CN107189753B - Deoximation type oil-resistant fluorosilicone sealant and preparation method thereof - Google Patents
Deoximation type oil-resistant fluorosilicone sealant and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
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Abstract
The invention relates to a deoximation type oil-resistant fluorosilicone sealant and a preparation method thereof, wherein the deoximation type oil-resistant fluorosilicone sealant is prepared by taking hydroxyl-terminated polydimethylsiloxane and hydroxyl-terminated trifluoropropylmethylsiloxane as base adhesives, adding hydrophobic modified white carbon black, performing vacuum drying on the obtained mixture, adding methyl tributyrinoxime silane and phenyl tributyrinoxime silane, and mixing the mixture with the following raw materials in a ratio of 1: and (3) mixing the cross-linking agent and the catalyst titanium complex in the proportion of 1.5, and stirring until the cross-linking agent and the catalyst titanium complex are fully mixed to obtain the required sealant. The sealant has good oil resistance, the oil resistance of the sealant is measured according to the GB/T1690-2006 standard, the mass change rate of the sealant is not higher than 10%, the mechanical property of the sealant is good, the sealant can replace the common sealant to be applied to the manufacturing and maintenance of engineering machinery and the automobile industry, and the prospect is good.
Description
Technical Field
The invention relates to a deoximation type oil-resistant fluorine-containing organosilicon sealant and a preparation method thereof, belonging to the field of fine chemical engineering technology and functional material preparation.
Background
The single-component room temperature vulcanized silicone rubber has excellent performances of high and low temperature resistance, weather resistance, ozone resistance, chemical stability and the like, also has the advantages of simple manufacture, convenient use, easy forming, convenient transportation and the like, and is widely applied to the aspects of aviation, aerospace, medical treatment, building, electronics and the like.
Sealants, sealing gaskets and the like required in the mechanical industry, particularly in the engineering machinery and automobile industry, must have good oil and heat resistance. The room temperature vulcanized silicone rubber has defects in mechanical strength, oil resistance, solvent resistance and the like, which limits the use of the silicone rubber in the industrial fields of engineering machinery manufacturing and maintenance, automobiles, oil fields and the like which are in more contact with solvents to a certain extent, although the varieties of the silicone rubber, the nitrile rubber and the like which are relatively good in non-polar solvent resistance appear, the production cost and the technical requirements are high, so that the silicone rubber cannot be used in a large area and can only be limited to be used on special parts, and the improved methyl silicone rubber is adopted in practical application.
The general improvement method comprises introducing polar groups, changing a production formula or a production process, adding part of oil-resistant auxiliary agents or fillers, blending and the like, however, the step of introducing the polar groups is complex, the success rate is not high, if only the formula process is changed or the oil-resistant auxiliary agents and the fillers are added, the effect is not obvious, and the mechanical property can be reduced, so that a lot of people adopt the blending method to modify the silicone rubber. However, most of blending materials have poor compatibility with silicone rubber, so that the research on proper blending oil-resistant materials has very important significance for improving the oil resistance of common silicone rubber.
Chinese patent document CN103436217A (application number: 201310405674.5) discloses a single-component dealcoholized oil-resistant silicone sealant and a preparation method thereof, and the single-component dealcoholized oil-resistant silicone sealant consists of 50-100 parts of polydimethylsiloxane with end methyl dimethoxy silica, 50-100 parts of calcium carbonate, 5-15 parts of fumed silica, 5-10 parts of silicone oil plasticizer, 5-15 parts of cross-linking agent, 0.5-7.5 parts of coupling agent and 0.1-5 parts of catalyst. In the raw materials added in the patent document, only one base rubber is selected, namely polydimethylsiloxane with terminal methyldimethoxysiloxane, and other raw materials are all the compounding agents used for preparing the silicone rubber, and because the blending of the silicone rubber refers to that two or more polymer components are uniformly mixed to obtain the base rubber, the method used in the patent does not belong to a blending method for modification, and the modified calcium carbonate is mainly used for improving the oil resistance of the sealant, so the method belongs to a method for adding an oil-resistant assistant. The oil resistance cannot be fundamentally improved in this way, and the results show that although the mechanical properties are improved, the change rate of each index is still high, and the oil resistance still has a room for improvement.
