WO2015154492A1 - 一种用于密封件的有机无机复合硫化丁腈橡胶及其制备方法 - Google Patents

一种用于密封件的有机无机复合硫化丁腈橡胶及其制备方法 Download PDF

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WO2015154492A1
WO2015154492A1 PCT/CN2014/093077 CN2014093077W WO2015154492A1 WO 2015154492 A1 WO2015154492 A1 WO 2015154492A1 CN 2014093077 W CN2014093077 W CN 2014093077W WO 2015154492 A1 WO2015154492 A1 WO 2015154492A1
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nitrile rubber
organic
inorganic composite
parts
nanoparticles
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戴李宗
许一婷
高辉
谢泓辉
叶华立
罗伟昂
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戴李宗
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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile

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  • the invention belongs to the technical field of sealing materials, and in particular relates to a composite vulcanized nitrile rubber for a sealing member and a preparation method thereof.
  • Nitrile rubber has excellent oil resistance, wear resistance and aging resistance, and is widely used in the preparation of various oil resistant products, antistatic products and various seals.
  • the long-term use temperature of seals made by NBR can only be below 120 °C, thus limiting its application in the automotive industry.
  • the methods used in the prior art are as follows: 1. Adding a coupling agent to enhance the high temperature resistance of the nitrile rubber (see CN103012881A); 2. Adding carbon black N660, high wear resistance Carbon black N330, titanate coupling agent TMC ⁇ TTS, N ⁇ 2 ⁇ (aminoethyl) ⁇ 3 ⁇ aminopropyltrimethoxysilane, silane coupling agent KH550, nano calcium carbonate and other fillers and coupling To modify the heat resistance of nitrile rubber (see CN102993502A); 3, blended with EPDM/butyronitrile rubber, and added montmorillonite to form an intercalation structure, the addition of montmorillonite The oil resistance and heat resistance of nitrile rubber are improved (see CN103012972A). However, the high temperature resistance of the nitrile rubber prepared by the above several methods is still difficult to meet the needs of the automobile manufacturing industry.
  • Another object of the present invention is to provide a method for producing the above-described organic-inorganic composite vulcanized nitrile rubber for a sealing member.
  • An organic-inorganic composite vulcanized nitrile rubber for a seal the raw material of which comprises the following parts by mass:
  • the nitrile rubber has an acrylonitrile content of from 36% to 42%.
  • the carboxylated nitrile rubber coating s the carboxybutyronitrile gum in the Si 3 N 4 nanoparticles in a mass content of 5% to 45%.
  • the plasticizer is dioctyl phthalate (DOP) or dibutyl phthalate (DBP).
  • the promoter is N,N-tetramethyldithiobisthiocarbonylamine (TMTD) or 2,2'-dithiodibenzothiazole (DM).
  • TMTD N,N-tetramethyldithiobisthiocarbonylamine
  • DM 2,2'-dithiodibenzothiazole
  • the active agent is zinc oxide or stearic acid.
  • the antioxidant is N-isopropyl-N-phenyl-p-phenylenediamine (anti-aging agent 4010NA), N-(1,3-dimethylbutyl)-N One or a mixture of '-phenyl-p-phenylenediamine (anti-aging agent 4020) and N-phenyl- ⁇ -naphthylamine (anti-aging agent A).
  • the above preparation method of the organic-inorganic composite vulcanized nitrile rubber for a seal comprises the following steps:
  • Step (1) preparing a carboxylated nitrile rubber coated Si 3 N 4 nanoparticle: after dissolving the liquid carboxylated nitrile rubber in toluene, adding a mixture of nano Si 3 N 4 powder therein, under the protection of N 2 gas The mixture is heated and refluxed, dried and ball milled to obtain the carboxylated nitrile rubber coated Si 3 N 4 nanoparticles.
  • Step (2) Preparation of raw rubber: The nitrile rubber is added to an open mill and kneaded at a roll distance of 2 - 3 mm, and then the carboxylated nitrile rubber is coated to coat the Si 3 N 4 nanoparticles at a roll distance of 1 - 2 mm. Continue to mix, then play 8-12 triangle bags, make a thin pass, get raw rubber.
  • Step (3) preparing a finished product: adding a promoter, an active agent, a plasticizer and an anti-aging agent to the raw rubber for mixing, adding 8-10 triangle bags, adding sulfur, and then playing 5-6 triangle bags, The vulcanization is carried out to obtain the organic-inorganic composite vulcanized nitrile rubber for the seal.
