WO2018036431A1 - 改性纳米复合硅胶密封圈及其制备 - Google Patents

改性纳米复合硅胶密封圈及其制备 Download PDF

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WO2018036431A1
WO2018036431A1 PCT/CN2017/098074 CN2017098074W WO2018036431A1 WO 2018036431 A1 WO2018036431 A1 WO 2018036431A1 CN 2017098074 W CN2017098074 W CN 2017098074W WO 2018036431 A1 WO2018036431 A1 WO 2018036431A1
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modified
parts
graphene
sealing ring
raw rubber
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段曦东
李晓丰
毛志浩
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广东纳路纳米科技有限公司
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    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • 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
    • C08K7/00—Use of ingredients characterised by shape
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    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C08K2201/011—Nanostructured additives
    • 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
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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 the technical field of sealing rings, in particular to a modified nano composite silicone sealing ring and a preparation thereof.
  • the silicone sealing ring As a key connector between the sealing member and the component, the silicone sealing ring is widely used in aerospace, medical, automotive, household appliances and the like because of its excellent heat resistance, low temperature elasticity and oxidation resistance.
  • the silicone sealing ring itself has high water vapor and gas permeability, which makes the sealing performance lower, and decays aging over time during use, silicone rubber Gradually losing the elasticity, the mechanical properties of the silicone sealing ring are reduced, and the reduction of the airtightness is further amplified, resulting in undesirable phenomena such as air leakage, water leakage, oil leakage, etc., which affects its application as a sealing material.
  • the present invention adopts the following technical solutions:
  • the modified nano composite silicone sealing ring of the invention comprises: a raw rubber mixing compound and a vulcanizing agent in a weight ratio of 100: 0.5-10;
  • the raw rubber compounding compound comprises: 70-100 parts of methyl vinyl silicone rubber, 1-20 parts of plasticizer, 0.01-10 parts of modified nano additive, 10 to 50 parts of reinforcing filler, 0.5 to 5 parts of coupling agent;
  • the modified nano additive is one of modified white graphene, modified graphene, and graphene oxide.
  • the raw rubber compounding compound comprises: 80-100 parts of methyl vinyl silicone rubber, 1-15 parts of plasticizer, 0.05-5 parts of nano-modifying additive, 15-40 parts by weight. Reinforcing filler, 0.5 ⁇ 3 parts coupling agent.
  • the methyl vinyl silicone rubber has a vinyl mole percentage of 0.12%, 0.25% or 0.56%.
  • the methyl vinyl silicone rubber has a vinyl mole percentage of 0.25% in consideration of the plasticity and mechanical properties of the raw rubber.
  • the modified white graphene is treated with 5 to 10 layers of white graphene via a long-chain Lewis base, a long-chain Lewis acid, a sulfonate, a quaternary amine or a nonionic surfactant to increase white graphite.
  • the affinity of the alkene to the substrate; the modified white graphene is 5 to 10 layers of graphene treated with polyvinylpyrrolidone (PVP) or sodium dodecylbenzenesulfonate (SDBS) surfactant to increase the graphene pair The affinity of the matrix.
  • PVP polyvinylpyrrolidone
  • SDBS sodium dodecylbenzenesulfonate
  • the long-chain Lewis base is oleylamine or the like; the long-chain Lewis acid is long-chain borane or the like; the sulfonate is sodium dodecylbenzenesulfonate or the like; and the quaternary amine is bromine
  • the cetylpyridine or the like; the nonionic surfactant is a polyethylene oxide alkyl alcohol amide or the like.
  • the plasticizer is selected from the group consisting of dimethicone, hydroxypolydimethylsiloxane, and vinyltrimethoxysilane;
  • the reinforcing filler is one of fumed silica, silicon micropowder, and carbon black;
  • the coupling agent is one of a silane coupling agent KH-550, a silane coupling agent KH-570, and n-butyl titanate;
  • the vulcanizing agent is one of benzoyl peroxide, di-tert-butyl peroxide, and dicumyl peroxide.
