WO2019010834A1 - 一种脱肟型耐油含氟有机硅密封胶及其制备方法 - Google Patents

一种脱肟型耐油含氟有机硅密封胶及其制备方法 Download PDF

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WO2019010834A1
WO2019010834A1 PCT/CN2017/104312 CN2017104312W WO2019010834A1 WO 2019010834 A1 WO2019010834 A1 WO 2019010834A1 CN 2017104312 W CN2017104312 W CN 2017104312W WO 2019010834 A1 WO2019010834 A1 WO 2019010834A1
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oil
sealant
parts
resistant
stirring
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PCT/CN2017/104312
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French (fr)
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刘少杰
陆文卿
陆玮洁
提雅嵋
孙安邦
姜红蕊
刘华飞
刘渊
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山东大学
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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
    • 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
    • C09J183/04—Polysiloxanes
    • C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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

Definitions

  • the invention relates to a deodorizing oil-resistant fluorine-containing silicone sealing glue and a preparation method thereof, and belongs to the field of fine chemical technology and functional material preparation.
  • One-component room temperature vulcanized silicone rubber has excellent resistance to high and low temperature, weather resistance, ozone resistance, chemical stability, etc. It also has the advantages of simple manufacture, convenient use, easy molding, convenient transportation, etc. in aviation, aerospace, medical, construction. , electronics and other aspects have been widely used.
  • the room temperature vulcanized silicone rubber itself still has shortcomings in terms of mechanical strength, oil resistance, solvent resistance, etc., which limits the silicone rubber to industrial fields such as construction machinery maintenance, automobile, oil field and other solvents. Although it has a relatively good variety of non-polar solvents such as fluorosilicone rubber and nitrile-silicone rubber, it has a high production cost and technical requirements, so it cannot be used in a large area and can only be used on special parts. In practice, improved methyl silicone rubber is used.
  • General improvements include introducing polar groups, changing production formulations or processes, adding some oil-resistant additives or fillers, blending, etc., however, the steps to introduce polar groups are more complicated and the success rate is not high, if only the formulation is changed
  • the process or the addition of oil-resistant auxiliaries and fillers is not very effective, and may reduce the mechanical properties, so many people use blending methods to modify silicone rubber.
  • most blended materials have poor compatibility with silicone rubber. Therefore, it is very important to study the suitable blending of oil-resistant materials to improve the oil resistance of general silicone rubber.
  • Chinese patent document CN103436217A (Application No.: 201310405674.5) discloses a one-component dealcoholized oil-resistant silicone sealant and a preparation method thereof, the one-component dealcoholized oil-resistant silicone sealant comprises 50-100 parts of terminal methyl group Dimethicone polydimethylsiloxane, 50-100 parts calcium carbonate, 5-15 parts fumed silica, 5-10 parts silicone oil plasticizer, 5-15 parts crosslinker, 0.5- 7.5 parts of coupling agent, 0.1-5 parts of catalyst.
  • the one-component dealcoholized oil-resistant silicone sealant comprises 50-100 parts of terminal methyl group Dimethicone polydimethylsiloxane, 50-100 parts calcium carbonate, 5-15 parts fumed silica, 5-10 parts silicone oil plasticizer, 5-15 parts crosslinker, 0.5- 7.5 parts of coupling agent, 0.1-5 parts of catalyst.
  • Blending refers to the uniform mixing of two or more polymer components to obtain a base rubber. Therefore, the method used in this patent is not modified by the blending method. It mainly uses modified calcium carbonate to improve the oil resistance of the sealant, so It is a method of adding an oil resistant auxiliaries. This method can not fundamentally improve the oil resistance. The results show that although the mechanical properties have improved, the rate of change of various indicators is still high, and oil resistance still has room for improvement.
  • Cipheral Patent Document CN 106833503A (Application No.: 201710058706.7) discloses a low modulus one-component deketoxime type room temperature vulcanization silicone sealant and a preparation method thereof, which are terminated by hydroxyl group polydimethylsiloxane Oxygenane, plasticizer, white mineral oil, fumed silica, reinforcing filler, aluminum stearate, pigment, crosslinking agent, vulcanization accelerator, silane coupling agent and catalyst.