  • the heating and refluxing temperature of the step (1) is 60-100 ° C for a period of 2-8 h.
  • the conditions for the vulcanization in the step (3) are 150 ° C ⁇ t 90 ⁇ 10 MPa.
  • the addition of Si 3 N 4 nanoparticles makes the heat resistance of the rubber compound significantly improved.
  • the present invention coats Si 3 N 4 nanoparticles with carboxylated nitrile rubber and introduces high temperature resistant Si into the nitrile rubber.
  • 3 N 4 nanoparticles which make Si 3 N 4 nanometer uniformly dispersed in the composite compound, and the carboxylated nitrile rubber coated with nanoparticles is chemically bonded to the nanoparticles and can be completely compatible with the nitrile rubber, and there is no compatibility. Problems such as interface, etc., make the organic-inorganic composite vulcanized nitrile rubber used for the seal excellent in high temperature resistance and physical and mechanical properties, and expand the application range of the nitrile rubber.
  • the preparation method of the invention utilizes existing processing equipment, has controllable production process, low cost and is suitable for industrial production.
  • Figure 1 TGA curve of the organic-inorganic composite vulcanized nitrile rubber prepared in Example 5.
  • the plasticizer used is dioctyl phthalate (DOP) or dibutyl phthalate (DBP);
  • the accelerator used is N,N-tetramethyldithiobisthiocarbonylamine (TMTD) or 2,2'-dithiodibenzothiazole (DM);
  • the active agent used is zinc oxide and stearic acid in a ratio of 3:1;
  • the antioxidant used is N-isopropyl-N-phenyl pair Phenylenediamine (anti-aging agent 4010NA), N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (anti-aging agent 4020) and N-phenyl- ⁇ -naphthylamine (anti-aging agent A ).
  • Step (1) taking a certain amount of liquid carboxylated nitrile rubber dissolved in toluene to form a solution and adding a certain amount of nano-Si 3 N 4 powder into a 500 mL three-necked flask, which is protected by N 2 gas and refluxed at a certain temperature. (The temperature of heating and refluxing is 60-100 ° C, time is 2-8 h), and after drying, the ball mill is taken out to obtain carboxylated nitrile rubber coated Si 3 N 4 nanoparticles. among them:
  • Example ⁇ Conditions temperature reflex Reaction time Carboxyl nitrile rubber mass / Si 3 N 4 powder 1 60 ° C 2h 25% 2 60 ° C 8h 25% 3 100 ° C 5h 25%
  • Step (2) Add the nitrile rubber to the open mill for mixing (rolling distance 2 ⁇ 3 mm), add the carboxylated nitrile rubber to coat the Si 3 N 4 nanoparticles, and continue mixing (rolling distance 1-2 mm). 8-12 triangle bags, thin pass, get raw rubber.
  • Step 2 100 parts by mass 30 parts by mass
  • Step (3) adding the above raw rubber to the accelerator N, N-tetramethyldithiobisthiocarbonylamine (TMTD) 2 parts by mass, active agent zinc oxide 3 parts by mass, stearic acid 1 part by mass, plasticizer adjacent 7.5 parts by mass of dioctyl phthalate (DOP) and 2 parts by mass of N-isopropyl-N-phenyl-p-phenylenediamine (anti-aging agent 4010NA), and 8-10 rounds are added to 2
  • the vulcanization time is determined by a vulcanizer, and finally vulcanized on a vulcanizing machine (vulcanization condition 150 ° C ⁇ t 90 ⁇ 10 MPa) to obtain the organic and inorganic materials for the seals.
  • Composite vulcanized nitrile rubber Composite vulcanized nitrile rubber.
  • Step (1) taking a certain amount of liquid carboxylated nitrile rubber dissolved in toluene to form a solution and adding a certain amount of nano-Si 3 N 4 powder into a 500 mL three-necked flask, which is protected by N 2 gas and refluxed at a certain temperature. (The temperature of heating and refluxing is 60-100 ° C, time is 2-8 h), and after drying, the ball mill is taken out to obtain carboxylated nitrile rubber coated Si 3 N 4 nanoparticles. among them:
  • Step (2) Add the nitrile rubber to the open mill for mixing (rolling distance 2 ⁇ 3 mm), add the carboxylated nitrile rubber to coat the Si 3 N 4 nanoparticles, and continue mixing (rolling distance 1-2 mm). 8-12 triangle bags, thin pass, get raw rubber.
