CN104177837B - Viscosifier and preparation method thereof, additional organosilicon rubber and preparation method thereof - Google Patents
Viscosifier and preparation method thereof, additional organosilicon rubber and preparation method thereof Download PDFInfo
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- CN104177837B CN104177837B CN201410384830.9A CN201410384830A CN104177837B CN 104177837 B CN104177837 B CN 104177837B CN 201410384830 A CN201410384830 A CN 201410384830A CN 104177837 B CN104177837 B CN 104177837B
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Abstract
The invention discloses a kind of viscosifier and preparation method thereof, additional organosilicon rubber and preparation method thereof, described viscosifier have a following molecular structural formula:Wherein R1Selected from methyl or hydrogen, R2Selected from methyl or ethyl.The viscosifier of the present invention are the most curable at 80 DEG C with base material in additional organosilicon rubber, and the lap shear strength to PC is 2.0～2.5MPa, and the lap shear strength to aluminum is 2.4～2.6MPa, and the lap shear strength to copper is 1.5～1.8MPa；Hot strength is 5.4～5.7MPa；Elongation at break is 180～183%；Hardness is 27～29Shore A.
Description
Technical field
The present invention relates to a kind of viscosifier for additional organosilicon rubber and preparation method thereof, and these viscosifier are used
In the method preparing additional organosilicon rubber.
Background technology
In recent years, along with development and the popularization of application technology of China's silicone industry, add-on type liquid silicon rubber conduct
Class is higher, product technology content compared with big and that added value is a high class organosilicon product, its research and development and application are achieved with the biggest
Progressive.Owing to add-on type liquid silicon rubber has many excellent performances, particularly its shaping speed is fast, production efficiency is high, nothing
Malicious, tasteless, corrosion-free, chemical inertness, linear shrinkage ratio are little, can deep layer vulcanization, and can by the regulation of temperature control sulfuration speed
The features such as degree, are widely used in all trades and professions such as electronics, automobile, historical relic, artware duplication, mould, compare condensed type silicone rubber
There is prominent advantage.
But addition-type silicon rubber is low due to self-molecules present polarity, with base material, especially plastics base after its solidification
The adhesive property of material is poor.When using as sealing, embedding, coating, inserts, injecting forming material, by improving it to being connect
Touch the cementability of material, the most in advance base material is made primary coat and processes or add viscosifier.Silane coupling agent is expensive and adds life
Produce operation, reduce in production efficiency, and silane coupling agent containing inflammable organic solvent, add the danger during accumulating, use
Dangerous.And in addition-type silicon rubber formula, add viscosifier do not have the problem of above-mentioned use silane coupling agent, can preferably carry
High silicone rubber and the cementability of base material, always improve the focus of addition-type silicon rubber and substrate bonding research.
A series of silicon azacyclo-viscosifier of United States Patent (USP) US 5945555 synthesis, add in addition-type silicon rubber, solidification
Although having good cementability afterwards with base material especially Merlon (Polycarbonate is abbreviated as PC), but silicone rubber being only
Have at a temperature of relatively high (120 DEG C) to solidify just to have bonding, higher solidification temperature to be on the one hand unfavorable for joint with base material
Can, on the other hand plastic basis material itself is likely to cause destruction, produces defect.
Therefore, synthesis has the viscosifier of good thickening property, preparation can lower temperature solidification and with base material especially PC
The additional organosilicon rubber with good bonding is of great significance, and in current patent to report in this respect relatively
Few.
Summary of the invention
An object of the present invention is to provide and can be used for improving additional organosilicon rubber and have with base material after intermediate temperature setting
The viscosifier of good bonding；The two of purpose are to provide the method preparing above-mentioned viscosifier；The three of purpose are to provide can middle Wen Gu
With base material especially Merlon additional organosilicon rubber having good bonding and preparation method thereof after change, solidification.
In order to reach above-mentioned technique effect, the present invention takes techniques below scheme:
A kind of viscosifier for additional organosilicon rubber, it has a following molecular structural formula:
Wherein R1Selected from methyl or hydrogen, R2Selected from first
Base or ethyl.
