CN1136993A - 含有氟塑料三元共聚物的软管构造 - Google Patents

含有氟塑料三元共聚物的软管构造 Download PDF

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CN1136993A
CN1136993A CN96106165A CN96106165A CN1136993A CN 1136993 A CN1136993 A CN 1136993A CN 96106165 A CN96106165 A CN 96106165A CN 96106165 A CN96106165 A CN 96106165A CN 1136993 A CN1136993 A CN 1136993A
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flexible pipe
endecatylene
diazabicylo
inner core
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CN1057251C (zh
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A·D·费特
G·A·查普曼
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Goodyear Tire and Rubber Co
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

本发明涉及含有氟塑料防渗层的软管构造。该软管包含(1)内芯,包含(a)丁腈橡胶和(b)0.05-25phr1,8-二氮杂二环[5,4,0]十一碳烯-7的未取代的或取代的苯酚盐;(2)防渗层,包含衍生自四氟乙烯、六氟丙烯和偏二氟乙烯的三元共聚物,其中所述防渗层直接粘着于所述内芯上;和(3)弹性体型外层。

Description

含有氟塑料三元共聚物 的软管构造
目前汽车使用的燃料管大部分是多层的构造。该软管的最内层由用于在管中存贮流体的弹性体型材料构成。内芯和弹性体型外层之间存在一防渗层(Barrier layer)。已使用过许多防渗层,但许多用在防渗层的这样的化合物不能粘着于用在最内管层中的常规弹性体型材料上。结果,本领域技术人员在内芯和防渗层之间使用了与用在内芯和防渗层中的弹性体均相容的层。这些“相容”层的使用又增加了成本并使这些用作燃料软管的直径增大。
本发明披露一种软管,包括(1)内芯,包含(a)丁腈橡胶和(b)0.05-25phr 1,8-二氮杂二环[5,4,0]十一碳烯-7的未取代的或取代的苯酚盐;(2)防渗层,包含衍生自四氟乙烯、六氟丙烯和偏二氟乙烯的三元共聚物,其中所述防渗层直接粘着于所述内芯上;和(3)弹性体型外层。
图1是按照本发明的软管的透视图。
图2是按照本发明的软管的透视图。
在制备例如如图1所示的软管时,本发明的内芯(1)即管芯由丁腈橡胶(NBR)构成。
可以使用各种丁腈橡胶。例如Mooney粘度(M/L1+4@100℃)和丙烯腈含量可随软管的用途而改变。丁腈橡胶的适宜实例可以具有20-91的Mooney粘度。丙烯腈含量可在15.9-46.2%范围内。可商购自Goodyear Tire & Rubber Company的有代表性的丙烯腈橡胶包括一族市售ChemigumTM系列的产品,例如ChemigumTM N206(Mooney55-70且ACN为46.2%),ChemigumTM N300(Mooney 50-63且ACN为40%),ChemigumTM N318(Mooney 68-82且ACN为40%),ChemigumTM N328(Mooney 65-80且ACN为41.5%),ChemigumTMN386B(Mooney 55-65且ACN为40.5%),ChemigumTM N608(Mooney 63-75且ACN为33.4%),ChemigumTM N612B(Mooney 20-30且ACN为33.4%),ChemigumTM N615B(Mooney 