  • the preparation method is as follows: 1) mixing the hydroxyl terminated polydimethylsiloxane, the plasticizer, the white mineral oil, the fumed silica, the reinforcing filler, the aluminum stearate and the pigment uniformly, and drying sufficiently to obtain a pre-preparation Mixing; 2) fully kneading the premixed vacuum to obtain a base rubber; 3) adding a crosslinking agent, a vulcanization accelerator and a silane coupling agent to the base rubber, and uniformly stirring under vacuum; 4) adding a catalyst to the base rubber; Stir well under vacuum, discharge, and seal.
  • This patent document is also not modified by the blending method.
  • the present invention provides a dislocation type oil-resistant fluorosilicone sealant and a preparation method thereof, which solve the problems of poor oil resistance and poor stability of the sealant.
  • a deodorizing oil-resistant fluorosilicone sealant comprising the following raw materials:
  • the hydroxyl terminated polydimethylsiloxane is a mixture of a terminal hydroxyl polydimethylsiloxane having a viscosity of 2,000 to 4,000 cp and a viscosity of 10,000 to 20,000 cp; further preferably, the viscosity
  • the mass ratio of the terminal hydroxyl dimethyl siloxane of 2,000 to 4,000 cp to the viscosity of 10,000 to 20,000 cp is (3-5): (0.5 - 1.5).
  • the viscosity of the hydroxyl terminated polydimethylsiloxane is too high, the processing property of the sealant will be poor, and if the viscosity is too low, the mechanical properties are poor, and the mixing of the high and low viscosity is beneficial to improve the overall performance of the sealant.
  • the hydroxy-terminated polytrifluoropropylmethylsiloxane is a perfluoropolysiloxane having a viscosity in the range of from 5,000 to 10,000 cp. If the viscosity is too low, the raw material synthesis process is difficult to control, and the viscosity is too high. When blended with the hydroxyl terminated polydimethylsiloxane, the overall performance is deteriorated.
  • the white carbon black is a fumed silica whose surface is hydrophobically modified. Further preferably, the white carbon black is hexamethyldisilazane, octamethylcyclotetra A fumed silica (D4) or dimethyldichlorosilane-modified, fumed silica having a specific surface area of from 80 to 250 m 2 /g.
  • the modification method can be carried out according to the prior art.
  • the crosslinking agent is a depurinating crosslinking agent, and further preferably methyltributyrin mercaptosilane.
  • a depurinating crosslinking agent and further preferably methyltributyrin mercaptosilane.
  • phenyltributyl ketone silane more preferably methyl tributyl sulfonyl silane and phenyl tributol sulfonyl silane according to (1 ⁇ 1.5): (1.5 ⁇ 2) mass ratio combination;
  • a combination of mass ratio of methyltributyl ketone silane: phenyl tributol ketone silane 1:1.5.
  • the choice of the type of the crosslinking agent is beneficial to increase the number of polar groups of the sealant and improve the oil resistance.
  • the selection of the ratio of the ratio determines the degree of crosslinking of the raw materials, the ratio is not suitable, and some small molecules remain, which affects the oil resistance.
  • the catalyst is a titanium complex; further preferably D-60, the molecular formula is as follows:
  • the choice of the catalyst is particularly effective for the fluorosilicone rubber, so that the blended rubber can be vulcanized at room temperature without affecting the oil resistance.
  • the hydroxyl terminated polydimethylsiloxane and the hydroxyl terminated polytrifluoropropylmethylsiloxane are in a mass ratio (6-8): (1-2.5) combination, hydroxyl terminated
  • the ratio of polytrifluoropropylmethylsiloxane is too low, and the oil resistance is limited.
  • the excessive ratio will reduce the mechanical properties of the blended rubber.
  • the selection of this ratio can improve the comprehensive performance of the blended rubber.
