CN106543734B - A kind of high-performance anti-tracking addition type liquid silicone rubber and its preparation method - Google Patents

Abstract

The invention discloses a high-performance tracking-resistant addition type liquid silicone rubber and a preparation method thereof. The raw material formula components of the addition-type liquid silicone rubber are: 100 parts of vinyl silicone oil, 30-60 parts of white carbon black, 1-10 parts of hydrogen-containing silicone oil, 2-6 parts of carbamate-containing silane, and 0.15 parts of platinum catalyst. ～2 parts, 0.004～0.03 parts of 1-ethynyl-1-cyclohexanol. The addition-type liquid silicone rubber of the invention has excellent tracking resistance and mechanical properties, and has broad application prospects in the fields of electrical external insulation materials and the like; and the invention has easy-to-obtain raw materials, simple processing technology, and is convenient for large-scale production.

Description

A kind of high-performance anti-tracking addition type liquid silicone rubber and its preparation method

technical field

The invention relates to the field of silicone rubber insulating materials, in particular to a high-performance tracking-resistant additive liquid silicone rubber and a preparation method thereof; belonging to the technical field of rubber insulating materials.

Background technique

In recent years, my country's electric power industry has developed rapidly, the operating voltage level of the power grid system has been continuously improved, and the network scale has gradually expanded. The major regional power grids have basically been integrated into a whole. accomplish. In the construction of the power grid, in order to ensure the safe transmission of electric energy, a large number of power equipment such as power transmission transformers, transformers and insulators are used. With the increasing voltage level of power transmission and transformation equipment, coupled with the aggravation of air pollution and frequent haze weather, the operating conditions of the external insulation of power equipment are deteriorating. Sexuality puts forward higher demands.

Due to its excellent high and low temperature resistance, weather resistance, electrical insulation, water repellency and water repellency, silicone rubber gradually replaces traditional ceramics and glass, and is widely used as external insulation materials for high-voltage and ultra-high-voltage power transmission and transformation equipment. Among various silicone rubbers, addition-type liquid silicone rubber has the advantages of no by-products in the vulcanization process, minimal shrinkage, deep vulcanization, etc., and is simple in process and low in cost, and has become the preferred raw material for insulating materials in the power industry. However, the addition-type liquid silicone rubber will be polluted by dirt, moisture, salt dew and other chemicals during long-term use. Repeated arc discharge causes the surface of silicone rubber to carbonize and form a conductive path (that is, leakage tracking damage). In severe cases, the surface of the material will burn for a short time, resulting in the failure of the addition-type liquid silicone rubber insulator, threatening the safe operation of the power grid. Therefore, it is very important to improve the tracking resistance of addition-type liquid silicone rubber.

At present, although some progress has been made in improving the tracking resistance of addition-type liquid silicone rubber, there are still some shortcomings: insulators play the role of electrical insulation and mechanical support in the transmission network, so the tensile strength of insulators is generally affected and tear strength requirements are high, but at present, in order to make the tracking resistance of addition-type liquid silicone rubber meet certain requirements, it is necessary to add a large amount of inorganic tracking resistance agent, which will greatly reduce the performance of addition-type liquid silicone rubber. Mechanical properties of rubber. In addition, the addition of a large amount of inorganic anti-tracking agent will seriously damage the hydrophobicity and hydrophobic recovery of addition-type liquid silicone rubber. This not only greatly limits the application range of addition-type liquid silicone rubber insulating materials, but also affects the protective performance of addition-type liquid silicone rubber products in long-term operation, and there are certain safety hazards. Therefore, it is of great significance to prepare a high-performance tracking-resistant addition-type liquid silicone rubber.

