CN1488495A - 冷冻剂软管 - Google Patents

冷冻剂软管 Download PDF

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CN1488495A
CN1488495A CNA031553613A CN03155361A CN1488495A CN 1488495 A CN1488495 A CN 1488495A CN A031553613 A CNA031553613 A CN A031553613A CN 03155361 A CN03155361 A CN 03155361A CN 1488495 A CN1488495 A CN 1488495A
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flexible pipe
layer
barrier layer
resin
rubber
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CN100354121C (zh
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R・P・威尔逊
R·P·威尔逊
B·亨利
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ContiTech America Co Ltd
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Goodyear Tire and Rubber Co
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    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
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    • B32B2323/00—Polyalkenes
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    • B32B2323/043—HDPE, i.e. high density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32—LAYERED PRODUCTS
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    • F16L11/00—Hoses, i.e. flexible pipes
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Abstract

一种适合用于制冷系统的软管。该软管具有由至少两个热塑性树脂层构成的阻隔层。至少一个层是乙烯基树脂。选择能够使软管的渗透率实际为零的树脂。

Description

冷冻剂软管
技术领域
本发明涉及一种适用于制冷系统如机动车、工业和住宅制冷系统中的软管。该软管是提供挠曲性的弹性体材料和提供不透性的热塑性材料的组合。
发明背景
软管在车辆空调系统和工业及住宅制冷系统中被用来输送冷冻剂。软管通常具有三层层合结构，由最内层、增强层和最外包覆层组成。一般而言，该内层和外层由橡胶构成，包括丁基橡胶(IIR(丁基橡胶)、CIIR(氯化丁基橡胶)、BIIR(溴化丁基橡胶)或BIMS(溴化异丁烯-甲基苯乙烯橡胶))、乙丙三元橡胶(EPDM)、氯丁橡胶(CR)、丁腈橡胶(NBR(丁腈)、HNBR(氢化丁腈))或乙烯-丙烯酸类共聚物橡胶(AEM)。增强纤维层通常由编织的有机纱线如聚酯纤维、人造丝纤维或尼龙纤维之类构成的网眼结构。最外包覆层通常由EPDM、CR、丁基橡胶或AEM构成。在各层之间可采用粘合层。
上面所讨论的软管具有高度挠曲性。正因为如此，橡胶软管可借助外鞘捆扎成束。然而，橡胶材料通常具有高气体渗透倾向。曾尝试改善传统橡胶软管防冷冻剂渗透能力，方法是结合进聚酰胺层如尼龙6、尼龙66、改性尼龙6或尼龙6的合金等作为内层。然而，此种聚酰胺层的使用虽然降低了渗透率，但也同时降低了软管的挠曲性。为在诸要求性能之间达到某种可接受的折中，尼龙内芯层的厚度传统上至少是0.5mm(0.02英寸)，还可参见US 4,633,912，文中公开一种聚酰胺共混物芯管，表尺厚度介于1.07mm～0.81mm。