According to embodiments of the invention, it has the property that in molecular structure containing the hydroxyl that can promote with substrate bonding
Base (-OH) and alkoxyl (-OCH3、-OC2H5), the existence of these groups, have with base material after making the sizing material solidification of addition viscosifier
Good cementability.
A kind of method preparing viscosifier, comprises the following steps:
A, the acryloxy silane that ratio is 1:1～1.04 of the amount of material is mixed with amino silane after in temperature 100
～react 6～10 hours at 150 DEG C, then cool the temperature to temperature 90～100 DEG C, the less molecule of removed under reduced pressure and unreacted
Amino silane, obtains the intermediate containing tertiary amine structure；Described acryloxy silane is selected from acryloxypropyl trimethoxy
Base silane or γ-methacryloxypropyl trimethoxy silane；Described amino silane is selected from aminopropyl trimethoxy silicon
Alkane or aminopropyl triethoxysilane；
B, by the mixing of the intermediate containing tertiary amine structure of the KH-560 that ratio is 1:1～1.02 of the amount of material and step A, then
Add toluene and solid promoter, react 3～5 hours, then by temperature in temperature 105～115 DEG C the most under nitrogen protection
It is down to temperature 50～60 DEG C of decompression distillation removing toluene, obtains described viscosifier.
According to a preferred embodiment of the invention, the method preparing viscosifier comprises the following steps:
A, the acryloxy silane that ratio is 1:1.02 of the amount of material is mixed with amino silane after in temperature 100～
React 6～10 hours at 150 DEG C, then cool the temperature to temperature 90～100 DEG C, the less molecule of removed under reduced pressure and unreacted ammonia
Base silane, obtains the intermediate containing tertiary amine structure；Described acryloxy silane is selected from acryloxypropyl trimethoxy
Silane or γ-methacryloxypropyl trimethoxy silane；Described amino silane is selected from aminopropyl trimethoxysilane
Or aminopropyl triethoxysilane；
B, by the mixing of the intermediate containing tertiary amine structure of the KH-560 that ratio is 1:1 of the amount of material and step A, add first
Benzene and DMP-30, react 3～5 hours in temperature 105～115 DEG C the most under nitrogen protection, then cool the temperature to temperature 50
～60 DEG C of decompression distillation removing toluene, obtain described viscosifier.
The preparation method of a kind of additional organosilicon rubber, comprises the following steps:
I) preparation of base glue
The poly dimethyl that the dimethyl ethenyl silyloxy of 100 weight portion viscosity 1000～20000mPa s is blocked
Siloxanes, 1～25 hexamethyldisiloxane, 0.5～20 weight portion distilled water, 10～60 weight part ratio surface areas of weight portion
150～400m2Mediate 1～3 hour in room temperature after the fume colloidal silica mixing of/g, then heat to 150～200 DEG C and mediate 2
～6 hours, add the poly-of the dimethyl ethenyl silyloxy end-blocking that 100 weight portion viscosity are 1000～20000mPa s
Dimethyl siloxane latting drown, obtains described base glue；
II) preparation of component A
The base glue 100 weight portion steps I prepared and the platinum complex of 0.35～0.55 weight portion platinum content 3000ppm mix
Described component A is obtained after closing uniformly；
III) preparation of B component
Base glue prepared by 94 weight portion steps I, 1～20 weight portion containing hydrogen silicone oils, 2～8 viscosifier described in weight portion
Described B component is uniformly obtained with 0.04～0.08 weight portion inhibitor mixed；
IV) preparation of additional organosilicon rubber
The B component that component A step II prepared is prepared with step III is mixed homogeneously, and obtains described addition after deaeration
Type organic silicon rubber.
According to embodiments of the invention, described inhibitor is selected from t etram-ethyltetravinylcyclotetrasiloxane, acetylene basic ring
Hexanol, tetramethylethylenediamine, diallyl maleate, 3-methyl isophthalic acid-butine-3-alcohol, 3-Phenyl-1-butyn-3-ol or 3-third
One or more of base-ethyl acetylene-3-alcohol.
