CN108219150A - 一种耐高温聚铝有机硅氧烷及制备方法 - Google Patents
一种耐高温聚铝有机硅氧烷及制备方法 Download PDFInfo
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- GIXWDMTZECRIJT-UHFFFAOYSA-N aurintricarboxylic acid Chemical compound C1=CC(=O)C(C(=O)O)=CC1=C(C=1C=C(C(O)=CC=1)C(O)=O)C1=CC=C(O)C(C(O)=O)=C1 GIXWDMTZECRIJT-UHFFFAOYSA-N 0.000 claims abstract description 12
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/10—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing aluminium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
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Abstract
本发明公开了一种耐高温聚铝有机硅氧烷及制备方法。所述聚铝有机硅氧烷的结构式为:制备方法包括:(1)R基硅烷的水解缩合;(2)水解缩合产物在碱的作用下生成二羟基R基硅醇钠;(3)二羟基R基硅醇钠与含铝试剂发生交换降解反应。本发明的聚铝有机硅氧烷具有优异的热稳定性和高温残炭率,高温粘接性能较好,应用范围广。
Description
技术领域
本发明涉及高分子材料技术领域,进一步地说,是涉及一种耐高温聚铝有机硅氧烷及制备方法。
背景技术
聚硅氧烷是一种主链以硅氧键为主的聚合物,习惯上称有机硅或聚硅醚,可以是线型、环状或交联的聚合物,由于硅氧烷独特的结构,兼备了无机材料与有机材料的优异性能,其中最突出的就是耐温性。由于硅氧烷主要以Si—O键为主链结构,Si—O键的键能远高于C—C键的键能,所以硅氧烷的热稳定性高,高温下或辐射照射时分子的化学键不断裂、不分解。有机硅不但可耐高温,而且也耐低温,可在一个很宽的温度范围内使用。无论是化学性能还是物理机械性能,随温度的变化都很小。
为进一步提高硅氧烷的耐温性,可将金属元素引入其分子结构中。19世纪50年代,前苏联的学者K A Andrianov便尝试将铝、钛、硼、铁等元素引入到硅氧烷链,合成了第一个聚金属有机硅氧烷。此后,更多的人对该方向进行了研究,在硅氧烷链中引入金属元素以提高其性能。这些聚合物可作为生产耐热塑料时的粘结剂,也可用作多种聚合物的改性剂,用作聚合物涂料的热稳定剂等。
陈友财,周文君,宋健,张敬礼.聚铝硅氧烷对聚碳酸酯阻燃性能的影响[J].中国塑料,2011,25(09):38-42.报道了一种制备了聚铝硅氧烷阻燃剂的方法,并应用热失重分析、锥形量热分析和极限氧指数测试研究了聚铝硅氧烷对聚碳酸酯(PC)热性能和阻燃性能的影响。结果表明,聚铝硅氧烷可降低PC的热降解速率,提高残炭量。用该方法合成的聚铝硅氧烷空间结构简单,仅仅是将含铝化合物嵌段聚合在有机硅分子链中,并未将铝元素引入硅氧烷单体中,因此相比传统聚硅氧烷,该聚铝硅氧烷的耐高温性能并未有质的提升。
专利201310118908.8公开了一种制备硅钛聚合物的方法,该方法以烷氧基硅烷和钛酸酯为原料,采用水解缩合两步反应,合成了硅钛聚合物,可用作粘接材料领域,但该法反应条件严格苛刻,同时原料成本较高,产率较低,不宜大规模生产。通过更改原料,优化反应路线等方式进一步研究聚元素有机硅氧烷的合成和性能,会极大地拓宽这些聚合物的工业生产应用。