Chinese patent document CN 106833503A (application number: 201710058706.7) discloses a low-modulus single-component ketoxime-removing room temperature vulcanized silicone sealant and a preparation method thereof, wherein the silicone sealant is prepared from hydroxyl-terminated polydimethylsiloxane, a plasticizer, white mineral oil, fumed silica, a reinforcing filler, aluminum stearate, a pigment, a cross-linking agent, a vulcanization accelerator, a silane coupling agent and a catalyst. The preparation method comprises the following steps: 1) uniformly mixing hydroxyl-terminated polydimethylsiloxane, a plasticizer, white mineral oil, fumed silica, a reinforcing filler, aluminum stearate and a pigment, and fully drying to obtain a premix; 2) fully kneading the premix in vacuum to obtain base rubber; 3) adding a cross-linking agent, a vulcanization accelerator and a silane coupling agent into the base rubber, and uniformly stirring in vacuum; 4) adding catalyst into the base rubber, stirring uniformly in vacuum, discharging, filling and sealing. The patent document does not belong to a blending method for modification, and the self-made alkoxy butanone oxime silane is mainly used as a vulcanization accelerator to improve the performance of the sealant, so that although the elongation at break and the bonding performance are improved, the oil resistance effect is not obviously improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a deoximation type oil-resistant fluorine-containing organosilicon sealant and a preparation method thereof, and solves the problems of poor oil resistance, poor stability and the like of the conventional sealant.
The technical scheme of the invention is as follows:
the oxime-removing type oil-resistant fluorosilicone sealant comprises the following raw materials in parts by mass:
60-80 parts of hydroxyl-terminated polydimethylsiloxane, 10-25 parts of hydroxyl-terminated polytrifluoropropylmethylsiloxane, 5-15 parts of white carbon black, 4-6 parts of cross-linking agent and 2-5 parts of catalyst.
According to the invention, the hydroxyl-terminated polydimethylsiloxane is a mixture of hydroxyl-terminated polydimethylsiloxane with the viscosity of 2,000-4,000 cp and the viscosity of 10,000-20,000 cp; more preferably, the mass ratio of the hydroxyl-terminated polydimethylsiloxane with the viscosity of 2,000-4,000 cp to the hydroxyl-terminated polydimethylsiloxane with the viscosity of 10,000-20,000 cp is (3-5): (0.5-1.5). The hydroxyl-terminated polydimethylsiloxane has poor processability of the sealant due to too high viscosity, and poor mechanical property due to too low viscosity, and the high and low viscosity mixing matching is favorable for improving the comprehensive performance of the sealant.
According to the invention, the hydroxyl-terminated polytrifluoropropylmethylsiloxane is a perfluoropolysiloxane with viscosity ranging from 5,000 to 10,000 cp. The viscosity is too low, the raw material synthesis process is difficult to control, the viscosity is too high, and the comprehensive performance is poor after the raw material is blended with the hydroxyl-terminated polydimethylsiloxane.
According to the invention, the white carbon black is preferably fumed silica with a surface subjected to hydrophobic modification, and more preferably, the white carbon black is modified by hexamethyldisilazane, octamethylcyclotetrasiloxane (D4) or dimethyldichlorosilane, and the specific surface area is 80-250 m2Fumed silica/g. The modification mode is carried out according to the prior art.
According to the invention, the cross-linking agent is a deoximation cross-linking agent, more preferably methyl tributyl ketoximino silane or/and phenyl tributyl ketoximino silane, and more preferably the combination of the methyl tributyl ketoximino silane and the phenyl tributyl ketoximino silane according to the mass ratio of (1-1.5) to (1.5-2); most preferably, methyl tributyrinoxime silane: phenyl tributyrinoxime silane in a mass ratio of 1: 1.5. The selection of the type of the cross-linking agent is beneficial to increasing the number of polar groups of the sealant, the oil resistance is improved, the selection of the proportion relation determines the cross-linking degree of the raw materials, the proportion is not appropriate, and small molecules can be remained to influence the oil resistance.
Preferably, according to the invention, the catalyst is a titanium complex; d-60 is further preferred, and the formula is as follows:
the selection of the catalyst has obvious effect on the fluorosilicone rubber, so that the blend rubber can be vulcanized at room temperature without affecting the oil resistance.
