CN116234686A - 车辆空调软管内层 - Google Patents
车辆空调软管内层 Download PDFInfo
- Publication number
- CN116234686A CN116234686A CN202180066314.XA CN202180066314A CN116234686A CN 116234686 A CN116234686 A CN 116234686A CN 202180066314 A CN202180066314 A CN 202180066314A CN 116234686 A CN116234686 A CN 116234686A
- Authority
- CN
- China
- Prior art keywords
- layer
- refrigerant hose
- innermost tube
- hose
- formaldehyde resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 27
- 239000011593 sulfur Substances 0.000 claims abstract description 27
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
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- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
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- STSDHUBQQWBRBH-UHFFFAOYSA-N n-cyclohexyl-1,3-benzothiazole-2-sulfonamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)(=O)NC1CCCCC1 STSDHUBQQWBRBH-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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Abstract
制冷剂软管具有在其中限定内腔的最内部管,并且该最内部管是基于氢化丁腈橡胶(HNBR)、含有HNBR的聚合物共混物或其共聚物之一,其用苯酚‑甲醛树脂固化。该制冷剂软管可进一步包括任选的渗透抑制层,当包括时其包围该最内部管,当使用此层时,从该最内部管和该任选的渗透抑制层向外布置的增强层,以及从该增强层向外布置的覆盖层。当在125℃下暴露于多元醇酯油或聚亚烷基二醇油168小时时,该最内部管具有10%或更低的体积膨胀百分比。此外,该最内部管不含过氧化物并且可进一步不含添加的元素硫、硫供体和/或在其分子结构内含有硫的添加剂。
Description
技术领域
本披露总体上涉及的领域是适合用于制冷剂系统如车辆、工业和住宅制冷剂系统,如汽车空调系统的软管。该软管具有在空调系统中使用的具有改进特性的内层。
背景技术
本部分提供背景信息以便于更好地理解本披露的各个方面。应当理解的是,本文件的此部分中的陈述将从这个角度阅读,并且不作为承认现有技术。
软管用于在车辆空调(AC)系统、以及工业和住宅制冷剂系统中输送制冷剂。此类软管用于连接制冷装置的主要操作部件的目的。软管典型地被设计成具有良好的柔性、高强度、弯曲到小半径而不扭结的能力、并且对其中存在的流体保持不渗透性。
