CN101463933A - 丁腈橡胶、氟树脂与氯醚橡胶汽车燃油胶管及制备方法 - Google Patents

丁腈橡胶、氟树脂与氯醚橡胶汽车燃油胶管及制备方法 Download PDF

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CN101463933A
CN101463933A CNA2008101539396A CN200810153939A CN101463933A CN 101463933 A CN101463933 A CN 101463933A CN A2008101539396 A CNA2008101539396 A CN A2008101539396A CN 200810153939 A CN200810153939 A CN 200810153939A CN 101463933 A CN101463933 A CN 101463933A
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nitrile butadiene
thickness
fluororesin
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CN101463933B (zh
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张洪起
孙佩祝
李风海
王金财
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Tianjin Peng Ling group Limited by Share Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/88Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/918Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
    • B29C48/9185Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/88Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/91Heating, e.g. for cross linking
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel or housing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92904Die; Nozzle zone
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92923Calibration, after-treatment or cooling zone

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Abstract

本发明涉及一种丁腈橡胶、氟树脂与氯醚橡胶汽车燃油胶管及其制备方法;汽车燃油胶管具有五层结构,丁腈橡胶内层(1)和氟树脂中层(2);丁腈橡胶中层(3);编织层(4);氯醚橡胶外层(5)。丁腈橡胶内层厚度为0.5~2.0mm;氟树脂中层厚度为0.05~0.3mm;丁腈橡胶中层厚度为0.3~1.5mm;氯醚橡胶外层(5),厚度为1~6mm;本发明的丁腈橡胶、氟树脂与氯醚橡胶汽车燃油胶管的制备方法采用管胚制造过程和硫化成型过程,制备的胶管满足耐高温、耐油的使用要求的前提下,解决现有低温燃油胶管渗透率高,污染环境的问题。

