CN109735107A - A method of low viscosity dimethyl silicone oil thermo oxidative stability in air is improved using the organo-metallic compound of nickel and zirconium - Google Patents
A method of low viscosity dimethyl silicone oil thermo oxidative stability in air is improved using the organo-metallic compound of nickel and zirconium Download PDFInfo
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Abstract
The present invention provides a kind of methods for improving low viscosity dimethyl silicone oil thermo oxidative stability in air using the organo-metallic compound of nickel and zirconium; under inert atmosphere protection and certain temperature; it is heat-treated first with dimethicone of the metal oxide Jing Guo vacuum drying treatment to low viscosity; after the operation such as being filtered, depressurizing de- low boiling, the silicone oil with low viscosity of metal oxide treated is obtained；Then the modified silicon oil of metal oxide treated is heat-treated under inert atmosphere protection and certain temperature with the organo-metallic compound of nickel and zirconium again; after removing low molecular compound under inert gas shielding, modified silicon oil that the organo-metallic compound and metal oxide treated for obtaining nickel and zirconium are crossed.Obtained silicone oil thermal decomposition temperature in air and oxygen is improved significantly, and operation of the present invention condition is simple, and step is simple, and modified silicon oil yield is high, is very suitable to be mass produced.
Description
Technical field
It is specifically a kind of that low viscosity is improved using the organo-metallic compound of nickel and zirconium the present invention relates to organic chemistry filed
The method of dimethicone thermo oxidative stability in air.
Background technique
Silicone oil is that the linear polysiloxane of liquid condition is made of and kept at room temperature duplicate Si-O-Si chain link, if Si
When the organo-functional group connected on atom is methyl, referred to as dimethicone, chemical structural formula are as shown in Equation 1:
The chemical structural formula of 1. dimethicone of formula
Me represents methyl in formula 1, and x represents the degree of polymerization of polysiloxanes.
With the increase of degree of polymerization x in linear polydimethylsiloxane- molecule, the viscosity of silicone oil is gradually increased.Different viscosities
Silicone oil national economy every field have different purposes, such as highly viscous silicone oil can be used as silicone grease, silicon cream, demoulding
The base polymer of agent, the silicone oil of low viscosity can be used as the personal nursings conduct such as cosmetics, hair protecting shampoo, lipstick, hand lotion
Industry.Compared with other synthetic polymers, silicone oil has excellent high-low temperature resistant, low viscosity-temperature coefficient, low surface tension, physiology lazy
Property, the characteristics such as good chemical stability, good electrical insulating property, weatherability, hydrophobicity, can be long-term at -50~200 DEG C
It uses；In addition, silicone oil has excellent physical characteristic, damp proof insulation can be directly used for, damp, damping, defoam, lubricate, polishing
Etc., it is widely used as insulation lubrication, shockproof, grease proofing dirt, dielectric liquid and heat carrier, and be used as defoaming, release agent, paint
And chemical product additive.
When temperature is more than 175 DEG C, degradation reaction will occur for polysiloxane molecule, and as temperature increases, polysiloxanes
Molecular degradation reaction aggravation leads to the silicone oil high temperature blanking labour lost of life or can not make for a long time under 250 DEG C and temperatures above
With.In oxygen-free environment, the degradation reaction product of polysiloxane molecule is hexamethyl cyclotrisiloxane (D3), prestox ring four
The cyclosiloxane of the small molecules such as siloxanes (D4), decamethylcyclopentaandoxane (D5), ten diformazan basic rings, six siloxanes (D6),
Mechanism is derived mainly from " button " degradation in polysiloxane molecule main chain；In aerobic environment, polysiloxane molecule side chain has
The oxidation of machine functional group generates free radical, other organic functionals of the further attack polysiloxane molecule side chain of the free radical of generation
Group, while generating the small molecule compounds such as alkane, aldehyde, ketone, acid, silicone cross causes silicon oil viscosity to increase, directly
To three-dimensional netted gel is finally gradually formed, silicone oil is caused to lose flowability.
For improve silicone oil thermo oxidative stability, United States Patent (USP) US4193885 disclose to silicone oil be added it is suitable containing
The method of Ti, Zr, Hf compound, these compounds can be by way of Ti, Zr, Hf obtain organosiloxy derivative and silicone oil
It is mixed；Or after mixing the organic derivative of suitable Ti, Zr, Hf with silicone oil, reheating decomposition is added organic
Derivative；Or excessive Ti, Zr, Hf compound and silicone oil are first mixed to form thermal stabilization additive, then again by additive
It dilutes to obtain Ti, Zr, Hf compound of suitable concentration using additional silicone oil.By the silicone oil containing Ti, Zr, Hf with contain on a small quantity
The compound of Si-H is mixed, and can further improve the thermal stability of silicone oil.The thermostabilization silicone oil of the disclosure of the invention is especially suitable
Together in as the organic heat carrier in anaerobic, water-less environment.