  • Step 2 100 parts by mass 30 parts by mass
  • Step (3) adding the above raw rubber to the active agent zinc oxide 3 parts by mass, stearic acid 1 part by mass, accelerator 2,2'-dithiodibenzothiazole (DM) 2 parts by mass, plasticizer ortho-benzene 7.5 parts by mass of dibutyl dicarboxylate (DBP) and 2 parts by mass of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (anti-aging agent 4020) 8 to 10 triangles were added with 2 parts by mass of sulfur, and then 5 to 6 triangles were used.
  • DM 2,2'-dithiodibenzothiazole
  • plasticizer ortho-benzene 7.5 parts by mass of dibutyl dicarboxylate (DBP) and 2 parts by mass of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (anti-aging agent 4020) 8 to 10 triangles were added with 2 parts by mass of sulfur, and then 5
  • the vulcanization time was measured by a vulcanizer, and finally vulcanized on a vulcanizing machine (vulcanization conditions: 150 ° C ⁇ t 90 ⁇ 10 MPa).
  • vulcanization conditions 150 ° C ⁇ t 90 ⁇ 10 MPa.
  • the organic-inorganic composite vulcanized nitrile rubber prepared in Example 5 exhibited good thermal stability (as shown in FIG. 1), and the physical and mechanical properties of the pure NBR vulcanized rubber after hot air aging test were as follows. The table shows.
  • Step (1) taking a certain amount of liquid carboxylated nitrile rubber dissolved in toluene to form a solution and adding a certain amount of nano-Si 3 N 4 powder into a 500 mL three-necked flask, which is protected by N 2 gas and refluxed at a certain temperature.
  • the temperature of heating and refluxing is 60-100 ° C, time is 2-8 h
  • the ball mill is taken out to obtain carboxylated nitrile rubber coated Si 3 N 4 nanoparticles.
  • carboxyl nitrile rubber mass / Si 3 N 4 powder is 25%, temperature 80 ° C, reflux 5h.
  • Step ⁇ condition temperature reflex Reaction time Carboxyl nitrile rubber mass / Si 3 N 4 powder 1 80 ° C 5h 25%
  • Step (2) Add the nitrile rubber to the open mill for mixing (rolling distance 2 ⁇ 3 mm), add the carboxylated nitrile rubber to coat the Si 3 N 4 nanoparticles, and continue mixing (rolling distance 1-2 mm). 8-12 triangle bags, thin pass, get raw rubber. among them:
  • Step (3) adding the above raw rubber to the accelerator 2,2'-dithiodibenzothiazole 2 parts by mass, the active agent zinc oxide 3 parts by mass, stearic acid 1 part by mass, plasticizer phthalic acid II 7.5 parts by mass of butyl ester and 2 parts by mass of N-phenyl- ⁇ -naphthylamine (anti-aging agent A) for anti-aging agent, mix 8 to 10 triangles to add 2 parts by mass of sulfur, and then 5 to 6 triangles
  • the vulcanization time was measured by a vulcanizer, and finally vulcanized on a flat vulcanizer (vulcanization condition: 150 ° C ⁇ t 90 ⁇ 10 MPa) to obtain the organic-inorganic composite vulcanized nitrile rubber for the seal.
  • Step (1) Take a certain amount of liquid carboxylated nitrile rubber dissolved in toluene to form a solution and add a certain amount of nano-Si 3 N 4 powder into a 500 mL three-necked flask, pass N 2 gas protection, and reflux at a certain temperature. After the hour, the mixture was taken out, and after drying, the ball mill was taken out to obtain a carboxylated nitrile rubber coated Si 3 N 4 nanoparticle. Among them: carboxyl nitrile rubber mass / Si 3 N 4 powder is 25%, temperature 80 ° C, reflux 5h.
  • Step ⁇ condition temperature reflex Reaction time Carboxyl nitrile rubber mass / Si 3 N 4 powder 1 80 ° C 5h 25%
  • Step (2) Add the nitrile rubber to the open mill for mixing (rolling distance 2 ⁇ 3 mm), add the carboxylated nitrile rubber to coat the Si 3 N 4 nanoparticles, and continue mixing (rolling distance 1-2 mm). 8-12 triangle bags, thin pass, get raw rubber. Among them: 100 parts by mass of nitrile rubber, and 25 parts by mass of Si 3 N 4 nanoparticles coated with carboxylated nitrile rubber.