  • the preparation method of the above-mentioned deodorized oil-resistant fluorosilicone sealant comprises the following steps:
  • the material processed in the step (4) is solidified and molded, that is, the disintegrated oil-resistant fluorosilicone sealant is obtained.
  • the white carbon black is added in multiple steps, and it is further preferred to add 5 to 10 times.
  • White carbon black is a commercially available product. It can avoid uneven dispersion and particle agglomeration, and can fully crosslink the white carbon black with the pretreated raw material A, and the internal three-dimensional network is more perfect.
  • the temperature control described in the step (3) is stirred at 100 to 120 ° C for 30 to 60 minutes, and after cooling to room temperature, stirring is continued. Increasing the temperature can completely remove the small molecules produced in step (2), otherwise it will affect the oil resistance of the sealant.
  • the vacuum conditions in the vacuum conditions in the steps (3) and (4) are from 1 ⁇ 10 -3 to 1 ⁇ 10 -4 Pa.
  • the oil-resistant dewaxing fluorosilicone sealant of the present invention uses a specific raw material, and a mixture of a hydroxyl group-terminated polydimethylsiloxane and a hydroxyl-terminated trifluoropropylmethylsiloxane is used as a base rubber. Due to the oil-resistant group trifluoropropyl group, the oil resistance and solvent resistance of the rubber are greatly improved, and the hydroxyl terminated polydimethylsiloxane has the same structure as the hydroxyl terminated trifluoropropylmethylsiloxane main chain, but only the side The chain is different, so the compatibility is good, no need to add other compatibilizers.
  • the sealant prepared by the method of the invention has outstanding oil resistance, and its oil resistance is determined according to the GB/T1690-2006 standard, and the quality change rate is not higher than 10%, which can effectively meet the requirements of the current automotive industry for the sealant.
  • the method of the invention has the advantages of simple process, small number of raw materials and easy requirement of condition, can overcome the shortcomings of general silicone sealant, expand its application range, and has good application prospect.
  • the preparation of the oil-resistant deodorized fluorine-containing silicone sealant is as follows:
  • the crosslinking agent is a combination of methyl tributyl sulfonyl silane and phenyl tributol sulfonyl silane having a mass ratio of 1:1.5, and the catalyst is a titanium complex (D-60);
  • the material processed in the step (4) is solidified and molded, that is, the disintegrated oil-resistant fluorosilicone sealant is obtained.
  • the preparation of the oil-resistant deodorized fluorine-containing silicone sealant is as follows:
  • the crosslinking agent is a combination of the methyl tributyl sulfonyl silane and the phenyl tributol sulfonyl silane having a mass ratio of 1.2: 1.4, and the catalyst is a titanium complex (D-60). ;
  • the material processed in the step (4) is solidified and molded, that is, the disintegrated oil-resistant fluorosilicone sealant is obtained.
  • the preparation of the oil-resistant deodorized fluorine-containing silicone sealant is as follows:
  • the crosslinking agent is a combination of the methyl tributyl sulfonyl silane and the phenyl tributol sulfonyl silane having a mass ratio of 1.1:1.7, and the catalyst is a titanium complex (D-60). .
  • the material processed in the step (4) is solidified and molded, that is, the disintegrated oil-resistant fluorosilicone sealant is obtained.
  • the preparation of the oil-resistant deodorized fluorine-containing silicone sealant is as follows:
  • the crosslinking agent is a combination of the methyl tributyl sulfonyl silane and the phenyl tributol sulfonyl silane having a mass ratio of 1:1.5, and the catalyst is a titanium complex (D-60). ;
  • the material processed in the step (4) is solidified and molded, that is, the disintegrated oil-resistant fluorosilicone sealant is obtained.