Chinese invention patent CN103694709A discloses that ureidosiloxane containing double bonds is used as a tracking resistance agent and compounded with white carbon black to prepare an addition-type liquid silicone rubber with good tracking resistance. However, the high nitrogen content of ureidosilane will prolong the vulcanization time of addition-type liquid silicone rubber and increase its industrial application cost. In addition, ureido-containing silicones have not been fully industrialized, mainly because in industry, ureido-containing siloxanes are generally prepared by isocyanate-containing siloxanes and organic amines, and organic amines are toxic and volatile. It is very harmful to the human body and the environment. More importantly, this preparation method has very strict requirements on the purification process, because in the synthetic product, the unremoved organic amine will make the addition-type liquid silicone rubber unable to vulcanize smoothly.

Contents of the invention

The object of the present invention is to address the deficiencies of the prior art, and provide an addition-type liquid silicone rubber that does not require high purification in the production process, does not affect the vulcanization of silicone rubber, is safe, environmentally friendly, and has excellent tracking resistance and mechanical properties.

The object of the present invention is also to provide a preparation method of the high-performance tracking-resistant addition-type liquid silicone rubber.

The purpose of the present invention can be achieved through the following technical solutions:

In parts by mass, its raw material formula consists of:

The structural formula of the carbamate-containing silane is:

Wherein R ₁ is -C _n H _2n+1 , n is 1 to 4; R ₂ is -CH ₃ or -CH ₂ CH ₃ ; R ₃ is -CH ₂ CH=CH ₂ , -CH ₂ CH=CHCH ₃ or -CH ₂ CH=C(CH ₃ ) ₂ ; i is 1 to 3;

The platinum catalyst is divinyltetramethyldisiloxane complex of chloroplatinic acid (Karstedt platinum catalyst).

To further realize the purpose of the present invention, preferably, the urethane-containing silane is prepared by the following method: under the action of an organotin catalyst, the alcohol compound is mixed with the isocyanate-containing siloxane compound at a temperature of 30-60°C Under the condition of stirring and reacting for 1 to 4 hours, and then distilled under reduced pressure to obtain the carbamate-containing siloxane compound; Mix, stir and react at a temperature of 70-90°C for 2-6 hours, and distill under reduced pressure to remove low boilers to obtain carbamate-containing silanes;

The isocyanate-containing siloxane compound has the following structure: O=C=NCH ₂ CH ₂ CH ₂ Si(OR) ₃ ; wherein R is -CH ₃ or -CH ₂ CH ₃ ;

The hydroxyl-containing olefins are propenol and 2-butenol or isopentenol.

Preferably, the organotin catalyst is dibutyltin dilaurate, stannous octoate or dibutyltin diacetate; the amount of the organotin catalyst is 0.05-0.30% of the total mass of reactants.

Preferably, the alcohol compound is methanol, ethanol, propanol or butanol; the molar ratio of the alcohol compound to the isocyanate-containing siloxane compound is 1.1:1˜1.3:1.

Preferably, the organic titanate is tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetra-tert-butyl titanate or diisopropyl di(acetylacetonate) titanate; The amount of organic titanate is 0.1-2.0% of the total mass of reactants.

Preferably, the molar ratio of the hydroxyl-containing olefin to the urethane-containing siloxane compound is 1:1˜3.3:1.

The preparation method of the high-performance tracking-resistant addition-type liquid silicone rubber: 100 parts by mass of vinyl silicone oil, 30-60 parts by mass of fumed silica and 3-15 parts by mass of hexamethyldisilazane in a vacuum Mix in a kneader, stir at 25-35°C, heat to a material temperature of 150-180°C and knead, then vacuumize and knead for 1-3 hours, cool and grind to obtain a liquid silicone rubber base compound; add 1-10 Parts by mass of hydrogen-containing silicone oil, 0.004-0.03 parts by mass of 1-ethynyl-1-cyclohexanol, 2-6 parts by mass of carbamate-containing silane, 0.15-2 parts by mass of platinum catalyst, mixed at 25-35°C Uniform, curing molding.

Preferably, the stirring time at 25-35° C. is 1-3 hours.

Preferably, the mixing time at 150-180°C is 1-4 hours

Preferably, the grinding is ground by a three-roll machine; the curing molding is curing at 100-150° C. for 0.1-2 hours.

