CN106543734A - A kind of high-performance anti creepage trace add-on type liquid silicon rubber and preparation method thereof - Google Patents
A kind of high-performance anti creepage trace add-on type liquid silicon rubber and preparation method thereof Download PDFInfo
- Publication number
- CN106543734A CN106543734A CN201610940468.8A CN201610940468A CN106543734A CN 106543734 A CN106543734 A CN 106543734A CN 201610940468 A CN201610940468 A CN 201610940468A CN 106543734 A CN106543734 A CN 106543734A
- Authority
- CN
- China
- Prior art keywords
- silicon rubber
- type liquid
- liquid silicon
- add
- creepage trace
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/46—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones
- H01B3/465—Silicone oils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
Abstract
The invention discloses a kind of high-performance anti creepage trace add-on type liquid silicon rubber and preparation method thereof.The composition of raw materials component of the add-on type liquid silicon rubber is：100 parts of vinyl silicone oil, 30～60 parts of white carbon, 1～10 part of containing hydrogen silicone oil, 2～6 parts of amido-containing acid ester base silane, 0.15～2 part of platinum catalyst, 0.004～0.03 part of 1 acetenyl, 1 cyclohexanol.The add-on type liquid silicon rubber of the present invention has excellent anti creepage trace performance and mechanical property, has a wide range of applications in fields such as electric outer insulating materials；And raw material of the present invention is easy to get, processing technology is simple, is easy to large-scale production.
Description
Technical field
The present invention relates to silicone rubber insulation material field, is specifically related to a kind of high-performance anti creepage trace add-on type liquid
Silicon rubber and preparation method thereof；Belong to rubber insulation material technical field.
Background technology
In recent years, China's electric utility quickly grows, and network system working voltage grade is improved constantly, and network size is progressively
Expand, each big regional power grid has been unified into an entirety substantially, and the general layout of " transferring electricity from the west to the east, north and south supply mutually, national network " is preliminary
Realize.In power grid construction, in order to ensure the safe transport of electric energy, using substantial amounts of power transmission and transformation transformer, transformer and insulation
The power equipments such as son.As the electric pressure of power transmission and transforming equipment is increasingly improved, atmosphere pollution aggravation is added, haze weather frequency is existing,
So that the service condition of power equipment external insulation constantly deteriorates, this to the electric property for power equipment outer insulating material and
Stability in use proposes higher requirement.
Silicon rubber due to the performance such as recovering with excellent high-low temperature resistant, weather-proof, electric insulation and hydrophobic and hydrophobic, and by
Gradually replace traditional ceramics and glass, be widely used in the outer insulating material of high-voltage and ultra-high power transmission and transforming equipment.In various silicon
In rubber, add-on type liquid silicon rubber is excellent with producing minimum, the energy deep layer vulcanization of accessory substance, shrinkage factor etc. in sulfidation
Point, and it is simple process, with low cost, become the preferred raw materials of power industry insulating materials.But add-on type liquid silicon rubber exists
Can be polluted by filth, moisture, salt dew and other chemicals during long-term use, in the effect of extraneous highfield
Under, can produce along face leakage current, promote its surface moisture to evaporate, cause pneumatic ash handling to discharge repeatedly, cause silastic surface
Conductive path (i.e. creepage trace destruction) is carbonized and is formed, material surface can occur to burn in short-term when serious, cause add-on type liquid
Body silicon rubber insulator fails, and threatens electric power netting safe running.Therefore, improve the anti creepage trace performance of add-on type liquid silicon rubber
It is highly important.
At present, although to improve add-on type liquid silicon rubber anti creepage trace performance have made some progress, but still
Come with some shortcomings：Insulator plays a part of electric insulation, mechanical support in power transmission network, therefore general to insulator
Tensile strength and tearing strength requirement are higher, and current, want to make the anti creepage trace performance of add-on type liquid silicon rubber to reach
Certain requirement, needs the substantial amounts of inorganic anti creepage trace agent of addition, and this will certainly substantially reduce add-on type liquid silicon rubber
Mechanical performance.Additionally, a large amount of additions of inorganic anti creepage trace agent, also can heavy damage add-on type liquid silicon rubber hydrophobicity
It is restorative with hydrophobic.This not only greatly limit the range of application of add-on type liquid silicon rubber insulating materials, have an effect on add-on type
, there is certain potential safety hazard in barrier propterty of the liquid silastic product in longtime running.Therefore, prepare a kind of high-performance resistance to
Creepage trace add-on type liquid silicon rubber, has great importance.