According to embodiments of the invention, described platinum complex is divinyl tetramethyl disiloxane and chloroplatinic acid complexation
Thing.
According to embodiments of the invention, described containing hydrogen silicone oil is the containing hydrogen silicone oil at least containing two reactive hydrogens, and it is lived
Property hydrogen content is 0.2%～1.5%.
A kind of additional organosilicon rubber using described preparation method to prepare.
According to embodiments of the invention, additional organosilicon rubber has the property that the lap shear strength to PC is
2.0～2.5MPa, the lap shear strength to aluminum is 2.4～2.6MPa, and the lap shear strength to copper is 1.5～1.8MPa；
Hot strength is 5.4～5.7MPa；Elongation at break is 180～183%；Hardness is 27～29Shore A.
The present invention is described more detail below.
The viscosifier that the present invention provides have a molecular structural formula of following four kinds:
(molecular formula 1)
(molecular formula 2)
(molecular formula 3)
(molecular formula 4)
In step A of the preparation method of viscosifier, acryloxy silane mix with amino silane after in temperature 100～
Reversal of the Michael addition is occurred to generate the intermediate containing tertiary amine structure at 150 DEG C.Acryloxy silane and the thing of amino silane
The ratio of the amount of matter is 1:1～1.04, preferably 1:1.02.Acryloxy silane and amino silane generation reversal of the Michael addition
Temperature ＜ 100 DEG C, then reaction carry out slower；Temperature ＞ 150 DEG C, then amino is oxidized easily, and produces side reaction, therefore propylene
Acyloxy silane and amino silane occur reversal of the Michael addition to be rational at temperature 100～150 DEG C.Acryloxy silicon
After alkane reacts with amino silane, cool the temperature to 90～100 DEG C and carry out reduce pressure de-low molecule and excess of ammonia base silane.
Described KH-560 is γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane of Chinese Academy of Sciences's research and development.
Described curing accelerator DMP-30 is 2, the abbreviation of 4,6 three (dimethylamino methyl) phenol.
Described acryloxypropyl trimethoxy silane is commercially available, and such as Jiang-Han Area Fine Chemical Co., Ltd produces
JH-O176；Described γ-methacryloxypropyl trimethoxy silane is commercially available, such as the limited public affairs of Jiang-Han Area fine chemistry industry
The JH-O174 that department produces.Described aminopropyl trimethoxysilane is commercially available, and example Jiang-Han Area Fine Chemical Co., Ltd produces
JH-A111；Described aminopropyl triethoxysilane is commercially available, such as the KBM-903 of SHIN-ETSU HANTOTAI of Japan chemical production.
In step B of the preparation method of viscosifier, the effect of toluene is to improve the compatibility between raw material；The effect of accelerator
It it is the ring-opening reaction promoting epoxy silane.In step B, reactant is under nitrogen protection in temperature 105～115 DEG C of reactions, reaction
During temperature ＜ 105 DEG C, then reaction carries out relatively slow, during reaction temperature ＞ 115 DEG C, the most easily produces by-product, therefore reaction temperature
It is rational for being 105～115 DEG C.
The synthetic reaction formula of viscosifier is as follows:
Wherein, R1For CH3Or H, R2For CH3Or C2H5。
The preparation method of a kind of additional organosilicon rubber, comprises the following steps:
I) preparation of base glue
The poly dimethyl that the dimethyl ethenyl silyloxy of 100 weight portion viscosity 1000～20000mPa s is blocked
Siloxanes, 1～25 hexamethyldisiloxane, 0.5～20 weight portion distilled water, 10～60 weight part ratio surface areas of weight portion
150～400m2Mediate 1～3 hour in room temperature after the fume colloidal silica mixing of/g, then heat to 150～200 DEG C and mediate 2
～6 hours, add the poly-of the dimethyl ethenyl silyloxy end-blocking that 100 weight portion viscosity are 1000～20000mPa s
Dimethyl siloxane latting drown, obtains described base glue；
The polydimethylsiloxane of dimethyl ethenyl silyloxy end-blocking is that Mianyang Wells Electronic Material Co., Ltd. is raw
Producing, the trade mark is 903.Equally, it is also possible to for the product of other companies on market, the limited public affairs of organosilicon material won by such as Jiande City's connection
The DY-V series of products that the LY-205 series of products of department's production and Shandong Dayi Chemical Industry Co., Ltd produce.