47-60且ACN为33.4%),ChemigumTM N624B(Mooney 38-50且ACN为32.9%).ChemigumTM N628B(Mooney 68-85且ACN为33.4%),ChemigumTM N683B(Mooney 25-35且ACN为33.4%),ChemigumTMN685B(Mooney 45-55且ACN为33.4%),ChemigumTM N687B(Mooney 65-75且ACN为33.4%),ChemigumTM N689B(Mooney 79-91且ACN为33.4%),ChemigumTM N715(Mooney 45-63且ACN为29.3%),ChemigumTM N785B(mooney 45-55且ACN为27.7%),ChemigumTM N917B(Mooney 55-70且ACN为22.8%),ChemigumTMN926(Mooney 55-70且ACN为15.9%)和ChemigumTM N984B(Mooney 35-45且ACN为20.0%)。
该NBR内芯(1)可用本领域技术人员公知的挤塑法来制备。此内芯(1)的厚度是重要的,因为壁厚度太薄或太厚会带来最终软管复合材料的柔软性问题或扭接问题或偶联相容性问题。据认为内芯(1)的内径应在4-75mm范围内。内芯的内径最好应在6-50mm范围内。内芯(1)的壁厚应在0.5-4.0mm范围内,优选在1.2-2.8mm范围内。
大约0.05-25phr的1,8-二氮杂二环[5,4,0]十一碳烯-7的未取代的或取代的苯酚盐均匀分布在该丁腈橡胶中。这样的化合物的实例包括1,8-二氮杂二环[5,4,0]十一碳烯-7的苯酚盐,1,8-二氮杂二环[5,4,0]十一碳烯-7的甲酚盐,1,8-二氮杂二环[5,4,0]十一碳烯-7的间苯二酚盐和1,8-二氮杂二环[5,4,0]十一碳烯-7的氢醌盐。优选1,8-二氮杂二环[5,4,0]十一碳烯-7的苯酚盐。所述未取代的或取代的苯酚盐的量最好在2.0-6.0phr范围内。特别优选的1,8-二氮杂二环[5,4,0]十一碳烯-7的未取代的苯酚盐可以Accelerator P152的商品名购自Mitsui & Co(Canada)Ltd。
除上述外,NBR内芯(1)组合物还可以含有常规添加剂,包括补强剂,填充剂,胶溶剂,颜料,硬脂酸,促进剂,硫化剂,抗臭氧剂,抗氧化剂,加工油,活化剂,引发剂,增塑剂,蜡类,预硫化抑制剂,增量油等。补强剂的代表物包括炭墨,加入量一般为每100重量份总橡胶大约5-200重量份(phr)。炭黑的用量最好在大约35-120phr范围内。所用的典型的炭黑包括N110,N330,N332,N472,N550,N630,N642,N650,N762,N770,N907,N908,N990和N991。当将软管用于传输可燃性流体时,可以使用导电黑。可以使用的非炭黑填充剂包括滑石,粘土,碳酸钙,二氧化硅等。非炭黑填充剂的用量可以在大约5-150phr范围内。还可以使用含有这样的填充剂的油分散体。有机硅烷例如四硫化3,3’-双(三乙氧基甲硅烷基丙基)的用量可以在0.1-20phr范围内。这样的有机硅烷的适当实例披露于美国专利第4128438号中,本文参考引用其全部内容。有代表性的硫化剂包括元素硫(单体硫)或给硫硫化剂,例如二硫化胺,聚合物多硫化物或硫烯烃加成物。若使用硫化剂,其用量将随橡胶的类型和硫化剂的具体类型变动,但一般在大约0.1-10phr范围内,优选在大约0.5-3phr范围内。可以存在于该橡胶组合物中的有代表性的抗降解剂包括微晶蜡,石蜡,一元酚,双酚,硫双酚,多元酚,氢醌衍生物,亚磷酸盐,磷酸盐共混物,硫代酯,萘胺,联苯酚胺,取代的和未取代的二芳基胺衍生物,二芳基苯二胺,对苯二胺,喹啉类和混合的胺类。抗降解剂的用量一般在大约0.1-10phr范围内。优选在大约2-6phr范围内。可使用的有代表性的胶溶剂是五氯苯酚,其用量可在大约0.1-0.4phr范围内,优选在大约0.2-0.3phr范围内。可用在本发明的橡胶组合物中的有代表性的加工油包括活化的二硫代双N-苯甲酰苯胺,聚对二亚硝基苯,二甲苯基硫醇,脂族-脂环烃芳族树脂,聚乙二醇,石油润滑油,酯类增塑剂,硫化植物油,松焦油,酚醛树脂,合成油,石油树脂,聚合物酯和松脂。这些加工油可以在大约0-140phr范围内的常规量来使用。可用的引发剂的代表物是硬脂酸。引发剂一般以在大约1-4phr范围内的常规量来使用。可用作多组分硫化剂组分的其它添加剂包括氧化钙,氧化锌和氧化镁。这些添加剂的常规用量在0.1-25phr范围内。