发明内容
为设计一种新型结构的硅氧烷分子来进一步提高其耐高温性能,本发明提供了一种耐高温聚铝有机硅氧烷及其制备方法。本发明的聚铝有机硅氧烷具有优异的热稳定性和高温残炭率,高温粘接性能较好,应用范围广。
本发明的目的是提供一种耐高温聚铝有机硅氧烷。
所述聚铝有机硅氧烷的结构式为:
其中,优选:
R1,R2,R3为苯基,甲基,乙基中的一种;n为1-4。
本发明的目的之二是提供一种耐高温聚铝有机硅氧烷的制备方法。
包括:
所述方法包括:
(1)R基硅烷的水解缩合
将R基硅烷加入有机溶剂1,配制物质的量浓度为0.8-1mol/L的R基硅烷的溶液,向体系慢速滴加去离子水,在30-50℃氮气保护下反应2-5小时,得到R基硅醇溶液;除去溶液中水解生成的小分子,然后在80-100℃氮气保护下高温缩合3-6小时,得到聚R基硅倍半氧烷;
(2)水解缩合产物在碱的作用下生成二羟基R基硅醇钠
向步骤(1)的产物中加入有机溶剂2,然后滴加氢氧化钠水溶液,在45-55℃氮气保护下生成二羟基R基硅醇钠;
氢氧化钠的物质的量为R基硅烷的1-1.05倍;
(3)二羟基R基硅醇钠与含铝试剂发生交换降解反应
配制0.05-0.1g/ml的含铝试剂水溶液,加入步骤(2)得到的体系中,在75-80℃氮气保护条件下反应2-4小时得到聚铝R基硅氧烷溶液,并进行水洗旋蒸得到所述耐高温聚铝有机硅氧烷;
含铝试剂用量要保证R基硅烷与铝元素的物质的量之比为(2.8-3):1,将其加入体系;
R基硅烷为苯基三氯硅烷、甲基三甲氧基硅烷或乙基三甲氧基硅烷。
其中,优选:
所述的有机溶剂1为苯、甲苯或甲基异丁基酮;所述的有机溶剂2为乙醇或丁醇,有机溶剂2的用量为有机溶剂1的1.2-1.5倍。
步骤(1)中,去离子水的物质的量为R基硅烷的20-50倍。
步骤(2)中,氢氧化钠溶液的浓度为0.05-0.1g/ml。
所述的含铝试剂为硫酸铝钾或氯化铝。
本发明具体可采用以下技术方案:
第一步是R基硅烷的水解缩合
将R基硅烷加入有机溶剂1,配制物质的量浓度为1mol/L的R基硅烷的溶液,向体系慢速滴加去离子水,R基硅烷和去离子水的物质的量之比为1:30,在50℃氮气保护下反应4小时,得到R基硅醇溶液;除去溶液中水解生成的小分子,然后在80-100℃氮气保护下高温缩合4小时,得到聚R基硅倍半氧烷。
第二步是水解缩合产物在碱的作用下生成二羟基R基硅醇钠
向体系中加入有机溶剂2,其用量为有机溶剂1的1.5倍,称取与R基硅烷等物质的量的氢氧化钠配制成0.1g/ml的水溶液,匀速滴加到聚R基硅倍半氧烷溶液中,在50℃氮气保护下生成二羟基R基硅醇钠。
第三步是二羟基R基硅醇钠与含铝试剂发生交换降解反应
配制0.1g/ml的含铝试剂水溶液,含铝试剂用量要保证R基硅烷与铝元素的物质的量之比为3:1,将其加入体系在75℃氮气保护条件下反应2-4小时得到聚铝R基硅氧烷溶液,并进行水洗旋蒸等后处理。
本发明的耐高温聚铝有机硅氧烷由于其特殊的梯形大分子结构以及较强的键能,该物质具有优异的热稳定性和高温残炭率。本发明可应用到粘接剂领域,用于生产耐热塑料、塑料层压板和其它材料;也可作为有机聚合物和有机硅聚合物的固化剂,还可用作多种聚合物的改性剂;还可作为成膜助剂,用于金属的精密成型;同时还可用作聚合物涂料的热稳定剂等。
与现有技术相比,本发明有以下优点:
1.由该法合成聚铝有机硅氧烷简便易行,成本低廉,反应条件温和可控;
2.产物具有优异的热稳定性和高温残炭率,应用范围广。
附图说明
图1是实施例1的红外光谱图.