  • Nitrile rubber Carboxylated nitrile rubber coated Si 3 N 4 nanoparticles Step 2 100 parts by mass 25 parts by mass
  • the organic-inorganic composite vulcanized nitrile rubber for seals prepared by the invention has excellent high temperature resistance and physical and mechanical properties, and has an expanded application range of nitrile rubber.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明公开了一种用于密封件的有机无机复合硫化丁腈橡胶及其制备方法，其原料包括如下质量份的组分：丁腈橡胶100，羧基丁腈胶包覆Si3N4纳米粒子5-40，促进剂1-3，活性剂2-5，硫磺1-3，增塑剂5-10，防老剂1-3。本发明利用羧基丁腈胶包覆Si3N4纳米粒子，在丁腈橡胶中引入耐高温的Si3N4纳米粒子，使Si3N4纳米在复合胶料中均匀分散，同时包覆纳米粒子的羧基丁腈橡胶与纳米粒子化学键接并且能与丁腈橡胶完全相容，不存在相容性，界面等问题，使得所制得的用于密封件的有机无机复合硫化丁腈橡胶的耐高温性能和物理机械性能优良，扩大的丁腈橡胶的应用范围。

Description

一种用于密封件的有机无机复合硫化丁腈橡胶及其制备方法 技术领域
本发明属于密封材料技术领域，具体涉及一种用于密封件的复合硫化丁腈橡胶及其制备方法。
背景技术
丁腈橡胶(NBR)具有耐油性、耐磨性和耐老化等性能优良，更是广泛用于各种耐油制品、抗静电制品及各种密封件的制备中。但NBR制作的密封件的长期使用温度只能在120℃以下，因此限制了其在汽车制造工业中的应用。
为了提高NBR的耐高温性能，现有技术中所采用的方法如下：1、添加偶联剂以增强丁腈橡胶的耐高温性能(参见CN103012881A)；2、采取的添加炭黑N660、高耐磨炭黑N330、钛酸酯偶联剂TMC‐TTS、N‐2‐(氨乙基)‐3‐氨丙基三甲氧基硅烷、硅烷偶联剂KH550、纳米碳酸钙等各种填料和偶联剂来改性丁腈橡胶的耐热性(参见CN102993502A)；3、采取了三元乙丙橡胶/丁腈橡胶共混，且加入了蒙脱土，形成了插层结构，蒙脱土的加入对丁腈橡胶的耐油性，耐热性有所提高(参见CN103012972A)。但上述几种方法所制备的丁腈橡胶的耐高温性能仍然难以满足汽车制造工业的需求。
发明内容
本发明的目的在于提供一种用于密封件的有机无机复合硫化丁腈橡胶。
本发明的另一目的在于提供上述用于密封件的有机无机复合硫化丁腈橡胶的制备方法。
本发明的技术方案具体如下：
一种用于密封件的有机无机复合硫化丁腈橡胶，其原料包括如下质量份的组分：
Figure PCTCN2014093077-appb-000001
Figure PCTCN2014093077-appb-000002
在本发明的一个优选实施方案中，所述丁腈橡胶中丙烯腈含量为36％‐42％。
在本发明的一个优选实施方案中，所述羧基丁腈胶包覆Si3N4纳米粒子中羧基丁腈胶的质量含量5％‐45％。
在本发明的一个优选实施方案中，所述增塑剂为邻苯二甲酸二辛酯(DOP)或邻苯二甲酸二丁酯(DBP)。
在本发明的一个优选实施方案中，所述促进剂为N,N‐四甲基二硫双硫羰胺(TMTD)或2,2'‐二硫代二苯并噻唑(DM)。
在本发明的一个优选实施方案中，所述活性剂为氧化锌或硬脂酸。