Silicone oil in addition to being heated or cooled that pipe-line system etc. is anhydrous, other than the heat transmission medium in oxygen-free environment for closed,
The heat transmission medium being also widely used in the unlimited systems such as chemistry, chemical industry, pharmacy, Polymer Synthesizing processing.With anhydrous and oxygen-free ring
Border is compared, and is opened wide silicone oil in system and is easier to cause because the organo-functional group of molecular side chain is attacked by free radical at high temperature
Crosslinking, gelation and solidification, cause silicone oil to lose flowability, heat can not transmit, and cross-linking products are smoldered by thermal oxide, very
To the danger for causing fire.
Silicone oil can be effectively improved in anhydrous and oxygen-free obturator although with technical solution disclosed in United States Patent (USP) US4193885
Thermal stability in system, but the technical solution has used the organic derivative of expensive Hf, and cost is caused to increase；On the other hand,
The technical solution of the patent disclosure is not suitable for aerobic, silicone oil hot property in open system raising.
Summary of the invention
There is silicon under using temperature not high or high temperature when in order to improve in aerobic environment using silicone oil as heat transfer media
Oil plant uses as a servant the defect of the lost of life, and reduces the cost of modified silicon oil, and the present invention proposes a kind of organic metal using nickel and zirconium
The method that compound improves low viscosity dimethyl silicone oil thermo oxidative stability in air, and is individually changed using metal oxide
Property obtained silicone oil compare, hot property of the silicone oil prepared by the present invention in aerobic environment be improved significantly, there is energy consumption
It is low, environmental pollution is small, safety and environmental protection, yield are high, be separated by solid-liquid separation be easy, the features such as Processes and apparatus is simple and production cost is low.
The present invention is achieved by following technical proposals:
It is a kind of that using the organo-metallic compound of nickel and zirconium raising low viscosity dimethyl silicone oil, thermal oxide is stablized in air
The method of property comprises the steps that
(1) under inert gas protection, silicone oil with low viscosity and metal oxide are added to reaction vessel by a certain percentage
In；
(2) under inert gas shielding and stirring, the mixture of silicone oil and metal oxide is increased to certain temperature from room temperature
Degree, and certain time is kept at this temperature；
(3) after being cooled to room temperature, inert gas is closed, solidliquid mixture is filtered under diminished pressure, collect filtrate；
(4) filtrate is transferred in de- low reaction kettle, vacuumizes under inert gas shielding and stirring, then gradually rises
Temperature removes remaining small molecule compound in filtrate；
(5) after the completion of taking off low-boiling-point substance operation, it is down to room temperature, inert gas and stirring is closed, obtains metal oxide treated
Modified silicon oil；
(6) modified silicon oil of metal oxide treated is added to by a certain percentage with the organo-metallic compound of nickel and zirconium
In reaction kettle, it is increased to certain temperature from room temperature under inert gas shielding, and keeps a period of time at this temperature；
(7) reaction mixture in step (6) is cooled to room temperature, and is transferred them in de- low reaction kettle, in inert gas
It is vacuumized under protection and stirring, then gradually rises temperature, remove remaining small molecule compound in filtrate；
(8) after the completion of taking off low-boiling-point substance operation, it is down to room temperature, inert gas and stirring is closed, obtains organic gold of nickel and zirconium
The modified silicon oil that category compound and metal oxide treated are crossed.
(20 DEG C) of viscosity of the low viscosity dimethyl silicone oil are less than or equal to 500mPa.s；Preferably, described
(20 DEG C) of viscosity of low viscosity dimethyl silicone oil are less than or equal to 200mPa.s；As particularly preferred, described low viscosity diformazan
(20 DEG C) of viscosity of base silicone oil are less than or equal to 100mPa.s.
The inert gas is selected from argon gas or nitrogen；Preferably, the inert gas is selected from nitrogen, purity
More than or equal to 99.9%.
The metal oxide is selected from one or more of ZnO, Al2O3, MgO, MnO2 or CeO2, and dosage is
The 1%~30% of silicone oil quality；Preferably, the metal oxide is selected from ZnO or CeO2, dosage is silicone oil quality
3%~20%.
The metal oxide is vacuum dried using preceding needing, and vacuum drying temperature is 110~160 DEG C, drying time
For 1~10h；Preferably, the vacuum drying temperature before the metal oxide use is 120~150 DEG C, drying time
For 2~8h.
The treatment temperature of the mixture of the silicone oil and metal oxide composition is 130~170 DEG C, and the processing time is 1
~8h；Preferably, the treatment temperature of the mixture of the silicone oil and metal oxide composition is 135~165 DEG C, processing
Time is 2~6h.