1130cm-1(Si-O-Si),1430cm-1(Si-Ph),3000cm-1(Si-O-Al),3422cm-1(Si-OH);
元素分析H的试验值和理论值分别为3.73%和4.01%,C的试验值和理论值分别为44.76%和45.60%;试验值和理论值较为较为接近,可确定铝元素成功合成到梯形硅氧烷分子中。
具体实施方式
下面结合实施例,进一步说明本发明。
实施例中所用原料均为市售。
实施例1
(1)在250ml三口烧瓶中加入苯基三氯硅烷6.36g(0.03mol),甲苯30ml,磁力搅拌下缓慢滴加去离子水10.8g,水与苯基三氯硅烷的摩尔比为20:1,控制滴加时间为5分钟,滴加完毕在50℃氮气保护下反应4小时;对生成的硅醇甲苯溶液进行除酸操作,使用分液漏斗对溶液进行反复水洗并检测下层水相PH直至中性,放净下层的水相;将溶液转移到新的三口烧瓶中,在80℃氮气环境下进行缩合反应4小时,得到聚苯基硅倍半氧烷的甲苯溶液。
(2)向体系中加入36ml乙醇,用量为甲苯的1.2倍,称取1.2g氢氧化钠配制浓度为0.1g/ml的氢氧化钠水溶液并加入体系,所用氢氧化钠与苯基三氯硅烷摩尔比为1:1,在50℃氮气环境下反应2小时,反应生成二羟基二苯基硅醇钠和水。
(3)称取2.76g硫酸铝钾配制0.1g/ml的硫酸铝钾水溶液,所用硫酸铝钾与苯基三氯硅烷摩尔比为1:2.8,加入体系,在75℃氮气环境下继续反应2小时,反应生成聚铝苯基硅氧烷,对溶液进行水洗操作,并用氯化钡检测其中的硫酸根残余,直至洗液变为中性,得到聚铝苯基硅氧烷清漆,旋转蒸出溶剂并对产物进行红外以及热失重测试。产物红外光谱测试结果如图1所示,为1130cm-1(Si-O-Si),1430cm-1(Si-Ph),3000cm-1(Si-O-Al),3422cm-1(Si-OH);热失重测试结果为620℃只分解5%,680℃分解20%,800℃的残碳率为81%。
实施例2
(1)在250ml三口烧瓶中加入苯基三氯硅烷6.36g(0.03mol),甲苯33ml,磁力搅拌下缓慢滴加去离子水18.9g,水与苯基三氯硅烷的摩尔比为35:1,控制滴加时间为5分钟,滴加完毕在50℃氮气保护下反应4小时;对生成的硅醇甲苯溶液进行除酸操作,使用分液漏斗对溶液进行反复水洗并检测下层水相PH直至中性,放净下层的水相;将溶液转移到新的三口烧瓶中,在90℃氮气环境下进行缩合反应4小时,得到聚苯基硅倍半氧烷的甲苯溶液。
(2)向体系中加入43ml乙醇,用量为甲苯的1.3倍,称取1.22g氢氧化钠配制浓度为0.08g/ml的氢氧化钠水溶液并加入体系,所用氢氧化钠与苯基三氯硅烷摩尔比为1.02:1,在50℃氮气环境下反应2小时,反应生成二羟基二苯基硅醇钠和水。
(3)称取2.67g硫酸铝钾配制0.08g/ml的硫酸铝钾水溶液,所用硫酸铝钾与苯基三氯硅烷摩尔比为1:2.9,加入体系,在75℃氮气环境下继续反应3小时,反应生成聚铝苯基硅氧烷,对溶液进行水洗操作,并用氯化钡检测其中的硫酸根残余,直至洗液变为中性,得到聚铝苯基硅氧烷清漆,旋转蒸出溶剂并对产物进行红外以及热失重测试。产物红外光谱测试结果为1130cm-1(Si-O-Si),1430cm-1(Si-Ph),3000cm-1(Si-O-Al),3422cm-1(Si-OH);热失重测试结果为640℃只分解5%,690℃分解20%,800℃的残碳率为83%。
实施例3
(1)在250ml三口烧瓶中加入苯基三氯硅烷6.36g(0.03mol),甲苯36ml,磁力搅拌下缓慢滴加去离子水27g,水与苯基三氯硅烷的摩尔比为50:1,控制滴加时间为5分钟,滴加完毕在50℃氮气保护下反应4小时;对生成的硅醇甲苯溶液进行除酸操作,使用分液漏斗对溶液进行反复水洗并检测下层水相PH直至中性,放净下层的水相;将溶液转移到新的三口烧瓶中,在100℃氮气环境下进行缩合反应4小时,得到聚苯基硅倍半氧烷的甲苯溶液。
