensile strength 1.8MPa, tensile elongation 200%.
Embodiment 6
1) the AgF aqueous solution of 500g 0.1mol/L, room temperature are added into the clean 1000ml there-necked flask with masking foil shading
Sodium borohydride aqueous solution with dropwise addition 40g 0.01mol/L in lower 40min is stirred, continues room temperature reaction for 24 hours after being added dropwise, will
System sedimentation, centrifugation, obtain solid；Drying is protected from light after obtained solid is washed 4 times with dehydrated alcohol under vacuum degree 0.08Mpa,
Obtain silver-colored quantum dot 4.416g.
2) 296g D4,400g octaphenylcyclotetrasiloxane, in 0.096MPa/ are added into 1000ml clean there-necked flask
Moisture is removed at 35~40 DEG C, 1.86g vinyl double seal head and 14.2g tetramethylammonium hydroxide silicon alkoxide is then added, 100
DEG C polymerization for 24 hours, then heat to decomposition catalyst about 3h between 135~140 DEG C, low point then taken off at 0.096MPa/180 DEG C
Sub- compound obtains 648g methyl phenyl vinyl silicone oil Me2ViSiO(Me2SiO)400(Ph2SiO)200SiViMe2(vinyl
Content 2.86 × 10-5mol/g)；Four silicon oxygen of 296g D4 and 272g methylbenzene basic ring is added in the there-necked flask clean to 1000ml
Alkane removes moisture at -0.096MPa/35~40 DEG C, and 12.4g D is then added4 H, 1.34g hydrogeneous double seal head and the large aperture 15g
Then cation exchange resin is filtered in 70 DEG C of polymerization 8h, clear liquid is taken off low molecular compound at 0.096MPa/180 DEG C,
Obtain 549g methyl and phenyl hydrogen-containing silicon oil Me2HSiO(Me2SiO)400(MePhSiO)200(MeHSiO)21SiHMe2(silicon hydrogen content
3.94×10-4mol/g)；
3) gained methyl phenyl vinyl silicone oil 15.39g and aminomethyl phenyl in take the silver-colored quantum dot 0.03g of gained in 1), 2)
Each 2.0g of containing hydrogen silicone oil (silicon hydrogen and silico ethylene base molar ratio 1.8: 1), is added 10g precipitated silica, 0.300g (about 80ppm)
Pt (PPh3)4, after mixing, through deaeration 15min under vacuum degree 0.08Mpa, vulcanize 4h, a kind of Ag quantum dot at 90 DEG C
Compound antistatic organic silicon rubber 6.
A kind of resulting 6 electrical conductivity of antistatic organic silicon rubber that Ag quantum dot is compound of embodiment 6 measures 1.5 × 10-11
Ω m, hardness 12ShoreA, tensile strength 1.8MPa, tensile elongation 200%.
Embodiment 7
1) AgNO of 600g 0.1mol/L is added into the clean 1000ml there-necked flask with masking foil shading3Aqueous solution, room
The potassium borohydride aqueous solution of 35g 0.01mol/L is added dropwise under gentle agitation in 30min, continues to react at room temperature 10h after being added dropwise,
By system sedimentation, centrifugation, solid is obtained；Baking is protected from light after obtained solid is washed 4 times with dehydrated alcohol under vacuum degree 0.07Mpa
It is dry, obtain silver-colored quantum dot 5.3580g.
2) the addition 148g D4 into 1000ml clean there-necked flask, 544g aminomethyl phenyl cyclotrisiloxane,
Moisture is removed at 0.096MPa/35~40 DEG C, and 1.86g vinyl double seal head and 8.64g tetramethylammonium hydroxide silicon is then added
Alkoxide then heats to decomposition catalyst about 3h between 135~140 DEG C, then at 0.096MPa/180 DEG C in 90 DEG C of polymerization 8h
De- low molecular compound down obtains 658g methyl phenyl vinyl silicone oil Me2ViSiO(Me2SiO)200(MePhSiO)400SiViMe2(contents of ethylene 2.86 × 10-5mol/g)；148g D4 and 544g first is added in the there-necked flask clean to 1000ml
Base phenyl hybrid ring siloxane removes moisture at -0.096MPa/35~40 DEG C, and 168g D is then added4 H, 1.34g hydrogeneous pair
Then end socket and the large aperture 15g cation exchange resin filter, by clear liquid at 0.096MPa/180 DEG C in 70 DEG C of polymerization 5h
De- low molecular compound, obtains 692g methyl and phenyl hydrogen-containing silicon oil Me2HSiO(Me2SiO)200(Me2SiO)400(MeHSiO)280SiHMe2(silicon hydrogen content 3.28 × 10-3mol/g)；
3) gained methyl phenyl vinyl silicone oil 28.66g in take the silver-colored quantum dot 2.0g of gained in 1), 2), aminomethyl phenyl contain
Hydrogen silicone oil 1g (silicon hydrogen and silico ethylene base molar ratio 2: 1), is added 10g precipitated silica, and the dichloro of 0.060g (about 16ppm) is double
The platinum complex of (triphenylphosphine) through deaeration 30min under vacuum degree 0.07Mpa, vulcanizes 4h at 110 DEG C, obtains after mixing
To a kind of antistatic organic silicon rubber 7 that Ag quantum dot is compound.