Fume colloidal silica is commercially available, the LM-150 that such as Cabot company produces, Zhejiang Fushite Group Co., Ltd.
FST-200, the FST-380 produced.White carbon specific surface area < 150m2/ g does not reaches preferable reinforcing effect；Specific surface area >
400m2/ g, adds thickening after sizing material, it is difficult to dispersion, therefore specific surface area 150～400m2The fume colloidal silica of/g is reasonable
's.
II) preparation of component A
Base glue prepared by 100 weight portion steps I and the platinum complex of 0.35～0.55 weight portion platinum content 3000 ppm
Described component A is obtained after mix homogeneously；
Platinum complex in the present invention is divinyl tetramethyl disiloxane and chloroplatinic acid complex, such as, congratulate Li Shi raw
The Karstedt catalyst produced.
III) preparation of B component
Base glue prepared by 94 weight portion steps I, 1～20 weight portion at least contain the containing hydrogen silicone oil of two reactive hydrogens, 2～
Viscosifier and 0.04～0.08 weight portion inhibitor mixed described in 8 weight portion claim 1 uniformly obtain described B component；
In the present invention, containing hydrogen silicone oil act as cross-linking agent, with dimethyl ethenyl silyloxy under the effect of platinum catalyst
The polydimethylsiloxane of end-blocking crosslinks reaction, makes sizing material solidify, and its active hydrogen content is 0.2%～1.5%.
The effect of the inhibitor of the present invention is suppression control and the curing rate of regulation sizing material, makes mixed sizing material have foot
Enough operable times, it can be selected from selected from t etram-ethyltetravinylcyclotetrasiloxane, ethynylcyclohexanol, tetramethyl second two
Amine, diallyl maleate, 3-methyl isophthalic acid-butine-3-alcohol, 3-Phenyl-1-butyn-3-ol or 3-propyl group-ethyl acetylene-3-alcohol etc.
One or more.
IV) preparation of additional organosilicon rubber
The B component that component A step II prepared is prepared with step III is mixed homogeneously, and obtains described addition after deaeration
Type organic silicon rubber.
In the present invention, the assay method of lap shear strength is as follows: be coated in base material test piece by additional organosilicon rubber,
Then base material test being overlapped, making the distance between bonding plane is 1 ± 0.1mm, it is steadily placed, and dries 80 DEG C of air blast
Case solidifies 60 minutes, prepares and shear sample, measure by GB/T7124-2008.
The hot strength of the present invention, elongation at break are tested according to GB/T528-2009 method, and hardness is according to GB/T531-
2008 method tests.
The present invention compared with prior art, has a following beneficial effect:
The viscosifier of the present invention are the most curable at 80 DEG C with base material in additional organosilicon rubber, cut the overlap joint of PC
Shearing stress is 2.0～2.5MPa, and the lap shear strength to aluminum is 2.4～2.6MPa, to the lap shear strength of copper be 1.5～
1.8MPa；Hot strength is 5.4～5.7MPa；Elongation at break is 180～183%；Hardness is 27～29Shore A.
Detailed description of the invention
Below in conjunction with embodiments of the invention, the invention will be further elaborated.