最近车辆空调系统的变化使得有必要改变用于形成车辆空调软管的某些层,并且特别地,软管的内表面的层(该层与软管内存在和含有的制冷剂和压缩机油接触)的传统化合物。在一个例子中,向具有低全球变暖潜能(GWP)的制冷剂如2,3,3,3-四氟丙烯(商业上称为R1234yf)发展给选择软管层的材料带来挑战。一些传统的软管内层可能降低这些新制冷剂的有效性。带有某些聚合引发剂(包括过氧化物)的橡胶材料可能导致2,3,3,3-四氟丙烯的聚合。
此外,随着车辆的混合动力化和电气化,已经从传统的聚亚烷基二醇(PAG)AC系统压缩机油转向多元醇酯(POE)压缩机油,同时要求提高工作温度。然而,POE油可能导致传统的车辆AC软管层化合物(如丁基、卤代丁基和氯丁二烯)的增加的膨胀和软化。此外,这些传统的AC软管层化合物可能不是为在工作高温下使用而设计的。
另一个考虑因素是在汽车AC压缩机中新兴的镍的使用。由于镍的腐蚀,这要求避免硫固化体系、硫供体和其他含硫的促进剂和添加剂。元素硫可以提供含有3至8个硫原子的交联。这些交联具有比碳与碳的键低的键能,并且那些具有最多硫原子数量的交联将提供最弱的键强度。这些较弱的硫与硫的键,当暴露于热或应力时,产生键断裂的机会。任何未反应的硫,连同这种键断裂可能提供硫,当使用镍和其他具有较低耐腐蚀性的材料时,这可能导致AC压缩机的硫腐蚀。为了减少硫交联的数量,可以减少或消除元素硫的量并且可以使用含硫促进剂。虽然与常规上用元素硫固化的橡胶相比,交联中的硫原子的数量将减少,但任何硫与碳或硫与硫键当暴露于热或应力时比碳与碳键将更容易键断裂。硫促进剂或硫供体的任何未反应部分也将可用于腐蚀容易被腐蚀的AC压缩机部件如镍。典型地,避免硫的需要或要求提高工作温度将促使材料选择向过氧化物固化的弹性体发展,这就出现了上述问题。
因此,对于具有由克服上述问题的材料层构成的某些层的空调软管存在持续的需求,并且通过根据以下披露的实施例,此种需求至少部分得到满足。
发明内容
本部分提供了本披露的总体发明内容,并且不一定是其全部范围或其所有特征的全面披露。
在本披露的第一方面,制冷剂软管具有在其中限定内腔的最内部管,并且最内部管是氢化丁腈橡胶(HNBR)、含有HNBR的聚合物共混物或其共聚物之一,其用苯酚-甲醛树脂固化。制冷剂软管可进一步包括任选的渗透抑制层,当包括时其包围最内部管,当使用此层时,从最内部管和任选的渗透抑制层向外布置的增强层,以及从增强层向外布置的覆盖层。当在125℃下暴露于多元醇酯油或聚亚烷基二醇油168小时时,最内部管具有10%或更低的体积膨胀百分比。此外,最内部管不含过氧化物并且可进一步不含添加的元素硫、硫供体和/或在其分子结构内含有硫的添加剂。当包括渗透阻隔层时,制冷剂软管可进一步包括布置在渗透抑制层与增强层之间的连接层。
在本披露的一些方面,2,3,3,3-四氟丙烯或1,1,1,2-四氟乙烷制冷剂的分子存在于内腔中,并且内腔可以不含聚合的2,3,3,3-四氟丙烯分子。
覆盖层可以基于任何合适的材料,如但不限于丁基(IIR)、卤代丁基(CIIR/BIIR)、HNBR(HNBR)、溴化异丁烯对甲基-苯乙烯(BIMS)、乙烯-丙烯-二烯单体橡胶等。在一些方面,增强层可以基于聚酯材料,如聚对苯二甲酸乙二醇酯,或其他合适的聚酯。增强层可以是包括玻璃纤维、棉纤维、聚酯纤维、聚芳酰胺纤维、芳纶纤维、或其合适的混合物的材料。
根据本披露的一些方面,苯酚-甲醛树脂可以是溴化辛基苯酚-甲醛树脂、辛基苯酚-甲醛树脂和以卤化有机化合物形式添加到组合物中的路易斯酸活化剂(卤素)、辛基苯酚-甲醛树脂和以金属卤化物形式添加到组合物中的路易斯酸活化剂(卤素)、或苯酚-甲醛和添加以提供路易斯酸活化剂的卤化有机化合物。
附图说明
以下将参照附图描述本披露的某些实施例,其中相似的附图标记表示相似的元件。然而,应当理解,附图展示了本文描述的各种实施方式并且不旨在限制本文描述的各种技术的范围,并且:
根据本披露,图1以剖面透视图展示了阻隔编织软管;
根据本披露,图2以剖面透视图描绘了全橡胶编织软管;
