CN114940739A - 一种高耐热易溶解tpu及其制备方法 - Google Patents
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Abstract
本发明公开了一种高耐易溶解TPU及其制备方法,高耐热易溶解TPU,其原料质量百分含量组成包括:多元醇70~95wt%,二异氰酸酯5~20wt%,扩链剂0~10wt%,交联剂0.03~0.5wt%,催化剂0~0.1wt%;所述交联剂,其中含有50~100wt%的山梨糖醇酐衍生物。本发明所述的TPU耐温可达90‑100℃,在低极性溶剂中可溶。同时兼具高粘结强度、耐湿热的特点,适用于鞋材、服装、纺织、家具、汽车领域。
Description
技术领域
本发明属于聚氨酯技术领域,涉及一种热塑性聚氨酯(TPU)及制备,具体涉及一种高耐热易溶解TPU及其制备方法。
背景技术
热塑性聚氨酯(TPU)由于其线性结构,可通过热熔或溶解进行加工。在作为胶黏剂使用时通过熔融或溶剂溶解而涂覆于粘结基材上,再经冷却而固化。固化过程主要是利用组成中氢键的作用发生物理交联,使得胶层拥有优良的强度和弹性。胶层再次受热后将失去氢键作用变成熔融态,具有可反复加热-冷却固化的特性。目前广泛应用于鞋材、纺织、建筑、汽车、家具等领域。
中国专利CN 101423598A公开了一种高光泽、高溶解性聚氨酯树脂及其制备方法,然而其只能在酮类、DMF、THF中溶解,在低极性溶剂(如乙酸乙酯、二甲苯、甲苯)中只能溶胀。
中国专利CN 103012719A公开了一种耐高温油墨用聚氨酯胶黏剂的制备方法,通过采用芳香族聚酯多元醇得到的聚氨酯能够溶解在醇酯类溶剂,但其粘结强度<2N/mm,且软化点高,限制了下游加工应用。
中国专利CN 103992459A公开了一种可溶解于乙醇的聚氨酯树脂材料及其制备方法,其通过在溶剂体系原位反应得到聚氨酯乙醇溶液,但得到的聚氨酯树脂剥离强度低于1N/mm,且仅适用于医用材料领域,较难工业化放大生产。
发明内容
针对现有技术中存在的上述问题,本发明的目的是提供一种高耐热且易溶解的TPU及其制备方法,该TPU可以作为胶黏剂应用,兼具高耐热性及易溶解性,耐温可达90-100℃,且在低极性溶剂中可溶。同时所述TPU还具有高粘结强度、耐湿热的特点,适用于鞋材、服装、纺织、家具、汽车领域。
为实现上述目的,本发明提供一种高耐热易溶解TPU,其原料质量百分含量组成包括:
多元醇70~95wt%,优选80~90wt%;
二异氰酸酯5~20wt%,优选7~14wt%;
扩链剂0~10wt%,优选3~6wt%;
交联剂0.03~0.5wt%,优选0.05~0.3wt%;
催化剂0~0.1wt%,优选0.02~0.05wt%;
所述交联剂,以交联剂总质量计,其中含有50~100wt%的山梨糖醇酐衍生物,所述山梨糖醇酐衍生物结构如式1所示:
式中,R为线性或支化的C1-C17烷基、线性或支化的C2-C6烯基,优选为C11-C17烷基、乙烯基;
R'、R″、R″'分别独立的为羟基(-OH)、线性或支化的C1-C6烷羟基(-CnH2nOH),优选为羟基、羟乙基;
优选地,所述山梨糖醇酐衍生物为山梨糖醇酐单月桂酸酯(R'、R″、R″'为羟基,R为C11烷基)、山梨糖醇酐十六酸酯(R'、R″、R″'为羟基,R为C15烷基)、山梨糖醇酐十八酸酯(R'、R″、R″'为羟基,R为C17烷基)。
本发明中,所述多元醇数均分子量为1000~5000g/mol,优选为2000-4000g/mol;
进一步的,所述多元醇选自聚酯多元醇、聚醚多元醇、聚己内酯多元醇中的任意一种或至少两种的组合。
优选地,所述聚酯多元醇是由己二酸与二元醇聚合反应制得,所述聚合反应方法为本领域公知的,本发明没有特别要求,可以通过行业公知的聚酯多元醇合成工艺制得;