Description

丁腈橡胶、氟树脂与氯醚橡胶汽车燃油胶管及制备方法
技术领域
本发明涉及汽车胶管技术领域,特别涉及一种丁腈橡胶、氟树脂与氯醚橡胶汽车燃油胶管及其制备方法。
背景技术
当汽车潮水般地涌进人们的现代生活,给我们带来不尽便利的时候,汽车尾气排放和日趋恶化的环境污染也随之到来。汽车排出的碳氢化物及其它污染大气层的物质,主要源头之一是来自汽车燃油胶管中渗透出的汽油。随着环境意识的增强,对燃油胶管的渗透性能要求越来越高,耐臭氧要求也由原来的50pphm提高到200pphm。目前通用的三层结构燃油胶管,由内至外依次是:丁腈橡胶层、芳纶线层、氯丁橡胶层。其燃油渗透率标准为80℃×24h,<15g/100cm;其外层氯丁橡胶抗臭氧老化只能满足在50pphm的环境使用。但对于燃油渗透率为80℃×24h,<4g/100cm,臭氧老化浓度为200pphm的燃油胶管来说,仍采用原三层结构的材料已经不能满足标准要求。
发明内容
为满足燃油胶管达到低渗透要求且在200pphm的臭氧环境下正常使用,我们开发研制了新结构的燃油胶管。此燃油胶管既能满足低渗透性,对环境污染小,并且满足耐油、耐臭氧的使用要求,并且成本相对较低。
本发明的丁腈橡胶与氟树脂、氯醚橡胶汽车燃油胶管具有五层结构,依次为丁腈橡胶内层1、氟树脂中层2、丁腈橡胶中层3、编织层4和氯醚橡胶外层5。
本发明的丁腈橡胶、氟树脂与氯醚橡胶汽车燃油胶管的制备方法,其特征包括如下步骤:
1)管胚制造过程
丁腈橡胶内层:挤出温度从机头到螺杆依次为80℃~50℃,70℃~40℃,70℃~40℃,70℃~40℃;厚度为0.5~2.0mm;
氟树脂中层:挤出温度从机头4、机头3、机头2、、机头1、抱夹、温区2到温区1依次为290℃~260℃,290℃~260℃,290℃~260℃,290℃~260℃,280℃~250℃,280℃~250℃,280℃~250℃;厚度为0.05~0.3mm;
丁腈橡胶中层挤出:挤出温度从机头到螺杆依次为80℃~50℃,70℃~40℃,70℃~40℃,70℃~40℃;厚度为0.3~1.5mm;
编织层:使用芳纶线编织生产,芳纶线从800dtx~1870dtx,编织行程20~60mm。
氯醚橡胶外层:挤出温度从机头到螺杆依次为90℃~60℃,80℃~40℃,80℃~40℃,80℃~40℃;厚度为1~6mm。
2)硫化成型过程:
采用一段硫化方法,一段硫化参数:硫化温度为130~180℃,硫化时间为5~60min;
氟树脂是四氟乙烯、六氟丙烯和偏氟乙烯的共聚物。它是具有优异的耐无机酸和有机酸、卤化物、碳氢化合物、醇类等的物质,具有提高其耐渗透性能的能力。并将其设计在燃油胶管结构的第二层,使管体柔软性好,与接头的装配牢固。氯醚橡胶系侧基上含有氯的聚醚型橡胶,是由含有环氧基的环状醚开环聚合而成的高分子弹性体。由于氯醚橡胶是主链含有醚键,侧链含氯甲基(-CH2CI)的饱和脂肪族聚醚。因此氯醚具有很好的耐臭氧性、耐热老化、和优异的耐油性,将其设置在燃油管的最外层对臭氧及热老化有很好的效果,能够在臭氧老化浓度为200pphm的环境中长期使用。
本发明的丁腈橡胶与氟树脂、氯醚橡胶的燃油管的结构是五层编织结构,丁腈橡胶设置在胶管的内层,氟树脂设置在胶管的中层,然后是丁腈橡胶中层、芳纶线编织层,氯醚橡胶设置在胶管的外层。胶管的孔径根据各种汽车胶管的要求具体配置,并且此种结构的氟树脂可以生产异型胶管。
本发明满足耐高温、耐油的使用要求的前提下,解决现有低温燃油胶管渗透率高,污染环境的问题。
附图说明
图1为本发明丁腈橡胶、氟树脂与氯醚橡胶汽车燃油胶管的剖面图。
具体实施方式
下面结合附图和具体实施方式对本发明作进一步详细的说明。
实施例1:
生产内径为5±0.3mm×壁厚为1.85±0.5mm(丁腈橡胶内层1厚度0.5mm、氟树脂中层2厚度0.05mm、丁腈橡胶中层3厚度0.3mm、氯醚橡胶外层5厚度1.0mm)的丁腈橡胶、氟树脂与氯醚橡胶汽车燃油胶管,方法步骤如下:
丁腈橡胶内层:挤出温度从机头到螺杆依次为50℃,40℃,40℃,40℃;
氟树脂中层:挤出温度从机头4、机头3、机头2、、机头1、抱夹、温区2到温区1依次为260℃,260℃,260℃,260℃,250℃,250℃,250℃。
丁腈橡胶中层:挤出温度从机头到螺杆依次为50℃,40℃,40℃,40℃。
编织层:使用芳纶线编织生产,芳纶线800dtx,编织行程20mm。
氯醚橡胶外层:挤出温度从机头到螺杆依次为60℃,40℃,40℃,40℃。
2)硫化成型过程:
采用一段硫化方法,一段硫化参数:硫化温度为180℃,硫化时间为5min;
下表是按照德国大众汽车的标准要求对胶管进行的测试,并得出以下结论。
 