The organo-metallic compound of the nickel is selected from diacetyl acetone nickel, bis- (triphenylphosphine) nickel chlorides, 1,3- bis- (two
Phenylphosphine propane) Nickel Chloride, nickel dibutyl dithiocarbamate, bis- (hexafluoroacetylacetones) conjunction nickel, nickel formate (II)
Salt, dimethylamino dithiocarbonic acid nickel, (1,1'- bis- (diphenylphosphine) ferrocene) Nickel Chloride, dicyclopentadienyl nickel, bis- (triphenyls
Phosphine) Nickel Bromide, double-(1,5- cyclo-octadiene) nickel, four (triphenylphosphine) nickel, bi triphenyl phosphine dicarbapentaborane nickel, nickel acetylacetonate
In dihydrate, bis- (2,2,6,6,-tetramethyl -3,5- heptadione acid) nickel or chlorine (cyclopentadienyl group) (triphenyl phasphine) nickel (II)
One or more, the modified silicon oil of organo-metallic compound (in terms of the Ni atom) and metal oxide treated of the nickel
Mass ratio be 0.00001~0.05:1, the organo-metallic compound of the zirconium be selected from acetylacetone,2,4-pentanedione zirconium, tetrabutyl zirconate,
One or more of vanadic acid zirconium, zirconium iso-octoate, bis- (lemon diethyl phthalate) dipropoxy zirconium chelates, the zirconium has
The mass ratio of machine metallic compound (in terms of Zr atom) and the modified silicon oil of metal oxide treated is 0.0001~0.10:1,
The treatment temperature for the silicone oil that the organo-metallic compound and metal oxide treated of the nickel and zirconium are crossed is 280~350 DEG C,
Handle the time be 2~for 24 hours；Preferably, the organo-metallic compound of the nickel is selected from diacetyl acetone nickel, dibutyl two
One or more of nickel dithiocarbamate, dicyclopentadienyl nickel, the organo-metallic compound (in terms of Ni atom) and gold of the nickel
The mass ratio for belonging to the modified silicon oil of oxide process is 0.00005~0.02:1, and the organo-metallic compound of the zirconium is selected from
One or more of acetylacetone,2,4-pentanedione zirconium, tetrabutyl zirconate, zirconium iso-octoate, the organo-metallic compound of the zirconium is (with Zr original
Son meter) it with the mass ratio of the modified silicon oil of metal oxide treated is 0.0005~0.05:1, organic gold of the nickel and zirconium
The treatment temperature for belonging to the silicone oil that compound is crossed with metal oxide treated is 290~330 DEG C, and the processing time is 5~18h.
De- low-boiling-point substance operation temperature in the step (4) and step (7) is 190~250 DEG C, the operating time is 2~
12 h, pressure (absolute pressure) are 0.0001~5000Pa；Preferably, the de- low boiling operation temperature is 195~230 DEG C, behaviour
Making the time is 3~10h, and pressure (absolute pressure) is 0.001~2000Pa.
Compared with prior art, the beneficial effects of the present invention are:
1, operating condition of the invention is simple, and step is simple, and yield is high.
2, in the present invention, silicone oil is first after metal oxide treated, then the metallo-organic compound through nickel and zirconium is further
Processing, resolution ratio is low in air for gained modified silicon oil, has good thermal stability.
Specific embodiment
Below with reference to embodiment, invention is further described in detail, but embodiment is not to the scope of the present invention
It limits, raw materials used in embodiment is commercial products.
Embodiment 1:
(20 DEG C) of the commercially available viscosity of 700g are added to for the dimethicone of 10mPa.s with reflux condenser, machinery
In the 1000mL three-neck flask of stirring and thermometer, ZnO powder of the 70g by 150 DEG C of vacuum drying 4h processing is then added,
After trace nitrogen gas (purity 99.9%) is passed through from bottom insert canal, stirring is opened, is gradually heated to 150 DEG C from room temperature, and at 150 DEG C
Lower maintenance 3h.It is cooled to room temperature, closes nitrogen and stirring, the mixture in three-neck flask is filtered under diminished pressure, collect filter
Liquid.
The filtrate of collection is transferred in removing low-boiling-point substance device, micro nitrogen (purity 99.9%) bubbling is passed through,
When system absolute pressure reaches 10-3Pa, gradually from room temperature to 200 DEG C, and maintain 3h to remove in filtrate at 200 DEG C
Low-boiling-point substance.It is cooled to room temperature to kettle liquid, closes stirring, increase nitrogen flow in bottom insert canal, taken off low system wait depressurize and restore to normal
After pressure, kettle liquid is collected, obtains the low viscosity dimethyl silicone oil of ZnO processing.
