CN1199020C - 致冷剂软管 - Google Patents

致冷剂软管 Download PDF

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CN1199020C
CN1199020C CN99810126.5A CN99810126A CN1199020C CN 1199020 C CN1199020 C CN 1199020C CN 99810126 A CN99810126 A CN 99810126A CN 1199020 C CN1199020 C CN 1199020C
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pipe
rubber
nylon
flexible pipe
layer
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CN1314979A (zh
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S·P·坎普贝尔
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Eaton Aeroquip LLC
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Abstract

本装置是空调用软管，是一种阻挡层软管。该软管包括热塑性硫化橡胶制成的最内层管(1)。热塑性硫化橡胶制成的最内层管与作为第二管(5)的柔性聚酰胺共挤压。热固性橡胶制成的背衬(2)挤压或压延在聚酰胺阻挡层上。接着是加强层(4)，然后用EPDM外皮(3)覆盖加强层。

Description

致冷剂软管
技术领域
本发明涉及汽车和工业空调以及管送、冷却和输送致冷剂的相关零件用的致冷剂软管。
背景技术
汽车工业使用软管输送例如氟代烃和含氯氟烃的致冷剂。并且有一种趋势是使用可替代的如二氧化碳和丙烷的致冷剂，这导致对可替代的软管材料的需求。软管通常具有由内管、外皮和加强纤维层构成的三层层状结构，外皮位于内管向外的径向上，加强纤维层设置在内管和外皮之间。通常，内管由丁腈橡胶(NBR)或氯磺化聚乙烯(CMS)形成。加强纤维层通常是通过编织如聚酯纤维、嫘萦纤维或尼龙纤维的有机丝形成的网状结构。外皮一般由乙烯丙烯二烯橡胶(EPDM)或氯丁橡胶(CR)形成。
现有的多层软管具有高度的柔韧性。由于橡胶材料具有这种性质，因此能够容易地加工软管。另外，软管没有由有害的金属物质引起的恶化，有害的金属物质如来自在致冷或冷却循环中使用的金属管的金属离子和/或金属氯化物。
然而，橡胶材料通常趁于具有高透气性，即低抗气体透过性。提高传统软管的耐致冷剂渗透性的一种尝试是使用尼龙作为软管的内管中的一层。令人遗憾地，具有尼龙内层的软管具有柔韧性降低的缺点。尼龙层也易于受到输送的化学制品的腐蚀。已经发现，利用本人的阻挡层软管结构可以提高耐致冷剂渗透性，以及减少致冷剂在管接头/软管界面的泻漏。
发明概述
已经设计了新型树脂，以扩大在软的、非极性和硬的、刚性、极性产品之间的组合的范围。过去，这些组合物不能通过共挤压形成在一起，只能通过注射成型形成。利用较高的处理温度和较长的材料接触时间，能够实现TPV最内层和尼龙阻挡层的共挤压。这能够获得热塑性硫化橡胶的性能和尼龙的优点。本发明的软管包括热塑性硫化橡胶的最内层管。热塑性硫化橡胶最内层管与作为第二管的柔性的聚酰胺阻挡层材料共挤压。由热固橡胶制成的第三管挤压或压延在聚酰胺阻挡层管的外面，而不需要化学浸蚀或液体粘结剂。接着是加强层，然后用EPDM外皮覆盖加强层。
本发明的最内层管从由热塑性硫化橡胶构成的成分形成，该硫化橡胶包含聚烯烃树脂和一种或多种选自三元乙丙橡胶或EPDM橡胶和丁基橡胶中的一或多种橡胶。
合适的热塑性硫化橡胶属于符合如ASTM D-638和D-1566规定的物理要求的那些橡胶。本发明的热塑性硫化橡胶表现出通常使用的硫化橡胶的物理性质，并象通常的热塑性树脂一样适合加工。
附图简要说明
图1是本发明致冷剂输送软管的透视图。
实施发明的最佳方式
更具体地，本人的致冷剂软管是一种阻挡层软管，包括由至少一种热塑性硫化橡胶形成的最内层管和沿由聚酰胺材料形成的最内层管径向向外设置的至少一层背衬层。紧接着沿由橡胶材料形成的聚酰胺内管径向向外设置的至少一层背衬层的，是沿内管径向向外设置的加强层。最后，沿由橡胶材料制成的加强层径向向外设置外皮。