  • the preparation method of the modified nano composite silicone sealing ring of the invention comprises:
  • Step 2 Raw rubber mixing: According to the parts by weight, the methyl vinyl silicone rubber, the plasticizer, the coupling agent, the modified nano additive and the reinforcing filler are respectively mixed, and after being mixed for several times by the internal mixer, the double is used. Extrusion by a screw extruder to obtain a raw rubber compound;
  • Step 3) Vulcanization molding: Weigh the raw rubber compound and vulcanizing agent in step 2) according to the proportion, mix and disperse uniformly in the internal mixer, and then put it into the mold and vulcanize it by hot press molding to obtain modification. Nano composite silicone sealing ring.
  • the raw rubber mixing process in the step 2) is that the components are kneaded in an internal mixer at a temperature of 40 to 120 ° C for 5 to 60 minutes, and then subjected to a twin screw extruder at a temperature of 80. Extrusion at -250 ° C to obtain a raw rubber compound.
  • the control temperature is 100 to 250 ° C
  • the pressure is 1 to 20 Mpa
  • the vulcanization molding time is 10 to 90 min.
  • Silica gel seals exist in high temperature and harsh environments for a long time, and the side chain methyl groups are easily oxidized to form crosslinks, which leads to hardening of the materials; the use of surfactant-treated white graphene, graphene and oxidation of the surface containing more active groups Graphene can achieve good wettability with the matrix when added in a small amount, increase the toughness to enhance the effect, and improve the mechanical strength of the silicone sealing ring.
  • the invention selects a material obtained by modifying 5 to 10 layers of white graphene, graphene or graphene oxide nano powder, wherein the atomic layer can effectively isolate gas atom molecules, and the gas molecules only pass through the silicone rubber.
  • the modified white graphene, modified graphene, and modified graphene oxide atomic layer are less than ten layers, the layer arrangement Compact, uniform, and a large number of barrier sheets, the gas bypasses the silicone rubber, the path becomes longer, and a small amount of addition can well block the passage of gas, increasing the airtightness of the nanocomposite silicone sealing ring.
  • the invention improves the water vapor, gas permeability deterioration and mechanical property degradation caused by aging of the silicone sealing ring during long-term use, greatly prolongs the service life of the sealing material, and has high application value.
  • Step 1) Modification of the nano additive 5 to 10 layers of white graphene are selected by soaking for 12 hours with 0.1% aqueous oleylamine solution, and the modified white graphene additive is obtained by centrifugation and vacuum drying;
  • Step 2 Raw rubber mixing: 100 parts by weight of methyl vinyl silicone rubber having a molar percentage of 0.25%, 15 parts of hydroxyl terminated polydimethylsiloxane, and 3 parts of a silane coupling agent are weighed by weight. KH-570, 0.1 parts of modified white graphene additive prepared in step 1) and 30 parts of carbon black, which are sequentially added to an internal mixer for kneading, the mixing temperature is 90 ° C, the mixing time is 50 min; The extruder is extruded at a temperature of 120 ° C to obtain a raw rubber compound;
  • Step 3) vulcanization molding: 100 parts by weight of the raw rubber mixing compound obtained in the step 2) and 3 parts of di-tert-butyl peroxide are respectively weighed, mixed and dispersed at room temperature by an internal mixer, and then placed in a special system.
  • the modified nanocomposite silicone sealing ring was obtained by hot pressing vulcanization in a mold at a temperature of 150 ° C, a pressure of 18 MPa, and a time of 40 min.
  • Step 1) Modification of the nano additive 5 to 10 layers of white graphene are selected by soaking for 12 hours with 0.1% aqueous oleylamine solution, and the modified white graphene additive is obtained by centrifugation and vacuum drying;
  • Step 2 Raw rubber mixing: 100 parts by weight of methyl vinyl silicone rubber having a molar percentage of 0.25%, 8 parts of hydroxyl terminated polydimethylsiloxane, and 1 part of a silane coupling agent are weighed in parts by weight. KH-570, 0.5 parts of modified white graphene additive prepared in step 1) and 20 parts of carbon black, which are sequentially added to an internal mixer for kneading, the mixing temperature is 60 ° C, the mixing time is 20 min; The screw extruder is extruded at a temperature of 180 ° C to obtain a raw rubber compound;
  • Step 3) vulcanization molding: 100 parts by weight of the raw rubber mixing compound obtained in the step 2) and 1.5 parts of di-tert-butyl peroxide are respectively weighed, mixed and dispersed at room temperature by an internal mixer, and then placed in a special system.