Chinese invention patent CN103694709A is disclosed the urea groups siloxanes containing double bond as anti creepage trace agent,
A kind of good add-on type liquid silicon rubber of anti creepage trace performance is obtained with white carbon compounding.But the nitrogen content of ureido silane
Height, can extend the cure time of add-on type liquid silicon rubber, increase its commercial Application cost.Additionally, siloxanes containing urea groups is not
There is complete industrialization, mainly due to industrially, contain to prepare with organic amine generally by radical siloxane containing isocyanates
Urea groups siloxanes, and organic amine is poisonous and volatile, has significant damage to human body and environment, it is often more important that this preparation side
Method is very harsh to purifying technique requirement, because in synthetic product, the organic amine not removed can make add-on type liquid silicon rubber
Smoothly cannot vulcanize.
The content of the invention
Present invention aims to the deficiencies in the prior art, there is provided a kind of production process is less demanding to purifying, no
Affect silicon rubber vulcanization, safety, environmental protection, and the add-on type liquid silicon rubber of anti creepage trace performance and good mechanical performance.
The present invention also aims to provide the preparation method of the high-performance anti creepage trace add-on type liquid silicon rubber.
The purpose of the present invention can be achieved through the following technical solutions：
In terms of mass parts, its composition of raw materials is consisted of：
The structural formula of the amido-containing acid ester base silane is：
Wherein R1For-CnH2n+1, n is 1～4；R2For-CH3Or-CH2CH3；R3For-CH2CH=CH2,-CH2CH=CHCH3
Or-CH2CH=C (CH3)2；I is 1～3；
Divinyl tetramethyl disiloxane complex compound (Karstedt platinum catalyst) of the platinum catalyst for chloroplatinic acid.
Further to realize the object of the invention, it is preferable that amido-containing acid ester base silane is prepared via a method which：Having
In the presence of machine tin catalyst, alcoholic compound is mixed with silicone compounds containing NCO, be 30～60 DEG C in temperature
Under the conditions of 1～4h of stirring reaction, then vacuum distillation obtains amido-containing acid ester radical siloxane compound；Again in organic titanate
In the presence of, the alkene of hydroxyl is mixed with amido-containing acid ester radical siloxane compound, is 70～90 DEG C of conditions in temperature
2～6h of lower stirring reaction, vacuum distillation remove low-boiling-point substance, obtain amido-containing acid ester base silane；
The silicone compounds containing NCO are following structures：O=C=NCH2CH2CH2Si(OR)3；Wherein R
For-CH3Or-CH2CH3；
The alkene of the hydroxyl is propenyl and 2- butenols or prenol.
Preferably, the organotin catalysts are dibutyl tin dilaurate, stannous octoate or dibutyltin diacetate；Institute
Organotin catalysts consumption is stated for the 0.05～0.30% of reactant gross mass.
Preferably, the alcoholic compound is methyl alcohol, ethanol, propyl alcohol or butanol；The alcoholic compound with contain NCO
The mol ratio of silicone compounds is 1.1:1～1.3:1.
Preferably,：The organic titanate is tetraethyl titanate, tetraisopropyl titanate, butyl titanate, four tertiary fourth of metatitanic acid
Ester or bis(acetylacetonate) titanium acid diisopropyl ester；The organic titanate consumption for reactant gross mass 0.1～2.0%.
Preferably, the alkene of the hydroxyl and the mol ratio of amido-containing acid ester radical siloxane compound are 1:1～
3.3:1。
The preparation method of the high-performance anti creepage trace add-on type liquid silicon rubber：By 100 mass parts vinyl silicone oils,
30～60 mass parts fume colloidal silicas and 3～15 mass parts HMDSs mix in vacuum kneader, 25～
Stir at 35 DEG C, be heated to 150～180 DEG C of mixings of temperature of charge, then 1～3h of pumping vacuum and mixing, grind after cooling, obtain liquid
Silicon rubber sizing；Add 1～10 mass parts containing hydrogen silicone oil, 0.004～0.03 mass parts 1- acetenyl -1- cyclohexanol, 2
～6 mass parts amido-containing acid ester base silanes, 0.15～2 mass parts platinum catalyst, are well mixed at 25～35 DEG C, are solidified into
Type.
Preferably, the time stirred at described 25～35 DEG C is 1～3h.
Preferably, the time of 150～180 DEG C of mixings is 1～4h
Preferably, the grinding is the grinding of Jing three-rollers；The curing molding is 0.1～2h of solidification at 100～150 DEG C
Shaping.
The resistance to leakage of add-on type liquid silicon rubber can be effectively improved for ureido silane in Chinese patent CN103694709A
Electricity plays trace effect, and prior art is it is believed that mainly platinum and nitrogen have good synergistic effect.On the one hand, nitrogenous silane can be with
The catalysis activity of platinum compounds is improved by coordination, so as to advantageously form the barrier layer of densification, suppresses the drop of silicon rubber
Solution；On the other hand, nitrogenous silane can discharge nitrogenous inert gas at high temperature, serve good blow-out effect.But
It is a discovery of the invention that the nitrogen content of amido-containing acid ester base silane is only the half of ureido silane nitrogen content, it is identical in addition
In the case of, amido-containing acid ester base silane is to the anti creepage trace effect of add-on type liquid silicon rubber unlike ureido silane
Difference, it is even better.Especially amido-containing acid ester base silane is prepared without the need for toxic raw materials, endangers little to human body environment；And it is right
The requirement of production process purification is low, does not affect the sulfuration of silicon rubber.