图1表示包括由热塑性硫化橡胶制成的最内层管1的致冷剂输送软管。绕着管1共挤压形成由聚酰胺制成的内层5。由热固性橡胶制成的背衬层2包在管5上。接下来是背衬层4，该层由EPDM橡胶制成的外皮3覆盖。
更具体地，最内层管1一般是EPDM改性聚烯烃材料的热塑性硫化橡胶。聚丙烯是特别优选的聚烯烃。在按化学方式的共挤压过程中，已被改性的所述聚烯烃成功地粘接到尼龙材料上。
EPDM是一种基于乙烯、丙烯和少量非共轭二烯的立体有择直链三聚物的合成橡胶，所述非共轭二烯例如环状或无环二烯。聚合物分子的非饱和部分从完全饱和的主链上悬垂下来。能用硫来硫化EPDM。在热塑性硫化橡胶中，用于EPDM橡胶的合适的二烯是双环戊二烯、亚乙基降冰片烯、1，4-己二烯等。
丁基橡胶可作为热塑性硫化橡胶或丁基或IIR橡胶、氯化丁基或CI-IIR橡胶、溴化丁基或Br-IIR橡胶等的成分。较好的选择是平均分子量为约35×104-45×104、氯化率为约1.1-1.3％的CI-IIR橡胶。
本发明的热塑性硫化橡胶高度防水、耐热抗老化、低蠕变、抗风化和在高温下能完全保持物理性能。与这种热塑性硫化橡胶相当的是可从Advanced Elastomer System购买到的Santoprene和Exxon的Trefsin，Santoprene中的聚丙烯树脂成分和EPDM橡胶成分均受到硫化处理，Trefsin中的聚丙烯用作树脂成分，并与丁基橡胶一起用作热固性成分。
Santoprene和其它热塑性硫化橡胶具有极好的抗压缩永久变形性。因此，可获得极好的连接保持(在连接处密封)。典型的EPDM配方如下：
EPDM配方
材料                     份数
EPDM                     93
CSM(氯磺化聚乙烯)        7
高补强黑(炭黑)           20
低补强黑(炭黑)           65
硅                       20
Ricobond1756           10
抗氧化剂                 2
过氧化物                 9
氧化锌                   5
间苯二酚/硬脂酸          7.5
石蜡油                   30
                         271.5
TPV的典型性能
聚烯烃EPDM最内层
硬度                     70-80(肖氏)
表观比重                 0.980
拉伸强度                 960psi
断裂延伸率               240％
用于阻挡层5的聚酰胺树脂可从诸如尼龙6、玻璃强化尼龙6、尼龙6和尼龙6，6的混合物、尼龙12和改性尼龙12材料的均聚物中选择。能用合适的聚烯烃材料使尼龙6或尼龙12改性，以进一步增进对TPV的粘结性。
尼龙6或尼龙12的典型性能是：
            阻挡层材料
表观比重                     1.08
拉伸强度                     5800psi
断裂延伸率                   340％
弯曲模量                     200,000psi
抗弯强度                     8000psi
硬度                         74(D-Scale)
内管2由单橡胶层或复橡胶层构成，橡胶层由例如乙烯丙烯二烯橡胶(EPDM)、氯化异丁二烯-异戊二烯橡胶(CI-IIR)、氯化聚乙烯(CPE)的橡胶材料以及通常用于橡胶管内层的例如丁腈橡胶(NBR)或氯硫化聚乙烯(CSM)的橡胶材料形成。内管2优选为卤化橡胶，例如溴化丁基橡胶。
加强层4可以是纤维层，一般用作常规橡胶软管的加强层。例如，通过编织、卷绕或针织主要由合成纤维构成的细丝形成纤维层4，合成纤维例如玻璃纤维、钢纤维、聚酯纤维或aramid纤维。
外皮3由与内管2相同的材料制成，优选是EPDM。
在优选实施例中，Santoprene(由聚丙烯和熟化EPDM合成橡胶的连续相构成)的内管与柔性尼龙6或尼龙12(用聚丙烯改性)阻挡层一起共挤压。一层EPDM或溴化丁基橡胶挤压或压延在整个阻挡层材料上。该热固性橡胶已被化合，为了是粘结到热塑性阻挡层材料上，而不需要化学侵蚀或液体粘结剂。增强物是经过化学处理以便粘结到相邻的热固性橡胶材料上的细丝聚酯材料。软管的外皮由以EPDM为基的热固性材料构成。
该结构提供了下述独特的加工特征。能够共挤压热塑性橡胶和热塑性阻挡层材料。而且，在制造过程中不需要使用液体粘结剂。该工艺可供无型芯结构使用。