在本发明的一个优选实施方案中，所述防老剂为N‐异丙基‐N‐苯基对苯二胺(防老剂4010NA)、N‐(1，3‐二甲基丁基)‐N'‐苯基对苯二胺(防老剂4020)和N‐苯基‐α萘胺(防老剂A)中的一种或混合。
上述用于密封件的有机无机复合硫化丁腈橡胶的制备方法，包括如下步骤：
步骤(1)制备羧基丁腈胶包覆Si3N4纳米粒子：将液态羧基丁腈橡胶溶解于甲苯后，在其中加入纳米Si3N4粉体得混合液，在N2气保护下对上述混合液进行加热回流，再经干燥和球磨，得到所述羧基丁腈胶包覆Si3N4纳米粒子。
步骤(2)制备生胶：将丁腈橡胶加入开炼机在辊距2‐3mm的条件下混炼后，加入羧基丁腈胶包覆Si3N4纳米粒子在辊距1‐2mm的条件下继续混炼，然后打8‐12个三角包，进行薄通，得到生胶。
步骤(3)制备成品：在上述生胶中加入促进剂、活性剂、增塑剂和防老剂进行混炼，打8‐10个三角包后加入硫磺，再打5‐6个三角包后，进行硫化，即得所述用于密封件的有机无机复合硫化丁腈橡胶。
在本发明的一个优选实施方案中，所述步骤(1)的加热回流的温度为60‐100℃，时间为2‐8h。
在本发明的一个优选实施方案中，所述步骤(3)中硫化的条件为150℃×t90×10MPa。
本发明的有益效果如下：
Si3N4纳米粒子的加入使符合胶料的耐热性得到了明显的提高，1、本发明利用羧基丁腈胶包覆Si3N4纳米粒子，在丁腈橡胶中引入耐高温的Si3N4纳米粒子，使Si3N4纳米在复合胶料中均匀分散，同时包覆纳米粒子的羧基丁腈橡胶与纳米粒子化学键接并且能与丁腈橡胶完全相容，不存在相容性，界面等问题，使得所制得的用于密封件的有机无机复合硫化丁腈橡胶的耐高温性能和物理机械性能优良，扩大的丁腈橡胶的应用范围。
2、本发明的制备方法利用现有的加工设备，生产工艺可控，成本低廉，适合工业化生产。
附图说明
图1：为实施例5所制备的有机无机复合硫化丁腈橡胶的TGA曲线。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
下述实施中，所用增塑剂为邻苯二甲酸二辛酯(DOP)或邻苯二甲酸二丁酯(DBP)；所用促进剂为N,N‐四甲基二硫双硫羰胺(TMTD)或2,2'‐二硫代二苯并噻唑(DM)；所用活性剂为氧化锌和硬脂酸按3：1使用；所用防老剂为N‐异丙基‐N‐苯基对苯二胺(防老剂4010NA)、N‐(1，3‐二甲基丁基)‐N'‐苯基对苯二胺(防老剂4020)和N‐苯基‐α萘胺(防老剂A)。
实施例1‐3
步骤(1)取一定量的液体羧基丁腈橡胶溶解于甲苯中配成溶液再加一定量纳米Si3N4粉体放入500mL三口烧瓶中，通入N2气保护，一定温度下回流后(加热回流的温度为60‐100℃，时间为2‐8h)取出,干燥处理后,取出球磨，得到羧基丁腈胶包覆Si3N4纳米粒子。其中：
实施例\条件 反应温度 反应时间 羧基丁腈橡胶质量/Si3N4粉体
1 60℃ 2h 25％
2 60℃ 8h 25％
3 100℃ 5h 25％
步骤(2)将丁腈橡胶加入开炼机混炼(辊距2‐3mm)，按比例加入羧基丁腈胶包覆Si3N4纳米粒子，继续混炼(辊距1‐2mm)，打8‐12个三角包，进行薄通，得到生胶。其中：丁腈橡胶100质量份，羧基丁腈胶包覆Si3N4纳米粒子30质量份。
步骤\物料 丁腈橡胶 羧基丁腈胶包覆Si3N4纳米粒子
步骤2 100质量份 30质量份
步骤(3)将上述生胶加入促进剂N,N‐四甲基二硫双硫羰胺(TMTD)2质量份、活性剂氧化锌3质量份，硬脂酸1质量份、增塑剂邻苯二甲酸二辛酯(DOP)7.5质量份和防老剂N‐异丙基‐N‐苯基对苯二胺(防老剂4010NA)2质量份进行混炼，打8‐10个三角包加入2质量份硫磺，再打5‐6个三角包后，用硫化仪测定其硫化时间，最后在平板硫化机上硫化(硫化条件150℃×t90×10MPa)，得到所述用于密封件的有机无机复合硫化丁腈橡胶。