  • the crosslinking agent is a combination of the methyl tributyl sulfonyl silane and the phenyl tributol sulfonyl silane having a mass ratio of 1:1.5, and the catalyst is a titanium complex (D-60). ;
  • the processed material is placed in a mold to be solidified.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)

Abstract

本发明涉及一种脱肟型耐油含氟有机硅密封胶及其制备方法，该方法是以端羟基聚二甲基硅氧烷和羟基封端三氟丙基甲基硅氧烷为基胶，加入疏水改性的白炭黑，所得混合料进行真空干燥，加入甲基三丁酮肟基硅烷与苯基三丁酮肟基硅烷以1：1.5比例混合的交联剂、催化剂钛络合物，搅拌至充分混合，即得所需密封胶。该密封胶有良好耐油性，根据GB/T1690-2006标准测定其耐油性能，其质量变化率不高于10％，力学性能较好，可代替一般密封胶应用到工程机械制造维修及汽车行业，前景良好。

Description

一种脱肟型耐油含氟有机硅密封胶及其制备方法 技术领域
本发明涉及一种脱肟型耐油含氟有机硅密封胶及其制备方法，属于精细化工技术及功能材料制备领域。
背景技术
单组份室温硫化硅橡胶具有优良的耐高低温、耐候、耐臭氧、化学稳定性等优异性能，还具有制造简单、使用方便、容易成型、运输便利等优点，在航空、航天、医疗、建筑、电子等方面得到普遍应用。
在机械行业，尤其是工程机械、汽车工业中需要的密封剂、密封垫圈等必须具有良好的耐油及耐热性能。而室温硫化硅橡胶本身在机械强度、耐油性、耐溶剂性等方面还存在不足，这在一定程度上限制了硅橡胶在工程机械制造维修、汽车、油田等与溶剂接触较多的工业领域的使用，虽然出现了氟硅橡胶、丁腈硅橡胶等耐非极性溶剂比较良好的品种，但是由于生产成本和技术要求高，使其不能大面积使用，只能限制在特殊部件上使用，所以实际应用中都是采用改进的甲基硅橡胶。
一般的改进方法包括引入极性基团、改变生产配方或工艺、加入部分耐油助剂或填料、共混等，然而引入极性基团的步骤比较复杂，而且成功率不高，如果仅仅改变配方工艺或者加入耐油助剂和填料，效果不是很明显，而且可能会降低力学性能，所以很多人都采用共混的方法改性硅橡胶。但是，大多数共混材料与硅橡胶相容性差，因此，研究合适的共混耐油材料对提高一般硅橡胶的耐油性有着十分重要的意义。
中国专利文件CN103436217A(申请号：201310405674.5)公开了一种单组份脱醇型耐油硅酮密封胶及其制备方法，该单组份脱醇型耐油硅酮密封胶由50-100份末端甲基二甲氧基硅氧的聚二甲基硅氧烷，50-100份碳酸钙，5-15份气相白炭黑，5-10份硅油增塑剂、5-15份交联剂，0.5-7.5份偶联剂，0.1-5份催化剂组成。该专利文件所添加的原料中，基胶只有一种，即末端甲基二甲氧基硅氧的聚二甲基硅氧烷，其他原料都是制备硅橡胶所用的配合剤，因为硅橡胶的共混是指由两种或多种聚合物组分均匀混合得到基胶，所以该专利所用方式不属于共混方法进行改性，它主要是用改性碳酸钙来提高密封胶耐油性，所以属于加入耐油助剂的方法。这种方式不能从根本上改善耐油性，结果显示虽然力学性能有所提高，但是各项指标的变化率依然很高，耐油性依然有提升空间。