In the present invention, amido-containing acid ester base silane can significantly improve the proof tracking of add-on type liquid silicon rubber
Energy.This is probably the carbamate groups and platinum catalyst synergistic on the one hand introducing, and promotes the side base of add-on type liquid silicon rubber
Fracture, forms methane and carbon dioxide, reduces the deposition of carbon granules.On the other hand, carbamate base silane decomposes at high temperature
Acid compounds containing isocyanide are generated, with the Si-OH reactions produced by the oxidation of silicon rubber pending methyl group, it is suppressed that silicon rubber main chain is tripped
Formula is degraded, and greatly reduces the release of ionogenic annular siloxane, reduces the intensity of electric arc.
Additionally, amido-containing acid ester base silane has preferable compatibility with silicon rubber, and contain multiple vinyl, in sulfuration
During Concentrative crosslinking point is formed in silicone rubber crosslinking network by hydrosilylation, be effectively improved add-on type liquid
The mechanical property of silicon rubber.
Relative to prior art, the invention has the advantages that：
1st, instant invention overcomes the big shortcoming of inorganic anti creepage trace agent addition, adds in add-on type liquid silicon rubber
On a small quantity (<6 mass parts) amido-containing acid ester base silane, its anti creepage trace performance can just reach 1A4.5 levels.
2nd, instant invention overcomes technology prejudice, has synthesized the relatively low amido-containing acid ester base silane of nitrogen content, but which is to adding
The effect of molding liquid silicon rubber anti creepage trace performance is poor unlike containing ureido silane.
3rd, amido-containing acid ester base silane prepared by the present invention is the silicone compounds containing thiazolinyl, with add-on type liquid
Rubber compatibility is good and advantageously forms Concentrative crosslinking structure, effectively increases the mechanical property of add-on type liquid silicon rubber
Energy.
4th, the nitrogen content of amido-containing acid ester base silane of the invention is relatively low, the sulfuration to add-on type liquid silicon rubber
Affect little, and preparation technology is easy, raw material is cheap and easy to get, it is easy to accomplish industrialized production, lead in electric outer insulating material etc.
Domain has a wide range of applications.
5th, the present invention is unused solvent in the building-up process of amido-containing acid ester base silane, and this can not only reduce
Synthesis cost, and be conducive to environmental protection.
Description of the drawings
Fig. 1 is the infrared spectrogram of the amido-containing acid ester base silane that embodiment 1-3 is obtained；Wherein curve a, b and c distinguishes
For 3- (carbamic acid isopropyl ester) propyl group triolefin npropoxysilane (IPURPAS), 3- (urethanes) propyl group allyloxy
The infrared spectrum of diethoxy silane (EURPAS) and 3- (methyl carbamate) propyl group triolefin npropoxysilane (MURPAS).
Fig. 2 is the proton nmr spectra of the amido-containing acid ester base silane that embodiment 1-3 is obtained；Wherein, in curve a, b and
C is respectively 3- (carbamic acid isopropyl ester) propyl group triolefin npropoxysilane (IPURPAS), 3- (urethanes) propyl group allyl
The nuclear-magnetism of epoxide diethoxy silane (EURPAS) and 3- (methyl carbamate) propyl group triolefin npropoxysilane (MURPAS) is altogether
The hydrogen that shakes is composed.
Specific embodiment
To more fully understand the present invention, with reference to embodiment, the present invention is further illustrated, but the present invention
Embodiment not limited to this.
Embodiment 1
Equipped with reflux condensing tube, mechanical agitation and thermometer 250mL four-hole boiling flasks in add 13.2g isopropanols,
49.4g3- isocyanatopropyls triethoxysilane and 0.18g dibutyl tin laurates, stirring reaction 3h at 50 DEG C, then
Vacuum distillation removes unreacted isopropanol, obtains 3- (carbamic acid isopropyl ester) propyl-triethoxysilicane (IPURPES).
By 23.5g allyl alcohols, 43.1g 3- (carbamic acid isopropyl ester) propyl-triethoxysilicanes and 0.66g metatitanic acid methyl esters
It is added in the 250mL four-hole boiling flasks equipped with reflux condensing tube, mechanical agitation and thermometer, uniform, intensification is stirred at room temperature
To 80 DEG C of back flow reactions 2h, last vacuum distillation removes low-boiling-point substance and obtains three allyl oxygen of product 3- (carbamic acid isopropyl ester) propyl group
Base silane (IPURPAS).