Embodiment 2:
Take that 100g embodiment 1 obtains be added to through the processed low viscosity dimethyl silicone oil of ZnO equipped with mechanical stirring and
In the 250mL three-neck flask of thermometer, nitrogen (purity 99.9%) protection is lower to be added 0.14g dibutyl dithiocaarbamate
Nickel and 0.73g acetylacetone,2,4-pentanedione zirconium, are to slowly warm up to 300 DEG C through 2h at room temperature, and keep 12h at such a temperature.Kettle liquid is cooling
To room temperature, is filtered through decompression and obtain the filtrate of clear.Then under nitrogen (purity 99.9%) protection, regulating system
Filtrate is warming up to 200 DEG C to 10-3Pa (absolute pressure) by pressure, and 6h is kept to carry out de- low boiling operation at this temperature, is cooled to
After room temperature, the modified silicone oil of organo-metallic compound and ZnO of the 89.8g through nickel and zirconium is obtained.
Embodiment 3:
Take that 100g embodiment 1 obtains be added to through the processed low viscosity dimethyl silicone oil of ZnO equipped with mechanical stirring and
In the 250mL three-neck flask of thermometer, argon gas protection is lower to be added 1.4g nickel dibutyl dithiocarbamate and 0.73g acetyl
Acetone zirconium is to slowly warm up to 300 DEG C through 3h at room temperature, and keeps 12h at such a temperature.After kettle liquid is cooled to room temperature, through subtracting
Pressure filters and obtains the filtrate of clear.Then under protection of argon gas, regulating system pressure will be filtered to 1.525kPa (absolute pressure)
Liquid is warming up to 220 DEG C, and 6h is kept to carry out de- low boiling operation at this temperature, after being cooled to room temperature, obtain 88.7 g through nickel and
The modified silicone oil of the organo-metallic compound and ZnO of zirconium.
Embodiment 4:
Take that 100g embodiment 1 obtains be added to through the processed low viscosity dimethyl silicone oil of ZnO equipped with mechanical stirring and
In the 250mL three-neck flask of thermometer, argon gas protection is lower to be added 0.07g nickel dibutyl dithiocarbamate and 0.365g second
Acyl acetone zirconium, is to slowly warm up to 300 DEG C through 4h at room temperature, and keep 12h at such a temperature.After kettle liquid is cooled to room temperature, warp
Decompression filters and obtains the filtrate of clear.Then under protection of argon gas, regulating system pressure is to 1Pa (absolute pressure), by filtrate liter
Temperature keeps 5h to carry out de- low boiling operation at this temperature to 210 DEG C, after being cooled to room temperature, obtains 89.9 g through nickel and zirconium
The silicone oil that organo-metallic compound and ZnO are modified.
Embodiment 5:
Take that 100g embodiment 1 obtains be added to through the processed low viscosity dimethyl silicone oil of ZnO equipped with mechanical stirring and
In the 250mL three-neck flask of thermometer, argon gas protection is lower to be added 0.14g nickel dibutyl dithiocarbamate and 7.3g acetyl
Acetone zirconium is warming up to 300 DEG C through 1h at room temperature, and keeps 16h at such a temperature.After kettle liquid is cooled to room temperature, taken out through decompression
Filter obtains the filtrate of clear.Then under protection of argon gas, filtrate is warming up to by regulating system pressure to 10Pa (absolute pressure)
215 DEG C, and 8h is kept to carry out de- low boiling operation at this temperature, after being cooled to room temperature, 86.5g is obtained through the organic of nickel and zirconium
The silicone oil that metallic compound and ZnO are modified.
Embodiment 6:
(20 DEG C) of the commercially available viscosity of 150g are added to for the dimethicone of 500mPa.s with reflux condenser, machinery
In the 250mL three-neck flask of stirring and thermometer, ZnO powder of the 5g by 120 DEG C of vacuum drying 8h processing is then added, from
After bottom insert canal is passed through micro argon gas, stirring is opened, is gradually heated to 160 DEG C from room temperature, and maintain 2h at 160 DEG C.It is down to room
Wen Hou closes argon gas and stirring, the mixture in three-neck flask is filtered under diminished pressure, and collects filtrate.Filtrate is transferred to de-
Except being passed through micro bubbling argon in low-boiling-point substance device, when system absolute pressure reaches 10-3Pa, gradually from room temperature to 210
DEG C, and maintain 5h to remove the low-boiling-point substance in filtrate at 210 DEG C.It is cooled to room temperature to kettle liquid, closes stirring, increased and insert bottom
Argon flow in pipe takes off low system and restores to normal pressure wait depressurize, and collects kettle liquid, obtains the low viscosity dimethyl-silicon of ZnO processing
Oil.