According to the invention, the hydroxyl-terminated polydimethylsiloxane and the hydroxyl-terminated polytrifluoropropylmethylsiloxane are in a mass ratio of (6-8): in the combination of (1-2.5), the hydroxyl-terminated polytrifluoropropylmethylsiloxane has too low proportion and limited improvement of oil resistance, the mechanical property of the blended rubber is reduced when the proportion is too high, and the comprehensive performance of the blended rubber can be improved by selecting the proportion.
According to the invention, the preparation method of the oxime-removing type oil-resistant fluorosilicone sealant comprises the following steps:
(1) adding hydroxyl-terminated polytrifluoropropylmethylsiloxane into hydroxyl-terminated polydimethylsiloxane at the rotating speed of 25-90 r/min, and vacuumizing to 1 × 10-3～1×10-4Pa, stirring and mixing for 20-40 minutes to obtain a pretreatment raw material A;
(2) under the stirring condition, adding the white carbon black into the pretreatment raw material A for multiple times, and stirring for 2-3.5 hours at the speed of 25-90 revolutions per minute to obtain a mixture B;
(3) under the vacuum condition, raising the temperature to 100-120 ℃, continuing stirring for 30-60 minutes, and cooling to room temperature to obtain a mixture C;
(4) adding a cross-linking agent into the mixture C under a vacuum condition, stirring for 0.5-1 hour at a speed of 25-90 rpm, adding a catalyst, and continuously stirring for 20-40 minutes;
(5) and (4) curing and forming the material treated in the step (4) to obtain the deoximation type oil-resistant fluorosilicone sealant.
According to the preferable preparation method of the invention, the white carbon black in the step (2) is added for multiple times, and the further preferable adding time is 5-10 times. The white carbon black is a commercial product, the phenomena of uneven dispersion and particle agglomeration can be avoided by adding the white carbon black for multiple times, the white carbon black and the pretreatment raw material A can be fully crosslinked, and an internal three-dimensional network is more perfect.
According to the preparation method of the invention, the temperature in the step (3) is controlled between 100 ℃ and 120 ℃, the stirring is carried out for 30-60 minutes, and the stirring is continued after the cooling to the room temperature. And (3) raising the temperature to sufficiently remove the small molecules generated in the step (2), otherwise, the oil resistance of the sealant is influenced.
According to the preparation method of the present invention, the vacuum degree of the vacuum condition in the steps (3) and (4) is preferably 1 × 10-3～1×10-4Pa。
The invention has the following characteristics and excellent effects:
1. the oil-resistant deoximation type fluorine-containing organosilicon sealant adopts specific raw materials, takes a mixture of hydroxyl-terminated polydimethylsiloxane and hydroxyl-terminated trifluoropropyl methyl siloxane as base rubber, greatly improves the oil resistance and solvent resistance of rubber due to the oil-resistant group trifluoropropyl, and has better compatibility without adding other compatibilizers because the main chain structures of the hydroxyl-terminated polydimethylsiloxane and the hydroxyl-terminated trifluoropropyl methyl siloxane are the same and only the side chains are different.
2. The sealant prepared by the method has outstanding oil resistance, the oil resistance of the sealant is measured according to the GB/T1690-2006 standard, the mass change rate of the sealant is not higher than 10%, and the sealant can effectively meet the requirements of the current automobile industry on the sealant.
3. The method has the advantages of simple and convenient process, small quantity of raw materials, easy achievement of condition requirements, capability of overcoming the defects of common organosilicon sealants, expansion of the application range and good application prospect.
The specific implementation mode is as follows:
the present invention is further illustrated by, but not limited to, the following examples.
The raw materials used in the examples are all conventional commercial products unless otherwise specified.