中国专利文件CN 106833503A(申请号：201710058706.7)公开了一种低模量单组分脱酮肟型室温硫化硅酮密封胶及其制备方法，该硅酮密封胶由羟基封端聚二甲基硅氧烷、增塑剂、白矿油、气相白炭黑、补强填料、硬脂酸铝、颜料、交联剂、硫化促进剂、硅烷偶联剂和催化剂制备而成。其制备方法如下：1)将羟基封端聚二甲基硅氧烷、增塑剂、白矿油、气相白炭黑、补强填料、硬脂酸铝和颜料混合均匀，充分干燥，得到预混料；2)将预混料真空充分捏合，得到基胶；3)在基胶中加入交联剂、硫化促进剂和硅烷偶联剂，真空搅拌均匀；4)在基胶中加入催化剂，真空搅拌均匀，出料，灌装密封。该专利文件同样不属于共混方法进行改性，其主要采用自制烷氧基丁酮肟基硅烷作为硫化促进剂来提高密封胶的性能，虽然断裂伸长率与粘结性能得到提高，但是耐油效果并没有明显改善。
发明内容
针对现有技术的不足，本发明提供一种脱肟型耐油含氟有机硅密封胶及其制备方法，来解决目前密封胶耐油性差、稳定性不好等问题。
本发明技术方案如下：
一种脱肟型耐油氟硅密封胶，包括如下质量份的原料组成：
端羟基聚二甲基硅氧烷60～80份、羟基封端聚三氟丙基甲基硅氧烷10～25份、白炭黑5～15份、交联剂4～6份和催化剂2～5份。
根据本发明优选的，所述的端羟基聚二甲基硅氧烷是粘度为2,000～4,000cp与粘度为10,000～20,000cp的端羟基聚二甲基硅氧烷的混合物；进一步优选的，粘度为2,000～4,000cp与粘度为10,000～20,000cp的端羟基聚二甲基硅氧烷的质量比为(3-5)：(0.5-1.5)。端羟基聚二甲基硅氧烷粘度过高，会导致密封胶加工性能差，粘度过低，则力学性能较差，高低粘度混合搭配有利于提高密封胶的综合性能。
根据本发明优选的，所述的羟基封端聚三氟丙基甲基硅氧烷为粘度范围是5,000～10,000cp的全氟聚硅氧烷。粘度过低，原料合成过程控制较难，粘度过高，与端羟基聚二甲基硅氧烷共混后，综合性能变差。
根据本发明优选的，所述的白炭黑为表面经过疏水改性的气相法白炭黑，进一步优选的，所述的白炭黑是经过六甲基二硅氮烷、八甲基环四硅氧烷(D4)或二甲基二氯硅烷改性的，比表面积为80～250m2/g的气相法白炭黑。改性方式按现有技术即可。
根据本发明优选的，所述的交联剂为脱肟型交联剂，进一步优选为甲基三丁酮肟基硅烷 或/和苯基三丁酮肟基硅烷，更优选为甲基三丁酮肟基硅烷和苯基三丁酮肟基硅烷按(1～1.5):(1.5～2)质量比的组合；最优选为，甲基三丁酮肟基硅烷：苯基三丁酮肟基硅烷＝1:1.5的质量比组合。该交联剂的种类选择有利于增加密封胶的极性基团数量，提高耐油性，配比关系的选择决定原料的交联程度，配比不合适，会残留一些小分子，影响耐油性。
根据本发明优选的，所述的催化剂为钛络合物；进一步优选D-60，分子式如下：
Figure PCTCN2017104312-appb-000001
该催化剂的选择对氟硅橡胶作用尤为明显，使共混胶可以在室温硫化，而不影响耐油性。
根据本发明，所述的端羟基聚二甲基硅氧烷与羟基封端聚三氟丙基甲基硅氧烷为质量比(6-8)：(1-2.5)的组合，羟基封端聚三氟丙基甲基硅氧烷比例过低，耐油性提高有限，比例过高会降低共混胶的力学性能，该比例的选择能使共混胶综合性能提高。
根据本发明，上述脱肟型耐油氟硅密封胶的制备方法，包括步骤如下：
(1)在25～90转/分钟的转速下，向端羟基聚二甲基硅氧烷中加入羟基封端聚三氟丙基甲基硅氧烷，抽真空至1×10-3～1×10-4Pa，搅拌混合20～40分钟，得预处理原料A；