根据本披露,图3以剖面透视图展示了螺旋阻隔软管;
图4展示了其中含有制冷剂和油的软管的截面。
附图标记清单
100 阻隔编织软管
200 全橡胶软管
300 螺旋阻隔软管
400 软管
102、202、302、402最内部管
104、304、404渗透抑制层
106、306、312、406连接层
108、208、408 编织增强层
308、314 螺旋增强层
110、210、310、410覆盖层
412 内腔
420 2,3,3,3-四氟丙烯制冷剂
或1,1,1,2-四氟乙烷制冷剂的分子
422 POE或PAG油珠
424 聚合的2,3,3,3-四氟丙烯
具体实施方式
以下对变体的描述本质上仅仅是说明性的,并且决不旨在限制本披露的范围、本披露的应用或用途。本文中呈现描述仅为了阐明本披露的不同实施例的目的,并且不应被解释为对本披露的范围和适用性的限制。在本披露的发明内容和此具体实施方式中,每个数值应该一次被读作由术语“约”修饰的那样(除非已经明确地被如此修饰),并且然后再次读作如没有被如此修饰的那样,除非在上下文中另外指明。此外,在本披露的发明内容和此具体实施方式中,应当理解,列出或描述为有用的、合适的等的值范围意图是在该范围内的全部值(包括端点)被认为已经进行陈述。例如,“1至10的范围”将被读为指示沿着在约1与约10之间的连续体的每一个可能的数字。因此,即使在该范围内的特定数据点,或者甚至没有在该范围内的数据点被明确地指明或仅仅是指几个特定点,应当理解,诸位发明人领会且理解,在该范围内的任何和所有数据点被认为是已经被指定的,并且诸位发明人拥有整个范围和在该范围内的所有点。
除非明确相反地说明,否则“或”是指包括性的或并且不是排他性的或。例如,通过以下任意一种情况都可以满足条件A或B:A为真(或存在)且B为假(或不存在),A为假(或不存在)且B为真(或存在),以及A与B均为真(或存在)。
此外,使用“一个/种(a/an)”用来描述本文中的实施例的元件和部件。这样做仅仅为了方便起见,并且给出根据本披露的概念的一般含义。此说明应被解读为包括一个/种或至少一个/种,并且单数还包括复数,除非另有说明。
本文中使用的术语和词组是为了描述的目的并且不应被解释为在范围上的限制。语言如“包括(including)”、“包含(comprising)”、“具有(having)”、“含有(containing)”或“涉及(involving)”及其变体旨在是广泛的并且包括其后列出的主题、等效物、和未被列出的附加主题。
此外,如本文中所使用的,对“一个(one)实施例”或“一个(an)实施例”的任何提及意味着在至少一个实施例中包括与该实施例有关所描述的具体元件、特征、结构或特性。在说明书中的不同地方出现的短语“在一个实施例中”不一定是指同一个实施例。
根据本披露的软管实施例总体上包括具有最内部管、至少一个增强层和外部覆盖层的橡胶软管。软管实施例还包括阻隔式软管,其通常包括阻隔层、至少一个增强层、任选的一个或多个增强层、任选的一个或多个连接层、外部覆盖层和最内部管。
最内部管是由弹性体材料形成的,该弹性体材料是由树脂固化的氢化丁腈橡胶(HNBR)、聚合物共混物内的HNBR或其共聚物形成的。树脂固化体系是基于使用苯酚甲醛树脂,其与略低于完全饱和的HNBR中剩余的少量不饱和点反应以形成交联。这些苯酚甲醛树脂可以直接添加到组合物中,或可以由苯酚和苯酚衍生物与各种醛反应原位形成。苯酚衍生物的实例包括但不限于双酚、苯酚、甲酚、间苯二酚和六亚甲基四胺(HMT)。由苯酚、或甲阶酚醛树脂和间苯二酚酚醛清漆树脂或间苯二酚苯酚酚醛清漆树脂的烷基化产生的苯酚-甲醛树脂是适合于交联弹性体的一些非限制性实例。商业实例是从圣莱科特国际集团(SIGroup)可获得的溴化辛基苯酚甲醛树脂SP-1055。