在软管结构中使用TPV/尼龙6或尼龙12组合的优点是：
·组合物的工作温度为-76至274°F。
·没有底层涂料或粘接所需粘结剂或材料。
·不需要结构用型芯。
·内管与各种致冷剂液体匹配。
例1
剥离强度-Santoprene/尼龙管：
用Santoprene内管与尼龙背衬层一起生产共挤压管。
结果：
尼龙是卡普纶8203(尼龙6的挤压等级)。
分析两个等级的Santoprene：
291-60PA和291-85PA。
挤压数据：
挤压机：Santoprene-1 1/4″David标准24:1 L/D
        尼龙-1 1/4″David标准20:1 L10
十字头：GENCA Model E5450
工具：Pin-.728″OD     Die-.900″ID
温度分/条件：
                 Zone1 Zone2 Zone3 Zone4 Head Die RPM
1 1/2″Davis Std.355F 365F 385F 385F 465F 450F 62
1″GENCA         525F 550F 550F ...            30
试验过程：
管形样品被剖开，尼龙外皮材料从样品的一端离Santoprene约一英寸，以便放置在拉伸试验机夹具中。
结果：
构成：              291-60PA        291-85PA
                    卡普纶8203      卡普纶8203
剥离强度(磅/英寸)
样品A               13.0            15.2
样品B               17.8            22.7
样品C               15.1            16.2
平均                15.3            18.0
两种内管组合的粘结性质均为极好。大多数致冷规程要求在最内层橡胶和热塑性背衬层之间具有较大的粘结值(6-101bf/in)。上述数据表明本发明的软管具有更高的剥高强度。
例II
按照例1构成的阻挡层软管具有下面的条件：
Santoprene内管，改性尼龙12阻挡层，EPDM背衬层，聚酯丝加强层和EPDM外皮材料。橡胶EPDM型芯用于制作目的。
特殊加工提示：
1.在EPDM型芯(0.600″)上共挤压191-85PA Santoprene和X51283尼龙12(由EMS American Grilon，Inc.提供)。
Santoprene在176°F干燥6小时，尼龙在176°F干燥6小时。
Santoprene在-360°F至480°F挤压成型，软化温度为500°F。
X51328在-400°F至435°F挤压成型，软化温度为455°F。
2.挤压薄EPDM背衬层(具有粘结剂-Aeroquip Part#30992-)。
3.编织(24导纱器Karg)由Bidd提供的经梅格纳熔接处理的聚酯丝1000/2-3。
4.挤压EPDM外皮。
5.盘绕并熟化。
特殊工艺或数据要求：
规格：
I.D.-0.600″
管-0.030″规格
阻挡层-0.010″规格
背衬层-0.015″规格
外皮-0.075″规格
Santoprene191-85PA和尼龙12×51283共挤压
在1.25英寸Genca挤压机上以20RPM加工尼龙。在1.25英寸Davis标准挤压机上以52.8RPM加工Santoprene。编织操作40纬纱/5英寸。EPDM挤压温度范围从150℃(zone1)直到190℃(模压/软化温度为190℃的zone4)。在固化循环之前将软管适当的盘绕好，软管在315°F固化30分钟。结果表明，在Santoprene和尼龙12材料的粘结试验过程中，Santoprene层相当好地粘结到阻挡层材料上。总之，Santoprene材料充分地粘结到尼龙12上。Santoprene的尺寸整体性看起来随着固化循环保持完整。Santoprene在固化循环过程中看起来是在流动，这导致尼龙阻挡层材料开始流入由编织物产生的空隙中。而且，EPDM外皮材料良好地粘结到编织层上。
例III
除了在尼龙和编织层之间的背衬层是溴化丁基橡胶以外，按照例II构成另一软管。溴化丁基橡胶良好地粘结在尼龙层上，但不如例II的EPDM好。由于溴化丁基橡胶没有同样地粘结到尼龙阻挡层材料上，软管结构优选是EPDM(用Ricobond)背衬层。
除了上述讨论的实施例以外，显然，本领域的技术人员能够对上述发明作出各种改进和变化而不背离本发明的实质和范围。