According to Chinese patent CN103694709A, ureidosilane can effectively improve the tracking resistance of addition-type liquid silicone rubber. It is generally believed in the prior art that platinum and nitrogen have a good synergistic effect. On the one hand, nitrogen-containing silanes can improve the catalytic activity of platinum compounds through coordination, which is conducive to the formation of a dense barrier layer and inhibit the degradation of silicone rubber; on the other hand, nitrogen-containing silanes will release nitrogen-containing silanes at high temperatures. The inert gas plays a good role in extinguishing the arc. But the present invention finds that the nitrogen content of urethane-containing silane is only half of that of ureido-silane, and under the same addition amount, the resistance of urethane-containing silane to addition-type liquid silicone rubber The tracking effect is not worse than that of ureidosilane, or even better. In particular, no toxic raw materials are required for the preparation of urethane-containing silane, and the harm to the human environment is small; and the requirements for purification in the production process are low, and the vulcanization of silicone rubber is not affected.

In the present invention, the carbamate-containing silane can significantly improve the tracking resistance of the addition-type liquid silicone rubber. This may be due to the fact that the introduced urethane group works synergistically with the platinum catalyst to promote the cleavage of the side group of the addition-type liquid silicone rubber, forming methane and carbon dioxide, and reducing the deposition of carbon particles. On the other hand, carbamate-based silane decomposes at high temperature to generate isocyanic acid-containing compounds, which react with Si-OH produced by side methyl oxidation of silicone rubber, which inhibits the release of the main chain of silicone rubber and greatly reduces The release of ionizable cyclic siloxane reduces the intensity of the arc.

In addition, urethane-containing silanes have good compatibility with silicone rubber, and contain multiple vinyl groups. During the vulcanization process, concentrated crosslinking points are formed in the silicone rubber crosslinking network through hydrosilylation reaction. Effectively improve the mechanical properties of addition-type liquid silicone rubber.

Compared with the prior art, the present invention has the following advantages:

1. The present invention overcomes the disadvantage of adding a large amount of inorganic anti-tracking agent, adding a small amount (<6 parts by mass) of urethane-containing silane to the addition-type liquid silicone rubber, and its anti-tracking performance can be Reach 1A4.5 level.

2. The present invention overcomes the technical prejudice and synthesizes urethane-containing silanes with lower nitrogen content, but its effect on the tracking resistance of addition-type liquid silicone rubber is not inferior to that of ureido-containing silanes.

3. The urethane-containing silane prepared by the present invention is a siloxane compound containing an alkenyl group, which has good compatibility with the addition-type liquid silicone rubber and is conducive to the formation of a concentrated cross-linking structure, effectively improving the addition-type liquid silicone rubber. mechanical properties.

4. The nitrogen content of the urethane-containing silane of the present invention is relatively low, and has little effect on the vulcanization of addition-type liquid silicone rubber, and the preparation process is simple, the raw materials are cheap and easy to obtain, and it is easy to realize industrial production. It has broad application prospects in the field of external insulation materials.

5. In the synthesis process of the urethane-containing silane, no solvent is used in the present invention, which not only reduces the synthesis cost, but also helps protect the environment.

Description of drawings

Fig. 1 is the infrared spectrogram of the urethane-containing silane that embodiment 1-3 obtains; Wherein curve a, b and c are respectively 3-(isopropyl carbamate) propyl triallyloxysilane (IPURPAS ), 3-(urethane) propyl allyloxydiethoxysilane (EURPAS) and 3-(methyl carbamate) propyl triallyloxysilane (MURPAS) infrared spectra.

Fig. 2 is the proton nuclear magnetic resonance spectrum of the carbamate-containing silane that embodiment 1-3 obtains; Wherein, a, b and c are respectively 3-(isopropyl carbamate) propyl triallyloxy group in the curve NMR of silane (IPURPAS), 3-(ethylcarbamate)propylallyloxydiethoxysilane (EURPAS) and 3-(methylcarbamate)propyltriallyloxysilane (MURPAS) hydrogen spectrum.