By 100 mass parts vinyl silicone oils, (viscosity at 25 DEG C is 25200mPas, and contents of ethylene is
0.25mol%), (specific surface area is 260m to 40 mass parts fume colloidal silicas3/ g), 7 mass parts HMDSs are true
Mix in empty kneader, 2h is stirred at 30 DEG C, be heated to 170 DEG C of temperature of charge and continue mixing 2h, then pumping vacuum and mixing 1h, it is cold
But after, the grinding of Jing three-rollers, obtains add-on type liquid silicon rubber basestocks.
In above-mentioned 100 mass parts sizing, add 3 mass parts IPURPAS, 4.01 mass parts containing hydrogen silicone oils (hydrogeneous
Measure as 0.75wt%), the divinyl tetramethyl of the 1- acetenyl -1- cyclohexanol of 0.01 mass parts and 0.25 mass parts chloroplatinic acid
Disiloxane complex compound (platinum content is 3000ppm), stirs at 30 DEG C, is molded 10min at 120 DEG C, make 6mm and
2mm thick film, carries out anti creepage trace test and Mechanics Performance Testing respectively, and the performance of sample is as shown in Tables 1 and 2.
Embodiment 2
11.0g ethanol, 49.4g are added in the 250mL four-hole boiling flasks equipped with reflux condensing tube, mechanical agitation and thermometer
3- isocyanatopropyls triethoxysilane and 0.06g stannous octoates, stirring reaction 4h at 30 DEG C, then vacuum distillation are removed not
The ethanol of reaction, obtains 3- (urethanes) propyl-triethoxysilicane (EURPES).
7.9g allyl alcohols, 41.1g 3- (urethanes) propyl-triethoxysilicanes and 0.98g butyl titanates are added
Enter in the 250mL four-hole boiling flasks equipped with reflux condensing tube, mechanical agitation and thermometer, be stirred at room temperature uniformly, be warming up to
70 DEG C of back flow reactions 3h, last vacuum distillation remove low-boiling-point substance and obtain product 3- (urethanes) propyl group allyloxy diethyl
TMOS (EURPAS).
In embodiment 1 IPURPAS is changed into into EPURPAS, consumption increases to 6 mass parts, corresponding containing hydrogen silicone oil consumption
For 2.94 mass parts, the performance of sample is as shown in Tables 1 and 2
Embodiment 3
8.3g methyl alcohol, 41.0g are added in the 250mL four-hole boiling flasks equipped with reflux condensing tube, mechanical agitation and thermometer
3- isocyanatopropyls trimethoxy silane and 0.03g dibutyl tin laurates, stirring reaction 1h at 40 DEG C, then decompression steam
Unreacted methyl alcohol is removed in distillation, obtains 3- (methyl carbamate) propyl trimethoxy silicane (MURPMS).
By 23.5g allyl alcohols, 33.3g 3- (methyl carbamate) propyl trimethoxy silicanes and 0.06g isopropyl titanates
It is added in the 250mL four-hole boiling flasks equipped with reflux condensing tube, mechanical agitation and thermometer, uniform, intensification is stirred at room temperature
To 90 DEG C of back flow reactions 6h, last vacuum distillation removes low-boiling-point substance and obtains three allyloxy of product 3- (methyl carbamate) propyl group
Silane (MURPAS).
In embodiment 1 IPURPAS is changed into into MPURPAS, consumption is 2 mass parts, corresponding containing hydrogen silicone oil consumption is
3.05 mass parts, the performance of sample is as shown in Tables 1 and 2
Comparative example 1
By 100 mass parts vinyl silicone oils, (viscosity at 25 DEG C is 25200mPas, and contents of ethylene is
0.25mol%), (specific surface area is 260m to 40 mass parts fume colloidal silicas3/ g), 7 mass parts HMDSs are true
Mix in empty kneader, 2h is stirred at 30 DEG C, be heated to 170 DEG C of temperature of charge and continue mixing 2h, then pumping vacuum and mixing 1h, it is cold
But after, the grinding of Jing three-rollers, obtains add-on type liquid silicon rubber sizing.
In above-mentioned 100 mass parts sizing, 1.50 mass parts containing hydrogen silicone oils of addition (hydrogen content is 0.75wt%),
The divinyl tetramethyl disiloxane complex compound of the 1- acetenyl -1- cyclohexanol and 0.25 mass parts chloroplatinic acid of 0.01 mass parts
(platinum content is 3000ppm), stirs at 30 DEG C, at 120 DEG C is molded 10min, makes the thick films of 6mm and 2mm, point
Anti creepage trace test and Mechanics Performance Testing are not carried out, the performance of sample is as shown in Tables 1 and 2.
Comparative example 2
By 100 mass parts vinyl silicone oils, (viscosity at 25 DEG C is 25200mPas, and contents of ethylene is
0.25mol%), 40 mass parts fume colloidal silicas (specific surface area is 260m3/g), 7 mass parts HMDSs are true
Mix in empty kneader, 2h is stirred at 30 DEG C, be heated to 170 DEG C of temperature of charge and continue mixing 2h, then pumping vacuum and mixing 1h, it is cold
But after, the grinding of Jing three-rollers, obtains add-on type liquid silicon rubber basestocks.