Example 1
The preparation method of the oil-resistant deoximation type fluorine-containing organosilicon sealant comprises the following steps:
(1) putting 66 parts by weight of hydroxyl-terminated polydimethylsiloxane raw material into a kneader, adding 25 parts by weight of hydroxyl-terminated polytrifluoropropylmethylsiloxane at the rotating speed of 50 revolutions per minute, and vacuumizing to 1 × 10-3～1×10-4Pa, stirring and mixing for 40 minutes to obtain a pretreatment raw material A;
(2) under the stirring condition, 12 parts by weight of hydrophobic modified surface with hexamethyldisilazane and with specific surface area of 80-250 m2Adding the fumed silica/g into the pretreatment raw material A five times, and stirring at the speed of 60 revolutions per minute for 3.5 hours to obtain a mixture B;
(3) at 1 × 10-3～1×10-4Under the Pa vacuum condition, the temperature is increased to 110 ℃, the mixture is continuously stirred for 30 minutes and cooled to the room temperature, and a mixture C is obtained;
(4) at 1 × 10-3～1×10-4Adding 5 parts of cross-linking agent under Pa vacuum, stirring for 0.5 hour at the speed of 40 revolutions per minute, adding 3 parts of catalyst, and continuing stirring for 35 minutes;
the cross-linking agent is a combination of methyl tributyrinoxime silane and phenyl tributyrinoxime silane in a mass ratio of 1:1.5, and the catalyst is a titanium complex (D-60);
(5) and (4) curing and forming the material treated in the step (4) to obtain the deoximation type oil-resistant fluorosilicone sealant.
Example 2
The preparation method of the oil-resistant deoximation type fluorine-containing organosilicon sealant comprises the following steps:
(1) 72 parts by weight of hydroxyl-terminated polydimethylsiloxane raw material is put into a kneader, 19 parts by weight of hydroxyl-terminated polytrifluoropropylmethylsiloxane is added at the rotating speed of 50 revolutions per minute, and the mixture is vacuumized to 1 × 10-3～1×10-4Pa, stirring and mixing for 35 minutes to obtain a pretreatment raw material A;
(2) under the stirring condition, 10 parts by weight of hydrophobic modified surface with hexamethyldisilazane and with specific surface area of 80-250 m2Adding the fumed silica/g into the pretreatment raw material A five times, and stirring at the speed of 65 revolutions per minute for 3.5 hours to obtain a mixture B;
(3) at 1 × 10-3～1×10-4Under the Pa vacuum condition, the temperature is increased to 110 ℃, stirring is continued for 35 minutes, and after cooling to the room temperature, a mixture C is obtained;
(4) at 1 × 10-3～1×10-4Adding 5 parts of cross-linking agent under the Pa vacuum condition, stirring for 1 hour at the speed of 40 revolutions per minute, adding 2 parts of catalyst, and continuing stirring for 40 minutes;
the cross-linking agent is a combination of methyl tributyrinoxime silane and phenyl tributyrinoxime silane in a mass ratio of 1.2:1.4, and the catalyst is a titanium complex (D-60);
(5) and (4) curing and forming the material treated in the step (4) to obtain the deoximation type oil-resistant fluorosilicone sealant.
Example 3
The preparation method of the oil-resistant deoximation type fluorine-containing organosilicon sealant comprises the following steps:
(1) putting 78 parts by weight of hydroxyl-terminated polydimethylsiloxane raw material into a kneader, adding 13 parts by weight of hydroxyl-terminated polytrifluoropropylmethylsiloxane at the rotating speed of 55 revolutions per minute, and vacuumizing to 1 × 10-3～1×10-4Pa, stirring and mixing for 40 minutes to obtain a pretreatment raw material A;
(2) under the stirring condition, 8 parts by weight of hydrophobic modified surface with hexamethyldisilazane and with specific surface area of 80-250 m2Adding the fumed silica/g into the pretreatment raw material A five times, and stirring at the speed of 65 revolutions per minute for 3 hours to obtain a mixture B;
(3) at 1 × 10-3～1×10-4Under the Pa vacuum condition, the temperature is increased to 120 ℃, the mixture is continuously stirred for 50 minutes and cooled to the room temperature, and a mixture C is obtained;
(4) at 1 × 10-3～1×10-4Adding 4.5 parts of cross-linking agent under Pa vacuum condition, stirring for 0.5 hour at the speed of 50 revolutions per minute, adding 2.5 parts of catalyst, and continuing stirring for 40 minutes;
the cross-linking agent is a combination of methyl tributyrinoxime silane and phenyl tributyrinoxime silane in a mass ratio of 1.1:1.7, and the catalyst is a titanium complex (D-60).
(5) And (4) curing and forming the material treated in the step (4) to obtain the deoximation type oil-resistant fluorosilicone sealant.