Figure PCTCN2014093077-appb-000003
实施例4‐6
步骤(1)取一定量的液体羧基丁腈橡胶溶解于甲苯中配成溶液再加一定量纳米Si3N4粉体放入500mL三口烧瓶中，通入N2气保护，一定温度下回流后(加热回流的温度为60‐100℃，时间为2‐8h)取出,干燥处理后,取出球磨，得到羧基丁腈胶包覆Si3N4纳米粒子。其中：
实施例\条件 反应温度 反应时间 羧基丁腈橡胶质量/Si3N4粉体
4 80℃ 5h 5％
5 80℃ 5h 25％
6 80℃ 5h 45％
步骤(2)将丁腈橡胶加入开炼机混炼(辊距2‐3mm)，按比例加入羧基丁腈胶包覆Si3N4纳米粒子，继续混炼(辊距1‐2mm)，打8‐12个三角包，进行薄通，得到生胶。其中：丁腈橡胶100质量份，羧基丁腈胶包覆Si3N4纳米粒子30质量份。
步骤\物料 丁腈橡胶 羧基丁腈胶包覆Si3N4纳米粒子
步骤2 100质量份 30质量份
步骤(3)将上述生胶加入活性剂氧化锌3质量份，硬脂酸1质量份、促进剂2,2'‐二硫代二苯并噻唑(DM)2质量份、增塑剂邻苯二甲酸二丁酯(DBP)7.5质量份和防老剂N‐(1，3‐二甲基丁基)‐N'‐苯基对苯二胺(防老剂4020)2质量份进行混炼，打8‐10个三角包加入2质量份硫磺，再打5‐6个三角包后，用硫化仪测定其硫化时间，最后在平板硫化机上硫化(硫化条件150℃×t90×10MPa)，得到所述用于密封件的有机无机复合硫化丁腈橡胶。
Figure PCTCN2014093077-appb-000004
其中实施例5的所制得的有机无机复合硫化丁腈橡胶表现出良好的热稳定性(如图1所示)，其与纯NBR硫化橡胶在热空气老化试验后的物理机械性能的对比结果如下表所示。
(老化温度100℃,老化时长72h)
Figure PCTCN2014093077-appb-000005
实施例7‐9
步骤(1)取一定量的液体羧基丁腈橡胶溶解于甲苯中配成溶液再加一定量纳米Si3N4粉体放入500mL三口烧瓶中，通入N2气保护，一定温度下回流后(加热回流的温度为60‐100℃，时间为2‐8h)取出,干燥处理后,取出球磨，得到羧基丁腈胶包覆Si3N4纳米粒子。其中：羧基丁腈橡胶质量/Si3N4粉体为25％，温度80℃，回流5h。
步骤\条件 反应温度 反应时间 羧基丁腈橡胶质量/Si3N4粉体
1 80℃ 5h 25％
步骤(2)将丁腈橡胶加入开炼机混炼(辊距2‐3mm)，按比例加入羧基丁腈胶包覆Si3N4纳米粒子，继续混炼(辊距1‐2mm)，打8‐12个三角包，进行薄通，得到生胶。其中：
实施例\物料 丁腈橡胶 羧基丁腈胶包覆Si3N4纳米粒子
7 100质量份 5质量份
8 100质量份 30质量份
9 100质量份 45质量份
步骤(3)将上述生胶加入促进剂2,2'‐二硫代二苯并噻唑2质量份、活性剂氧化锌3质量份，硬脂酸1质量份、增塑剂邻苯二甲酸二丁酯7.5质量份和防老剂N‐苯基‐α萘胺(防老剂A)2质量份进行混炼，打8‐10个三角包加入2质量份硫磺，再打5‐6个三角包后，用硫化仪测定其硫化时间，最后在平板硫化机上硫化(硫化条件150℃×t90×10MPa)，得到所述用于密封件的有机无机复合硫化丁腈橡胶。
Figure PCTCN2014093077-appb-000006
实施例10‐12
步骤(1)取一定量的液体羧基丁腈橡胶溶解于甲苯中配成溶液再加一定量纳米Si3N4粉体放入500mL三口烧瓶中，通入N2气保护，一定温度下回流若干小时后取出,干燥处理后,取出球磨，得到羧基丁腈胶包覆Si3N4纳米粒子。其中：羧基丁腈橡胶质量/Si3N4粉体为25％，温度80℃，回流5h。
步骤\条件 反应温度 反应时间 羧基丁腈橡胶质量/Si3N4粉体
1 80℃ 5h 25％