为了催化苯酚甲醛树脂的固化反应,使用路易斯酸活化剂如卤化物质的存在。此卤化物质可以是树脂本身的一部分,这是前面提到的溴化辛基苯酚甲醛树脂的情况。卤素也通常以少量卤化有机化合物如但不限于氯丁二烯或卤代丁基的形式添加到含有非卤化苯酚甲醛树脂的组合物中。卤素也可以作为许多合适的金属卤化物材料之一添加,包括但不限于氯化亚锡(即SnCl2)。
诸位发明人观察到,通过使用此种树脂固化的HNBR最内部管,通过避免对最内部管使用过氧化物固化体系来改进制冷剂的有效性,因为残留的过氧化物可能导致制冷剂的交联。诸位发明人观察到,通过使用此种树脂固化的HNBR最内部管,通过避免使用已知腐蚀AC压缩机中的镍的硫来改进压缩机完整性。
关于阻隔层,在构建阻隔式软管时,可使用任何合适的材料来形成该层。在全橡胶结构中不使用阻隔层。阻隔材料的一些合适的、但非限制性的实例包括聚酰胺,如PA11、PA46、PA6、PA66、PA6,66、PA66,6、PA69、PA610、PA612、PA1010、PA1212、PA4T、PA6T、PA9T和PA10T;基于聚醚-酯嵌段共聚物的热塑性聚酯弹性体,如以商品名供应的那些;或由聚酰胺和聚醚骨架嵌段构成的热塑性弹性体,如以商品名/>供应的那些。
当使用时,一个或多个连接层典型地由任何合适的热固性材料构成,包括但不限于聚丁二烯(BR)、丁二烯和丙烯腈的共聚物(NBR)、丁基橡胶(IIR)、氯丁橡胶(CIIR)、溴丁橡胶(BIIR)、丁二烯和苯乙烯的共聚物(SBR)、聚氯丁烯(CR)、乙烯丙烯橡胶(EPM)、或乙烯丙烯二烯(EPDM)。在一个实施例中,该层的基本原料材料是EPDM。
增强层可以基于通过纱线的编织、扭绞、针织或螺旋针织形成的材料。增强层可以基于织造的或非织造的材料。材料可以选自常规的软管增强纱线,如玻璃、棉、聚酯或芳纶纤维,或任何这些纤维的共混物。在一些方面,软管中的增强层是聚酯或芳纶织物,或甚至是聚对苯二甲酸乙二醇酯纱线和聚萘二甲酸乙二醇酯纱线的共混物以形成织物。
本披露的实施例中采用的覆盖层选自橡胶,包括但不限于以下橡胶及其共混物或共聚物,选自乙烯丙烯二烯橡胶(EPDM)、乙烯丙烯橡胶(EPR)、丁基橡胶(IIR)、氯丁橡胶(CIIR)、溴丁橡胶(BIIR)、氯丁二烯橡胶(CR)、丁腈橡胶(NBR)、氯磺化聚乙烯橡胶(CSM)、环氧氯丙烷橡胶(ECO)、丙烯酸橡胶(ACM)、氯丁二烯橡胶(CR)、乙烯-丙烯酸弹性体(AEM)、或氯化聚乙烯(CPE)等。在一个实施例中,覆盖层的基本原料是EPDM。
除了最内部管层之外,本披露的软管实施例中使用的各种材料组分可以用常规的固化剂固化,包括但不限于过氧化物、硫、硫供体固化剂、胺固化剂、树脂固化体系、金属氧化物固化剂等。例如过氧化物如过氧化二异丙苯、α-α-双(叔丁基过氧化物)二异丙苯、过氧化苯甲酰、2,4-二氯过氧化苯甲酰、1,1-双(叔丁基过氧)3,3,5-三甲基环己烷、2,5-二甲基-2,5-双(叔丁基过氧)己烷、2,5-二甲基-2,5-双(叔丁基过氧)己炔-3和4,4-双(叔丁基过氧)戊酸正丁酯可用于固化软管的橡胶组分。基于100份基础聚合物,一般使用1至约10份过氧化物。过氧化物优选作为固化剂,因为它们对过早交联(焦烧)不太敏感。硫/硫供体固化剂也是通常使用的。可用于橡胶固化体系的许多含硫促进剂和供硫剂的几个实例包括二硫化四甲基秋兰姆、4,4’-二硫基二吗啉、四硫化双五亚甲基秋兰姆、硫代氨基甲酰次磺酰胺、巯基苯并噻唑、二甲基氨基甲酸锌、二苯并噻唑二硫化物和N-环己基-2-苯并噻唑磺酰胺。
本发明的软管中使用的橡胶组分还可以含有常规或合适量的各种添加剂。此类添加剂可以包括并且不限于防止过度快速固化的缓凝剂、抗氧化剂、加工助剂、增强剂和填充剂,如炭黑、二氧化硅、偶联剂、分散剂、粘合促进剂等。