It takes 100g above-mentioned and is added to through the processed low viscosity dimethyl silicone oil of ZnO equipped with mechanical stirring and thermometer
In 250 mL three-neck flasks, argon gas protection is lower to be added 0.07g diacetyl acetone nickel and 0.365g acetylacetone,2,4-pentanedione zirconium, at room temperature through 4h
320 DEG C are to slowly warm up to, and keeps 6h at such a temperature.After kettle liquid is cooled to room temperature, is filtered through decompression and obtain clear
Filtrate.Then under protection of argon gas, filtrate is warming up to 220 DEG C to 1Pa (absolute pressure) by regulating system pressure, and in this temperature
Lower holding 6h carries out de- low boiling operation, after being cooled to room temperature, obtains organo-metallic compound and ZnO of the 85.3g through nickel and zirconium and changes
The silicone oil of property.
Embodiment 7:
(20 DEG C) of the commercially available viscosity of 150g are added to for the dimethicone of 100mPa.s with reflux condenser, machinery
In the 250mL three-neck flask of stirring and thermometer, CeO2 powder of the 30g by 140 DEG C of vacuum drying 2h processing is then added,
After micro argon gas is passed through from bottom insert canal, stirring is opened, is gradually heated to 140 DEG C from room temperature, and maintain 5h at 140 DEG C.It is down to
After room temperature, argon gas and stirring are closed, the mixture in three-neck flask is filtered under diminished pressure, collects filtrate.Filtrate is transferred to
It removes in low-boiling-point substance device, is passed through micro bubbling argon, when system absolute pressure reaches 5Pa, gradually from room temperature to 215
DEG C, and maintain 4h to remove the low-boiling-point substance in filtrate at 215 DEG C.It is cooled to room temperature to kettle liquid, closes stirring, increased and insert bottom
Argon flow in pipe takes off low system and restores to normal pressure wait depressurize, and collects kettle liquid, obtains the low viscosity dimethyl of CeO2 processing
Silicone oil.
It takes 100g above-mentioned and is added to through the processed low viscosity dimethyl silicone oil of CeO2 equipped with mechanical stirring and thermometer
In 250 mL three-neck flasks, argon gas protection is lower to be added 1.0g diacetyl acetone nickel and 0.365g zirconium iso-octoate, slow through 2h at room temperature
Slowly 305 DEG C are warming up to, and keep 16h at such a temperature.After kettle liquid is cooled to room temperature, is filtered through decompression and obtain clear
Filtrate.Then under protection of argon gas, filtrate is warming up to 210 DEG C to 5Pa (absolute pressure) by regulating system pressure, and in this temperature
Lower holding 6h carries out de- low boiling operation, after being cooled to room temperature, obtains organo-metallic compound and CeO2 of the 86.7g through nickel and zirconium
Modified silicone oil.
Embodiment 8:
(20 DEG C) of the commercially available viscosity of 150g are added to for the dimethicone of 20mPa.s with reflux condenser, machinery
In the 250mL three-neck flask of stirring and thermometer, MgO powder of the 7.5g by 130 DEG C of vacuum drying 3h processing is then added,
After trace nitrogen gas (purity 99.9%) is passed through from bottom insert canal, stirring is opened, is gradually heated to 150 DEG C from room temperature, and at 150 DEG C
Lower maintenance 3h.It is cooled to room temperature, closes nitrogen and stirring, the mixture in three-neck flask is filtered under diminished pressure, collect filter
Liquid.Filtrate is transferred in removing low-boiling-point substance device, it is passed through micro nitrogen (purity 99.9%) bubbling, is reached in system absolute pressure
When to 100Pa, gradually from room temperature to 210 DEG C, and maintain 5h to remove the low-boiling-point substance in filtrate at 210 DEG C.To kettle liquid
It is cooled to room temperature, closes stirring, increase nitrogen (purity 99.9%) flow in bottom insert canal, take off low system wait depressurize and restore to normal
After pressure, kettle liquid is collected, obtains the low viscosity dimethyl silicone oil of MgO processing.
It takes 100g above-mentioned and is added to through the processed low viscosity dimethyl silicone oil of MgO equipped with mechanical stirring and thermometer
In 250 mL three-neck flasks, nitrogen (purity 99.9%) protection is lower to be added 2.0g dicyclopentadienyl nickel and 5.0g tetrabutyl zirconate, at room temperature
325 DEG C are to slowly warm up to through 3h, and keeps 6h at such a temperature.After kettle liquid is cooled to room temperature, filters and clarified through decompression
Transparent filtrate.Then under nitrogen (purity 99.9%) protection, regulating system pressure to 100Pa (absolute pressure) heats up filtrate
To 210 DEG C, and 6h is kept to carry out de- low boiling operation at this temperature, after being cooled to room temperature, obtains 83.1 g having through nickel and zirconium
The silicone oil that machine metallic compound and MgO are modified.