Synthesis example 1:
58.6g acryloxypropyl trimethoxy silane (0.25mol), 45.72g ammonia is added in 250mL there-necked flask
Propyl trimethoxy silicane (0.255mol), is stirred at room temperature 30 minutes, is warming up to 100 DEG C of reactions 8 the most under nitrogen protection little
Time, it is cooled to 90 DEG C, the little molecule of removed under reduced pressure and unreacted aminopropyl trimethoxysilane.Then add in reaction system
59.08g KH-560 (0.25mol), 50mL toluene and 0.5gDMP-30, under nitrogen protection in 110 DEG C of reactions 4 hours, then
Cooling, at 50～60 DEG C of decompression distillation removing toluene, prepares viscosifier 1, yield 92%.Infrared absorption spectroscopy (KBr tabletting) is special
Levy peak: 1190cm-1(C-N stretching vibration), 1720cm-1(-COO-stretching vibration), 2960～2910cm-1(-CH3With-CH2-stretch
Contracting vibration), 1130cm-1(-C-O-asymmetrical stretching vibration), 1020cm-1(-C-O-symmetrical stretching vibration), 3620cm-1(-OH
Stretching vibration), 750～660cm-1(-Si-CH2-stretching vibration), 1250～1200cm-1(-Si-CH2-bending vibration).
Synthesis example 2:
62.00g γ-methacryloxypropyl trimethoxy silane (0.25mol) is added in 250mL there-necked flask,
45.72g aminopropyl trimethoxysilane (0.255mol), is stirred at room temperature 30 minutes, is warming up to 150 DEG C the most under nitrogen protection
React 8 hours, be cooled to 90 DEG C, the little molecule of removed under reduced pressure and unreacted aminopropyl trimethoxysilane.Then to reactant
System adds 59.08g KH-560 (0.25mol), 51mL toluene and 0.5g DMP-30, reacts 4 in 110 DEG C under nitrogen protection
Hour, then lower the temperature, at 50～60 DEG C of decompression distillation removing toluene, prepare viscosifier 2, yield 91%.Infrared absorption spectroscopy
(KBr tabletting) characteristic peak: 1190cm-1(C-N stretching vibration), 1710cm-1(-COO-stretching vibration), 2960～2920cm-1(-
CH3With-CH2-stretching vibration), 1120cm-1(-C-O-asymmetrical stretching vibration), 1020cm-1(-C-O-symmetrical stretching vibration),
3600cm-1(-OH stretching vibration), 760～660cm-1(-Si-CH2-stretching vibration), 1250～1210cm-1(-Si-CH2-bending
Vibration).
Synthesis example 3:
58.6g acryloxypropyl trimethoxy silane (0.25mol), 56.45g ammonia is added in 250mL there-necked flask
Propyl-triethoxysilicane (0.255mol), is stirred at room temperature 30min, is warming up to 100 DEG C of reactions 8 the most under nitrogen protection little
Time, it is cooled to 90 DEG C, the little molecule of removed under reduced pressure and unreacted aminopropyl triethoxysilane.Then add in reaction system
59.08g KH-560 (0.25mol), 55mL toluene and 0.5gDMP-30, under nitrogen protection in 110 DEG C of reactions 4 hours, then
Cooling, at 50～60 DEG C of decompression distillation removing toluene, prepares viscosifier 3, yield 89%.Infrared absorption spectroscopy (KBr tabletting) is special
Levy peak: 1190cm-1(C-N stretching vibration), 1730cm-1(-COO-stretching vibration), 2970～2910cm-1(-CH3With-CH2-stretch
Contracting vibration), 1110cm-1(-C-O-asymmetrical stretching vibration), 1010cm-1(-C-O-symmetrical stretching vibration), 3600cm-1(-OH
Stretching vibration), 770～670cm-1(-Si-CH2-stretching vibration), 1270～1220cm-1(-Si-CH2-bending vibration).
Synthesis example 4:
62.00g γ-methacryloxypropyl trimethoxy silane (0.25mol) is added in 250mL there-necked flask,
56.45g aminopropyl triethoxysilane (0.255mol), is stirred at room temperature 30 minutes, is warming up to 150 DEG C the most under nitrogen protection
React 8 hours, be cooled to 100 DEG C, the little molecule of removed under reduced pressure and unreacted aminopropyl triethoxysilane.Then to reactant
System adds 59.08g KH-560 (0.25mol), 60mL toluene and 0.5g DMP-30, reacts 4 in 110 DEG C under nitrogen protection
Hour, then lower the temperature, at 50～60 DEG C of decompression distillation removing toluene, prepare viscosifier 4, yield 87%.Infrared absorption spectroscopy
(KBr tabletting) characteristic peak: 1180cm-1(C-N stretching vibration), 1730cm-1(-COO-stretching vibration), 2960～2930cm-1(-
CH3With-CH2-stretching vibration), 1130cm-1(-C-O-asymmetrical stretching vibration), 1020cm-1(-C-O-symmetrical stretching vibration),
3550cm-1(-OH stretching vibration), 750～660cm-1(-Si-CH2-stretching vibration), 1250～1200cm-1(-Si-CH2-bending
Vibration).