现在参考图1至4,其描绘了根据本披露的一些软管实施例。图1以剖面透视图展示了阻隔编织软管100。软管100包括最内部管102,其被渗透抑制层104包围。与渗透抑制层104相邻布置的是连接层106,其具有从其向外布置的增强层108。覆盖层110是软管100的最外层。
参考图2,其描绘了全橡胶编织软管200,在剖面透视图中,软管200包括被增强层208包围的最内层202,并且覆盖层210是软管200的最外层。
现在参考图3,其以剖面透视图展示了螺旋阻隔软管300。软管300包括最内部弹性体管302,其被渗透抑制层304包围。与渗透抑制层304相邻的是连接层306,其具有从其向外布置的螺旋增强层308。包围螺旋增强层308的是第二连接层312,其具有布置在其上的第二螺旋增强层314。覆盖层310是软管300的最外层。
现在参考图4,其展示了根据本披露的一个实施例的隔离软管的截面,其中存在和含有制冷剂和油。截面是在平行于软管的纵向中心线的平面内取的,该中心线用+表示。另外,为了说明所提出的概念的目的,所提出的这种描述是线性无量纲的。软管400包括最内部管402,在一些方面,该管被任选的渗透抑制层404包围,并且与渗透抑制层404相邻布置的是任选的连接层406。从其向外布置增强层408。覆盖层410是软管400的最外层。存在于最内部管402内限定的内腔412内的是2,3,3,3-四氟丙烯制冷剂的分子420和POE油珠422。由于最内部管402是由反应性苯酚-甲醛树脂固化的氢化丁腈橡胶(HNBR)形成的,所以2,3,3,3-四氟丙烯制冷剂被稳定化,由于最内部管402的内壁与POE油接触而导致的膨胀被最小化,或者基本上被消除,并且避免了聚合的2,3,3,3-四氟丙烯分子424的形成。因此,最内部管402不含过氧化物,并且不含任何添加的硫或含硫材料,并且内腔412也不含聚合的2,3,3,3-四氟丙烯分子424。
实例
由以下实例阐明本披露的一些实施例,这些实例仅仅是为了阐明的目的,并且不被认为是限制本披露的范围或其可以被实践的方式。除非另外特别指出,否则份(phr)是基于HNBR树脂的量按重量计给出的。在此实验中,制备了用于AC软管的最内层的橡胶配制品,将其固化并测试了指示的物理特性。
表1:
经测定,固化的橡胶配制品具有表2中提供的物理特性。
表2:
以上实例说明了形成最内部管的橡胶材料具有用于此层的足够的特性,并且具有当在125℃下暴露于多元醇酯油168小时时10%或更低的体积膨胀百分比和小于10点肖氏A硬度计的硬度变化。
为了说明和描述的目的,已经提供了对实施例的前述描述。提供示例性实施例,使得本披露将是充分彻底的,并且将范围传达给本领域技术人员。阐述许多具体细节,如特定部件、装置和方法的实例,以提供对本披露的实施例的彻底理解,但并不旨在是穷尽的或限制本披露。应当理解,在本披露的范围内的是具体实施例的单独的元件或特征通常不限于该具体实施例,而是在适用的情况下是可互换的并且可以在所选择的实施例(即使不是明确示出或描述的)中使用。本披露也可以以许多方式变化。此类变化不被视为偏离本披露,并且所有此类修改旨在被包括在本披露的范围内。
另外,在一些示例性实施例中,没有详细描述熟知的方法、熟知的装置结构和熟知的技术。进一步地,对于本领域技术人员将显而易见的是,在用来实现本披露中所描述的内容的装置的设计、制造和操作中,例如可能存在装置设计、构造、状态、部件的腐蚀、部件间的间隙上的变化。
尽管在此可以使用术语第一、第二、第三等来描述各种元件、部件、区域、层和/或部分,但是这些元件、部件、区域、层和/或部分不应受这些术语的限制。这些术语可以仅用于将一个元件、部件、区域、层或部分与另一个区域、层或部分区分开。除非上下文明确指出,否则术语如“第一”、“第二”、以及其他数字术语当在此使用时不暗示次序或顺序。因此,在不脱离示例性实施例的传授内容的情况下,下面讨论的第一元件、部件、区域、层或部分可以被称为第二元件、部件、区域、层或部分。