A kind of resulting 7 electrical conductivity of antistatic organic silicon rubber that Ag quantum dot is compound of embodiment 7 measures 4.5 × 10-8
Ω m, hardness 65Shore A, tensile strength 3.5MPa, tensile elongation 40%.
Embodiment 8
The silver-colored quantum dot 3.7g of gained, vinyl silicone oil Me in Example 12ViSiO(Me2SiO)400SiViMe215.1g and
Containing hydrogen silicone oil Me2HSiO(Me2SiO)400(MeHSiO)7SiHMe24.66g (silicon hydrogen and silico ethylene base molar ratio 1.4: 1), is added
The platinum complexing of the methyl vinyl silicone coordination of 10g fume colloidal silica, 2g precipitated silica and 0.043g (about 15ppm)
Object through deaeration 5min under vacuum degree 0.09Mpa, vulcanizes 10h at 80 DEG C after mixing, and it is compound to obtain a kind of Ag quantum dot
Antistatic organic silicon rubber 8.
A kind of resulting 8 electrical conductivity of antistatic organic silicon rubber that Ag quantum dot is compound of embodiment 8 measures 1.0 × 10-9
Ω m, hardness are 48shore A, tensile strength 2.30MPa, elongation 200%.
Embodiment 9
The silver-colored quantum dot 3.75g of gained, commercially available hydroxy silicon oil HOMe in Example 12SiO(Me2SiO)400SiMe2OH 20g
With methyl orthosilicate 0.01g and methyltrimethoxysilane 0.005g, 10g fume colloidal silica, 1g precipitated silica is added
Through vacuum degree 0.06Mpa deaeration 20min, vulcanize 72h after mixing with 0.002g stannous octoate at 20 DEG C, obtain one kind
The compound antistatic organic silicon rubber 9 of Ag quantum dot.
A kind of resulting 9 electrical conductivity of antistatic organic silicon rubber that Ag quantum dot is compound of embodiment 9 measures 1.0 × 10-9
Ω m, hardness are 54.5shore A, tensile strength 3.6MPa, elongation 180%.
Embodiment 10
The silver-colored quantum dot 0.03g of gained, commercially available hydroxy silicon oil HOMe in Example 12SiO(Me2SiO)50(MePhSiO)800SiMe25g fume colloidal silica, the 0.5g precipitation method is added in OH 20g, KH-5700.2g and methyltrimethoxysilane 0.1g
White carbon black and 0.004g diisobutyl tin laurate, after mixing, through deaeration 10min under vacuum degree 0.06Mpa, in 150 DEG C
Lower vulcanization 50h obtains a kind of antistatic organic silicon rubber 10 that Ag quantum dot is compound.
A kind of resulting antistatic organic silicon rubber electrical conductivity that Ag quantum dot is compound of embodiment 10 measures 1.4 × 10-9
Ω m, hardness are 62.0shore A, tensile strength 3.3MPa, elongation 120%.
Embodiment 11
The silver-colored quantum dot 2.4g of gained, commercially available hydroxy silicon oil HOMe in Example 12SiO(Me2SiO)50(Ph2SiO)1000SiMe20.4g fume colloidal silica and 0.08g titanium is added in OH 20g, KH-560 0.3g and phenyltrimethoxysila,e 0.3g
The acetylacetonate complex of sour positive fourth rouge through deaeration 25min under vacuum degree 0.08Mpa, vulcanizes at 60 DEG C after mixing
48h obtains a kind of antistatic organic silicon rubber 11 that Ag quantum dot is compound.
A kind of resulting 11 electrical conductivity of antistatic organic silicon rubber that Ag quantum dot is compound of embodiment 11 measures 5.5 ×
10-8Ω m, hardness 32.0shoreA, tensile strength 2.1MPa, elongation 380%.