  • the modified nanocomposite silicone sealing ring was obtained by hot pressing vulcanization in a mold at a temperature of 180 ° C, a pressure of 12 MPa, and a time of 20 min.
  • Step 1) modification of the nano additive using 5 to 10 layers of graphene dispersed in a concentration of 0.3 mg / ml polyvinylpyrrolidone aqueous solution for 10 hours, after centrifugation, vacuum drying to obtain a modified graphene additive;
  • Step 2 Raw rubber mixing: 100 parts by weight of methyl vinyl silicone rubber having a molar percentage of 0.25%, 15 parts of hydroxyl terminated polydimethylsiloxane, and 3 parts of a silane coupling agent are weighed by weight. KH-570, 0.1 parts of modified graphene additive prepared in step 1) and 30 parts of carbon black, which are sequentially added to an internal mixer for kneading, the mixing temperature is 90 ° C, the mixing time is 50 min; The machine is extruded at a temperature of 120 ° C to obtain a raw rubber compound;
  • Step 3) vulcanization molding: 100 parts by weight of the raw rubber mixing compound obtained in the step 2) and 3 parts of di-tert-butyl peroxide are respectively weighed, mixed and dispersed at room temperature by an internal mixer, and then placed in a special system.
  • the modified nanocomposite silicone sealing ring was obtained by hot pressing vulcanization in a mold at a temperature of 150 ° C, a pressure of 18 MPa, and a time of 40 min.
  • Step 1) modification of the nano additive using 5 to 10 layers of graphene dispersed in a concentration of 0.3 mg / ml polyvinylpyrrolidone aqueous solution for 10 hours, after centrifugation, vacuum drying to obtain a modified graphene additive;
  • Step 2 Raw rubber mixing: 100 parts by weight of methyl vinyl silicone rubber having a molar percentage of 0.25%, 8 parts of hydroxyl terminated polydimethylsiloxane, and 1 part of a silane coupling agent are weighed in parts by weight. KH-570, 0.6 parts of modified graphene additive prepared in step 1) and 20 parts of carbon black, which are sequentially added to an internal mixer for kneading, the mixing temperature is 60 ° C, the mixing time is 20 min; Extrusion at a temperature of 180 ° C to obtain a raw rubber compound;
  • Step 3) vulcanization molding: 100 parts by weight of the raw rubber mixing compound prepared in the step 2) and 1.5 parts of di-tert-butyl peroxide are respectively weighed, mixed and dispersed at room temperature by an internal mixer, and then placed in a special system.
  • the modified nanocomposite silicone sealing ring was obtained by hot pressing vulcanization in a mold at a temperature of 180 ° C, a pressure of 12 MPa, and a time of 20 min.
  • Step 1) Raw rubber mixing: 100 parts by weight of methyl vinyl silicone rubber having a molar percentage of 0.25%, 15 parts of hydroxyl terminated polydimethylsiloxane, and 3 parts of a silane coupling agent are weighed by weight. KH-570, 0.1 part of graphene oxide additive and 30 parts of carbon black, which are sequentially added to the mixer for mixing, the mixing temperature is 90 ° C, the mixing time is 50 min, and the temperature of the twin-screw extruder is 120 ° C. Extrusion to obtain a raw rubber compound;
  • Step 2 Silica gel vulcanization molding: 100 parts by weight of the raw rubber mixing compound prepared in the step 2) and 3 parts of di-tert-butyl peroxide are separately weighed, mixed and dispersed at room temperature by an internal mixer, and then placed.
  • the modified nanocomposite silicone sealing ring was obtained by hot pressing vulcanization at a temperature of 150 ° C, a pressure of 18 MPa and a time of 40 min in a special mold.
  • Step 1) Raw rubber mixing: 100 parts by weight of methyl vinyl silicone rubber having a molar percentage of 0.25%, 8 parts of hydroxyl terminated polydimethylsiloxane, and 1 part of a silane coupling agent are weighed by weight. KH-570, 0.4 parts of graphene oxide additive and 20 parts of carbon black, which are sequentially added to the mixer for mixing, the mixing temperature is 60 ° C, the mixing time is 20 min, and the temperature of the twin-screw extruder is 180 ° C. Extrusion to obtain a raw rubber compound;
  • Step 3) vulcanization molding: 100 parts by weight of the raw rubber mixing compound obtained in the step 2) and 1.5 parts of di-tert-butyl peroxide are respectively weighed, mixed and dispersed at room temperature by an internal mixer, and then placed in a special system.