In above-mentioned 100 mass parts sizing, add 3 mass parts IPURPAS, 4.01 mass parts containing hydrogen silicone oils (hydrogeneous
Measure as 0.75wt%), the divinyl tetramethyl of the 1- acetenyl -1- cyclohexanol of 0.01 mass parts and 0.1 mass parts chloroplatinic acid
Disiloxane complex compound (platinum content is 3000ppm), stirs at 30 DEG C, is molded 10min at 120 DEG C, make 6mm and
2mm thick film, carries out anti creepage trace test and Mechanics Performance Testing respectively, and the performance of sample is as shown in Tables 1 and 2.
The amido-containing acid ester base silane obtained to embodiment 1-3 has carried out infrared spectrum analysis, as a result as shown in Figure 1.
As seen from the figure, the amido-containing acid ester base silane that prepared by embodiment 1-3 is in 3365cm-1Place all occurs in that N-H stretching vibrations absorb
Peak；In 1723cm-1、1525cm-1And 1249cm-1The stretching vibration absworption peak of C=O, C-N and C-O is all occurred in that respectively nearby；
In 3082cm-1And 958cm-1Place all occurs in that-CH=CH2C-H stretching vibration absworption peaks and rocking vibration absworption peak；
1086cm-1And 955cm-1Place all occurs in that the asymmetric stretching vibration absworption peak and symmetrical stretching vibration of Si-O-C absorbs respectively
Peak.Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of amido-containing acid ester base silane in embodiment 1-3.As seen from the figure, prepared by embodiment 1-3
Amido-containing acid ester base silane all occur in that-CH=CH at chemical shift 5.0-6.0ppm2Middle C-H proton uptakes peak,
All occur N-H proton uptakes peak in carbamate groups near chemical shift 4.3ppm, all occur in that at 3.8-3.9ppm-
SiOCH2Proton uptake peak.Infrared spectrum analysis and hydrogen nuclear magnetic resonance analysis of spectrum all indicate the amido-containing acid ester of the present invention
Base silane successfully synthesizes.
As can be seen from Table 1, it is not added with the add-on type liquid silicon rubber cure time T of amido-containing acid ester base silane90For
194s (see comparative example 1).When the amido-containing acid ester base silane that with the addition of the present invention, the cure time of add-on type liquid silicon rubber
T90Change is little, between 181～202s (see embodiment 1-3)；Show synthesized amido-containing acid ester base silane to addition
The cure time of type liquid silastic affects little.
As shown in Table 2, the add-on type liquid silicon rubber for being not added with amido-containing acid ester base silane fails by the resistance to of 4.5kV
Tracking test (see comparative example 1).But the amido-containing acid ester base silane of the present invention is with the addition of, add-on type liquid silicon rubber
Anti creepage trace performance is attained by 1A4.5 levels (see embodiment 1-3), shows that synthesized amido-containing acid ester base silane can be with
Significantly improve the anti creepage trace performance of add-on type liquid silicon rubber.But, it is from embodiment 1 and comparative example 2, same to add
The IPURPAS of 3 mass parts, when the consumption of the divinyl tetramethyl disiloxane complex compound of chloroplatinic acid is 0.1 mass parts, plus
Molding liquid silicon rubber fails to test by the anti creepage trace of 4.5kV, and works as two silica of divinyl tetramethyl of chloroplatinic acid
When the consumption of alkane complex compound is 0.25 mass parts, add-on type liquid silicon rubber can be tested by the anti creepage trace of 4.5kV, table
The consumption of bright platinum catalyst has the big impact of friendship to the anti creepage trace performance of the add-on type liquid silicon rubber of the present invention.
By table 2 it will also be appreciated that, be not added with the add-on type liquid silicon rubber of amido-containing acid ester base silane, tensile strength and tear
Resistance to spalling is respectively 7.6MPa and 31.6kN/m (see comparative example 1).But the amido-containing acid ester base silane of the present invention is with the addition of, plus
The tensile strength and tearing strength of molding liquid silicon rubber does not only decline, and has different degrees of raising (see implementing
Example 1-3), show that the amido-containing acid ester base silane of the present invention can effectively improve the mechanical property of add-on type liquid silicon rubber.
In table 1 and 2, properties of product method of testing is as follows：
1st, the vulcanization characteristics of silicon rubber is determined according to GB/T 16584-1996.
2nd, the tensile strength and elongation at break of silicon rubber are determined according to GB/T 528-2009.
3rd, the tearing strength of silicon rubber is determined according to GB/T 529-2008.
4th, the Shore A hardness of silicon rubber is determined according to GB/T 531-2008.
5th, the anti creepage trace test of silicon rubber is carried out according to GB/T 6553-2003.Using constant-voltage method, test voltage is
4.5kV；Endpoint is from " the endpoint determination A " in the test method：It is used as when 60mA is more than by the electric current of sample
Electric trace punctures.