促进剂可以常规量例如大约0.1-10phr使用。在仅使用主促进剂的情况下,该量在大约0.1-10phr范围内。在配合使用两种或更多种促进剂的情况下,主促进剂的用量通常0.1-10.0phr范围内,而副促进剂的用量在大约0.1-10.0phr范围内。已知促进剂组合能产生协调作用。适宜的常规促进剂的类型是胺类,二硫化物,胍类,硫脲类,噻唑类,秋兰姆类,硫醇类,次磺酰胺类,二硫代氨基甲酸酯类和黄原酸酯类。
本发明的一个优点在于:内芯(1)可被直接粘着于用在本发明中的防渗层(3)上。因此在内芯(1)与本发明的防渗层(3)之间无需存在“相容性”聚合物层。
在本发明中使用的防渗层(3)由衍生自四氟乙烯、六氟丙烯和偏二氟乙烯的三元共聚物获得。该防渗层(3)的厚度是重要的,因为壁厚度大薄或太厚会产生柔软性或扭接问题或所需要的防渗性能方面的问题。一般来讲,防渗层(3)的厚度在大约0.02-0.76mm范围内。优选在大约0.12-0.25mm范围内。如上所述,本发明的优点之一在于该三元共聚物可被直接挤塑在由丁腈橡胶构成的内芯(1)上。可用于形成本发明的软管的防渗层(3)的优选的三元共聚物是可商购自3MCompany的商品名为THV 200、THV300、THV400和THV500的产品。THV500的熔点范围为165-180℃,熔体流动指数为5-15(265℃/5kg)(按ASTM 1238测得),比重为1.98g/cm3(根据ASTM792),拉伸强度20N/m2(根据ASTM638)和伸长率为450%(根据ASTM638)。
本发明软管中所需的最后构件是弹性体型外层(5)。该外层(5)可被挤塑在下垫层上,所述下垫层可以是防渗层(3)或者是如下所述的各种其它的可任选层。可用于形成本发明软管的外层的弹性体包括本领域技术人员公知的弹性体,例如氯磺酰化聚乙烯,氯化聚乙烯,丁腈橡胶/PVC共混物,氯醚橡胶,EPDM,氯丁二烯,EVA和EVM。用在该外层中的弹性体最好是氯化聚乙烯或NBR/PVC共混物。该弹性体型外层(5)的厚度显然取决于该软管的所需性能和所用的弹性体。一般来讲,弹性体型外层(5)的厚度在大约0.5-2.5mm范围内,优选在1.0-1.5mm范围内。
上面已经讨论了对本发明是必不可少的三个基本层,而本发明的软管还可以具有可选的特征。例如,当制备具有内芯(10)和防渗层(12)的如图2所示的软管时,分布在防渗层(12)外侧的可以是另一聚合物的第一层(14)。这样的聚合物可以与内芯的组成相同。在另一个实施方案中,用在该与防渗层(12)邻接的第一层(14)中的聚合物可以是氯醚橡胶。该与防渗层(12)邻接的第一层(14)的厚度可以取决于所选择的聚合物。一般来讲,该层的厚度应在大约0.25-1.5mm范围内,优选在大约0.50-1.0mm范围内。
本发明的另一个可选的特征是增强材料(16)可以被加在与防渗层(12)邻接的第一层(14)的顶部。这样的增强材料是本领域技术人员公知的,可以包括螺旋的、针织的或编织的纱线。这样的增强材料一般源自聚酯、尼龙、嫘萦或聚芳基酰胺绳。增强材料(16)最好在足够的张力下被螺旋缠绕至该第一层上以增强软管结构的强度。最好将增强材料层(16)以使该软管的屈挠不会产生皱缩或扭接的角度螺旋缠绕。可以采用例如与软管的中心线成0-89.9°的角度。最好采用不高于54°73’的中心角用于螺旋缠绕。
如上所述,弹性体型外层(18)是该外层。
下面的实施例用于说明本发明,但对本发明无限制。除另作说明外,所有份数均为重量份数。
                         实施例1
按照本发明的说明制备软管,该软管结构包含NBR胶料内芯。所述NBR胶料含有100phr ChemigumTM N608,2phr P152和常规量的抗降解剂、MgO、炭黑、加工油、有机硅烷、CaO和促进剂。