  • the modified nanocomposite silicone sealing ring was obtained by hot pressing vulcanization in a mold at a temperature of 180 ° C, a pressure of 12 MPa, and a time of 20 min.
  • Step 1) Raw rubber mixing: 100 parts of methyl vinyl silicone rubber having a vinyl mole fraction of 0.25%, 15 parts of hydroxyl terminated polydimethylsiloxane, and 3 parts of a silane coupling agent are weighed by weight. KH-570, and 30 parts of fumed silica, which are sequentially added to an internal mixer for kneading, the kneading temperature is 90 ° C, the kneading time is 50 min; and the twin-screw extruder is extruded at a temperature of 120 ° C. Obtaining the compound after mixing;
  • Step 2) vulcanization molding: 100 parts by weight of the compounded compound obtained in the step 2) and 3 parts of di-tert-butyl peroxide are respectively weighed, mixed and dispersed at room temperature by an internal mixer, and then placed in a special mold.
  • the medium-temperature thermoforming machine is hot-pressed and vulcanized at a temperature of 150 ° C, a pressure of 18 MPa, and a time of 40 min to obtain a composite silicone sealing ring.
  • Step 1) Raw rubber mixing: 100 parts by weight of methyl vinyl silicone rubber having a molar percentage of 0.25%, 8 parts of hydroxyl terminated polydimethylsiloxane, and 1 part of a silane coupling agent are weighed by weight. KH-570, and 20 parts of carbon black, which are sequentially added to the mixer for mixing, the mixing temperature is 60 ° C, the mixing time is 20 min; and the twin-screw extruder is extruded at 180 ° C to obtain a mixture. Refining rubber compound;