Detailed ways

In order to better understand the present invention, the present invention will be further described below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

Example 1

Add 13.2g of isopropanol, 49.4g of 3-isocyanatopropyl triethoxysilane and 0.18g of dibutyltin dilaurate into a 250mL four-neck flask equipped with a reflux condenser, mechanical stirring and a thermometer. The reaction was stirred for 3 h, and then the unreacted isopropanol was distilled off under reduced pressure to obtain 3-(isopropyl carbamate)propyltriethoxysilane (IPURPES).

Add 23.5g allyl alcohol, 43.1g 3-(isopropyl carbamate) propyltriethoxysilane and 0.66g methyl titanate into a 250mL four-necked flask equipped with a reflux condenser, mechanical stirring and a thermometer , stir evenly at room temperature, heat up to 80° C. for reflux reaction for 2 h, and finally remove low boilers by distillation under reduced pressure to obtain the product 3-(isopropyl carbamate) propyl triallyloxysilane (IPURPAS).

100 parts by mass of vinyl silicone oil (viscosity at 25°C is 25200mPa·s, vinyl content is 0.25mol%), 40 parts by mass of fumed silica (specific surface area is 260m ³ /g), 7 parts by mass of six Methyldisilazane was mixed in a vacuum kneader, stirred at 30°C for 2 hours, heated to a material temperature of 170°C and continued to mix for 2 hours, then vacuumed and mixed for 1 hour, after cooling, it was ground by a three-roller machine to obtain an addition liquid Silicone rubber base material.

In the above-mentioned 100 parts by mass base compound, add 3 parts by mass of IPURPAS, 4.01 parts by mass of hydrogen-containing silicone oil (hydrogen content is 0.75wt%), 0.01 parts by mass of 1-ethynyl-1-cyclohexanol and 0.25 parts by mass of chlorine Divinyltetramethyldisiloxane complex of platinum acid (platinum content is 3000ppm), stirred evenly at 30°C, molded at 120°C for 10min, made into 6mm and 2mm thick films, respectively tested for leakage resistance Tracking test and mechanical performance test, the properties of the samples are shown in Tables 1 and 2.

Example 2

Add 11.0 g of ethanol, 49.4 g of 3-isocyanatopropyltriethoxysilane and 0.06 g of stannous octoate into a 250 mL four-neck flask equipped with a reflux condenser, mechanical stirring and a thermometer, and stir the reaction at 30 ° C for 4 h. Then unreacted ethanol was distilled off under reduced pressure to obtain 3-(ethylcarbamate)propyltriethoxysilane (EURPES).

7.9g allyl alcohol, 41.1g 3-(urethane) propyltriethoxysilane and 0.98g butyl titanate were added to a 250mL four-necked flask equipped with a reflux condenser, mechanical stirring and a thermometer, Stir evenly at room temperature, raise the temperature to 70° C. for reflux reaction for 3 h, and finally remove low boilers by distillation under reduced pressure to obtain the product 3-(urethane)propylallyloxydiethoxysilane (EURPAS).

The IPURPAS of 1 in the embodiment is changed into EPURPAS, and the consumption is increased to 6 mass parts, and the corresponding hydrogen-containing silicone oil consumption is 2.94 mass parts, and the performance of the sample is shown in Tables 1 and 2

Example 3

Add 8.3g of methanol, 41.0g of 3-isocyanatopropyltrimethoxysilane and 0.03g of dibutyltin dilaurate into a 250mL four-necked flask equipped with a reflux condenser, mechanical stirring and a thermometer, and stir the reaction at 40°C for 1h , and then distilled off unreacted methanol under reduced pressure to obtain 3-(methyl carbamate)propyltrimethoxysilane (MURPMS).