Compared with Chinese patent CN103694709A, amido-containing acid ester radical siloxane of the present invention is by containing isocyanates
Radical siloxane is prepared with Organic Alcohol, Organic Alcohol low price, small toxicity.Additionally, Organic Alcohol can't poison add-on type liquid
The platinum catalyst of silicon rubber, therefore, not harsh to purifying technique requirement, synthesis technique is simple, with low cost, it is easier to industry
Change.
The vulcanization characteristics of 1 add-on type liquid silicon rubber of table
The mechanical property and anti creepage trace performance of 2 add-on type liquid silicon rubber of table
Study of China patent of invention CN103694709A, one skilled in the art will appreciate that ureido silane can be effectively improved
The anti creepage trace effect of add-on type liquid silicon rubber, it is believed that mainly platinum and nitrogen have good synergistic effect.One side
The catalysis activity of platinum compounds can be improved in face, nitrogenous silane by coordination, so as to advantageously form the barrier layer of densification,
Suppress the degraded of silicon rubber；On the other hand, nitrogenous silane can discharge nitrogenous inert gas at high temperature, serve good
Blow-out effect.But the above embodiment of the present invention is proved：The nitrogen content of amido-containing acid ester base silane is only that ureido silane contains
The half of nitrogen quantity, in the case of addition identical, resistance to electric leakage of the amido-containing acid ester base silane to add-on type liquid silicon rubber
Play trace effect poor unlike ureido silane, it is even better.
The present invention it is emphasized that：Amido-containing acid ester base silane is prepared without the need for toxic raw materials, and human body environment is endangered
Evil is little；And the requirement to production process purification is low, the sulfuration of silicon rubber, but prior art CN103694709A are not affected by containing
Isocyanates radical siloxane prepares siloxanes containing urea groups with organic amine, and organic amine is poisonous and volatile, to human body and environment
There is significant damage.This preparation methods of CN103694709A are very harsh to purifying technique requirement, because in synthetic product,
The organic amine not removed can be such that add-on type liquid silicon rubber smoothly cannot vulcanizes；The present invention effectively overcomes prior art, and these are asked
Topic.
Claims (10)
1. a kind of high-performance anti creepage trace add-on type liquid silicon rubber, it is characterised in that in terms of mass parts, its composition of raw materials group
Become：
The structural formula of the amido-containing acid ester base silane is：
Wherein R1For-CnH2n+1, n is 1～4；R2For-CH3Or-CH2CH3；R3For-CH2CH=CH2,-CH2CH=CHCH3Or-
CH2CH=C (CH3)2；I is 1～3；
Divinyl tetramethyl disiloxane complex compound of the platinum catalyst for chloroplatinic acid.
2. high-performance anti creepage trace add-on type liquid silicon rubber according to claim 1, it is characterised in that：First containing amino
Acid esters base silane is prepared via a method which：In the presence of organotin catalysts, by alcoholic compound and silicon containing NCO
Siloxane compound mixes, and 1～4h of stirring reaction under the conditions of temperature is for 30～60 DEG C, then vacuum distillation are obtained containing carbamic acid
Ester group silicone compounds；Again in the presence of organic titanate, by the alkene of hydroxyl and amido-containing acid ester radical siloxane
Compound mixes, and 2～6h of stirring reaction under the conditions of temperature is for 70～90 DEG C, vacuum distillation remove low-boiling-point substance, obtain containing amino
Formic acid esters base silane；
The silicone compounds containing NCO are following structures：O=C=NCH2CH2CH2Si(OR)3；Wherein R is-CH3
Or-CH2CH3；
The alkene of the hydroxyl is propenyl and 2- butenols or prenol.
3. high-performance anti creepage trace add-on type liquid silicon rubber according to claim 2, it is characterised in that：It is described organic
Tin catalyst is dibutyl tin dilaurate, stannous octoate or dibutyltin diacetate；The organotin catalysts consumption is anti-
Answer the 0.05～0.30% of thing gross mass.
4. high-performance anti creepage trace add-on type liquid silicon rubber according to claim 2, it is characterised in that：The alcoholization
Compound is methyl alcohol, ethanol, propyl alcohol or butanol；The alcoholic compound with containing the mol ratio of NCO silicone compounds is
1.1:1～1.3:1.
5. high-performance anti creepage trace add-on type liquid silicon rubber according to claim 2, it is characterised in that：It is described organic
Titanate esters are that the acid two of tetraethyl titanate, tetraisopropyl titanate, butyl titanate, four tert-butyl ester of metatitanic acid or bis(acetylacetonate) titanium is different
Propyl ester；The organic titanate consumption for reactant gross mass 0.1～2.0%.
6. high-performance anti creepage trace add-on type liquid silicon rubber according to claim 2, it is characterised in that：It is described containing hydroxyl
The alkene of base is 1 with the mol ratio of amido-containing acid ester radical siloxane compound:1～3.3:1.