Embodiment 9:
(20 DEG C) of the commercially available viscosity of 150g are added to for the dimethicone of 50mPa.s with reflux condenser, machinery
In the 250mL three-neck flask of stirring and thermometer, Al2O3 powder of the 15g by 130 DEG C of vacuum drying 3h processing is then added,
After trace nitrogen gas (purity 99.9%) is passed through from bottom insert canal, stirring is opened, is gradually heated to 140 DEG C from room temperature, and at 140 DEG C
Lower maintenance 2h.It is cooled to room temperature, closes nitrogen and stirring, the mixture in three-neck flask is filtered under diminished pressure, collect filter
Liquid.Filtrate is transferred in removing low-boiling-point substance device, it is passed through micro nitrogen (purity 99.9%) bubbling, is reached in system absolute pressure
When to 100Pa, gradually from room temperature to 210 DEG C, and maintain 5h to remove the low-boiling-point substance in filtrate at 210 DEG C.To kettle liquid
It is cooled to room temperature, closes stirring, increase nitrogen (purity 99.9%) flow in bottom insert canal, take off low system wait depressurize and restore to normal
After pressure, kettle liquid is collected, obtains the low viscosity dimethyl silicone oil of Al2O3 processing.
It takes 100g above-mentioned and is added to through the processed low viscosity dimethyl silicone oil of Al2O3 equipped with mechanical stirring and thermometer
In 250 mL three-neck flasks, nitrogen (purity 99.9%) protection is lower to be added 14.0g nickel dibutyl dithiocarbamate and 20.0g
Tetrabutyl zirconate is to slowly warm up to 315 DEG C through 2h at room temperature, and keeps 8h at such a temperature.After kettle liquid is cooled to room temperature,
It is filtered through decompression and obtains the filtrate of clear.Then under nitrogen (purity 99.9%) protection, regulating system pressure is extremely
Filtrate is warming up to 220 DEG C by 100Pa (absolute pressure), and 3h is kept to carry out de- low boiling operation at this temperature, after being cooled to room temperature,
Obtain the modified silicone oil of organo-metallic compound and Al2O3 of the 85.4g through nickel and zirconium.
Using the Discovery TGA of TA company, the U.S. to embodiment 1 to 5 gained modified silicon of embodiment in air atmosphere
Oil samples and embodiment 6 to embodiment 9 use nickel and the silicone oil sample of the compound modified front and back of zirconium metal-organic to carry out thermogravimetric
(TGA) it tests, Range of measuring temp is 40~800 DEG C, heating rate 10K/min, air velocity 30mL/min and measures
Each sample relative weight loss 10% (Td10), 20% (Td20) and 50% (Td50) corresponding temperature are as shown in table 1.
The aerial hot property comparison of the silicone oil that 1 Examples 1 to 9 of table obtains
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (16)
1. a kind of improve low viscosity dimethyl silicone oil thermo oxidative stability in air using the organo-metallic compound of nickel and zirconium
Method, it is characterised in that: the preparation method the following steps are included:
(1) under inert gas protection, silicone oil with low viscosity and metal oxide are added in reaction vessel by a certain percentage；
(2) it is stirred under inert gas shielding, and the mixture of silicone oil and metal oxide is increased to certain temperature from room temperature
Degree, then keeps certain time at this temperature；
(3) after being cooled to room temperature, inert gas is closed, solidliquid mixture is filtered under diminished pressure, collect filtrate；
(4) filtrate is transferred in de- low reaction kettle, is vacuumized under inert gas shielding and stirring, then gradually rises temperature
Degree removes remaining small molecule compound in filtrate；
(5) after the completion of taking off low-boiling-point substance operation, it is down to room temperature, inert gas and stirring is closed, obtains changing for metal oxide treated
Property silicone oil；
(6) modified silicon oil of metal oxide treated is added to by a certain percentage with the organo-metallic compound of nickel and zirconium and is reacted
In kettle, it is increased to certain temperature from room temperature under inert gas protection, and keeps a period of time at this temperature；
(7) reaction mixture in step (6) is cooled to room temperature, is transferred them in de- low reaction kettle, protected in inert gas
It is vacuumized under shield and stirring, then gradually rises temperature, remove remaining small molecule compound in filtrate；
(8) after the completion of taking off low-boiling-point substance operation, it is down to room temperature, inert gas and stirring is closed, obtains the organometallic of nickel and zirconium
The modified silicon oil that conjunction object and metal oxide treated are crossed.
2. a kind of as described in claim 1 improve low viscosity dimethyl silicone oil in sky using the organo-metallic compound of nickel and zirconium
The method of thermo oxidative stability in gas, it is characterised in that: the silicone oil with low viscosity is selected from dimethicone, viscosity (20 DEG C)
Less than or equal to 500mPa.s.