软管被表征为阻隔或镶面软管两种，二者的区别在于形成最内层的材料类型。阻隔软管的最内层由弹性体材料构成，而包在最内层外面的是阻隔层。在阻隔层作为最内层的软管中，软管被称作镶面软管。某些用途可使用二者中任何一种类型，例如燃料软管，而其他用途可能要求特定内层材料，因而只有一种类型软管适合。
发明概述
本发明涉及一种适合输送冷冻剂的软管。该软管具有强防渗透和高挠曲性。该软管包含阻隔层、中间弹性体层、增强层和包覆层。为实现高度防渗透以制成几乎零渗透率软管，阻隔层由至少两种树脂层构成，其中至少一个树脂层由乙烯基树脂构成。
在公开的发明的一个方面，该软管是阻隔软管。位于多层阻隔层的径向内侧的是弹性体层。弹性体层构成该软管的最内层并直接接触任何可能流经软管的流体或气体。
在本发明另一个方面，该软管是镶面(veneer)软管。就是说，阻隔层是该软管的径向最内层并直接接触任何可能流经软管的流体或气体。
在另一个方面，软管的阻隔层由三种树脂层构成。在此种构造中，径向最外树脂层重复采用构成最内树脂层的材料制作。此种构造在制造方面是最方便的；然而，也可由第三树脂材料构成第三树脂层。
在本发明一个方面，构成阻隔层之一的乙烯基树脂选自醋酸乙烯(EVA)、聚乙烯醇(PVA)、乙烯醇/乙烯共聚物(EVOH)、聚偏二氯乙烯(PVDC)、聚氯乙烯(PVC)、氯乙烯/偏二氯乙烯共聚物和偏二氯乙烯/丙烯酸甲酯共聚物。
在本发明另一个方面，非乙烯基树脂阻隔层由选自聚烯烃热塑性树脂或聚酰胺热塑性树脂的材料构成。
在本发明另一个方面，中间橡胶层，以及当软管构造是阻隔软管时的最内橡胶层，由选自下列的材料制成氯丁橡胶、丁腈橡胶、乙丙橡胶、乙丙三元橡胶(EPDM)、丁基橡胶(IIR、CIIR、BIIR)、氯磺化聚乙烯橡胶(CSM)、乙烯-丙烯酸类共聚物橡胶(AEM)、氯化聚乙烯橡胶(CPE)或者溴化异丁烯对甲基苯乙烯(BIMS)。
在本发明另一个方面，阻隔层中的每一个树脂层具有0.001～0.005英寸(0.025～0.127mm)径向厚度。
附图简述
下面将通过实施例并参照附图来描述本发明，附图包括：
图1是部分本发明软管的断面视图；
图2是本发明软管的另一种实施方案；
图3是本发明软管的另一种实施方案；
图4是稳态渗透速率之间比较的曲线图。
发明详述
本发明冷冻剂软管10示于图1。软管10具有，相对于软管径向和软管纵轴而言的芯层12。芯层12由弹性体材料构成。在芯层12的外面是由至少两个热塑性层16、18构成的阻隔层14。在阻隔层外面是中间弹性体层20、增强层22和包覆层24。
芯层12由弹性体材料构成。由于该层12与镶面阻隔层相邻，因此它必须能粘合在阻隔层14上。此类材料包括但不限于，氯丁橡胶、丁腈橡胶、乙丙橡胶、乙丙三元橡胶(EPDM)、丁基橡胶(IIR、CIIR、BIIR)、氯磺化聚乙烯橡胶(CSM)、乙烯-丙烯酸类共聚物橡胶(AEM)、氯化聚乙烯橡胶(CPE)或者溴化异丁烯对甲基苯乙烯(BLMS)。芯层12也可由热塑性弹性体或热塑性硫化胶如聚丙烯、聚乙烯或其他聚烯烃与EPDM、IIR、NBR或者丙烯酸类橡胶的共混物构成。
阻隔层14由第一热塑性层16构成，该材料具有低渗透率。合适的低渗透率材料包括聚烯烃热塑性树脂如高密度聚乙烯(HDPE)、超高分子量聚乙烯(UHMWPE)、聚丙烯(PP)和乙丙共聚物热塑性树脂；以及聚酰胺热塑性树脂如尼龙6(N6)、尼龙66(N66)、尼龙46(N46)、尼龙11(N11)、尼龙12(N12)、尼龙610(N610)、尼龙612(N612)、尼龙6/66共聚物(N6/66)、尼龙6/66/610共聚物(N6/66/610)、尼龙MXD6(MXD6)、尼龙6T、尼龙6/6T共聚物、尼龙66/PP共聚物以及尼龙66/PPS共聚物。为实现成品软管的低渗透，当采用聚酰胺树脂，或者聚酰胺树脂的共混物时，聚酰胺优选是非增塑的。增塑剂在聚酰胺中的加入虽可改善材料的挠曲性；但是它也将降低尼龙的渗透特性。因此，非增塑聚酰胺是优选的。
在阻隔层14中的第二层18是不同于第一热塑性层16的低渗透材料。优选的材料是乙烯基树脂如醋酸乙烯(EVA)、聚乙烯醇(PVA)、乙烯醇/乙烯共聚物(EVOH)、聚偏二氯乙烯(PVDC)、聚氯乙烯(PVC)、氯乙烯/偏二氯乙烯共聚物和偏二氯乙烯/丙烯酸甲酯共聚物。
在构造阻隔层14的过程中，第一层16可以是径向最内层或者第二层18可以是径向最内层。为保持所要求的软管10的挠曲性，每个单独树脂层16、18具有0.001～0.005英寸(0.025～0.127mm)的径向厚度。
中间层20必须能粘合在阻隔层上。该层用与适合最内层12的相同材料构成。