23.5g allyl alcohol, 33.3g 3-(methyl carbamate) propyltrimethoxysilane and 0.06g isopropyl titanate were added to a 250mL four-necked flask equipped with a reflux condenser, mechanical stirring and a thermometer, Stir evenly at room temperature, raise the temperature to 90° C. for reflux reaction for 6 h, and finally remove low boilers by distillation under reduced pressure to obtain the product 3-(methyl carbamate)propyltriallyloxysilane (MURPAS).

The IPURPAS of 1 in the embodiment is changed to MPURPAS, the consumption is 2 mass parts, and the corresponding hydrogen-containing silicone oil consumption is 3.05 mass parts, and the performance of the sample is as shown in Tables 1 and 2

Comparative example 1

100 parts by mass of vinyl silicone oil (viscosity at 25°C is 25200mPa·s, vinyl content is 0.25mol%), 40 parts by mass of fumed silica (specific surface area is 260m ³ /g), 7 parts by mass of six Methyldisilazane was mixed in a vacuum kneader, stirred at 30°C for 2 hours, heated to a material temperature of 170°C and continued to mix for 2 hours, and then vacuumed and mixed for 1 hour, after cooling, it was ground by a three-roller machine to obtain an addition liquid Silicone rubber base compound.

In the above-mentioned 100 parts by mass base compound, add 1.50 parts by mass of hydrogen-containing silicone oil (hydrogen content is 0.75 wt%), 0.01 parts by mass of 1-ethynyl-1-cyclohexanol and 0.25 parts by mass of diethylene chloroplatinic acid Tetramethyldisiloxane complex (with a platinum content of 3000ppm), stirred evenly at 30°C, molded at 120°C for 10min, made into 6mm and 2mm thick films, and carried out tracking resistance test and mechanical Performance test, the performance of the sample is shown in Table 1 and 2.

Comparative example 2

100 parts by mass of vinyl silicone oil (viscosity at 25°C is 25200mPa·s, vinyl content is 0.25mol%), 40 parts by mass of fumed silica (specific surface area is 260m3/g), 7 parts by mass of Hexa The base disilazane was mixed in a vacuum kneader, stirred at 30°C for 2h, heated to a material temperature of 170°C and continued to knead for 2h, then vacuumized and kneaded for 1h, after cooling, it was ground by a three-roller machine to obtain an addition-type liquid silicon Rubber base.

In the above-mentioned 100 parts by mass base compound, add 3 parts by mass of IPURPAS, 4.01 parts by mass of hydrogen-containing silicone oil (hydrogen content is 0.75wt%), 0.01 parts by mass of 1-ethynyl-1-cyclohexanol and 0.1 parts by mass of chlorine Divinyltetramethyldisiloxane complex of platinum acid (platinum content is 3000ppm), stirred evenly at 30°C, molded at 120°C for 10min, made into 6mm and 2mm thick films, respectively tested for leakage resistance Tracking test and mechanical performance test, the properties of the samples are shown in Tables 1 and 2.

The urethane-containing silanes obtained in Examples 1-3 were analyzed by infrared spectroscopy, and the results are shown in FIG. 1 . It can be seen from the figure that the urethane ^- containing silanes prepared in Examples 1-3 have NH stretching vibration absorption peaks at ^{3365cm-1 ; C} = stretching vibration absorption peaks of O, CN and CO; CH stretching vibration absorption peaks and in-plane rocking vibration absorption peaks of -CH=CH ₂ appeared at 3082cm -1 and 958cm ^-1 ; at 1086cm ^-1 and ^{955cm -1 The} asymmetric stretching vibration absorption peak and the symmetric stretching vibration absorption peak of Si-OC appeared in both places. Figure 2 is the hydrogen nuclear magnetic resonance spectrum of the urethane-containing silane in Examples 1-3. As can be seen from the figure, the carbamate-containing silanes prepared in Examples 1-3 all appear at the chemical shift 5.0-6.0ppm. The CH proton absorption peak in -CH= _CH2 appears, and the carbamate appears near the chemical shift 4.3ppm. The NH proton absorption peak in the ester group, the proton absorption peak of -SiOCH ₂ appeared at 3.8-3.9ppm. Both the infrared spectrum analysis and the proton nuclear magnetic resonance spectrum analysis indicated that the carbamate group-containing silane of the present invention was successfully synthesized.