3. a kind of as claimed in claim 2 improve low viscosity dimethyl silicone oil in sky using the organo-metallic compound of nickel and zirconium
The method of thermo oxidative stability in gas, it is characterised in that: the viscosity (20 DEG C) of the silicone oil with low viscosity is less than or equal to
200mPa.s。
4. a kind of as claimed in claim 3 improve low viscosity dimethyl silicone oil in sky using the organo-metallic compound of nickel and zirconium
The method of thermo oxidative stability in gas, it is characterised in that: the viscosity (20 DEG C) of the silicone oil with low viscosity is less than or equal to
100mPa.s。
5. a kind of as described in claim 1 improve low viscosity dimethyl silicone oil in sky using the organo-metallic compound of nickel and zirconium
The method of thermo oxidative stability in gas, it is characterised in that: the inert gas is selected from argon gas or nitrogen.
6. a kind of as claimed in claim 5 improve low viscosity dimethyl silicone oil in sky using the organo-metallic compound of nickel and zirconium
The method of thermo oxidative stability in gas, it is characterised in that: the inert gas is selected from nitrogen, and purity is greater than or equal to
99.9%.
7. a kind of as described in claim 1 improve low viscosity dimethyl silicone oil in sky using the organo-metallic compound of nickel and zirconium
The method of thermo oxidative stability in gas, it is characterised in that: the metal oxide is selected from ZnO, Al2O3、MgO、MnO2Or CeO2
One or more of, dosage is the 1%~30% of silicone oil quality.
8. a kind of as claimed in claim 7 improve low viscosity dimethyl silicone oil in sky using the organo-metallic compound of nickel and zirconium
The method of thermo oxidative stability in gas, it is characterised in that: the metal oxide is selected from ZnO or CeO2, dosage is silicone oil
The 3%~20% of quality.
9. a kind of as described in claim 1 improve low viscosity dimethyl silicone oil in sky using the organo-metallic compound of nickel and zirconium
The method of thermo oxidative stability in gas, it is characterised in that: the metal oxide is vacuum dried using preceding needing, vacuum drying
Temperature is 110~160 DEG C, and drying time is 1~10h.
10. a kind of as claimed in claim 9 existed using the organo-metallic compound of nickel and zirconium raising low viscosity dimethyl silicone oil
The method of thermo oxidative stability in air, it is characterised in that: the vacuum drying temperature before the metal oxide use is 120
~150 DEG C, drying time is 2~8h.
11. a kind of as described in claim 1 existed using the organo-metallic compound of nickel and zirconium raising low viscosity dimethyl silicone oil
The method of thermo oxidative stability in air, it is characterised in that: the processing of the mixture of the silicone oil and metal oxide composition
Temperature is 130~170 DEG C, and the processing time is 1~8h.
12. a kind of as claimed in claim 11 existed using the organo-metallic compound of nickel and zirconium raising low viscosity dimethyl silicone oil
The method of thermo oxidative stability in air, it is characterised in that: the processing of the mixture of the silicone oil and metal oxide composition
Temperature is 135~165 DEG C, and the processing time is 2~6h.
13. a kind of as described in claim 1 existed using the organo-metallic compound of nickel and zirconium raising low viscosity dimethyl silicone oil
The method of thermo oxidative stability in air, it is characterised in that: the organo-metallic compound of the nickel be selected from diacetyl acetone nickel,
Bis- (diphenylphosphine propane) Nickel Chlorides of bis- (triphenylphosphine) nickel chlorides, 1,3-, nickel dibutyl dithiocarbamate, bis- (six
Acetyl fluoride acetone) close nickel, nickel formate (II) salt, dimethylamino dithiocarbonic acid nickel, (1,1'- bis- (diphenylphosphine) ferrocene) two
Nickel chloride, dicyclopentadienyl nickel, bis- (triphenylphosphine) Nickel Bromides, double-(1,5- cyclo-octadiene) nickel, four (triphenylphosphine) nickel, double triphens
Base phosphine dicarbapentaborane nickel, nickel acetylacetonate dihydrate, bis- (2,2,6,6,-tetramethyl -3,5- heptadione acid) nickel or chlorine (ring penta 2
One or more of alkenyl) (triphenyl phasphine) nickel (II), the organo-metallic compound (in terms of Ni atom) and metal of the nickel
The mass ratio of the modified silicon oil of oxide process is 0.00001~0.05:1, and the organo-metallic compound of the zirconium is selected from second
One of acyl acetone zirconium, tetrabutyl zirconate, vanadic acid zirconium, zirconium iso-octoate, bis- (lemon diethyl phthalate) dipropoxy zirconium chelates
Or several, the mass ratio of the modified silicon oil of the organo-metallic compound (in terms of Zr atom) and metal oxide treated of the zirconium
For 0.0001~0.10:1, the processing temperature for the silicone oil that the organo-metallic compound and metal oxide treated of the nickel and zirconium are crossed
Degree be 280~350 DEG C, processing the time be 2~for 24 hours.