增强层22可通过纱线的编织、螺旋缠绕、针织或螺旋针织来成形。纱线可选自传统软管增强用纱线，如玻璃、钢、棉、聚酯或芳族聚酰胺纤维或者这些纤维的任意共混物的纱线。
包覆层24选自已知的软管包覆层材料，包括但不限于丁腈橡胶(NBR)、氯磺化聚乙烯橡胶(CSM)、EPDM、丁基橡胶、氯化丁基橡胶(Cl-IIR)、溴化丁基橡胶(Br-IIR)、表氯醇橡胶、丙烯酸类橡胶(AEM)氯丁二烯橡胶(CR)、BIMS以及诸如此类。类似于芯层12，包覆层也可由热塑性弹性体或热塑性硫化胶构成。
软管10的渗透率不大于0.0003g/cm/d。如此低的渗透率可视为零渗透率。传统上要获得如此低的渗透率，须在软管内采用一个薄金属层。本发明达到近似于零的非常低的渗透率却不需要在软管内使用金属箔或层。
本发明第二实施方案表示在图2中。软管10′具有最内层12、阻隔层14、相邻弹性体摩擦层20、增强层22和包覆层24。在此种实施方案中，软管10′的阻隔层14具有三层，16、18、16′。径向最内层选择的材料被重复用来作该第三层，以及径向最外层。优选的是，中间层由渗透率最低的材料构成。
本发明第三种实施方案表示在图3中。在该实施方案中，软管10″不具有最内弹性体层12。替代地，阻隔层14构成最内层，而软管10 ″是一种镶面软管。在图示的实施方案中，阻隔层由两个阻隔层，16、18组成，其制作材料和方式如上面所讨论的。类似于第二种实施方案，镶面软管10″也可以具有由三层构成的阻隔层14，其中最内层16重复一次，从而将第二阻隔层18夹在中间。
软管的预期用途，包括预期流过软管的流体或气体，将决定所公开的各种各样阻隔或镶面软管构造当中哪一种适合。
软管10的构造是按照如下所述实现的。
最内层挤出到挠性或固定的芯轴上。阻隔层通过在该最内层上同时共挤出不同的层而制成。多层挤出模头被用于该挤出。当阻隔层成形为三层元件时，采用三层的模头。当阻隔层成形为两层元件时，可采用双层模头或者采用三层挤出模头但其中一个进料口为空白。不同层之间不施加任何粘合剂，因为层与层之间的粘合是通过熔融粘合完成的。
阻隔层成形以后，施加另一个弹性体层或者直接施加增强层。最后施加包覆层。随后，成形的软管全长进行硫化以便使弹性体层硫化。软管全长可在硫化之前或以后切断为有限长度。如果软管全长在硫化之前切断，则典型情况下一段段长度的软管将在固定曲线的短长度芯轴上进行硫化，旨在赋予软管固定和最终的构型。
范例软管
构造一种本发明软管。最内层由CR构成。阻隔层由三层组成：尼龙6与尼龙66的非增塑共聚物、EVOH的中间层以及重复非增塑尼龙6，66共聚物的层。阻隔层中每一层的厚度为约0.002英寸(0.007mm)，总共约0.006英寸(0.024mm)。在阻隔层外面，施加另一个CR层。施加聚酯增强层。由丁基橡胶形成包覆层。
对比例1
购入一种市售供应、低渗透率软管。该软管具有：CR最内层、增塑尼龙6-66共聚物的阻隔层、NBR摩擦层、聚酯增强层和氯化丁基橡胶包覆层。该软管是固特异轮胎及橡胶公司销售的Goodyear Galaxy534-860-013软管。
对比例2
购入第二种市售供应、低渗透率软管。该软管具有：CR最内层、非增塑尼龙6-66共聚物阻隔层、CR摩擦层、聚酯增强层和氯化丁基橡胶包覆层。该软管是固特异轮胎及橡胶公司销售的Goodyear Galaxy534-890-013软管。
三种软管被切断成短段并试验各自的渗透率。渗透试验程序为：封住软管段的至少一端，将冷冻剂流体引入到软管中，然后封住敞口端。称取软管及其内装流体的总重量。随后，软管段被置于90℃的常压环境中。每天称取软管重量持续两周，然后每隔一天称重再持续一周。于是，渗透率根据最后五日(稳态)每段长度每日失重(量)计算出来。
本发明软管和两种对比例软管的渗透率结果示于图4。对比例软管1显示0.0064g/英寸/日(2.52×10-3g/cm/d)的渗透率。对比例2显示0.0013g/英寸/日(5.12×10-4g/cm/d)的渗透率。本发明软管显示0.0001g/英寸/日(3.94×10-5g/cm/d)的渗透率。本发明软管表现出在低渗透方面与其他软管相比的显著改进。
虽然至此该软管被描述为可用于冷冻剂，包括但不限于R134A，但也可用于其他类型流体或气体，例如，二氧化碳。
根据本文提供的说明还可在本发明范围内演绎出各种变换方案。虽然为说明本发明的目的在上面给出某些代表性实施方案和细节，但本领域技术人员清楚，在不偏离本发明范围的条件下还可制定出各种变化和修改。因此，要知道，在所述特定实施方案中所演绎的改变都将属于后面所附权利要求规定的本发明涵盖广泛的范围之内。