Contrast synthesis example 1:
It is sequentially added into 64.29g trimethylolpropane allyl ether (0.3mol), 35.45gKH-to 250mL there-necked flask
560 (0.15mol) and 35.15g acryloxypropyl trimethoxy silane (0.15mol), after stirring, add 1.5g phthalein
Acid butyl ester, in nitrogen protection is lower, temperature rise is reacted 2 hours to 80 DEG C, the then little molecule of removed under reduced pressure, prepares contrast viscosifier 1, receives
Rate 91%.
Contrast synthesis example 2:
It is sequentially added into 64.29g trimethylolpropane allyl ether (0.3mol), 35.45gKH-to 250mL there-necked flask
560 (0.15mol) and 37.25g γ-methacryloxypropyl trimethoxy silane (0.15mol), after stirring, adds
Entering 1.5g Butyl Phthalate, in nitrogen protection is lower, temperature rise is reacted 2 hours to 80 DEG C, the then little molecule of removed under reduced pressure, prepares contrast and increases
Stick 2, yield 88%.
Embodiment 1:
The preparation method of a kind of additional organosilicon rubber, comprises the following steps
I) preparation of base glue
The polydimethylsiloxane that the dimethyl ethenyl silyloxy of 100 weight portion viscosity 5000mPa s is blocked
(903-5000), the hexamethyldisiloxane of 20 weight portions, 10 weight portion distilled water, 50 weight part ratio surface area 150m2/ g's
Mediate 1 hour in room temperature after fume colloidal silica mixing, then heat to 170 DEG C and mediate 3 hours, add 100 weight portions and glue
The polydimethylsiloxane latting drown of the dimethyl ethenyl silyloxy end-blocking that degree is 5000mPa s, obtains described base glue；
II) preparation of component A
Base glue prepared by 100 weight portion steps I and the platinum complex mix homogeneously of 0.54 weight portion platinum content 3000ppm
After obtain described component A；
III) preparation of B component
The base glue 94 weight portion steps I prepared, 2.5 parts by weight of activated hydrogen contents are containing hydrogen silicone oil, 4 weight of 0.8%
Part viscosifier 1 and 0.04 weight portion t etram-ethyltetravinylcyclotetrasiloxane mix homogeneously obtains described B component；
IV) preparation of additional organosilicon rubber
The B component that component A step II prepared is prepared with step III is mixed homogeneously, and obtains described addition after deaeration
Type organic silicon rubber.
It is coated on copper sheet, aluminium flake and urethane film, the test piece of two identical materials is overlapped, makes between bonding plane
Distance be 1 ± 0.1mm, it is steadily placed, in 80 DEG C of convection oven solidify 60 minutes, prepare shear sample.
Hot strength, elongation at break are tested according to GB/T528-2009 method, and hardness is according to GB/T531-2008 method
Test.
Embodiment 2:
With embodiment 1, except using viscosifier 2 replacement viscosifier 1 in B component.
Embodiment 3:
With embodiment 1, except using viscosifier 3 replacement viscosifier 1 in B component.
Embodiment 4:
With embodiment 1, except using viscosifier 4 replacement viscosifier 1 in B component.