It can be seen from Table 1 that the vulcanization time T90 of the addition-type liquid silicone rubber without adding urethane-containing silane is _194s (see Comparative Example 1). When the carbamate-containing silane of the present invention is added, the vulcanization time T90 of the addition-type liquid silicone rubber does not change much, between 181 and _202s (see Example 1-3); it shows that the synthesized carbamate-containing silane Ester silanes have little effect on the vulcanization time of addition-type liquid silicone rubber.

It can be seen from Table 2 that the addition-type liquid silicone rubber without urethane-containing silane failed to pass the 4.5kV tracking resistance test (see Comparative Example 1). But adding the urethane-containing silane of the present invention, the tracking resistance of the addition-type liquid silicone rubber can reach 1A4.5 grades (see Examples 1-3), indicating that the synthesized urethane-containing silane Base silane can significantly improve the tracking resistance of addition-type liquid silicone rubber. However, as can be seen from Example 1 and Comparative Example 2, 3 mass parts of IPURPAS are also added, and when the consumption of the divinyltetramethyldisiloxane complex of chloroplatinic acid is 0.1 mass parts, the addition type liquid silicon The rubber failed to pass the 4.5kV tracking resistance test, and when the amount of the divinyltetramethyldisiloxane complex of chloroplatinic acid was 0.25 parts by mass, the addition-type liquid silicone rubber could pass the 4.5kV The tracking resistance test shows that the amount of platinum catalyst has a great influence on the tracking resistance of the addition-type liquid silicone rubber of the present invention.

It can also be seen from Table 2 that the tensile strength and tear strength are respectively 7.6 MPa and 31.6 kN/m without adding the addition-type liquid silicone rubber containing urethane silane (see Comparative Example 1). But adding the urethane-containing silane of the present invention, the tensile strength and tear strength of the addition-type liquid silicone rubber not only do not decline, but also increase in varying degrees (see Examples 1-3), showing that the present invention The urethane-containing silane can effectively improve the mechanical properties of addition-type liquid silicone rubber.

The product performance test methods in Tables 1 and 2 are as follows:

1. Determine the vulcanization characteristics of silicone rubber according to GB/T 16584-1996.

2. Determine the tensile strength and elongation at break of silicone rubber according to GB/T 528-2009.

3. Determine the tear strength of silicone rubber according to GB/T 529-2008.

4. Determine the Shore A hardness of silicone rubber according to GB/T 531-2008.

5. Carry out the tracking resistance test of silicone rubber according to GB/T 6553-2003. The constant voltage method is adopted, and the test voltage is 4.5kV; the "end point judgment method A" in the test method is selected for the end point judgment: when the current passing through the sample is greater than 60mA, it is regarded as electric trace breakdown.

Compared with Chinese patent CN103694709A, the urethane-containing siloxane of the present invention is prepared by isocyanate-containing siloxane and organic alcohol, and the organic alcohol is cheap and less toxic. In addition, the organic alcohol will not poison the platinum catalyst of the addition-type liquid silicone rubber. Therefore, the requirements for the purification process are not strict, the synthesis process is simple, the cost is low, and it is easier to industrialize.

Table 1 Vulcanization characteristics of addition-type liquid silicone rubber

Table 2 Mechanical properties and tracking resistance of addition-type liquid silicone rubber

Studying Chinese invention patent CN103694709A, those skilled in the art know that ureidosilane can effectively improve the tracking resistance of addition-type liquid silicone rubber. It is generally believed that platinum and nitrogen have a good synergistic effect. On the one hand, nitrogen-containing silanes can improve the catalytic activity of platinum compounds through coordination, which is conducive to the formation of a dense barrier layer and inhibit the degradation of silicone rubber; on the other hand, nitrogen-containing silanes will release nitrogen-containing silanes at high temperatures. The inert gas plays a good role in extinguishing the arc. But above-mentioned embodiment of the present invention proves: the nitrogen content of carbamate-containing silane is only half of the nitrogen content of ureido-silane, and under the same addition amount, the carbamate-containing silane has an effect on addition-type liquid silicon The tracking resistance of rubber is not worse than that of ureidosilane, or even better.