Claims (10)

1.一种软管，包含内阻隔层、径向外侧的中间层、增强层以及包覆层，其中阻隔层由至少两种树脂层组成，软管的特征在于，这两个树脂层由两种不同材料构成并且其中至少一个树脂层是乙烯基树脂。
2.权利要求1的软管，其特征在于，阻隔层的径向内侧是弹性体层。
3.权利要求1的软管，其特征在于，阻隔层是软管的径向最内层。
4.权利要求1的软管，其特征在于，阻隔层由三个树脂层组成。
5.权利要求4的软管，其特征在于，径向最内树脂层和径向最外树脂层由同一树脂材料构成。
6.权利要求1的软管，其特征在于，乙烯基树脂选自醋酸乙烯(EVA)、聚乙烯醇(PVA)、乙烯醇/乙烯共聚物(EVOH)、聚偏二氯乙烯(PVDC)、聚氯乙烯(PVC)、氯乙烯/偏二氯乙烯共聚物和偏二氯乙烯/丙烯酸甲酯共聚物。
7.权利要求1的软管，其特征在于，非乙烯基树脂阻隔层由选自聚烯烃热塑性树脂或聚酰胺热塑性树脂的材料构成。
8.权利要求1的软管，其特征在于，该软管的渗透率不大于0.0003g/cm/天。
9.权利要求1的软管，其特征在于，阻隔层中的每个树脂层具有0.001～0.005英寸(0.025～0.127mm)的径向厚度。
10.权利要求1的软管，其特征在于，中间层由选自氯丁橡胶、丁腈橡胶、乙丙橡胶、乙丙三元橡胶(EPDM)、丁基橡胶(IIR、CIIR、BIIR)、氯磺化聚乙烯橡胶(CSM)、乙烯-丙烯酸类共聚物橡胶(AEM)、氯化聚乙烯橡胶(CPE)、溴化异丁烯-对甲基苯乙烯(BIMS)、热塑性弹性体和热塑性硫化橡胶的材料构成。
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