  • Step 2) vulcanization molding: 100 parts by weight of the compounded mixture obtained in step 2) And 1.5 parts of di-tert-butyl peroxide, mixed and dispersed uniformly at room temperature by an internal mixer, and then placed in a special mold to obtain a modified nanocomposite by hot pressing vulcanization at a temperature of 180 ° C, a pressure of 12 MPa, and a time of 20 min. Silicone sealing ring.
  • Table 1 shows the performance parameters of each example:
  • the modified nano-composite silicone sealing ring of the invention can significantly reduce the permeability of the composite silicone sealing ring to gas and water vapor and effectively improve the mechanical strength, and greatly prolong the service life of the sealing material, which is high. Value.

Abstract

一种改性纳米复合硅胶密封圈，包括：重量比为100:0.5～10的生胶混炼胶料和硫化剂；所述生胶混炼胶料包括重量份数为：70～100份甲基乙烯基硅橡胶，1-20份增塑剂，0.01～10份改性纳米添加剂，10～50份补强填料，0.5～5份偶联剂；所述的改性纳米添加剂为改性白石墨烯、改性石墨烯、氧化石墨烯中的一种。复合硅胶密封圈少量添加纳米改性微粒，有利于增加密封性能和机械强度，而其他性能则不受影响。有效改善了硅胶密封圈在长时间使用过程中出现老化导致的水蒸汽、气体透过性变差和机械性能的降低，大大延长了密封材料使用寿命。

Description

[根据细则37.2由ISA制定的发明名称]　改性纳米复合硅胶密封圈及其制备 技术领域
本发明涉及密封圈技术领域，具体涉及一种改性纳米复合硅胶密封圈及其制备。
背景技术
硅胶密封圈作为密封部件与部件间的关键连接件，因具有优异的耐热性、低温弹性和耐氧化性被广泛应用于航空航天、医疗、汽车、家用电器等领域中。相比于聚硫橡胶、氟橡胶等密封圈，硅胶密封圈本身又具有很高的水汽、气体透过性，使得密封性能降低，而且在使用过程中随着时间的推移而衰减老化，硅橡胶逐渐失去弹性，降低了硅胶密封圈的机械性能，同时其气密性的降低得到进一步的放大，导致漏气、漏水、漏油等不良现象，影响了其作为密封材料的应用。
发明内容
有鉴于此，有必要针对上述问题，提供一种简单有效的改性纳米复合硅胶密封圈及其制备。
为实现上述目的，本发明采取以下技术方案：
本发明的改性纳米复合硅胶密封圈，包括：重量比为100:0.5～10的生胶混炼胶料和硫化剂；
所述生胶混炼胶料包括重量份数为：70～100份甲基乙烯基硅橡胶，1-20份增塑剂，0.01～10份改性纳米添加剂，10～50份补强填料，0.5～5份偶联剂；
所述的改性纳米添加剂为改性白石墨烯、改性石墨烯、氧化石墨烯中的一种。
作为优选的，所述生胶混炼胶料包括重量份数为：80～100份甲基乙烯基硅橡胶，1-15份增塑剂，0.05～5份纳米改性添加剂，15～40份补强填料，0.5～3份偶联剂。
作为优选的，所述甲基乙烯基硅橡胶的乙烯基摩尔百分数为0.12％、0.25％或0.56％。
综合考虑生胶的塑炼性和机械性能，进一步优选，所述甲基乙烯基硅橡胶的乙烯基摩尔百分数为0.25％。
作为优选，所述改性白石墨烯为5～10层白石墨烯经长链路易斯碱、长链路易斯酸、磺酸化物、季胺化物或非离子型表面活性剂处理，以此增加白石墨烯对基体的亲和力；所述改性白石墨烯为5～10层石墨烯经过聚乙烯吡咯烷酮(PVP)或十二烷基苯磺酸钠(SDBS)表面活性剂处理，以此增加石墨烯对基体的亲和力。
进一步优选，所述长链路易斯碱为油胺等；所述长链路易斯酸为长链硼烷等；所述磺酸化物为十二烷基苯磺酸钠等；所述季胺化物为溴化十六烷基吡啶等；所述非离子型表面活性剂为聚环氧乙烷烷基醇酰胺等。