Example 4
The preparation method of the oil-resistant deoximation type fluorine-containing organosilicon sealant comprises the following steps:
(1) 80 parts by weight of hydroxyl-terminated polydimethylsiloxane raw material is put into a kneader, 20 parts by weight of hydroxyl-terminated polytrifluoropropylmethylsiloxane is added at the rotating speed of 55 revolutions per minute, and the mixture is vacuumized to 1 × 10-3～1×10-4Pa, stirring and mixing for 35 minutes to obtain a pretreatment raw material A;
(2) under the stirring condition, 6 parts by weight of hydrophobic modified surface with hexamethyldisilazane and with specific surface area of 80-250 m2Adding the fumed silica/g into the pretreatment raw material A five times, and stirring at the speed of 60 revolutions per minute for 3.5 hours to obtain a mixture B;
(3) at 1 × 10-3～1×10-4Under the Pa vacuum condition, the temperature is raised to 110 ℃, stirring is continued for 60 minutes, and after cooling to the room temperature, a mixture C is obtained;
(4) at 1 × 10-3～1×10-4Adding 5.5 parts of cross-linking agent under Pa vacuum condition, stirring for 0.7 hour at the speed of 40 revolutions per minute, adding 3.5 parts of catalyst, and continuing stirring for 40 minutes;
the cross-linking agent is a combination of methyl tributyrinoxime silane and phenyl tributyrinoxime silane in a mass ratio of 1:1.5, and the catalyst is a titanium complex (D-60);
(5) and (4) curing and forming the material treated in the step (4) to obtain the deoximation type oil-resistant fluorosilicone sealant.
Comparative example
The preparation method of the deoximation type room temperature vulcanized silicone rubber sealant comprises the following steps:
(1) 100 parts by weight of hydroxyl-terminated polydimethylsiloxane raw material is put into a container and is vacuumized to 1 × 10 under the rotating speed of 50 r/min-3～1×10-4Pa, stirring for 30 minutes to obtain a pretreatment raw material A;
(2) under the stirring condition, 10 parts by weight of hydrophobic modified surface with hexamethyldisilazane and with specific surface area of 80-250 m2Adding the fumed silica/g into the pretreatment raw material A five times, and stirring at the speed of 60 revolutions per minute for 3.5 hours to obtain a mixture B;
(3) at 1 × 10-3～1×10-4Under the Pa vacuum condition, the temperature is raised to 110 ℃, stirring is continued for 60 minutes, and after cooling to the room temperature, a mixture C is obtained;
(4) at 1 × 10-3～1×10-4Adding 5 parts of cross-linking agent under Pa vacuum, stirring for 1 hour at the speed of 40 revolutions per minute, adding 3 parts of catalyst, and continuing stirring for 40 minutes;
the cross-linking agent is a combination of methyl tributyrinoxime silane and phenyl tributyrinoxime silane in a mass ratio of 1:1.5, and the catalyst is a titanium complex (D-60);
(5) and placing the treated material into a mold for curing and molding.
Test examples
The sealants obtained in examples 1 to 4 and comparative example were tested for their properties, and the results are shown in Table 1.
TABLE 1 physical Properties of the Silicone rubber vulcanizates
As can be seen from Table 1, the vulcanized silicone rubber prepared by the invention has small change range of each index, and even in ASTM3# oil, the mass change rate is still within 10%, and the oil resistance is better.
Claims (6)
1. The oxime-removing type oil-resistant fluorosilicone sealant is characterized by comprising the following raw materials in parts by mass:
60-80 parts of hydroxyl-terminated polydimethylsiloxane, 10-25 parts of hydroxyl-terminated polytrifluoropropylmethylsiloxane, 5-15 parts of white carbon black, 4-6 parts of cross-linking agent and 2-5 parts of catalyst;
the hydroxyl-terminated polydimethylsiloxane is prepared from the hydroxyl-terminated polydimethylsiloxane with the viscosity of 2,000-4,000 cp and the viscosity of 10,000-20,000 cp according to the mass ratio of (3-5): (0.5-1.5);
the hydroxyl-terminated polytrifluoropropylmethylsiloxane is perfluoropolysiloxane with the viscosity ranging from 5,000 to 10,000 cp;
the cross-linking agent is a combination of methyl tributyrinoxime silane and phenyl tributyrinoxime silane according to the mass ratio of (1-1.5) to (1.5-2);
the catalyst is a titanium complex D-60, and the molecular formula is as follows:
2. the deoximation type oil resistant fluorosilicone sealant according to claim 1, wherein said white carbon black is hexamethyldisilazane and octamethylcyclotetrasiloxane D4Or dimethyl dichlorosilane modified, and the specific surface area is 80-250 m2Fumed silica/g.