用Berstorff 4.5英寸(11.43cm)直径16∶1 L/D橡胶挤塑机和具有如表1所示的温度分布图的直机头挤塑NBR内芯管。将该管用1.290英寸(3.28cm)OD内模头和1.430英寸(3.63cm)ID外模头挤塑。螺杆每分钟转34-37转,形成每分60钟英尺(每分钟18.29米)的线速度。将挤出物喷水冷却,并将过量的水用强制鼓风装置去除。然后将该NBR挤出物卷绕在盘上并送至下一步骤中。
将NBR挤出物通过具有24∶1L/D的装在Sterling 3英寸(7.62cm)直径的塑料挤塑机上的Davis-Standard直角机头拉出。用表1中所示的温度分布图通过2.69英寸(6.83cm)OD内模头和2.77英寸(7.04cm)ID外模头挤出THV500防渗层并牵引至该管上。该塑料挤出机以3.6-4.0RPM运转,线速度为每分钟26-28英尺(每分钟7.92-8.53米)。将THV500防渗层压延至0.010英寸的厚度并在该管上放冷。
然后将该管和防渗层通过具有表1所示的温度分布图的安装在直径为3.5英寸(8.89cm)的12∶1 L/D NRM橡胶挤塑机的直角机头拉伸。借助真空将0.035英寸(0.89mm)厚度的NBR摩擦层(组成与内芯的相同)放到该THV500层上。使用1.906英寸(4.3cm)OD锥形内模头和1.875英寸(4.76cm)ID锥形外模头制备挤出物。该挤出机以2.5的速度设定和每分钟27-28英尺(每分钟8.23-8.53米)的线速度运转。喷水将挤出物冷却。过量的水用强制鼓风装置去除。将水去除后,将挤出的层状物卷绕在盘上并转送至下一步骤中。
将该挤塑层由该盘中拉出并通过编织机。用20号针编织机以每英寸9针(≈每厘米3.5针)平针编织加入聚芳基酰胺增强纱(1500旦尼尔)。将1.860英寸(4.72cm)OD编织坯料缠绕在盘上,进入外层的制备。
通过将该针织挤塑物层从盘中拉出并通过连到4.5英寸(11.43cm)NRM橡胶挤塑机上的NRM橡胶直角机头施加0.040英寸(4.8mm)氯磺酰化聚苯乙烯外层。该挤出机的温度分布图见表1所示。用1.875英寸(4.76cm)OD锥形内模头和1.813英寸(4.60cm)ID锥形外模头制备挤出物。以每分钟34英尺(每分钟10.36米)施加该外层。在该软管上喷水以帮助冷却,过量的水用强制鼓风装置去除。施加润滑剂以避免软管粘在一起。然后将软管切成定长。
将切成定长的软管放在1.56英寸(3.96cm)OD成型芯模上,然后于常温(160-185℃)固化成型。
固化后,将形成的软管从芯模上取下,洗涤,然后切割成成品长度。
                               表  1
                             挤塑机温度分布图℃
                                机筒加热区
挤塑机   材料    螺杆    供料   变流区    计量1    计量2  轴颈  机头   模头
管子   NBR     71     66     77     93     93   N/A   110   N/A
防渗层   THV     N/A     235     246     252     254   257   257   257
摩擦层   NBR     66     N/A     82     82     82   N/A   110   N/A
外层   CSM     66     71     77     82     82   N/A   104   N/A
                             实施例2
为证实本发明的优点,制备两个NBR样品。一个样品含有2.0phrP152。另一个样品不含P152。除P152外,两个样品的配方相同。按照Drum Adhesion Method ASTM D1871-89方法2测定各NBR样品对THV500层的粘着力。结果见下表2。
                       表2
    样品     A     B
 P152浓度(phr)     2     0
 粘着力,ppiw,原始(N/mm)     18(3.15)     0(0)