作为优选的，所述增塑剂选为二甲基硅油、端羟基聚二甲基硅氧烷、乙烯基三甲氧基硅烷中的一种；
所述补强填料为气相二氧化硅、硅微粉、炭黑中的一种；
所述偶联剂为硅烷偶联剂KH-550、硅烷偶联剂KH-570、钛酸正丁酯中的一种；
所述的硫化剂为过氧化苯甲酰、过氧化二叔丁基、过氧化二异丙苯中的一种。
本发明改性纳米复合硅胶密封圈的制备方法，包括：
步骤1)选择改性白石墨烯、改性石墨烯、氧化石墨烯中的一种作为纳米 添加剂；改性方法：选用5-10层的白石墨烯用质量百分浓度为0.1％的长链路易斯碱、长链路易斯酸、磺酸化物、季胺化物或者非离子型表面活性剂水溶液浸泡24小时，经离心、真空干燥后得改性白石墨烯添加剂；用5～10层的石墨烯分散在浓度为0.3mg/ml聚乙烯吡咯烷酮或十二烷基苯磺酸钠水溶液中超声10小时，经离心、真空烘干后得改性石墨烯添加剂；
步骤2)生胶混炼：按重量份数分别称甲基乙烯基硅橡胶、增塑剂、偶联剂、改性纳米添加剂和补强填料，经密炼机多次混炼后，用双螺杆挤出机挤出，得到生胶混炼胶料；
步骤3)硫化成型：按比例分别称量步骤2)中的生胶混炼胶料和硫化剂，经密炼机混合分散均匀后，放入模具中经热压成型机硫化成型，得到改性纳米复合硅胶密封圈。
作为优选的，步骤2)所述的生胶混炼过程为各组份在密炼机中，温度为40～120℃、时间5～60min混炼，再经双螺杆挤出机于温度为80～250℃挤出，得到生胶混炼胶料。
作为优选的，步骤3)中所述热压成型机硫化成型过程中控制温度为100～250℃、压力1～20Mpa、硫化成型时间10～90min。
与现有技术相比，本发明的有益效果为：
硅胶密封圈长时间存在于高温苛刻环境中，侧链甲基易被氧化形成交联，导致材料硬化；用经表面活性剂处理的白石墨烯、石墨烯以及表面含有较多活性基团的氧化石墨烯，少量添加时即可达到与基体良好的润湿性，增加韧性起到补强效果，提高硅胶密封圈的机械强度。
本发明选用5～10层白石墨烯、石墨烯或氧化石墨烯的纳米粉体经改性而得的材料，其原子层能有效隔离气体原子分子，气体分子仅仅在硅橡胶中通行。当改性白石墨烯、改性石墨烯、改性氧化石墨烯原子层少于十层时，片层排列 紧凑、均匀，且阻挡片层数目较多，气体在硅橡胶中绕行，路径变长，少量添加就能很好的阻挡气体通过，增加了纳米复合硅胶密封圈的气密性。
本发明改善了硅胶密封圈在长时间使用过程中出现老化导致的水蒸汽、气体透过性变差和机械性能的降低，大大延长了密封材料使用寿命，具有很高的应用价值。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明的技术方案作进一步清楚、完整地描述。需要说明的是，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
步骤1)纳米添加剂的改性：选用5～10层的白石墨烯用0.1％油胺水溶液浸泡24小时，经离心、真空干燥后得到改性白石墨烯添加剂；
步骤2)生胶混炼：按重量份数分别称取100份乙烯基摩尔百分数为0.25％的甲基乙烯基硅橡胶、15份端羟基聚二甲基硅氧烷、3份硅烷偶联剂KH-570、步骤1)制备的0.1份改性白石墨烯添加剂和30份炭黑，依次加入到密炼机中混炼，混炼温度为90℃，混炼时间为50min；再经过双螺杆挤出机在温度为120℃下挤出，得到生胶混炼胶料；
步骤3)硫化成型：按重量份数分别称取100份步骤2)得到的生胶混炼胶料和3份过氧化二叔丁基，经密炼机常温混合分散均匀后，再放入特制模具中经热压成型机在温度150℃、压力18Mpa、时间40min下热压硫化得到改性纳米复合硅胶密封圈。
实施例2
步骤1)纳米添加剂的改性：选用5～10层的白石墨烯用0.1％油胺水溶液浸泡24小时，经离心、真空干燥后得到改性白石墨烯添加剂；
步骤2)生胶混炼：按重量份数分别称取100份乙烯基摩尔百分数为0.25％的甲基乙烯基硅橡胶、8份端羟基聚二甲基硅氧烷、1份硅烷偶联剂KH-570、步骤1)制备的0.5份改性白石墨烯添加剂和20份炭黑，依次加入到密炼机中混炼，混炼温度为60℃，混炼时间为20min；，再经过双螺杆挤出机在温度为180℃下挤出，得到生胶混炼胶料；