Claims (6)
1. a kind of preparation method for the antistatic organic silicon rubber that Ag quantum dot is compound, which is characterized in that the preparation method
For following steps:
(1) it prepares Ag quantum dot: the aqueous solution of borohydride salts being added dropwise into the silver soluble saline solution of stirring, is protected from light at room temperature
After being stirred to react 0.2-24h, centrifugation obtains solid, several times with ethyl alcohol and water washing, obtains silver-colored quantum dot；
(2) the compound antistatic organic silicon rubber of Ag quantum dot, Ag are prepared after mixing liquid silastic with Ag quantum dot
0.1% ~ 15%, the Ag quantum dot and liquid silastic that quantum dot usage amount is liquid silastic quality are through three-roller or ball mill
It is uniformly mixed, through room temperature in vacuo 5 ~ 30min of deaeration, curing temperature is sulfidization molding at 20 ~ 150 DEG C, and it is compound to obtain Ag quantum dot
Antistatic organic silicon rubber；
Liquid silastic is selected from one of add-on type silicon liquid body rubber or condensed type silicon rubber, and add-on type liquid silicon rubber is by second
Alkenyl silicone oil, containing hydrogen silicone oil, reinforced filling, platinum complex catalyst are mixed；Condensed type liquid silastic by hydroxy silicon oil,
Silane coupling agent, reinforced filling, curing catalysts are mixed；
Add-on type liquid silicon rubber medium vinyl silicone molecule structural formula is Me2ViSiO(Me2SiO)a(R1R2SiO) b
SiViMe2, R1、R2It is respectively and independently selected from one of methyl, phenyl, but R1With R2Not simultaneously be methyl, a be 5 ~ 4000 it is just whole
Number, the positive integer that b is 0 or 0 ~ 1000,0≤b/ (a+b)≤0.99；Containing hydrogen silicone oil molecular structure is Me2R3SiO(Me2SiO)c
(MeHSiO)d(R4R5SiO)eSiR3Me2, R in formula3It is a kind of in Me, H, R4、R5It is respectively and independently selected from methyl, in phenyl
One kind, but R4And R5Not simultaneously be methyl, c be 4 ~ 900 positive integer, d be 4 ~ 600 positive integer, e be 0 or 0 ~ 900 it is just whole
The usage amount of number, 0≤e/ (c+d+e)≤0.99, containing hydrogen silicone oil and vinyl silicone oil is silicon hydrogen and the molar ratio of silico ethylene base is
0.7 ~ 2:1；
Hydroxy silicon oil molecular structural formula is OHMe in condensed type liquid silastic2SiO(Me2SiO)a (R1R2SiO) b SiMe2OH,
R1、R2It is respectively and independently selected from one of methyl, phenyl, but R1With R2It is not simultaneously methyl, the positive integer that a is 5 ~ 4000, b 0
Or 0 ~ 1000 positive integer, 0≤b/ (a+b)≤0.99；
Described 5 ~ 65 Shore A of organic silicon rubber hardness, 0.2 ~ 3.8 MPa of tensile strength, elongation at break 40% ~
300%.
2. a kind of preparation method of antistatic organic silicon rubber that Ag quantum dot is compound according to claim 1, feature
It is, silver soluble saline solution is selected from AgF, AgNO in step (1)3And AgClO4The mixing of one or more of aqueous solution
Object；Borohydride salts are selected from the mixture of one or both of sodium borohydride, potassium borohydride, and usage amount is that soluble silver salt is water-soluble
The 0.01% ~ 0.1% of the amount of silver salt substance in liquid.
3. according to right want 1 described in a kind of preparation method for the antistatic organic silicon rubber that Ag quantum dot is compound, feature exists
Be selected from one or both of fume colloidal silica, precipitated silica in, reinforced filling, usage amount be silicone oil quality 2% ~
55 %。
4. a kind of preparation method of antistatic organic silicon rubber that Ag quantum dot is compound according to claim 1, feature
It is, platinum complex catalyst is selected from H2PtCl6Aqueous isopropanol, H2PtCl6Tetrahydrofuran solution, Pt (PPh3)4, first
The platinum complex of base vinylsiloxane coordination, the platinum complex of diethyl phthalate coordination, dicyclopentadiene dichloride
One or more of the platinum complex of platinum, dichloro bis- (triphenylphosphines), the usage amount of platinum complex catalyst are to make platinum
Element quality is 1 ~ 150ppm of add-on type liquid silicon rubber quality.
5. a kind of preparation method of antistatic organic silicon rubber that Ag quantum dot is compound according to claim 1, feature
It is, silane coupling agent is selected from ethyl orthosilicate, methyl orthosilicate, trimethoxy silane, triethoxysilane, three isopropoxies
Silane, γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, n- are pungent
One of base trimethoxy silane, n- octyltri-ethoxysilane, n- propyl-triethoxysilicane are several, and usage amount is
The 0.05 ~ 3% of condensed type liquid silastic quality, curing catalysts are selected from stannous octoate, dibutyl tin dilaurate, two isobutyls
One or more of base tin laurate, tetrabutyl titanate, acetylacetonate complex of tetrabutyl titanate, usage amount is condensed type
0.005% ~ 0.1 % of liquid silastic quality.
What 6. a kind of preparation method of the antistatic organic silicon rubber compound by Ag quantum dot as described in claim 1 obtained
Application of the compound antistatic organic silicon rubber of Ag quantum dot in electronic component encapsulation.
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Non-Patent Citations (2)
| Title |
|---|
| "Photopatternable Conductive PDMS Materials for Microfabrication";Hailin Cong,et al;《Advanced functional materials》;20081231;第18卷;第1912-1921页 |
| "Study of Isotropically Conductive Bondings Filled with Aggregates of Nano-Sized Ag-Particles";Stefan Kotthaus,et al;《IEEE TRANSACTIONS ON COMPONENTS, PACKAGING, AND MANUFACTURING TECHNOLOGY—PART A》;19970331;第20卷(第1期);第15-20页 |
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