7. the preparation method of high-performance anti creepage trace add-on type liquid silicon rubber described in any one of claim 1-6, its feature
It is：By 100 mass parts vinyl silicone oils, two silicon nitrogen of 30～60 mass parts fume colloidal silicas and 3～15 mass parts hexamethyl
Alkane mixes in vacuum kneader, stirs at 25～35 DEG C, is heated to 150～180 DEG C of mixings of temperature of charge, then vacuumizes mixed
1～3h of refining, grinds after cooling, obtains liquid silicon rubber sizing；Add 1～10 mass parts containing hydrogen silicone oil, 0.004～
0.03 mass parts 1- acetenyl -1- cyclohexanol, 2～6 mass parts amido-containing acid ester base silanes, 0.15～2 mass parts platinum catalysis
Agent, is well mixed at 25～35 DEG C, curing molding.
8. the preparation method of high-performance anti creepage trace add-on type liquid silicon rubber according to claim 7, its feature exist
In the time stirred at described 25～35 DEG C is 1～3h.
9. the preparation method of high-performance anti creepage trace add-on type liquid silicon rubber according to claim 7, its feature exist
In the time of 150～180 DEG C of mixings is 1～4h.
10. the preparation method of high-performance anti creepage trace add-on type liquid silicon rubber according to claim 7, its feature exist
In the grinding is the grinding of Jing three-rollers；The curing molding is to solidify 0.1～2h shapings at 100～150 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610940468.8A CN106543734B (en) | 2016-10-25 | 2016-10-25 | A kind of high-performance anti creepage trace add-on type liquid silicon rubber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610940468.8A CN106543734B (en) | 2016-10-25 | 2016-10-25 | A kind of high-performance anti creepage trace add-on type liquid silicon rubber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106543734A true CN106543734A (en) | 2017-03-29 |
| CN106543734B CN106543734B (en) | 2019-11-15 |
Family
ID=58393086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610940468.8A Active CN106543734B (en) | 2016-10-25 | 2016-10-25 | A kind of high-performance anti creepage trace add-on type liquid silicon rubber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106543734B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107129689A (en) * | 2017-04-18 | 2017-09-05 | 华南理工大学 | High-performance anti creepage trace add-on type liquid silicon rubber composition and preparation method thereof |
| CN107446356A (en) * | 2017-08-07 | 2017-12-08 | 华南理工大学 | A kind of heat resistant transparent add-on type liquid silicon rubber and preparation method thereof |
| WO2021050463A1 (en) * | 2019-09-09 | 2021-03-18 | Dow Silicones Corporation | Method of preparing alkoxy-functional organosilicon compounds |
| CN113817286A (en) * | 2021-08-24 | 2021-12-21 | 安徽众博新材料有限公司 | Salt spray resistant, high-pressure scratch resistant and pollution flashover resistant insulating part material |
| CN114752223A (en) * | 2022-05-13 | 2022-07-15 | 成都拓利科技股份有限公司 | High-strength tracking-resistant liquid silicone rubber and preparation method thereof |
| CN116675986A (en) * | 2023-06-06 | 2023-09-01 | 广东澳通特种电缆有限公司 | Silicon rubber high-temperature-resistant cable and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760275A (en) * | 2004-10-14 | 2006-04-19 | 瓦克化学有限公司 | Polysiloxane rubber composition having improved durability |
| CN101778885A (en) * | 2007-08-10 | 2010-07-14 | 汉高两合股份公司 | Curable compositions composed of silanes with two hydrolyzable groups |
| CN101993522A (en) * | 2009-08-19 | 2011-03-30 | 赢创高施米特有限公司 | Novel urethane-containing silylated prepolymers and process for preparation thereof |
| CN102924926A (en) * | 2012-11-01 | 2013-02-13 | 深圳市森日有机硅材料有限公司 | Liquid silicone rubber composition and preparation method thereof |
| CN103694709A (en) * | 2013-12-09 | 2014-04-02 | 华南理工大学 | Creepage-resistant tracking agent for addition-type liquid silicon rubber and preparation method and application thereof |
| CN104086772A (en) * | 2014-06-24 | 2014-10-08 | 华南理工大学 | Uramido modified MQ silicon resin, and preparation method and application thereof |
-
2016
- 2016-10-25 CN CN201610940468.8A patent/CN106543734B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760275A (en) * | 2004-10-14 | 2006-04-19 | 瓦克化学有限公司 | Polysiloxane rubber composition having improved durability |
| CN101778885A (en) * | 2007-08-10 | 2010-07-14 | 汉高两合股份公司 | Curable compositions composed of silanes with two hydrolyzable groups |
| CN101993522A (en) * | 2009-08-19 | 2011-03-30 | 赢创高施米特有限公司 | Novel urethane-containing silylated prepolymers and process for preparation thereof |
| CN102924926A (en) * | 2012-11-01 | 2013-02-13 | 深圳市森日有机硅材料有限公司 | Liquid silicone rubber composition and preparation method thereof |
| CN103694709A (en) * | 2013-12-09 | 2014-04-02 | 华南理工大学 | Creepage-resistant tracking agent for addition-type liquid silicon rubber and preparation method and application thereof |