Embodiment 5:
The preparation method of a kind of additional organosilicon rubber, comprises the following steps:
I) preparation of base glue
The polydimethylsiloxane that the dimethyl ethenyl silyloxy of 100 weight portion viscosity 1000mPa s is blocked
(903-1000), the hexamethyldisiloxane of 16 weight portions, 5 weight portion distilled water, 40 weight part ratio surface area 380m2The gas of/g
Mediate 3 hours in room temperature after phase method white carbon (FST-380) mixing, then heat to 180 DEG C and mediate 3 hours, add 100 weights
Amount part viscosity is polydimethylsiloxane (903-5000) latting drown of the dimethyl ethenyl silyloxy end-blocking of 5000mPa s,
Obtain described base glue；
II) preparation of component A
Base glue prepared by 100 weight portion steps I and the platinum complex mix homogeneously of 0.35 weight portion platinum content 3000ppm
After obtain described component A；
III) preparation of B component
The base glue 94 weight portion steps I prepared, 1.8 parts by weight of activated hydrogen contents are containing hydrogen silicone oil, 4 weight of 0.8%
Part viscosifier 1 and 0.04 weight portion t etram-ethyltetravinylcyclotetrasiloxane mix homogeneously obtains described B component；
IV) preparation of additional organosilicon rubber
The B component that component A step II prepared is prepared with step III is mixed homogeneously, and obtains described addition after deaeration
Type organic silicon rubber.
Embodiment 6:
The preparation method of a kind of additional organosilicon rubber, comprises the following steps:
I) preparation of base glue
The polydimethylsiloxane that the dimethyl ethenyl silyloxy of 100 weight portion viscosity 1000mPa s is blocked
(903-1000), the hexamethyldisiloxane of 25 weight portions, 20 weight portion distilled water, 50 weight part ratio surface area 200m2/ g's
Mediate 3 hours in room temperature after fume colloidal silica (FST-200) mixing, then heat to 200 DEG C and mediate 2 hours, add 100
Weight portion viscosity is that the polydimethylsiloxane (903-20K) of the dimethyl ethenyl silyloxy end-blocking of 20000mPa s is converted
Dilute, obtain described base glue；
II) preparation of component A
Base glue prepared by 100 weight portion steps I and the platinum complex mix homogeneously of 0.42 weight portion platinum content 3000ppm
After obtain described component A；
III) preparation of B component
The base glue 94 weight portion steps I prepared, 1.5 parts by weight of activated hydrogen contents are containing hydrogen silicone oil, 4 weight of 0.8%
Part viscosifier 2 and 0.05 weight portion t etram-ethyltetravinylcyclotetrasiloxane mix homogeneously obtains described B component；
IV) preparation of additional organosilicon rubber
The B component that component A step II prepared is prepared with step III is mixed homogeneously, and obtains described addition after deaeration
Type organic silicon rubber.
Comparative example 1:
With embodiment 1, except using contrast viscosifier 1 replacement viscosifier 1 in B component.
Comparative example 2:
With embodiment 1, except using contrast viscosifier 2 replacement viscosifier 1 in B component.
The test result of embodiment 1-6 and comparative example 1-2 is shown in Table 1.
Table 1: embodiment 1-6 and the test result of comparative example 1-2
Although reference be made herein to invention has been described for the explanatory embodiment of the present invention, and above-described embodiment is only this
Bright preferably embodiment, embodiments of the present invention are also not restricted to the described embodiments, it should be appreciated that people in the art
Member can be designed that a lot of other amendments and embodiment, and these amendments and embodiment will fall in principle disclosed in the present application
Within scope and spirit.
Claims (9)
1. the viscosifier for additional organosilicon rubber, it is characterised in that it has a following molecular structural formula:
Wherein R1Selected from methyl or hydrogen, R2Selected from first
Base or ethyl.
2. the method for the viscosifier prepared described in claim 1, it is characterised in that the method comprises the following steps:
A, the acryloxy silane that ratio is 1:1～1.04 of the amount of material is mixed with amino silane after in temperature 100～150
React 6～10 hours at DEG C, then cool the temperature to 90～100 DEG C, the less molecule of removed under reduced pressure and unreacted amino silane,
Obtain the intermediate containing tertiary amine structure；
Described acryloxy silane is selected from acryloxypropyl trimethoxy silane or γ-methacryloxypropyl
Trimethoxy silane；Described amino silane is selected from aminopropyl trimethoxysilane or aminopropyl triethoxysilane；
B, by the mixing of the intermediate containing tertiary amine structure of the KH-560 that ratio is 1:1～1.02 of the amount of material and step A, add
Toluene and curing accelerator, react 3～5 hours in temperature 105～115 DEG C the most under nitrogen protection, then cool the temperature to
50～60 DEG C of decompression distillation removing toluene, obtain described viscosifier.