(2)在搅拌条件下，将白炭黑分多次加入到预处理原料A中，以25～90转/分钟的速度搅拌2～3.5小时，得混合料B；
(3)在真空条件下，将温度升至100～120℃，继续搅拌30～60分钟，冷却至室温后，得混合料C；
(4)在真空条件下，向混合料C中加入交联剂，保持25～90转/分钟的速度搅拌0.5～1小时，再加入催化剂，继续搅拌20～40分钟；
(5)将步骤(4)处理好的物料固化成型，即得脱肟型耐油氟硅密封胶。
根据本发明制备方法优选的，步骤(2)中白炭黑多次投料方式加入，进一步优选加入次数为5～10次。白炭黑为现有市售商品，多次加入可以避免分散不均，粒子团聚的现象，还能使白炭黑与预处理原料A充分交联，内部三维网络更加完善。
根据本发明制备方法，步骤(3)中所述的温度控制在100-120℃之间搅拌30～60分钟，冷却至室温后继续搅拌。升高温度可以将步骤(2)中产生的小分子充分去除，否则会影响密封胶耐油性能。
根据本发明制备方法优选的，步骤(3)和(4)中真空条件的真空度为1×10-3～1×10-4Pa。
本发明的特点和优良效果如下：
1、本发明的耐油性的脱肟型含氟有机硅密封胶采用特定的原料，将端羟基聚二甲基硅氧烷与羟基封端三氟丙基甲基硅氧烷混合物为基胶，由于含有耐油基团三氟丙基，大大提高橡胶的耐油、耐溶剂性能，而且端羟基聚二甲基硅氧烷与羟基封端三氟丙基甲基硅氧烷主链结构相同，只是侧链不同，所以相容性较好，不需要添加其他增容剂。
2、用本发明方法制备的密封胶，有突出耐油性，根据GB/T1690-2006标准测定其耐油性能，其质量变化率不高于10％，能有效满足目前汽车行业对密封胶的要求。
3、本发明所述方法，工艺简便，原材料数量少，条件要求容易达到，能克服一般有机硅密封胶的缺点，扩大其应用范围，应用前景好。
具体实施方式:
下面结合实施例对本发明做进一步说明，但不限于此。
实施例中所用原料如无特殊说明，均为常规市购产品。
实施例1
耐油性脱肟型含氟有机硅密封胶的制备，步骤如下：
(1)将66重量份的端羟基聚二甲基硅氧烷原料放入捏合机中，在50转/分钟的转速下，加入25重量份的羟基封端聚三氟丙基甲基硅氧烷，抽真空至1×10-3～1×10-4Pa，搅拌混合40分钟，得预处理原料A；
(2)在搅拌条件下，将12重量份的表面经过六甲基二硅氮烷疏水改性的、比表面积为80～250m2/g气相法白炭黑分五次加入到预处理原料A中，以60转/分钟的速度搅拌3.5小时，得混合料B；
(3)在1×10-3～1×10-4Pa真空条件下，将温度升至110℃，继续搅拌30分钟，冷却至室温后，得混合料C；
(4)在1×10-3～1×10-4Pa真空条件下加入5份交联剂，保持40转/分钟的速度搅拌0.5小时，加入3份催化剂，继续搅拌35分钟；
所述的交联剂为甲基三丁酮肟基硅烷与苯基三丁酮肟基硅烷质量比为1:1.5的组合，催化剂为钛络合物(D-60)；
(5)将步骤(4)处理好的物料固化成型，即得脱肟型耐油氟硅密封胶。
实施例2
耐油性脱肟型含氟有机硅密封胶的制备，步骤如下：
(1)将72重量份的端羟基聚二甲基硅氧烷原料放入捏合机中，在50转/分钟的转速下，加入19重量份的羟基封端聚三氟丙基甲基硅氧烷，抽真空至1×10-3～1×10-4Pa，搅拌混合35分钟，得预处理原料A；
(2)在搅拌条件下，将10重量份的表面经过六甲基二硅氮烷疏水改性的、比表面积为80～250m2/g气相法白炭黑分五次加入到预处理原料A中，以65转/分钟的速度搅拌3.5小时，得混合料B；