步骤(2)将丁腈橡胶加入开炼机混炼(辊距2‐3mm)，按比例加入羧基丁腈胶包覆Si3N4纳米粒子，继续混炼(辊距1‐2mm)，打8‐12个三角包，进行薄通，得到生胶。其中：丁腈橡胶100质量份，羧基丁腈胶包覆Si3N4纳米粒子25质量份。
物料 丁腈橡胶 羧基丁腈胶包覆Si3N4纳米粒子
步骤2 100质量份 25质量份
步骤(3)将羧基丁腈胶包覆Si3N4纳米粒子/丁腈橡胶有机无机复合生胶加入促进剂N,N‐四甲基二硫双硫羰胺(TMTD)、活性剂氧化锌和硬脂酸按3：1使用、增塑剂邻苯二甲酸二辛酯(DOP)和防老剂N‐异丙基‐N‐苯基对苯二胺(防老剂 4010NA)进行混炼，打8‐10个三角包加入硫磺，再打5‐6个三角包后，用硫化仪测定其硫化时间，最后在平板硫化机上硫化(硫化条件150℃×t90×10MPa)，得到复合硫化橡胶。其中：
Figure PCTCN2014093077-appb-000007
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。
工业实用性
本发明所制得的用于密封件的有机无机复合硫化丁腈橡胶的耐高温性能和物理机械性能优良，扩大的丁腈橡胶的应用范围。

Claims (10)

  1. 一种用于密封件的有机无机复合硫化丁腈橡胶，其特征在于：其原料包括如下质量份的组分：
    Figure PCTCN2014093077-appb-100001
  2. 如权利要求1所述的一种用于密封件的有机无机复合硫化丁腈橡胶，其特征在于：所述丁腈橡胶中丙烯腈含量为36％‐42％。
  3. 如权利要求1所述的一种用于密封件的有机无机复合硫化丁腈橡胶，其特征在于：所述羧基丁腈胶包覆Si3N4纳米粒子中羧基丁腈胶的质量含量5％‐45％。
  4. 如权利要求1所述的一种用于密封件的有机无机复合硫化丁腈橡胶，其特征在于：所述增塑剂为邻苯二甲酸二辛酯或邻苯二甲酸二丁酯。
  5. 如权利要求1所述的一种用于密封件的有机无机复合硫化丁腈橡胶，其特征在于：所述促进剂为N,N‐四甲基二硫双硫羰胺或2,2'‐二硫代二苯并噻唑。
  6. 如权利要求1所述的一种用于密封件的有机无机复合硫化丁腈橡胶，其特征在于：所述活性剂为氧化锌或硬脂酸。
  7. 如权利要求1所述的一种用于密封件的有机无机复合硫化丁腈橡胶，其特征在于：所述防老剂为N‐异丙基‐N‐苯基对苯二胺、N‐(1，3‐二甲基丁基)‐N'‐苯基对苯二胺和N‐苯基‐α萘胺中的一种或混合。
  8. 一种权利要求1至7中任一权利要求所述的用于密封件的有机无机复合硫化丁腈橡胶的制备方法，其特征在于：包括如下步骤：
    (1)制备羧基丁腈胶包覆Si3N4纳米粒子：将液态羧基丁腈橡胶溶解于甲苯后，在其中加入纳米Si3N4粉体得混合液，在N2气保护下对上述混合液进行加 热回流，再经干燥和球磨，得到所述羧基丁腈胶包覆Si3N4纳米粒子；(2)制备生胶：将丁腈橡胶加入开炼机在辊距2‐3mm的条件下混炼后，加入羧基丁腈胶包覆Si3N4纳米粒子在辊距1‐2mm的条件下继续混炼，然后打8‐12个三角包，进行薄通，得到生胶；
    (3)制备成品：在上述生胶中加入促进剂、活性剂、增塑剂和防老剂进行混炼，打8‐10个三角包后加入硫磺，再打5‐6个三角包后，进行硫化，即得所述用于密封件的有机无机复合硫化丁腈橡胶。
  9. 如权利要求8所述的一种用于密封件的有机无机复合硫化丁腈橡胶的制备方法，其特征在于：所述步骤(1)中加热回流的温度为60‐100℃，时间为2‐8h。
  10. 如权利要求8所述的一种用于密封件的有机无机复合硫化丁腈橡胶的制备方法，其特征在于：所述步骤(3)中硫化的条件为150℃×t90×10MPa。
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