Method the most according to claim 2, it is characterised in that the method comprises the following steps:
A, the acryloxy silane that ratio is 1:1.02 of the amount of material is mixed with amino silane after in temperature 100～150 DEG C
Lower reaction 6～10 hours, then cool the temperature to 90～100 DEG C, the less molecule of removed under reduced pressure and unreacted amino silane,
To the intermediate containing tertiary amine structure；Described acryloxy silane selected from acryloxypropyl trimethoxy silane or γ-
Methacryloxypropyl trimethoxy silane；Described amino silane is selected from aminopropyl trimethoxysilane or aminopropyl three
Ethoxysilane；
B, by the mixing of the intermediate containing tertiary amine structure of the KH-560 that ratio is 1:1 of the amount of material and step A, add toluene and
DMP-30, reacts 3～5 hours in temperature 105～115 DEG C the most under nitrogen protection, then cools the temperature to 50～60 DEG C and subtract
Pressure distillation removing toluene, obtains described viscosifier.
4. the preparation method of an additional organosilicon rubber, it is characterised in that the method comprises the following steps:
I) preparation of base glue
The polydimethylsiloxanes that the dimethyl ethenyl silyloxy of 100 weight portion viscosity 1000～20000mPa s is blocked
Alkane, 1～25 weight portion hexamethyldisiloxane, 0.5～20 weight portion distilled water, 10～60 weight part ratio surface area 150～
400m2Mediate 1～3 hour in room temperature after the fume colloidal silica mixing of/g, then heat to 150～200 DEG C of kneadings 2～6 little
Time, add the poly dimethyl of the dimethyl ethenyl silyloxy end-blocking that 100 weight portion viscosity are 1000～20000mPa s
Siloxanes latting drown, obtains described base glue；
II) preparation of component A
The base glue 100 weight portion steps I prepared and the platinum complex mixing of 0.35～0.55 weight portion platinum content 3000ppm are all
Described component A is obtained after even；
III) preparation of B component
Base glue prepared by 94 weight portion steps I, 1～20 weight portion containing hydrogen silicone oils, 2～8 increasing described in weight portion claim 1
Stick and 0.04～0.08 weight portion inhibitor mixed uniformly obtain described B component；
IV) preparation of additional organosilicon rubber
The B component that component A step II prepared is prepared with step III is mixed homogeneously, and obtaining described add-on type after deaeration has
Machine silicone rubber.
Preparation method the most according to claim 4, it is characterised in that described inhibitor is selected from tetramethyl tetravinyl ring
Tetrasiloxane, ethynylcyclohexanol, butynol, tetramethylethylenediamine, diallyl maleate, 3-methyl isophthalic acid-butine-3 alcohol, 3-
One or more of phenyl-ethyl acetylene-3 alcohol or 3-propyl group-ethyl acetylene-3 alcohol.
Preparation method the most according to claim 4, it is characterised in that described platinum complex is divinyl tetramethyl two
Siloxanes and chloroplatinic acid complex.
Preparation method the most according to claim 4, it is characterised in that described containing hydrogen silicone oil is at least to contain two activity
The containing hydrogen silicone oil of hydrogen, its active hydrogen content is 0.2%～1.5%.
8. the additional organosilicon rubber prepared according to the preparation method described in claim any one of claim 4～7.
Additional organosilicon rubber the most according to claim 8, it is characterised in that it has the property that
Lap shear strength to PC is 2.0～2.5MPa, and the lap shear strength to aluminum is 2.4～2.6MPa, takes copper
Connecing shear strength is 1.5～1.8MPa；Hot strength is 5.4～5.7MPa；Elongation at break is 180～183%；Hardness is 27
～29Shore A.
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