| CN104086772A (en) * | 2014-06-24 | 2014-10-08 | 华南理工大学 | Uramido modified MQ silicon resin, and preparation method and application thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107129689A (en) * | 2017-04-18 | 2017-09-05 | 华南理工大学 | High-performance anti creepage trace add-on type liquid silicon rubber composition and preparation method thereof |
| CN107446356A (en) * | 2017-08-07 | 2017-12-08 | 华南理工大学 | A kind of heat resistant transparent add-on type liquid silicon rubber and preparation method thereof |
| CN107446356B (en) * | 2017-08-07 | 2019-10-18 | 华南理工大学 | A kind of heat resistant transparent add-on type liquid silicon rubber and preparation method thereof |
| WO2021050463A1 (en) * | 2019-09-09 | 2021-03-18 | Dow Silicones Corporation | Method of preparing alkoxy-functional organosilicon compounds |
| US11859054B2 (en) | 2019-09-09 | 2024-01-02 | Dow Silicones Corporation | Method of preparing alkoxy-functional organosilicon compounds |
| CN113817286A (en) * | 2021-08-24 | 2021-12-21 | 安徽众博新材料有限公司 | Salt spray resistant, high-pressure scratch resistant and pollution flashover resistant insulating part material |
| CN114752223A (en) * | 2022-05-13 | 2022-07-15 | 成都拓利科技股份有限公司 | High-strength tracking-resistant liquid silicone rubber and preparation method thereof |
| CN116675986A (en) * | 2023-06-06 | 2023-09-01 | 广东澳通特种电缆有限公司 | Silicon rubber high-temperature-resistant cable and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106543734B (en) | 2019-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106543734B (en) | A kind of high-performance anti creepage trace add-on type liquid silicon rubber and preparation method thereof | |
| CN104974530B (en) | A kind of high-performance anti creepage trace silicon rubber and preparation method thereof | |
| CN110305621B (en) | Dealcoholized room-temperature curing organosilicon sealant and preparation method thereof | |
| CN103589387B (en) | LED high strength bonding self-vulcanizing organic silicon potting adhesive and preparation method thereof | |
| CN101260190A (en) | Multiple functionality degree polysiloxane coupling agent and preparation method thereof | |
| CN102093721B (en) | Single-component alcohol/ketoxime-removed room temperature vulcanizing silicone rubber and preparation method thereof | |
| CN102532907B (en) | Preparation method of oil-resistant room temperature vulcanization deoximation silicon rubber | |
| CN104387546A (en) | Phenyl organic silicon modified polyurethane resin, preparation method and application thereof | |
| CN104710962B (en) | Room temperature vulcanized silicone rubber adhesive and preparation method thereof | |
| CN101058640A (en) | Organic silicon polyurea base polymer, elastic body prepared by the same, preparation method and application thereof | |
| CN103044920B (en) | One-component room temperature vulcanized and methyl alcohol-removed silicon rubber of starting-resistant engine oil and preparation method of rubber | |
| CN103044683A (en) | Modified MQ silicone resin and preparation method thereof | |
| CN104086772A (en) | Uramido modified MQ silicon resin, and preparation method and application thereof | |
| CN112029463A (en) | Epoxy modified phenyl hydrogen-containing silicone oil, composite epoxy adhesive and preparation method thereof | |
| CN103694709A (en) | Creepage-resistant tracking agent for addition-type liquid silicon rubber and preparation method and application thereof | |
| CN108517198A (en) | A kind of single-component room-temperature vulcanized organosilicon adhesive and preparation method thereof | |
| CN105754087B (en) | A kind of preparation method of end polyether silicon | |
| CN102408719A (en) | Room temperature-vulcanized single-component transparent methanol-removing type silicone rubber sealant and preparation method thereof | |
| CN102952270A (en) | Polysiloxane polymer and preparation method thereof, as well as single-component dealcoholized silicon rubber and preparation method thereof | |
| CN102775793A (en) | Preparation method of addition-type vulcanized rubber | |
| CN109852338A (en) | Fluorosilicone rubber composition, preparation method and the sealant and coating prepared by the composition | |
| CN106832947B (en) | A kind of enhanced abietyl room temperature vulcanized silicone rubber of one-component and preparation method thereof | |
| CN106867024A (en) | A kind of Abietyl modified organosilane cross-linking agent of dealcoholized type room temperature vulcanized silicone rubber and preparation method thereof | |
| CN105368339A (en) | Tackifier for addition-cured organosilicone adhesive sealant, preparation method and composition used in preparation | |
| CN106380603A (en) | Bis-amino-containing MQ silicone resin, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |