CN105969313B - 一种碳氢制冷剂用单组分添加剂 - Google Patents

一种碳氢制冷剂用单组分添加剂 Download PDF

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CN105969313B
CN105969313B CN201610328131.1A CN201610328131A CN105969313B CN 105969313 B CN105969313 B CN 105969313B CN 201610328131 A CN201610328131 A CN 201610328131A CN 105969313 B CN105969313 B CN 105969313B
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江安峰
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Abstract

本发明是碳氢制冷剂用单组分添加剂,所述碳氢制冷剂用单组分添加剂的母体结构为1,8‑萘酰亚胺类,氮原子上连接有卤代烷烃类基团(R1),萘环上连接有巯基或烃硫基(R2),使用所述碳氢制冷剂用单组分添加剂前先溶解到冷冻机油中,随冷冻机油共同添加到制冷设备中。所述碳氢制冷剂用单组分添加剂的添加量占冷冻机油总质量的5%~20%。

Description

一种碳氢制冷剂用单组分添加剂
技术领域
本发明涉及一种用单组分添加剂,尤其是一种碳氢制冷剂用单组分添加剂。
背景技术
碳氢制冷剂是指由低碳链烷烃组成的单一化合物或多组分混合物,最常见的碳氢制冷剂为丙烷、异丁烷、正丁烷或其混合物。碳氢制冷剂不损害臭氧层,无温室效应,具有天然环保、高效节能、制冷优质、省钱省量、油混率高、适用广泛等优点,是最具应用前景的制冷剂。然而,碳氢制冷剂长久以来广受非议,难以推广应用的主要原因,在于其无色无味,泄露后不易察觉,且本身燃点相对较低,在空气中积聚达到浓度下限后会与空气形成具有爆炸性的混合气体。
目前,提高碳氢制冷剂使用安全性的手段主要有如下几种:
(1)在体系中添加警示气味剂,使人们很容易觉察到制冷剂的泄露,起到警告或报警物作用。例如采用硫化氢、乙硫醇、烷基硫醚、丙烯酸酯等作为警示气味,提高了警示效果。但硫化氢稳定性差,腐蚀管路;乙硫醇、烷基硫醚、丙烯酸酯等毒性大,易分解失效。而采用噻吩衍生物和吡啶作为警示气体,具有较好的警示效果和良好的安定性及体系相容性,但添加的警示剂用途单一,只是提醒使用者注意,对提高制冷剂的检漏效率及本质安全性没有任何影响。
(2)在体系中添加爆炸抑制剂,降低爆炸几率。现有技术中采用了大量二氧化碳制冷剂为惰性填充剂,抑制爆炸反应发生。由于高含量的两组分的密度、挥发性差异大,缩短了压缩机的使用寿命;也有采用含氟卤代烷制冷剂作为抑爆剂,但用量大,成本高。另外,采用烷基铅和五羰基铁作为抑爆剂,抑爆效果明显,但体系混合均匀性差,且泄漏时无法快速找到渗漏位置。
(3)在体系中添加示踪剂,提高检漏效率。现有技术中一般以氢氟烃、氟代醚、烃醇、烃胺、氮氧化物、氨等化合物作为示踪剂,这些物质本身无色无味或嗅觉阈极低,需借助化学/电活性阵列检测器、超声波检测器等专用设备进行检测,无法直观察觉。荧光检漏技术已用于发现查找汽车空调系统的泄漏。然而,受限于荧光剂分子设计水平,现有荧光剂只有在紫外灯照射下才能发出荧光,而在制冷剂泄漏环境下打开紫外灯本身就具有一定的安全隐患。故该技术仅适合R22、R134a等无燃烧爆炸特性的含氟制冷剂体系。与碳氢制冷剂匹配的荧光剂尚未见报导。
由此可见,不论是添加警示剂、抑爆剂、还是示踪剂,均是从某一方面部分解决问题。多组分复配虽有可能达到较好的综合效果,但组分间相容性差、添加量过大等问题限制了其应用。更重要的是,现有添加剂都是直接与制冷剂混合。由于绝大多数添加剂均是液态或固态(CO2、NH3除外),采与气态碳氢制冷剂混合-出售-充装的方式不可避免地会出现由于密度差异而引起的各批次产品性能迥异的缺陷。
故,需要提出一种新的技术方案。
发明内容
本发明的目的是提供一种具有示警、检漏、抑爆功能的碳氢制冷剂用单组分添加剂。
为达到上述目的,本发明可采用如下技术方案:
一种碳氢制冷剂用单组分添加剂,使用所述碳氢制冷剂用单组分添加剂前先溶解到冷冻机油中,随冷冻机油共同添加到制冷设备中;碳氢制冷剂用单组分添加剂的添加量占冷冻机油总质量的5%~20%,碳氢制冷剂用单组分添加剂的母体结构为1,8-萘酰亚胺类,氮原子上连接有卤代烷烃类基团(R1),萘环上连接有巯基或烃硫基(R2),所述的母体结构式为:
与现有技术相比,本发明碳氢制冷剂用单组分添加剂具有良好的油溶性,可随着冷冻机油共同进入制冷系统;气味阈值极低,随制冷剂泄露后具有示警功能;分子内含有荧光发色基团,自然光下即可发出明亮的黄绿光,可精确显示渗漏位置,提高检漏效率;抑爆基团可有效抑制碳氢制冷剂的爆炸趋势,提高制冷剂的本质安全性。适用于空调器、电冰箱和冷柜等各种制冷设备。
附图说明
图1是本发明的流程图。
具体实施方式
本发明是一种碳氢制冷剂用单组分添加剂。
使用所述碳氢制冷剂用单组分添加剂前先溶解到冷冻机油中,随冷冻机油共同添加到制冷设备中;碳氢制冷剂用单组分添加剂的添加量占冷冻机油总质量的5%~20%,碳氢制冷剂用单组分添加剂的母体结构为1,8-萘酰亚胺类,氮原子上连接有卤代烷烃类基团(R1),萘环上连接有巯基或烃硫基(R2),所述的母体结构式为:
所述卤代烷烃类基团(R1)属于碳原子数低于4的低碳链卤代烷烃。所述卤代烷烃类基团(R1)的化学分子式为-CF2I、-CHFCF3、-CF2CF3、-CH2CF2CF3、-CHFCF2CF3、-CF2CF2CF3、-CH(CF3)2、-CHFCF2CHF2或-CHFCF3CH2F。
所述巯基或烃硫基(R2)位于萘环的5号位或6号位,所述烃硫基(R2)属于碳原子数低于4的低碳链烃硫基。所述烃硫基(R2)的化学分子式为-SCH3、-SCH2CH3或-SCH2CH2CH3。
将少量油溶性添加剂溶解于冷冻机油中,并共同进入制冷系统。在制冷设备运转过程中,与碳氢制冷剂混合成均相,不影响制冷体系的正常运行。体系泄漏时,由于添加剂具有明显的异味,可以起到警示的作用;该添加剂吸收波长峰值为320~475nm,故可从自然光获取产生荧光所需的能量;发射波长为450~650nm,可发出人类最为敏感的黄绿色荧光,便于观察。故如有泄露,肉眼可直接观测到渗漏位置;同时,在危险环境下(如电火花、明火等),添加剂会分解产生大量的阻化剂自由基(CF2,NH2),通过与碳氢制冷剂产生的活化基团(CH3,OH,HCO等)发生碰撞,清除爆炸反应所需的活化自由基,从而达到抑爆的作用。
本发明提出的一种碳氢制冷剂用单组分添加剂,所述碳氢制冷剂用单组分添加剂具有示警、检漏及抑爆功能。在具体实施中,碳氢制冷剂选取丙烷为代表,根据市场上常见制冷剂与冷冻机油的质量比确定匹配的冷冻机油的质量(按100%计),再确定本发明中单组分碳氢制冷剂用添加剂的加入量。其中:单组分碳氢制冷剂用添加剂为自制,纯度≥99%。添加剂的加入量(按冷冻机油的总质量计)为5%~20%。丙烷为市售化工原料,有效组分纯度≥99.6%,含水量≤0.002%;冷冻机油为市售产品,含水量≤0.05%。
选取某可正常运行的空调作为实施对象。空调管外接一个流量可控的调节阀,供模拟制冷剂泄漏用。将空调内的原制冷剂及冷冻油除尽,根据空调的功率加注相应量的丙烷,按照丙烷与冷冻机油质量比2:1,将不同碳氢制冷剂用单组分添加剂含量的冷冻机油从空调低压口注入系统,碳氢制冷剂用单组分添加剂的添加量占冷冻机油总质量的5%~20%。加注后通电运行20min,使各组分混合均匀。
本发明的碳氢制冷剂用单组分添加剂的示警评价方法为:在无风、无明火的半封闭区间,打开空调管外接的调节阀,气体流量固定为100ml/min。2min后由5名站在离调节阀5m处的独立试验者对含碳氢制冷剂用单组分添加剂的制冷剂在嗅觉方面进行示警强度评价。碳氢制冷剂成品的气味强度即可评价添加剂的示警能力,分别设为1级(非常微弱)、2级(微弱)、3级(一般)、4级(较强烈)、5级(强烈)。
本发明的碳氢制冷剂用单组分添加剂的检漏评价方法为:在无风、无明火、无强光的半封闭区间,打开空调管外接的调节阀,气体流量固定为100ml/min。2min后由5名站在离调节阀1m处的独立试验者观测调节阀出口是否有荧光产生。荧光的强度评价即可判定添加剂的检漏能力,分别设为1级(非常微弱)、2级(微弱)、3级(一般)、4级(较强烈)、5级(强烈)。
本申请单组分碳氢制冷剂用添加剂的抑爆评价方法为:通过调节阀将碳氢制冷剂放出,并与空气按1:5(质量比)混合均匀,灌入预先抽真空的不锈钢防爆钢球中至体系压力为0.1MPa。其中,爆炸室尺寸为Φ×h=300mm×300mm,容积约为20L;放电击针为针—针结构,材料为黄铜,曲率半径为0.5~1mm,放电间隙为2mm,放电回路阻值为0Ω,点火电压为8kV。爆炸罐壁上安有压力传感器,传感器与记录仪相连。测量电火花点火30min后钢球内的压力。测得的压力值(绝对压力)可以确定钢球内气体的爆炸情况,从而衡量添加剂的抑爆效果。
实施例1:本发明的单组分碳氢制冷剂用添加剂为6-甲硫基-2-二氟碘甲基-1H-苯并异喹啉-1,3(2H)-二酮,分子结构式为:
其在冷冻机油中的添加量(按冷冻机油的总质量计)为5%。测得通过本发明添加剂制备的成品制冷剂泄漏后的示警强度评价为2级(微弱),检漏能力评价为3级(一般),点火后压力值为0.9MPa(制冷剂部分爆炸)。
实施例2:本发明的单组分碳氢制冷剂用添加剂为5-巯基-2-五氟乙基-1H-苯并异喹啉-1,3(2H)-二酮,分子结构式为:
其在冷冻机油中的添加量(按冷冻机油的总质量计)为20%。测得通过本发明添加剂制备的成品制冷剂泄漏后的示警强度评价为5级(强烈),检漏能力评价为5级(强烈),点火后压力值为0.1MPa(制冷剂没有发生爆炸)。
实施例3:本发明的单组分碳氢制冷剂用添加剂为6-丙硫基-2-(2,2,3,3,3-五氟丙烷)-1H-苯并异喹啉-1,3(2H)-二酮,分子结构式为:
其在冷冻机油中的添加量(按冷冻机油的总质量计)为10%。测得通过本发明添加剂制备的成品制冷剂泄漏后的示警强度评价为3级(一般),检漏能力评价为4级(较强烈),点火后压力值为0.3MPa(制冷剂少部分发生爆炸)。
实施例4:本发明的单组分碳氢制冷剂用添加剂为5-乙硫基-2-(1,2,2,3-三氟丙基)-1H苯并异喹啉-1,3(2H)-二酮,分子结构式为:
其在冷冻机油中的添加量(按冷冻机油的总质量计)为15%。测得通过本发明添加剂制备的成品制冷剂泄漏后的示警强度评价为4级(较强烈),检漏能力评价为5级(强烈),点火后压力值为0.1MPa(制冷剂没有发生爆炸)。
本发明提供的具有示警、检漏、抑爆功能的碳氢制冷剂用单组分添加剂,与现有技术相比,具有如下优点:第一,添加剂溶解于冷冻机油中进入制冷系统,而非与碳氢制冷剂预混后再充装,避免了组分由于密度差异而引起的各批次产品性能迥异的缺陷;第二,单组分集“示警、检漏、抑爆”功能与一身,避免了各种单功能添加剂间相容性差、以及添加量过大等问题;第三,气味特殊,明显区别周围环境中常见物质的气味(如煤气、下水道、食物腐烂的味道),嗅觉分辨性高,即使泄漏在空气中被稀释100倍时仍可明显察觉,预防泄漏的警示作用显著;第四,无需专业仪器,肉眼即可观察到人类最为敏感的黄绿色荧光,便于观察;第五,抑爆性能好,利用化学抑爆原理,在准爆轰情况下对化学反应进行直接干预,具有用量少、效果好的特点;第六,存储稳定性高。本发明的添加剂在100℃的恒温条件下、经过360天的加速老化试验,其体系组分不发生明显变化,仍具有显著的功能特性,能够满足长期循环使用的要求;第七,抗腐蚀性好。本发明的添加剂与(铜质、铁质或铝质材料)管道均具有良好的相容性,不发生腐蚀性,以利于在制冷设备长期使用。
本发明的具体实现方法和途径很多,以上所述仅是本发明的优选实施方式。应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。

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1.一种碳氢制冷剂用单组分添加剂的使用方法,其特征在于,所述碳氢制冷剂用单组分添加剂的母体结构为1,8-萘酰亚胺类,氮原子上连接有卤代烷烃类基团(R1),萘环上连接有巯基或烃硫基(R2),所述的母体结构式为:
所述卤代烷烃类基团(R1)的化学分子式为-CF2I、-CHFCF3、-CF2CF3、-CH2CF2CF3、-CHFCF2CF3、-CF2CF2CF3、-CH(CF3)2、-CHFCF2CHF2或-CHFCF3CH2F;
所述巯基或烃硫基(R2)位于萘环的5号位或6号位;所述烃硫基(R2)的化学分子式为-SCH3、-SCH2CH3或-SCH2CH2CH3
使用所述碳氢制冷剂用单组分添加剂前先溶解到冷冻机油中,随冷冻机油共同添加到制冷设备中,所述碳氢制冷剂用单组分添加剂的添加量占冷冻机油总质量的5%~20%。
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