(2)向体系中加入54ml乙醇,用量为甲苯的1.5倍,称取1.26g氢氧化钠配制浓度为0.05g/ml的氢氧化钠水溶液并加入体系,所用氢氧化钠与苯基三氯硅烷摩尔比为1.05:1,在50℃氮气环境下反应2小时,反应生成二羟基二苯基硅醇钠和水。
(3)称取2.58g硫酸铝钾配制0.05g/ml的硫酸铝钾水溶液,所用硫酸铝钾与苯基三氯硅烷摩尔比为1:3,加入体系,在75℃氮气环境下继续反应4小时,反应生成聚铝苯基硅氧烷,对溶液进行水洗操作,并用氯化钡检测其中的硫酸根残余,直至洗液变为中性,得到聚铝苯基硅氧烷清漆,旋转蒸出溶剂并对产物进行红外以及热失重测试。产物红外光谱测试结果为1130cm-1(Si-O-Si),1430cm-1(Si-Ph),3000cm-1(Si-O-Al),3422cm-1(Si-OH);热失重测试结果为655℃只分解5%,695℃分解20%,800℃的残碳率为86%,充分说明了聚铝苯基硅氧烷具有超高的耐高温性能。
实施例4
(1)在250ml三口烧瓶中加入甲基三甲氧基硅烷4.09g(0.03mol),甲基异丁基酮30ml,磁力搅拌下缓慢滴加去离子水16.2g,水与甲基三甲氧基硅烷的摩尔比为30:1,控制滴加时间为5分钟,滴加完毕在50℃氮气保护下反应4小时,在0.2MPa的真空度条件下脱除体系中水解生成的甲醇,之后在80℃氮气环境下进行缩合反应4小时,得到聚甲基硅倍半氧烷的甲基异丁基酮溶液。
(2)向体系中加入45ml乙醇,用量为甲基异丁基酮的1.5倍,称取1.2g氢氧化钠配制浓度为0.1g/ml的氢氧化钠水溶液并加入体系,所用氢氧化钠与甲基三甲氧基硅烷摩尔比为1:1,,在50℃氮气环境下反应2小时,反应生成二羟基二甲基硅醇钠和水。
(3)称取1.33g氯化铝配制0.1g/ml的氯化铝水溶液,所用氯化铝与甲基三甲氧基硅烷摩尔比为1:3,加入体系,在75℃氮气环境下继续反应4小时,反应生成聚铝甲基硅氧烷,对溶液进行水洗操作直至洗液变为中性,得到聚铝甲基硅氧烷清漆,旋转蒸出溶剂并对产物进行热失重测试。热失重测试结果为560℃只分解5%,640℃分解20%,800℃的残碳率为76%。
实施例5
(1)在250ml三口烧瓶中加入乙基三甲氧基硅烷4.50g(0.03mol),甲基异丁基酮30ml,磁力搅拌下缓慢滴加去离子水,水与乙基三甲氧基硅烷的摩尔比为30:1,控制滴加时间为5分钟,滴加完毕在50℃氮气保护下反应4小时,在0.2MPa的真空度条件下脱除体系中水解生成的甲醇,之后在80℃氮气环境下进行缩合反应4小时,得到聚乙基硅倍半氧烷的甲基异丁基酮溶液。
(2)向体系中加入45ml乙醇,用量为甲基异丁基酮的1.5倍,称取1.2g氢氧化钠配制浓度为0.1g/ml的氢氧化钠水溶液并加入体系,所用氢氧化钠与乙基三甲氧基硅烷摩尔比为1:1,,在50℃氮气环境下反应2小时,反应生成二羟基二乙基硅醇钠和水。
(3)配制0.1g/ml的氯化铝水溶液,所用氯化铝与乙基三甲氧基硅烷摩尔比为1:3,加入体系,在75℃氮气环境下继续反应4小时,反应生成聚铝乙基硅氧烷,对溶液进行水洗操作直至洗液变为中性,得到聚铝乙基硅氧烷清漆,旋转蒸出溶剂并对产物进行红外以及热失重测试。热失重测试结果为565℃只分解5%,665℃分解20%,800℃的残碳率为78%。
实施例6
向10g环氧树脂E51中加入1.2g二乙烯三胺固化剂,充分搅拌后在45#钢表面涂胶,控制厚度0.2mm左右,将45#钢搭接,给予一定压力,使其紧密贴合,升温到120℃,固化4h,依照GBT7124-2008(胶粘剂拉伸剪切强度的测定)进行拉伸剪切强度测试,拉伸剪切强度为3.6Mpa;对其进行热失重测试,在氮气气氛下800℃烧蚀后的残炭率为23.6%。