(3)在1×10-3～1×10-4Pa真空条件下，将温度升至110℃，继续搅拌35分钟，冷却至室温后，得混合料C；
(4)在1×10-3～1×10-4Pa真空条件下加入5份交联剂，保持40转/分钟的速度搅拌1小时，加入2份催化剂，继续搅拌40分钟；
所述交联剂为所述的交联剂为甲基三丁酮肟基硅烷与苯基三丁酮肟基硅烷质量比为1.2:1.4的组合，催化剂为钛络合物(D-60)；
(5)将步骤(4)处理好的物料固化成型，即得脱肟型耐油氟硅密封胶。
实施例3
耐油性脱肟型含氟有机硅密封胶的制备，步骤如下：
(1)将78重量份的端羟基聚二甲基硅氧烷原料放入捏合机中，在55转/分钟的转速下，加入13重量份的羟基封端聚三氟丙基甲基硅氧烷，抽真空至1×10-3～1×10-4Pa，搅拌混合40分钟，得预处理原料A；
(2)在搅拌条件下，将8重量份的表面经过六甲基二硅氮烷疏水改性的、比表面积为80～250m2/g气相法白炭黑分五次加入到预处理原料A中，以65转/分钟的速度搅拌3小时，得混合料B；
(3)在1×10-3～1×10-4Pa真空条件下，将温度升至120℃，继续搅拌50分钟，冷却至室温后，得混合料C；
(4)在1×10-3～1×10-4Pa真空条件下加入4.5份交联剂，保持50转/分钟的速度搅拌0.5小时，加入2.5份催化剂，继续搅拌40分钟；
所述交联剂为所述的交联剂为甲基三丁酮肟基硅烷与苯基三丁酮肟基硅烷质量比为1.1:1.7的组合，催化剂为钛络合物(D-60)。
(5)将步骤(4)处理好的物料固化成型，即得脱肟型耐油氟硅密封胶。
实施例4
耐油性脱肟型含氟有机硅密封胶的制备，步骤如下：
(1)将80重量份的端羟基聚二甲基硅氧烷原料放入捏合机中，在55转/分钟的转速下，加入20重量份的羟基封端聚三氟丙基甲基硅氧烷，抽真空至1×10-3～1×10-4Pa，搅拌混合35分钟，得预处理原料A；
(2)在搅拌条件下，将6重量份的表面经过六甲基二硅氮烷疏水改性的、比表面积为80～250m2/g气相法白炭黑分五次加入到预处理原料A中，以60转/分钟的速度搅拌3.5小时，得混合料B；
(3)在1×10-3～1×10-4Pa真空条件下，将温度升至110℃，继续搅拌60分钟，冷却至室温后，得混合料C；
(4)在1×10-3～1×10-4Pa真空条件下加入5.5份交联剂，保持40转/分钟的速度搅拌0.7小时，加入3.5份催化剂，继续搅拌40分钟；
所述交联剂为所述的交联剂为甲基三丁酮肟基硅烷与苯基三丁酮肟基硅烷质量比为1:1.5的组合，催化剂为钛络合物(D-60)；
(5)将步骤(4)处理好的物料固化成型，即得脱肟型耐油氟硅密封胶。
对比例
一种脱肟型室温硫化硅橡胶密封胶的制备，步骤如下：
(1)将100重量份的端羟基聚二甲基硅氧烷原料放入容器中，在50转/分钟的转速下，抽真空至1×10-3～1×10-4Pa，搅拌30分钟，得预处理原料A；
(2)在搅拌条件下，将10重量份的表面经过六甲基二硅氮烷疏水改性的、比表面积为80～250m2/g气相法白炭黑分五次加入到预处理原料A中，以60转/分钟的速度搅拌3.5小时，得混合料B；
(3)在1×10-3～1×10-4Pa真空条件下，将温度升至110℃，继续搅拌60分钟，冷却至室温后，得混合料C；
(4)在1×10-3～1×10-4Pa真空条件下加入5份交联剂，保持40转/分钟的速度搅拌1小时，加入3份催化剂，继续搅拌40分钟；
所述交联剂为所述的交联剂为甲基三丁酮肟基硅烷与苯基三丁酮肟基硅烷质量比为1:1.5的组合，催化剂为钛络合物(D-60)；
