CN104479184A - 一种复合材料及其制备方法 - Google Patents
一种复合材料及其制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000002131 composite material Substances 0.000 title abstract description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920001971 elastomer Polymers 0.000 claims abstract description 23
- 239000005060 rubber Substances 0.000 claims abstract description 23
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- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical group [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 claims description 6
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 206010044565 Tremor Diseases 0.000 description 1
- 241000863032 Trieres Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- B29B7/00—Mixing; Kneading
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- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
- B29B7/726—Measuring properties of mixture, e.g. temperature or density
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- B29B7/00—Mixing; Kneading
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- B29B7/58—Component parts, details or accessories; Auxiliary operations
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Abstract
本发明涉及一种复合材料,由以下组分按照重量份数制备而成:橡胶体系:丁苯橡胶(SBR)100份,高岭土10-20份,炭黑(N774)10-15份,防老剂4010NA 2-3份,S 2-4份,氧化锌3-5份,硬脂酸0.5-2份,古马隆树脂3~6份,橡胶硫化促进剂CZ 1.5~2.5份,助促进剂TMTD 0.05~0.2份,机油5~10份。微晶陶瓷体系:硅酸盐类微晶陶瓷30-56份,氧化锌(细度≥800目)60-66份,蒙脱土2-3份,钛酸酯偶联剂2-3份;橡胶体系和微晶陶瓷体系的重量比为:100∶20~35。本发明的优点在于:本发明涉及用化学交联的方法使橡胶分子间产生交联反应,形成橡胶大分子间的立体互穿网络结构,从而赋予橡胶不溶不熔、耐化学腐蚀、耐温(寒)、抗老化以及增强该复合材料的力学性能,例如拉伸强度、抗冲击性和模量。
Description
技术领域
本发明涉及复合材料及其制备技术领域,特别涉及一种具有高防腐、高强度、高耐温、高耐磨等特殊性能的功能化、高性能复合新材料及其制备方法。
背景技术
我国石油、天然气资源的输送主要依靠管道来实现,管道一般为钢制螺旋焊管。由于管道穿越的地形复杂,所处环境不仅在空间上不同,而且还会随时间的变化遭受各种介质的侵蚀。这些管道的泄露事故中有28%是由于腐蚀穿孔造成的。管道的腐蚀不仅会造成因穿孔而引起的油、气跑漏损失,引起火灾等,而且还有维修带来的材料和人力的浪费。