序号 测试项目及指标要求 实施例1胶管
1 燃油渗透性80℃×24h,<4g/100cm2              2.82
2 耐臭氧200pphm×23℃×46h 产品表面无裂纹
3 附着力≥2N/mm 2.26
4 耐寒性-25℃×22h胶管无裂纹       无裂纹
实施例2:
生产一种如图1所示的内径为7.5±0.3mm×壁厚为3.55±0.5mm(丁腈橡胶内层1厚度0.8mm、氟树脂中层2厚度0.15mm、丁腈橡胶中层3厚度0.6mm、氯醚橡胶外层5厚度2.0mm)的丁腈橡胶、氟树脂与氯醚橡胶汽车燃油胶管,方法步骤如实施例1所示,所不同的是:
1)管胚制造过程
丁腈橡胶内层:挤出温度从机头到螺杆依次为70℃,50℃,50℃,50℃;
氟树脂中层:挤出温度从机头4、机头3、机头2、、机头1、抱夹、温区2到温区1依次为280℃,280℃,280℃,280℃,270℃、270℃、270℃。
丁腈橡胶中层:挤出温度从机头到螺杆依次为70℃,50℃,50℃,50℃;
编织层:使用芳纶线编织生产,芳纶线1100dtx,编织行程40mm。
氯醚橡胶外层:挤出温度从机头到螺杆依次为75℃,60℃,60℃,60℃。
2)硫化成型过程:
采用一段硫化方法,一段硫化参数:硫化温度为170℃,硫化时间为20min;
下表是按照德国大众汽车的标准要求对胶管进行的测试,并得出以下结论。
 
序号 测试项目及指标要求 实施例2胶管
1 燃油渗透性80℃×24h,<4g/100cm2              3.16
2 耐臭氧200pphm×23℃×46h 产品表面无裂纹
3 附着力≥2N/mm 2.41
4 耐寒性-25℃×22h胶管无裂纹       无裂纹
实施例3:
生产一种如图1所示的内径为9.0±0.3mm×壁厚为5.4±0.5mm(丁腈橡胶内层1厚度1.2mm、氟树脂中层2厚度0.2mm、丁腈橡胶中层3厚度1.0mm、氯醚橡胶外层5厚度3.0mm)的丁腈橡胶、氟树脂与氯醚橡胶汽车燃油胶管,方法步骤如实施例1所示,所不同的是::
1)管胚制造过程
丁腈橡胶内层:挤出温度从机头到螺杆依次为75℃,60℃,60℃,60℃;
氟树脂中层:挤出温度从机头4、机头3、机头2、、机头1、抱夹、温区2到温区1依次为285℃,282℃,282℃,282℃,275℃,275℃,275℃,。
丁腈橡胶中层:挤出温度从机头到螺杆依次为75℃,60℃,60℃,60℃;
编织层:使用芳纶线编织生产,芳纶线1100dtx,编织行程45mm。
氯醚橡胶外层:挤出温度从机头到螺杆依次为85℃,70℃,70℃,70℃。
2)硫化成型过程:
采用一段硫化方法,一段硫化参数:硫化温度为170℃,硫化时间为25min;下表是按照德国大众汽车的标准要求对胶管进行的测试,并得出以下结论。
 
序号 测试项目及指标要求 实施例3胶管
1 燃油渗透性80℃×24h,<4g/100cm2              3.32
2 耐臭氧200pphm×23℃×46h 产品表面无裂纹
3 附着力≥2N/mm 2.33
4 耐寒性-25℃×22h胶管无裂纹       无裂纹
实施例4:
生产内径为19±0.3mm×壁厚为9.8±0.5mm(丁腈橡胶内层1厚度2.0mm、氟树脂中层2厚度0.3mm、丁腈橡胶中层3厚度1.5mm、氯醚橡胶外层5厚度6.0mm)的丁腈橡胶、氟树脂与氯醚橡胶汽车燃油胶管,方法步骤如实施例1所示,所不同的是:
丁腈橡胶内层:挤出温度从机头到螺杆依次为80℃,70℃,70℃,70℃;
氟树脂中层:挤出温度从机头4、机头3、机头2、、机头1、抱夹、温区2到温区1依次为290℃,290℃,290℃,290℃,280℃,280℃,280℃,。
丁腈橡胶中层:挤出温度从机头到螺杆依次为80℃,70℃,70℃,70℃;
编织层:使用芳纶线编织生产,芳纶线1870dtx,编织行程60mm。
氯醚橡胶外层:挤出温度从机头到螺杆依次为90℃,80℃,80℃,80℃。
2)硫化成型过程:
采用一段硫化方法,一段硫化参数:硫化温度为130℃,硫化时间为60min;
下表是按照德国大众汽车的标准要求对胶管进行的测试,并得出以下结论。
 