14. a kind of as claimed in claim 13 existed using the organo-metallic compound of nickel and zirconium raising low viscosity dimethyl silicone oil
The method of thermo oxidative stability in air, it is characterised in that: the organo-metallic compound of the nickel be selected from diacetyl acetone nickel,
One or more of nickel dibutyl dithiocarbamate, dicyclopentadienyl nickel, the organo-metallic compound of the nickel is (with Ni atom
Meter) it with the mass ratio of the modified silicon oil of metal oxide treated is 0.00005~0.02:1, the Organometallic compounds of the zirconium
Object is selected from one or more of acetylacetone,2,4-pentanedione zirconium, tetrabutyl zirconate, zirconium iso-octoate, the organo-metallic compound of the zirconium
The mass ratio of the modified silicon oil of (in terms of Zr atom) and metal oxide treated is 0.0005~0.05:1, the nickel and zirconium
The treatment temperature for the silicone oil that organo-metallic compound and metal oxide treated are crossed is 290~330 DEG C, the processing time is 5~
18h。
15. a kind of as described in claim 1 existed using the organo-metallic compound of nickel and zirconium raising low viscosity dimethyl silicone oil
The method of thermo oxidative stability in air, it is characterised in that: the de- low-boiling-point substance in the step (4) and step (7) operates temperature
Degree is 190~250 DEG C, and the operating time is 2~12h, and pressure (absolute pressure) is 0.0001~5000Pa.
16. a kind of as claimed in claim 15 existed using the organo-metallic compound of nickel and zirconium raising low viscosity dimethyl silicone oil
The method of thermo oxidative stability in air, it is characterised in that: the de- low boiling operation temperature is 195~230 DEG C, the operating time
For 3~10h, pressure (absolute pressure) is 0.001~2000Pa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113388117A (en) * | 2021-03-02 | 2021-09-14 | 杭州师范大学 | Cerium-containing multi-element metal organic compound modified dimethyl silicone oil and preparation method and application thereof |
| CN113388118A (en) * | 2021-03-02 | 2021-09-14 | 杭州师范大学 | Hafnium-containing multi-metal organic compound modified dimethyl silicone oil and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4193885A (en) * | 1977-08-02 | 1980-03-18 | Dow Corning Corporation | Method for preparing a thermal-stability additive and a thermally stabilized methylpolysiloxane and compositions therefrom |
| JPS60163966A (en) * | 1984-02-06 | 1985-08-26 | Shin Etsu Chem Co Ltd | Heat-resistant organopolysiloxane composition |
| EP0406672A1 (en) * | 1989-06-27 | 1991-01-09 | Dow Corning Corporation | A method to prepare thermo-oxidatively stable phenylmethylsiloxane fluids |
| CN101294067A (en) * | 2008-06-20 | 2008-10-29 | 清华大学 | Heat conductive silicone grease composition |
| CN107760033A (en) * | 2017-10-19 | 2018-03-06 | 中国石油化工股份有限公司 | A kind of methyl-silicone oil composition and preparation method thereof |
-
2018
- 2018-12-26 CN CN201811600870.7A patent/CN109735107B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4193885A (en) * | 1977-08-02 | 1980-03-18 | Dow Corning Corporation | Method for preparing a thermal-stability additive and a thermally stabilized methylpolysiloxane and compositions therefrom |
| JPS60163966A (en) * | 1984-02-06 | 1985-08-26 | Shin Etsu Chem Co Ltd | Heat-resistant organopolysiloxane composition |
| EP0406672A1 (en) * | 1989-06-27 | 1991-01-09 | Dow Corning Corporation | A method to prepare thermo-oxidatively stable phenylmethylsiloxane fluids |
| CN101294067A (en) * | 2008-06-20 | 2008-10-29 | 清华大学 | Heat conductive silicone grease composition |
| CN107760033A (en) * | 2017-10-19 | 2018-03-06 | 中国石油化工股份有限公司 | A kind of methyl-silicone oil composition and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 张玉环 等: "金属化合物对硅橡胶耐热性能的影响", 《科技通报》 * |
| 张超: "有机硅热载体的制备与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 曹凯 等: "硅油热氧化稳定剂的考察", 《合成润滑材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113388117A (en) * | 2021-03-02 | 2021-09-14 | 杭州师范大学 | Cerium-containing multi-element metal organic compound modified dimethyl silicone oil and preparation method and application thereof |
| CN113388118A (en) * | 2021-03-02 | 2021-09-14 | 杭州师范大学 | Hafnium-containing multi-metal organic compound modified dimethyl silicone oil and preparation method and application thereof |
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