本发明的复合材料主要针对油气输送管道特别是海洋油气输送管道的海水腐蚀问题,这种复合材料可用于钢塑复合管道的内外层塑管,复合材料吸收湿气使锌粉离子化,对金属起电化学保护作用,同时具有很好的耐磨和耐温性能。
一般而言,通常在聚合复合材料中加入填料,以取代昂贵的聚合物成分,或改善复合材料整体的特定性能,或者同时实现这两个目的。通常,为了对性能产生明显的影响,必需采用大量的填料。然而,大量填料的加入在使复合材料的至少一种力学性能增强的同时,经常会对其它的力学性能产生不利的影响。
发明内容
针对现有技术中存在的问题,本发明的目的是提供一种复合材料及其制备方法。
具体的技术方案如下:
一种复合材料,由以下组分按照重量份数制备而成:
橡胶体系:丁苯橡胶(SBR)100份,高岭土10-20份,炭黑(N774)10-15份,防老剂4010NA 2-3份,S 2-4份,氧化锌3-5份,硬脂酸0.5-2份,古马隆树脂3~6份,橡胶硫化促进剂CZ 1.5~2.5份,助促进剂TMTD 0.05~0.2份,机油5~10份。
微晶陶瓷体系:硅酸盐类微晶陶瓷30-56份,氧化锌(细度≥800目)60-66份,蒙脱土2-3份,钛酸酯偶联剂2-3份;
橡胶体系和微晶陶瓷体系的重量比为:100∶20~35。
在上述方案的基础上,一种复合材料,由以下组分按照重量份数制备而成:
橡胶体系:丁苯橡胶(SBR)100份,高岭土12份,炭黑(N774)15份,防老剂4010NA 2份,S 2份,橡胶硫化促进剂CZ 1.8份,助促进剂TMTD 0.1份,氧化锌4份,硬脂酸1份,古马隆树脂5份,机油8份。
微晶陶瓷体系:硅酸盐类微晶陶瓷45份,氧化锌(细度≥800目)62份,蒙脱土3份,钛酸酯偶联剂3份。
橡胶体系和微晶陶瓷体系的重量比为:100∶28。
所述高岭土为纳米级高岭土,平均粒径300~500nm,325目筛余量≤0.02%。
所述钛酸酯偶联剂为三异硬脂酰基钛酸异丙酯(TTS)。
一种如上所述的复合材料,具体的制备方法如下:
1)按量称取微晶陶瓷体系中各组分,将各组分输入高速混料机中,在高速混料机搅拌叶片转速1000转/分,温度≥100℃的条件下捏合20分钟,然后放料冷却至室温;
2)按量称取橡胶体系中各组分,将丁苯橡胶投入密闭式炼胶机中,开机以40转/分的速度进行生胶塑炼,时间3分钟;然后依次加入防老剂4010NA、硬脂酸、高岭土、炭黑(N774)、机油、古马隆树脂,再按比例加入步骤1)制备的复配材料,混炼10分钟,排出胶料至开放式炼胶机上,排出胶料的温度在100~130℃范围内;
3)将开放式炼胶机辊筒温度设定在40~55℃,辊距为6~10mm,使胶料在开放式炼胶机上得以快速冷却;待胶料冷却至100℃以下时,加入S、橡胶硫化促进剂CZ、助促进剂TMTD和氧化锌,使其充分混合均匀,然后出片或切割成颗粒,冷却至室温后进行包装。
本发明的优点在于:本发明制备的复合材料解决传统的油气集输管道在使用过程中存在的腐蚀、磨损问题。本发明用化学交联的方法使橡胶分子间产生交联反应,形成橡胶大分子间的立体互穿网络结构,从而赋予橡胶不溶不熔、耐化学腐蚀、耐温(寒)、抗老化以及增强该复合材料的力学性能,例如拉伸强度、抗冲击性和模量。
具体实施方式
以下实施例仅用于对本发明做进一步的描述,并不是用来限制本发明的范围。
丁苯橡胶(SBR):齐鲁石油化工公司;
高岭土:枣庄三兴高新材料有限公司;
炭黑N774:美国卡博特公司;
防老剂4010NA:威海华恩橡塑新材料有限公司;
S:山东新泰市汶河化工厂;
氧化锌:山东邹平荣昊化工有限公司;
硬脂酸:淄博天合生物科技有限公司;
古马隆:山东齐邦树脂有限公司。
促进剂CZ:东营金正石油化工有限公司
TMTD:上海加成化工有限公司
硅酸盐类微晶陶瓷:英杰惠能(北京)能源新技术有限公司与青岛科技大学高分子工程材料研究所合作生产,商品名:盖世盾类微晶无机陶瓷粉体
蒙脱土:浙江丰虹新材料股份有限公司
三异硬脂酰基钛酸异丙酯(TTS):扬州市立达树脂有限公司
设备型号和供应厂家:
密闭式炼胶机:X(S)N35/30:江苏双象橡塑机械有限公司;
开放式炼胶机:XK450:青岛环宇科技有限公司;
高速混料机:SHR100A:张家港永利机械有限公司
实施例1
一种复合材料,具体的制备方法如下:
1)称取硅酸盐类微晶陶瓷30kg,氧化锌(细度≥800目)60kg,蒙脱土2kg,三异硬脂酰基钛酸异丙酯(TTS)2kg,将各组分输入捏合机中,在捏合机搅拌叶片转速1000转/分,捏合机温度≥100℃的条件下捏合20分钟,然后放料冷却至室温;
2)将丁苯橡胶100kg投入密闭式炼胶机中,开机以40转/分的速度进行生胶塑炼,时间3分钟;然后依次加入防老剂4010NA 2kg、硬脂酸0.5kg、纳米级高岭土(平均粒径300nm,325目筛余量0.02%)10kg、炭黑(N774)10kg、机油5kg和古马隆树脂3kg,加入步骤1)制备的复配材料28kg,混炼10分钟,排出胶料至开炼机上,排出胶料的温度在100℃;
3)将开炼机辊筒温度设定在40℃,辊距为6mm,使胶料在开炼机上得以快速冷却。待胶料冷却至90℃时,加入S 2kg、橡胶硫化促进剂CZ 1.5kg、助促进剂TMTD 0.05kg、氧化锌3kg,使其充分混合均匀,然后出片或切割成颗粒,冷却至室温后进行包装。
实施例2
一种复合材料,具体的制备方法如下:
1)称取硅酸盐类微晶陶瓷45kg,氧化锌(细度≥800目)62kg,蒙脱土3kg,三异硬脂酰基钛酸异丙酯(TTS)3kg,将各组分输入捏合机中,在捏合机搅拌叶片转速1000转/分,捏合机温度≥100℃的条件下捏合20分钟,然后放料冷却至室温;
2)将丁苯橡胶100kg投入密闭式炼胶机中,开机以40转/分的速度进行生胶塑炼,时间3分钟;然后依次加入防老剂4010NA 2kg、硬脂酸1kg、纳米级高岭土(平均粒径400nm,325目筛余量0.01%)12kg、炭黑(N774)15kg、机油8kg和古马隆树脂5kg,加入步骤1)制备的复配材料45kg,混炼10分钟,排出胶料至开炼机上,排出胶料的温度在120℃;
3)将开炼机辊筒温度设定在42℃,辊距为8mm,使胶料在开炼机上得以快速冷却。待胶料冷却至90℃时,加入S 2kg、橡胶硫化促进剂CZ 1.8kg、助促进剂TMTD 0.1kg、氧化锌4kg,使其充分混合均匀,然后出片或切割成颗粒,冷却至室温后进行包装。
实施例3
一种复合材料,具体的制备方法如下:
1)称取硅酸盐类微晶陶瓷56kg,氧化锌(细度≥800目)66kg,蒙脱土3kg,三异硬脂酰基钛酸异丙酯(TTS)3kg,将各组分输入捏合机中,在捏合机搅拌叶片转速1000转/分,捏合机温度≥100℃的条件下捏合20分钟,然后放料冷却至室温;
2)将丁苯橡胶100kg投入密闭式炼胶机中,开机以40转/分的速度进行生胶塑炼,时间3分钟;然后依次加入防老剂4010NA 4kg、硬脂酸2kg、纳米级高岭土(平均粒径500nm,325目筛余量≤0.02%)20kg、炭黑(N774)15kg、机油10kg和古马隆树脂6kg,加入步骤1)制备的复配材料59kg,混炼10分钟,排出胶料至开炼机上,排出胶料的温度在130℃;
3)将开炼机辊筒温度设定在55℃,辊距为10mm,使胶料在开炼机上得以快速冷却。待胶料冷却至90℃时,加入S 4kg、橡胶硫化促进剂CZ 2.5kg、助促进剂TMTD 0.2kg、氧化锌5kg,使其充分混合均匀,然后出片或切割成颗粒,冷却至室温后进行包装。
实施例4
耐高温和低温的实验:
测定高低温状态下的力学性能,特别是低温冲击强度:依据GB/T2490-2007和GB/T17748-2008标准,耐热性用维卡软化点表征,依照GB/T 8802-2001热塑性塑料管材、管件维卡软化温度的测定,测试结果如表1所示。
表1:复合材料力学性能和软化点测试结果
实施例5
耐磨性试验,按照GB/T 3960-1983塑料滑动摩擦磨损试验方法进行测试。摩擦系数0.19,实施例1-3中最大的体积磨损2.48×10-4cm3,比普通聚乙烯磨损量减少2倍。
试验机为北京冠测试验仪器有限公司生产的SLMC-04塑料滑动摩擦试验机,技术参数如下:
试样尺寸:30mm*7mm*6mm±0.1mm
转动速度:0-200转/分连续可调(同类设备无此项功能)
负荷:196N±0.2%(可扩充到392N)
摩擦环尺寸:倒角0.5×45°外圆表面与内圆同心度偏差小于0.01
摩擦力矩:0--4N·m±0.5%
实施例6
该复合材料用于钢塑复合管的内、外层连续复合挤出实验,挤出温度控制在150-230℃,发现塑料层和钢结构层粘接良好,挤出顺利、稳定。
将本发明制备的复合材料敷设在1m*1m的不锈钢表面,在温度150℃、压力0.6~1Mpa的条件下经过15分钟,即完全附着在不锈钢表面,之后进行下列测试:
附着性测试
根据GB/T11211-2009标准,本发明实施例1-3制备的复合材料进行附着性测试,附着力均达到6Mpa以上。
耐热性测试
根据CNS 10757(1995)标准,对实施例1-3制备的复合材料进行耐热性测试,在120℃和160℃分别测试2h,-50℃测试48h,均无膨胀、剥落、龟裂、气泡等异常现象。
酸浸渍试验
根据CNS 10757(1995)标准,对实施例1-3制备的复合材料进行酸浸渍试验,3%H2SO4中浸泡168h均无异常。
耐油性试验
根据CNS 10757(1995)标准,对实施例1-3制备的复合材料进行耐油性试验,无铅汽油中浸泡72h后均无异常。
上述参照实施例是说明性的而不是限定性的,可按照所限定范围列举出若干个实施例,因此在不脱离本发明总体构思下的变化和修改,应属本发明的保护范围之内。
Claims (7)
1.一种复合材料,其特征在于:由以下组分按照重量份数制备而成:
橡胶体系:丁苯橡胶(SBR)100份,高岭土10-20份,炭黑(N774)10-15份,防老剂4010NA 2-3份,S 2-4份,氧化锌3-5份,硬脂酸0.5-2份,古马隆树脂3~6份,橡胶硫化促进剂CZ 1.5~2.5份,助促进剂TMTD 0.05~0.2份,机油5~10份。
微晶陶瓷体系:硅酸盐类微晶陶瓷30-56份,氧化锌(细度≥800目)60-66份,蒙脱土2-3份,钛酸酯偶联剂2-3份;
橡胶体系和微晶陶瓷体系的重量比为:100∶20~35。
2.根据权利要求1所述的一种复合材料,其特征在于:由以下组分按照重量份数制备而成:
橡胶体系:丁苯橡胶(SBR)100份,高岭土12份,炭黑(N774)15份,防老剂4010NA 2份,S 2份,橡胶硫化促进剂CZ 1.8份,助促进剂TMTD 0.1份,氧化锌4份,硬脂酸1份,古马隆树脂5份,机油8份。
微晶陶瓷体系:硅酸盐类微晶陶瓷45份,氧化锌(细度≥800目)62份,蒙脱土3份,钛酸酯偶联剂3份。
橡胶体系和微晶陶瓷体系的重量比为:100∶28。
3.根据权利要求1或2所述的复合材料,其特征在于:所述高岭土为纳米级高岭土,平均粒径300~500nm,325目筛余量≤0.02%。
4.根据权利要求1或2所述的复合材料,其特征在于:所述钛酸酯偶联剂为三异硬脂酰基钛酸异丙酯(TTS)。
5.一种如权利要求3或4所述的复合材料,其特征在于:具体的制备方法如下:
1)按量称取微晶陶瓷体系中各组分,将各组分输入高速混料机中,在高速混料机搅拌叶片转速1000转/分,温度≥100℃的条件下捏合20分钟,然后放料冷却至室温;
2)按量称取橡胶体系中各组分,将丁苯橡胶投入密闭式炼胶机中,开机以40转/分的速度进行生胶塑炼,时间3分钟;然后依次加入防老剂4010NA、硬脂酸、高岭土、炭黑(N774)、机油、古马隆树脂,再按比例加入步骤1)制备的复配材料,混炼10分钟,排出胶料至开放式炼胶机上,排出胶料的温度在100~130℃范围内;
3)将开放式炼胶机辊筒温度设定在40~55℃,辊距为6~10mm,使胶料在开放式炼胶机上得以快速冷却;待胶料冷却至100℃以下时,加入S、橡胶硫化促进剂CZ、助促进剂TMTD和氧化锌,使其充分混合均匀,然后出片或切割成颗粒,冷却至室温后进行包装。
6.权利要求5制备的复合材料用作防腐材料。
7.根据权利要求6所述的防腐材料,其特征在于:用作金属管道及管件表面的防腐材料。
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