(5)将处理好的料放到模具中固化成型。
试验例
测试实施例1-4和对比例得到的密封胶的性能，结果如表1所示。
表1硅橡胶硫化胶的物理性能
Figure PCTCN2017104312-appb-000002
由表1可知，本发明制得的硫化硅橡胶各项指标的变化幅度都不大，即使在ASTM3#油中，质量变化率仍然在10％以内，耐油性能较好。

Claims (10)

  1. 一种脱肟型耐油含氟有机硅密封胶，其特征在于，该密封胶包括如下质量份的原料组成：
    端羟基聚二甲基硅氧烷60～80份、羟基封端聚三氟丙基甲基硅氧烷10～25份、白炭黑5～15份、交联剂4～6份和催化剂2～5份。
  2. 根据权利要求1所述的脱肟型耐油氟硅密封胶，其特征在于，所述的端羟基聚二甲基硅氧烷是粘度为2,000～4,000cp与粘度为10,000～20,000cp的端羟基聚二甲基硅氧烷的混合物；
    优选的，粘度为2,000～4,000cp与粘度为10,000～20,000cp的端羟基聚二甲基硅氧烷的质量比为(3-5)：(0.5-1.5)。
  3. 根据权利要求1所述的脱肟型耐油氟硅密封胶，其特征在于，所述的羟基封端聚三氟丙基甲基硅氧烷为粘度范围是5,000～10,000cp的全氟聚硅氧烷。
  4. 根据权利要求1所述的脱肟型耐油氟硅密封胶，其特征在于，所述的白炭黑为表面经过疏水改性的气相法白炭黑；
    优选的，所述的白炭黑是经过六甲基二硅氮烷、八甲基环四硅氧烷(D4)或二甲基二氯硅烷改性的，比表面积为80～250m2/g的气相法白炭黑。
  5. 根据权利要求1所述的脱肟型耐油氟硅密封胶，其特征在于，所述的交联剂为脱肟型交联剂；
    优选为甲基三丁酮肟基硅烷或/和苯基三丁酮肟基硅烷，更优选为甲基三丁酮肟基硅烷和苯基三丁酮肟基硅烷按(1～1.5):(1.5～2)质量比的组合。
  6. 根据权利要求1所述的脱肟型耐油氟硅密封胶，其特征在于，所述的催化剂为钛络合物D-60，分子式如下：
    Figure PCTCN2017104312-appb-100001
  7. 一种权利要求1-6任一项所述的脱肟型耐油氟硅密封胶的制备方法，包括步骤如下：
    (1)在25～90转/分钟的转速下，向端羟基聚二甲基硅氧烷中加入羟基封端聚三氟丙基甲基硅氧烷，抽真空至1×10-3～1×10-4Pa，搅拌混合20～40分钟，得预处理原料A；
    (2)在搅拌条件下，将白炭黑分多次加入到预处理原料A中，以25～90转/分钟的速度搅拌2～3.5小时，得混合料B；
    (3)在真空条件下，将温度升至100～120℃，继续搅拌30～60分钟，冷却至室温后，得混合料C；
    (4)在真空条件下，向混合料C中加入交联剂，保持25～90转/分钟的速度搅拌0.5～1小时，再加入催化剂，继续搅拌20～40分钟；
    (5)将步骤(4)处理好的物料固化成型，即得脱肟型耐油氟硅密封胶。
  8. 根据权利要求7所述的制备方法，其特征在于，步骤(2)中白炭黑多次投料方式加入，加入次数为5～10次。
  9. 根据权利要求7所述的制备方法，其特征在于，步骤(3)中所述的温度控制在100-120℃之间搅拌30～60分钟，冷却至室温后继续搅拌。
  10. 根据权利要求7所述的制备方法，其特征在于，步骤(3)和(4)中真空条件的真空度为1×10-3～1×10-4Pa。
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