步骤3)硫化成型：按重量份数分别称取100份步骤2)得到的生胶混炼胶料和1.5份过氧化二叔丁基，经密炼机常温混合分散均匀后，再放入特制模具中经热压成型机在温度180℃、压力12Mpa、时间20min下热压硫化得到改性纳米复合硅胶密封圈。
实施例3
步骤1)纳米添加剂的改性：用5～10层的石墨烯分散在浓度为0.3mg/ml聚乙烯吡咯烷酮水溶液中超声10小时，经离心、真空烘干后得改性石墨烯添加剂；
步骤2)生胶混炼：按重量份数分别称取100份乙烯基摩尔百分数为0.25％的甲基乙烯基硅橡胶、15份端羟基聚二甲基硅氧烷、3份硅烷偶联剂KH-570、步骤1)制备的0.1份改性石墨烯添加剂和30份炭黑，依次加入到密炼机中混炼，混炼温度为90℃，混炼时间为50min；再经过双螺杆挤出机在温度为120℃下挤出，得到生胶混炼胶料；
步骤3)硫化成型：按重量份数分别称取100份步骤2)得到的生胶混炼胶料和3份过氧化二叔丁基，经密炼机常温混合分散均匀后，再放入特制模具中经热压成型机温度在150℃、压力18Mpa、时间40min下热压硫化得到改性纳米复合硅胶密封圈。
实施例4
步骤1)纳米添加剂的改性：用5～10层的石墨烯分散在浓度为0.3mg/ml聚乙烯吡咯烷酮水溶液中超声10小时，经离心、真空烘干后得改性石墨烯添加剂；
步骤2)生胶混炼：按重量份数分别称取100份乙烯基摩尔百分数为0.25％的甲基乙烯基硅橡胶、8份端羟基聚二甲基硅氧烷、1份硅烷偶联剂KH-570、步骤1)制备的0.6份改性石墨烯添加剂和20份炭黑，依次加入到密炼机中混炼，混炼温度为60℃，混炼时间为20min；再经过双螺杆挤出机温度为180℃下挤出，得到生胶混炼胶料；
步骤3)硫化成型：按重量份数分别称取100份步骤2)制备的生胶混炼胶料和1.5份过氧化二叔丁基，经密炼机常温混合分散均匀后，再放入特制模具中经热压成型机在温度180℃、压力12Mpa、时间20min下热压硫化得到改性纳米复合硅胶密封圈。
实施例5
步骤1)生胶混炼：按重量份数分别称取100份乙烯基摩尔百分数为0.25％的甲基乙烯基硅橡胶、15份端羟基聚二甲基硅氧烷、3份硅烷偶联剂KH-570、0.1份氧化石墨烯添加剂和30份炭黑，依次加入到密炼机中混炼，混炼温度为90℃，混炼时间为50min；再经过双螺杆挤出机温度为120℃下挤出，得到生胶混炼胶料；
步骤2)硅胶硫化成型：按重量份数分别称取100份步骤2)制备的生胶混炼胶料和3份过氧化二叔丁基，经密炼机常温混合分散均匀后，再放入特制模具中经热压成型机在温度150℃、压力18Mpa、时间40min下热压硫化得到改性纳米复合硅胶密封圈。
实施例6
步骤1)生胶混炼：按重量份数分别称取100份乙烯基摩尔百分数为0.25％的甲基乙烯基硅橡胶、8份端羟基聚二甲基硅氧烷、1份硅烷偶联剂KH-570、0.4份氧化石墨烯添加剂和20份炭黑，依次加入到密炼机中混炼，混炼温度为60℃，混炼时间为20min；再经过双螺杆挤出机温度为180℃下挤出，得到生胶混炼胶料；
步骤3)硫化成型：按重量份数分别称取100份步骤2)得到的生胶混炼胶料和1.5份过氧化二叔丁基，经密炼机常温混合分散均匀后，再放入特制模具中经热压成型机在温度180℃、压力12Mpa、时间20min下热压硫化得到改性纳米复合硅胶密封圈。
对比实施例1
步骤1)生胶混炼：按重量份数分别称取100份乙烯基摩尔分数为0.25％的甲基乙烯基硅橡胶、15份端羟基聚二甲基硅氧烷、3份硅烷偶联剂KH-570、和30份气相二氧化硅，依次加入到密炼机中混炼，混炼温度为90℃，混炼时间为50min；再经过双螺杆挤出机温度为120℃下挤出，得到混炼后胶料；
步骤2)硫化成型：按重量份数分别称取100份步骤2)得到的混炼后胶料和3份过氧化二叔丁基，经密炼机常温混合分散均匀后，再放入特制模具中经热压成型机在温度150℃、压力18Mpa、时间40min下热压硫化得到复合硅胶密封圈。
对比实施例2
步骤1)生胶混炼：按重量份数分别称取100份乙烯基摩尔百分数为0.25％的甲基乙烯基硅橡胶、8份端羟基聚二甲基硅氧烷、1份硅烷偶联剂KH-570、和20份炭黑，依次加入到密炼机中混炼，混炼温度为60℃，混炼时间为20min；再经过双螺杆挤出机温度为180℃下挤出，得到混炼后胶料；