ppiw=每英寸宽度磅数N/mm=每毫米宽度牛顿数
                      实施例3
就对THV500的粘着力测试一系列含P152的NBR胶料样品。所用的测试方法是Drum Adhesion Method ASTM D1871-89方法2。在组成中除P152的浓度不同外,所有的NBR胶料均相同。测试结果见下表3。
                        表3
    样品     A     B     C     D
 P152浓度(phr)     1     2     4     10
 粘着力,ppiw,原始(N/mm)     15(2.63)     15(2.63)     19(3.33)     11(1.93)
 粘着力,ppiw,老化后(N/mm)     14(2.45)     18(3.15)     9(1.58)     19(3.33)
1在gasohol(25%甲醇和75%ASTM燃料C)中于23℃浸48小时后。ppiw=每英寸宽度磅数N/mm=每毫米宽度牛顿数

Claims (10)

1.一种软管,其特征在于:它包括(a)内芯,包含(1)丁腈橡胶和(2)0.05-25phr 1,8-二氮杂二环[5,4,0]十一碳烯-7的未取代的或取代的苯酚盐;(b)防渗层,包含衍生自四氟乙烯、六氟丙烯和偏二氟乙烯的三元共聚物,其中所述防渗层直接粘着于所述内芯上;和(3)弹性体型外层。
2.权利要求1的软管,其特征在于:所述1,8-二氮杂二环[5,4,0]十一碳烯-7的取代的苯酚盐选自1,8-二氮杂二环[5,4,0]十一碳烯-7的甲酚盐,1,8-二氮杂二环[5,4,0]十一碳烯-7的间苯二酚盐和1,8-二氮杂二环[5,4,0]十一碳烯-7的氢醌盐。
3.权利要求1的软管,其特征在于:在所述防渗层和弹性体型外层之间设置有第一层,所述第一层包含选自下列的聚合物:(a)含有大约0.05-2.5phr 1,8-二氮杂二环[5,4,0]十一碳烯-7的未取代的或取代的苯酚盐的丁腈橡胶,和(b)氯醚橡胶。
4.权利要求3的软管,其特征在于:在所述第一层和所述弹性体型外层之间设置有张拉增强线料层。
5.权利要求1的软管,其特征在于:构成所述弹性体型外层的所述弹性体选自氯磺酰化聚乙烯,氯化聚乙烯,丁腈橡胶/PVC共混物,氯醚橡胶,EPDM,氯丁二烯,EVA和EVM。
6.权利要求4的软管,其特征在于:所述增强材料来自聚酯、尼龙、嫘萦和聚芳基酰胺的纺织纱线。
7.权利要求1的软管,其特征在于:内芯的内径在大约4-75mm范围内。
8.权利要求1的软管,其特征在于:内芯的壁的直径在大约0.5-4.0mm范围内。
9.权利要求1的软管,其特征在于:防渗层的厚度在大约0.02-0.76mm范围内。
10.权利要求1的软管,其特征在于:弹性体型外层的厚度在大约0.5-2.5mm范围内。
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CN112145822A (zh) * 2020-09-28 2020-12-29 烟台泰悦流体科技有限公司 一种用于食品输送的软管
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US5639528A (en) 1997-06-17
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CA2157996A1 (en) 1996-10-25
EP0739712A2 (en) 1996-10-30
TW340093B (en) 1998-09-11
KR960037272A (ko) 1996-11-19
EP0739712A3 (en) 1999-03-24
BR9602015A (pt) 1998-10-06
KR100392800B1 (ko) 2004-02-11
EP0739712B1 (en) 2003-01-15
CN1057251C (zh) 2000-10-11

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