向100ml烧杯中加入1.0g实施例3制备的聚铝苯基硅氧烷和10ml四氢呋喃,充分搅拌使其溶解,将其与10g环氧树脂E51混合均匀,室温下放置过夜以充分挥发除去四氢呋喃,向体系加入1.2g二乙烯三胺固化剂并搅拌均匀,将配制好的胶黏剂在45#钢表面涂胶,控制厚度0.2mm左右,将45#钢搭接,给予一定压力,使其紧密贴合,升温到120℃,固化4h,依照GBT7124-2008(胶粘剂拉伸剪切强度的测定)进行拉伸剪切强度测试和热失重测试,相比于不加入聚铝苯基硅氧烷的环氧树脂E51,添加聚铝苯基硅氧烷后的环氧胶黏剂固化后拉伸剪切强度从3.9MPa提高到5.3Mpa,胶层致密性更好,800℃的残炭率从23.6%增加到33.5%。
实施例7
向100ml烧杯中加入2.0g实施例3制备的聚铝苯基硅氧烷和10ml四氢呋喃,充分搅拌使其溶解,将其与10g环氧树脂E51混合均匀,室温下放置过夜以充分挥发除去四氢呋喃,向体系加入1.2g二乙烯三胺固化剂并搅拌均匀,将配制好的胶黏剂在45#钢表面涂胶,控制厚度0.2mm左右,将45#钢搭接,给予一定压力,使其紧密贴合,升温到120℃,固化6h,依照GBT7124-2008(胶粘剂拉伸剪切强度的测定)进行拉伸剪切强度测试和热失重测试,相比于不加入聚铝苯基硅氧烷的环氧树脂E51,添加聚铝苯基硅氧烷后的环氧胶黏剂固化后拉伸剪切强度从3.9MPa提高到5.4Mpa,胶层致密性更好,800℃的残炭率从23.6%增加到45.6%。
实施例8
将PC和5%的实施例3制取的聚铝有机硅氧烷在250℃下混合均匀,在280℃注塑成型,获得所需的增强后的PC样品,对其进行N2气氛下的TGA测试,测试结果为120℃分解5%,700℃时分解20%,800℃的高温残碳率为76%,因此将铝元素引入硅氧烷的梯形结构中,可充分发挥其耐高温性能。
Claims (7)
1.一种耐高温聚铝有机硅氧烷,其特征在于:
所述聚铝有机硅氧烷的结构式为:
2.如权利要求1所述的耐高温聚铝有机硅氧烷,其特征在于:
R1,R2,R3为苯基,甲基,乙基中的一种;n为1-4。
3.如权利要求1~2之一所述的耐高温聚铝有机硅氧烷的制备方法,其特征在于所述方法包括:
(1)R基硅烷的水解缩合
将R基硅烷加入有机溶剂1,配制物质的量浓度为0.8-1mol/L的R基硅烷的溶液,向体系慢速滴加去离子水,在30-50℃氮气保护下反应2-5小时,得到R基硅醇溶液;除去溶液中水解生成的小分子,然后在80-100℃氮气保护下高温缩合3-6小时,得到聚R基硅倍半氧烷;
(2)水解缩合产物在碱的作用下生成二羟基R基硅醇钠
向步骤(1)的产物中加入有机溶剂2,然后滴加氢氧化钠水溶液,在45-55℃氮气保护下生成二羟基R基硅醇钠;
氢氧化钠的物质的量为R基硅烷的1-1.05倍;
(3)二羟基R基硅醇钠与含铝试剂发生交换降解反应
配制0.05-0.1g/ml的含铝试剂水溶液,加入步骤(2)得到的体系中,在75-80℃氮气保护条件下反应2-4小时得到聚铝R基硅氧烷溶液,并进行水洗旋蒸得到所述耐高温聚铝有机硅氧烷;
含铝试剂用量要保证R基硅烷与铝元素的物质的量之比为(2.8-3):1,将其加入体系;
R基硅烷为苯基三氯硅烷、甲基三甲氧基硅烷或乙基三甲氧基硅烷。
4.如权利要求3所述的耐高温聚铝有机硅氧烷的制备方法,其特征在于:
所述的有机溶剂1为苯、甲苯或甲基异丁基酮;所述的有机溶剂2为乙醇或丁醇,有机溶剂2的用量为有机溶剂1的1.2-1.5倍。
5.如权利要求3所述的耐高温聚铝有机硅氧烷的制备方法,其特征在于:
步骤(1)中,去离子水的物质的量为R基硅烷的20-50倍。
6.如权利要求3所述的耐高温聚铝有机硅氧烷的制备方法,其特征在于:
步骤(2)中,氢氧化钠溶液的浓度为0.05-0.1g/ml。
7.如权利要求3所述的耐高温聚铝有机硅氧烷的制备方法,其特征在于:
所述的含铝试剂为硫酸铝钾或氯化铝。
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