3. A method for preparing the deoximation type oil resistant fluorosilicone sealant according to any one of claims 1 to 2, comprising the steps of:
(1) adding hydroxyl-terminated polytrifluoropropylmethylsiloxane into hydroxyl-terminated polydimethylsiloxane at the rotating speed of 25-90 r/min, and vacuumizing to 1 × 10-3～1×10-4Pa, stirring and mixing for 20-40 minutes to obtain a pretreatment raw material A;
(2) under the stirring condition, adding the white carbon black into the pretreatment raw material A for multiple times, and stirring for 2-3.5 hours at the speed of 25-90 revolutions per minute to obtain a mixture B;
(3) under the vacuum condition, the temperature is increased to 100-120 ℃, the stirring is continued for 30-60 minutes, after the mixture is cooled to the room temperature,
obtaining a mixture C;
(4) adding a cross-linking agent into the mixture C under a vacuum condition, stirring for 0.5-1 hour at a speed of 25-90 rpm, adding a catalyst, and continuously stirring for 20-40 minutes;
(5) and (4) curing and forming the material treated in the step (4) to obtain the deoximation type oil-resistant fluorosilicone sealant.
4. The preparation method according to claim 3, wherein the white carbon black is added in the step (2) in a multiple feeding manner, and the adding time is 5-10 times.
5. The method as claimed in claim 3, wherein the temperature in step (3) is controlled at 120 ℃ and stirred for 30-60 minutes, and the stirring is continued after cooling to room temperature.
6. The method according to claim 3, wherein the degree of vacuum in the vacuum condition in steps (3) and (4) is 1 × 10-3～1×10-4Pa。
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| PCT/CN2017/104312 WO2019010834A1 (en) | 2017-07-12 | 2017-09-29 | Deoximated, oil-resistant, and fluorine-containing organosilicone sealant and preparation method therefor |
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| CN107189753B (en) * | 2017-07-12 | 2020-08-14 | 山东大学 | Deoximation type oil-resistant fluorosilicone sealant and preparation method thereof |
| CN107513366A (en) * | 2017-09-11 | 2017-12-26 | 江苏天辰新材料股份有限公司 | A kind of oil resistant fluid sealant and preparation method thereof |
| CN109852239A (en) * | 2017-11-30 | 2019-06-07 | 深圳市冠恒新材料科技有限公司 | Fluorosilicone rubber composition, preparation method and the sealant and coating prepared by the composition |
| CN110144192B (en) * | 2018-03-13 | 2021-02-26 | 苏州大学 | Preparation method of organic silicon pressure-sensitive adhesive |
| CN109777347A (en) * | 2018-12-29 | 2019-05-21 | 山东华夏神舟新材料有限公司 | Double component room temperature vulcanization fluorine silicone sealant and preparation method thereof |
| CN113372812B (en) * | 2021-06-18 | 2022-07-26 | 广州汇纳新材料科技有限公司 | Organic silicon elastic coating for building waterproofing and preparation method and application thereof |
| CN115806796A (en) * | 2021-12-29 | 2023-03-17 | 上海市塑料研究所有限公司 | Room-temperature vulcanized oil-resistant fireproof organic silicon adhesive and preparation method thereof |
| CN114989780B (en) * | 2022-07-18 | 2023-03-21 | 广东高士高科实业有限公司 | Oil-resistant silicone sealant and preparation method and application thereof |
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| CN104232011A (en) * | 2014-09-28 | 2014-12-24 | 浙江时间新材料有限公司 | Neutral transparent silicone weather-resistant sealing adhesive for building |
| CN106433455A (en) * | 2016-09-15 | 2017-02-22 | 武汉中新化工有限公司 | Low-surface-energy coating and preparation method thereof |
| CN106675502A (en) * | 2016-12-13 | 2017-05-17 | 厦门三维丝环保股份有限公司 | High-temperature-resistant and low-expansion adhesive sealant for filter cartridge |
| CN107189753B (en) * | 2017-07-12 | 2020-08-14 | 山东大学 | Deoximation type oil-resistant fluorosilicone sealant and preparation method thereof |
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| CN107189753A (en) | 2017-09-22 |
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