The present invention needs to emphasize that no toxic raw materials are required for the preparation of urethane-containing silanes, and the harm to the human environment is small; and the requirements for purification in the production process are low, and the vulcanization of silicone rubber is not affected. Urea-based siloxanes and organic amines are used to prepare ureido-containing siloxanes, and organic amines are toxic and volatile, which are harmful to human body and environment. CN103694709A This preparation method has very strict requirements on the purification process, because in the synthetic product, the unremoved organic amine will make the addition-type liquid silicone rubber unable to vulcanize smoothly; the present invention effectively overcomes these problems in the prior art.

Claims (10)

1. a kind of high-performance anti creepage trace add-on type liquid silicon rubber, which is characterized in that in terms of mass parts, composition of raw materials group Become:

The structural formula of the amido-containing acid ester base silane are as follows:

Wherein R₁For-C_nH_2n+1, n is 1~4；R₂For-CH₃Or-CH₂CH₃；R₃For-CH₂CH=CH₂,-CH₂CH=CHCH₃Or- CH₂CH=C (CH₃)₂；I is 1~3；

The platinum catalyst is the divinyl tetramethyl disiloxane complex compound of 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: under the action of organotin catalysts, by alcoholic compound and silicon containing isocyanate group Siloxane compound mixing, is stirred to react 1~4h under the conditions of temperature is 30~60 DEG C, and then vacuum distillation is obtained containing carbamic acid Ester group silicone compounds；Again under the action of organic titanate, by the alkene of hydroxyl and amido-containing acid ester radical siloxane Compound mixing is stirred to react 2~6h under the conditions of temperature is 70~90 DEG C, and vacuum distillation removes low-boiling-point substance, obtains containing amino Formic acid esters base silane；

The silicone compounds containing isocyanate group are following structures: O=C=NCH₂CH₂CH₂Si(OR)₃；Wherein R is-CH₃ Or-CH₂CH₃；

The alkene of the hydroxyl is propenyl and 2- butenol or prenol.

3. high-performance anti creepage trace add-on type liquid silicon rubber according to claim 2, it is characterised in that: described organic Tin catalyst is dibutyl tin dilaurate, stannous octoate or dibutyltin diacetate；The organotin catalysts dosage is anti- Answer the 0.05~0.30% of object 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 Conjunction object is methanol, ethyl alcohol, propyl alcohol or butanol；The molar ratio of the alcoholic compound and the silicone compounds containing isocyanate group 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: described organic Titanate esters are that tetraethyl titanate, tetraisopropyl titanate, butyl titanate, four tert-butyl ester of metatitanic acid or bis(acetylacetonate) titanium acid two are different Propyl ester；The organic titanate dosage is the 0.1~2.0% of reactant gross mass.

6. high-performance anti creepage trace add-on type liquid silicon rubber according to claim 2, it is characterised in that: described to contain hydroxyl The alkene of base and the molar ratio of amido-containing acid ester radical siloxane compound are 1:1~3.3:1.

7. the preparation method of any one of the claim 1-6 high-performance anti creepage trace add-on type liquid silicon rubber, feature It is: by two silicon nitrogen of 100 mass parts vinyl silicone oils, 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 temperature of charge mixings, then vacuumize mixed 1~3h is refined, is ground 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 uniformly mixed, curing molding at 25~35 DEG C.

8. the preparation method of high-performance anti creepage trace add-on type liquid silicon rubber according to claim 7, 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, 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, feature exist In the grinding is ground through three-roller；The curing molding is to solidify 0.1~2h molding at 100~150 DEG C.