步骤2)硫化成型：按重量份数分别称取100份步骤2)得到的混炼后胶料 和1.5份过氧化二叔丁基，经密炼机常温混合分散均匀后，再放入特制模具中经热压成型机温度在180℃、压力12Mpa、时间20min下热压硫化得到改性纳米复合硅胶密封圈。
表1中为测定各实施例的各项性能参数：
表1上述各实施例中所得产品的各项性能
Figure PCTCN2017098074-appb-000001
从上表可知，本发明的改性纳米复合硅胶密封圈，可以明显降低复合硅胶密封圈对气体和水蒸汽的透过率和有效提高机械强度，大大延长了作为密封材料使用寿命，具有很高应用价值。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种改性纳米复合硅胶密封圈，包括，重量比为100:0.5～10的生胶混炼胶料和硫化剂；
    所述生胶混炼胶料包括重量份数为：70～100份甲基乙烯基硅橡胶，1-20份增塑剂，0.01～10份改性纳米添加剂，10～50份补强填料，0.5～5份偶联剂；
    所述的改性纳米添加剂为改性白石墨烯、改性石墨烯、氧化石墨烯中的一种。
  2. 根据权利要求1所述的改性纳米复合硅胶密封圈，其特征在于，所述生胶混炼胶料包括重量份数为：80～100份甲基乙烯基硅橡胶，1-15份增塑剂，0.05～5份纳米改性添加剂，15～40份补强填料，0.5～3份偶联剂。
  3. 根据权利要求1或2所述的改性纳米复合硅胶密封圈，其特征在于，所述甲基乙烯基硅橡胶的乙烯基摩尔百分数为0.12％、0.25％或0.56％。
  4. 根据权利要求3所述的纳米改性硅橡胶制备的复合硅胶密封圈，其特征在于，所述甲基乙烯基硅橡胶的乙烯基摩尔百分数为0.25％。
  5. 根据权利要求1或2所述的改性纳米复合硅胶密封圈，其特征在于，所述改性白石墨烯为5～10层白石墨烯经长链路易斯碱、长链路易斯酸、磺酸化物、季胺化物或非离子型表面活性剂处理；所述改性白石墨烯为5～10层石墨烯经过聚乙烯吡咯烷酮或十二烷基苯磺酸钠表面活性剂处理。
  6. 根据权利要求5所述的改性纳米复合硅胶密封圈，其特征在于，所述长链路易斯碱为油胺；所述长链路易斯酸为长链硼烷；所述磺酸化物为十二烷基苯磺酸钠；所述季胺化物为溴化十六烷基吡啶；所述非离子型表面活性剂为聚环氧乙烷烷基醇酰胺。
  7. 根据权利要求1或2所述的改性纳米复合硅胶密封圈，其特征在于，所 述增塑剂选为二甲基硅油、端羟基聚二甲基硅氧烷、乙烯基三甲氧基硅烷中的一种；
    所述补强填料为气相二氧化硅、硅微粉、炭黑中的一种；
    所述偶联剂为硅烷偶联剂KH-550、硅烷偶联剂KH-570、钛酸正丁酯中的一种；
    所述的硫化剂为过氧化苯甲酰、过氧化二叔丁基、过氧化二异丙苯中的一种。
  8. 一种权利要求1或2所述的改性纳米复合硅胶密封圈的制备方法，其特征在于，包括：
    步骤1)选择改性白石墨烯、改性石墨烯、氧化石墨烯中的一种作为纳米添加剂；改性方法：选用5-10层的白石墨烯用质量百分浓度为0.1％的长链路易斯碱、长链路易斯酸、磺酸化物、季胺化物或者非离子型表面活性剂水溶液浸泡24小时，经离心、真空干燥后得改性白石墨烯添加剂；用5～10层的石墨烯分散在浓度为0.3mg/ml聚乙烯吡咯烷酮或十二烷基苯磺酸钠水溶液中超声10小时，经离心、真空烘干后得改性石墨烯添加剂；
    步骤2)生胶混炼：按重量份数分别称甲基乙烯基硅橡胶、增塑剂、偶联剂、改性纳米添加剂和补强填料，经密炼机多次混炼后，用双螺杆挤出机挤出，得到生胶混炼胶料；
    步骤3)硫化成型：按比例分别称量步骤2)中的生胶混炼胶料和硫化剂，经密炼机混合分散均匀后，放入模具中经热压成型机硫化成型，得到改性纳米复合硅胶密封圈。
  9. 根据权利要求8所述的改性纳米复合硅胶密封圈的制备方法，其特征在于：步骤2)所述的生胶混炼过程为各组份在密炼机中，温度为40～120℃、时间5～60min混炼，再经双螺杆挤出机于温度为80～250℃挤出，得到生胶混炼胶 料。
  10. 根据权利要求8所述的改性纳米复合硅胶密封圈的制备方法，其特征在于：步骤3)中所述热压成型机硫化成型过程中控制温度为100～250℃、压力1～20Mpa、硫化成型时间10～90min。
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