为便于描述,空间相对术语,如“内部”、“相邻”、“外部”、“下面”、“下方”、“下部”、“上方”、“上部”等,可以在此处用于描述一种元件或特征与另外的一种或多种元件或特征的关系,如图所示。除了图中描绘的取向之外,空间相对术语可以旨在涵盖使用或操作中的装置的不同取向。例如,如果图中的装置被翻转过来,则被描述为在其他元件或特征“下方”或“下面”的元件将被定向在其他元件或特征“上方”。因此,示例术语“下方”可以涵盖上方和下方的取向两者。装置可以以其他方式定向(旋转90度或在其他取向),并且相应地解释在此使用的空间相对描述符。
虽然上面已经详细描述了本披露的几个实施例,但是本领域普通技术人员将容易地理解,在实质上不脱离本披露的传授内容的情况下,许多修改是可能的。因此,此类修改旨在被包括在如权利要求中限定的本披露的范围内。
Claims (13)
1.一种制冷剂软管(400),其包括:
(a)在其中限定内腔(412)的最内部管(402),该最内部管(402)包含氢化丁腈橡胶(HNBR)、含有HNBR的聚合物共混物或其共聚物,其用苯酚-甲醛树脂固化;
(b)包围该最内部管(402)的任选的渗透抑制层(404);
(c)从该最内部管(402)和该任选的渗透抑制层(404)向外布置的增强层(408);以及,
(d)从该增强层(408)向外布置的覆盖层(410);
其中该最内部管(402)当在125℃下暴露于多元醇酯油或聚亚烷基二醇油168小时时具有10%或更低的体积膨胀百分比;并且,
其中该最内部管(402)不含过氧化物,并且不含添加的元素硫、供硫剂、或在添加剂的分子结构内含有硫的添加剂。
2.根据权利要求1所述的制冷剂软管(400),其进一步包括当该任选的渗透抑制层(404)包括在该制冷剂软管(400)中时,布置在该任选的渗透抑制层(404)与该增强层(408)之间的连接层(406)。
3.根据权利要求1所述的制冷剂软管(400),其进一步包括该内腔(412)中的2,3,3,3-四氟丙烯分子(420)。
4.根据权利要求3所述的制冷剂软管(400),其中,该内腔(412)不含聚合的2,3,3,3-四氟丙烯分子(420)。
5.根据权利要求1所述的制冷剂软管(400),其中,该覆盖层(410)由丁基(IIR)、卤代丁基(CIIR/BIIR)、HNBR(HNBR)、溴化异丁烯对甲基-苯乙烯(BIMS)或乙烯-丙烯-二烯单体橡胶(EPDM)构成。
6.根据权利要求1所述的制冷剂软管(400),其中,该增强层(408)是织造聚酯织物。
7.根据权利要求6所述的制冷剂软管(400),其中,该织造聚酯织物是织造聚对苯二甲酸乙二醇酯织物。
8.根据权利要求1所述的制冷剂软管(400),其中,该增强层(408)是由玻璃纤维、棉纤维、聚酯纤维、聚芳酰胺纤维或芳纶纤维构成的织造织物。
9.根据权利要求1所述的制冷剂软管(400),其中,该增强层(408)是螺旋增强层(408),并且其中该制冷剂软管(400)进一步包括包围该螺旋增强层(408)的第二连接层(312),以及布置在该覆盖层(410)与该第二连接层之间的第二螺旋增强层(314)。
10.根据权利要求1所述的制冷剂软管(400),其中,该苯酚-甲醛树脂是溴化辛基苯酚-甲醛树脂。
11.根据权利要求1所述的制冷剂软管(400),其中,该苯酚-甲醛树脂是具有以卤化有机化合物形式添加的路易斯酸活化剂(卤素)的辛基苯酚-甲醛树脂。
12.根据权利要求1所述的制冷剂软管(400),其中,该苯酚-甲醛树脂是具有以金属卤化物形式添加的路易斯酸活化剂(卤素)的辛基苯酚-甲醛树脂。
13.根据权利要求1所述的制冷剂软管(400),其中,添加卤化有机化合物以提供路易斯酸活化剂。
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