序号 测试项目及指标要求 实施例4胶管
1 燃油渗透性80℃×24h,<4g/100cm2              3.84
2 耐臭氧200pphm×23℃×46h 产品表面无裂纹
3 附着力≥2N/mm 2.56
4 耐寒性-25℃×22h胶管无裂纹       无裂纹
通过上述的实验可以明显看出,本发明的丁腈橡胶、氟树脂与氯醚橡胶汽车燃油胶管既满足低渗透性,并且满足耐臭氧的使用要求,完全符合汽车燃油胶管标准要求。

Claims (3)

1.一种丁腈橡胶、氟树脂与氯醚橡胶汽车燃油胶管,具有五层结构,其特征是五层结构依次为丁腈橡胶内层(1)、氟树脂中层(2)、丁腈橡胶中层(3)、编织层(4)和氯醚橡胶外层(5)。
2.如权利要求1所述的丁腈橡胶、氟树脂与氯醚橡胶汽车燃油胶管,其特征是所述的丁腈橡胶内层厚度为0.5~2.0mm;氟树脂中层厚度为0.05~0.3mm;丁腈橡胶中层厚度为0.3~1.5mm;氯醚橡胶外层5,厚度为1~6mm。
3.权利要求1的丁腈橡胶、氟树脂与氯醚橡胶汽车燃油胶管的制备方法,其特征是包括如下步骤:
1)管胚制造过程
丁腈胶内层:挤出温度从机头到螺杆依次为80℃~50℃,70℃~40℃,70℃~40℃,70℃~40℃;
氟树脂中层:挤出温度从机头4、机头3、机头2、、机头1、抱夹、温区2到温区1依次为290℃~260℃,290℃~260℃,290℃~260℃,290℃~260℃,280℃~250℃,280℃~250℃,280℃~250℃;
丁腈胶中层:挤出温度从机头到螺杆依次为80℃~50℃,70℃~40℃,70℃~40℃,70℃~40℃;
编织层:使用芳纶线编织生产,芳纶线从800dtx~1870dtx,编织行程20~60mm;
氯醚橡胶外层:挤出温度从机头到螺杆依次为90℃~60℃,80℃~40℃,80℃~40℃,80℃~40℃。
2)硫化成型过程:
采用一段硫化方法,一段硫化参数:硫化温度为130~180℃,硫化时间为5~60min。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102146173A (zh) * 2011-01-25 2011-08-10 天津鹏翎胶管股份有限公司 与氟树脂或氟橡胶粘接的丁腈橡胶及作为燃油管的应用
CN103115203A (zh) * 2013-02-04 2013-05-22 安徽中鼎密封件股份有限公司 一种燃油管及其制备方法
CN106397877A (zh) * 2016-08-31 2017-02-15 天津鹏翎胶管股份有限公司 一种丁腈橡胶复合氟树脂的多层燃油胶管

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102146173A (zh) * 2011-01-25 2011-08-10 天津鹏翎胶管股份有限公司 与氟树脂或氟橡胶粘接的丁腈橡胶及作为燃油管的应用
CN103115203A (zh) * 2013-02-04 2013-05-22 安徽中鼎密封件股份有限公司 一种燃油管及其制备方法
CN103115203B (zh) * 2013-02-04 2016-03-02 安徽中鼎密封件股份有限公司 一种燃油管及其制备方法
CN106397877A (zh) * 2016-08-31 2017-02-15 天津鹏翎胶管股份有限公司 一种丁腈橡胶复合氟树脂的多层燃油胶管
CN106397877B (zh) * 2016-08-31 2018-07-27 天津鹏翎胶管股份有限公司 一种丁腈橡胶复合氟树脂的多层燃油胶管

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