Claims (15)

1.一种致冷剂输送软管，是一种阻挡层软管，包括：
由至少一种热塑性硫化橡胶形成的最内层管；
由聚酰胺材料形成的沿最内层管径向向外设置的至少一个阻挡层材料；
由橡胶材料形成的沿聚酰胺内管径向向外设置的至少一个背衬层材料；
沿内管径向向外设置的一加强层；以及
由橡胶材料制成的沿加强层径向向外设置的一外皮；
其中，热塑性硫化橡胶形成的最内层管和聚酰胺阻挡层材料共同挤压而不用粘结剂。
2.按照权利要求1的软管，其中热塑性硫化橡胶是聚烯烃以及EPDM橡胶和丁基橡胶中的一种橡胶。
3.按照权利要求1的软管，其中热塑性硫化橡胶是聚丙烯和EPDM橡胶。
4.按照权利要求1的软管，其中聚酰胺内管是纯尼龙6或改性尼龙6。
5.按照权利要求1的软管，其中聚酰胺内管是尼龙6。
6.按照权利要求1的软管，其中橡胶内管是EPDM或卤化丁基橡胶。
7.按照权利要求1的软管，其中橡胶内管是溴化丁基橡胶。
8.按照权利要求1的软管，其中加强层是编织、卷绕或针织形成的丝。
9.按照权利要求1的软管，其中加强层由编织的聚酯纤维制成。
10.按照权利要求1的软管，其中外皮是EPDM橡胶或卤化丁基橡胶。
11.按照权利要求1的软管，其中橡胶内管是EPDM橡胶。
12.按照权利要求1的软管，其中外皮是EPDM橡胶。
13.一种致冷剂输送软管，是一种阻挡层软管，包括：
由聚丙烯和EPDM橡胶的热塑性硫化橡胶形成的一最内层管；
由尼龙6或尼龙12形成的沿最内层管径向向外设置的至少一个内管；
由EPDM橡胶形成的沿聚酰胺内管径向向外设置的至少一个内管；
沿橡胶内管径向向外设置的由聚酯编织物形成的一加强层；
由EPDM橡胶制成的沿加强层径向向外设置的一外皮；
其中：热塑性硫化橡胶形成的最内层管和尼龙内管共同挤压而不用粘结剂。
14.一种致冷剂输送软管，是一种阻挡层软管，包括：
由聚丙烯和EPDM橡胶的热塑性硫化橡胶形成的最内层管；
由尼龙6或尼龙12形成的沿最内层管径向向外设置的至少一个内管；
由溴化丁基橡胶形成的沿聚酰胺内管径向向外设置的至少一个内管；
沿橡胶内管径向向外设置的由聚酯编织物形成的一加强层；
由EPDM橡胶制成的沿加强层径向向外设置的一外皮；
其中：热塑性硫化橡胶形成的最内层管和尼龙内管共同挤压而不用粘结剂。
15.按照权利要求8所述的软管，其中所述丝由玻璃、钢、聚酯、酰胺、尼龙或嫘萦纤维形成。
CN99810126.5A 1998-09-10 1999-04-13 致冷剂软管 Expired - Fee Related CN1199020C (zh)

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