其中所述二元醇选自乙二醇、二乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、一缩二乙二醇、一缩二丙二醇、新戊二醇、3-甲基-1,5-戊二醇、甲基丙二醇中的任意一种或至少两种的组合,更优选为聚己二酸丁二醇酯、聚己二酸乙二醇酯、聚己二酸己二醇酯中的任意一种或至少两种的组合,最优选聚己二酸丁二醇酯。
优选地,所述聚醚多元醇是以含活泼氢化合物作为起始剂与环氧化合物开环聚合制得,该聚合反应在催化剂(例如钛酸酯类、有机锡类)存在下进行,具体可以采用任何可实现方法来制备得到,本发明没有特别要求;
其中所述含活泼氢化合物选自乙二醇、二乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇中的任意一种或至少两种的组合,优选为乙二醇、二乙二醇、1,2-丙二醇中的任意一种或至少两种的组合。
所述环氧化合物选自环氧丙烷、四氢呋喃、环氧乙烷中的任意一种或至少两种的组合,优选聚四氢呋喃醚二醇。
优选地,所述聚己内酯多元醇是以小分子醇作为起始剂与ε-己内酯开环聚合制得,该聚合反应在催化剂(例如钛酸酯类、有机锡类)存在下进行,具体可以采用任何可实现方法来制备得到,本发明没有特别要求;
其中所述小分子醇起始剂选自乙二醇、二乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、一缩二乙二醇、一缩二丙二醇、新戊二醇、3-甲基-1,5-戊二醇、甲基丙二醇中任意一种或至少两种的组合,优选为乙二醇、1,4-丁二醇、新戊二醇中任意一种或至少两种的组合。
本发明中,所述二异氰酸酯选自芳香族异氰酸酯、脂肪族异氰酸酯中的任意一种或至少两种的组合。
优选地,所述芳香族二异氰酸酯选自4,4-二苯基甲烷二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、对苯二异氰酸酯中任意一种或至少两种的组合,更优选4,4-二苯基甲烷二异氰酸酯。
优选地,所述脂肪族二异氰酸酯选自六亚甲基二异氰酸酯、4,4-二环己基甲烷二异氰酸酯、异氟尔酮二异氰酸酯、环己烷二亚甲基二异氰酸酯中任意一种或至少两种的组合,更优选六亚甲基二异氰酸酯。
本发明中,所述扩链剂选自乙二醇、二乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、一缩二乙二醇、一缩二丙二醇、新戊二醇、3-甲基-1,5-戊二醇、甲基丙二醇中的任意一种或至少两种的组合,优选1,4-丁二醇和/或1,6-己二醇。
本发明中,所述交联剂,还包括任选的三羟甲基丙烷、丙三醇、季戊四醇中的任意一种或至少两种的组合,优选三羟甲基丙烷;或者
所述交联剂,包括任选的以三羟甲基丙烷、丙三醇或季戊四醇作为起始剂由ε-己内酯反应制得的低分子量聚己内酯多元醇;其中所述起始剂优选三羟甲基丙烷;
优选地,所述低分子量聚己内酯多元醇,其分子量为300~1000g/mol,优选400~800g/mol。
本发明中,所述催化剂选自叔胺类化合物、有机锡类化合物、有机重金属盐类化合物的中的任意一种或至少两种的组合;其中,所述叔胺类化合物选自三乙胺、三亚乙基二胺、二甲基环己胺中的任意一种或至少两种的组合,所述有机锡类化合物选自二月桂酸二丁基锡、辛酸亚锡、二(十二烷基硫)二丁基锡、二乙酸二丁基锡中的任意一种或至少两种的组合,所述有机重金属盐类化合物选自异辛酸铅、乙酸苯汞、异辛酸锌、异辛酸锌铋中的任意一种或至少两种的组合;
优选地,所述催化剂为二月桂酸二丁基锡。
本发明中,所述高耐热易溶解TPU,其原料中还包括任选的助剂,所述助剂选自抗氧剂(如抗氧剂1010)、耐uv剂(如UV-1);
优选地,以高耐热易溶解TPU总质量为100%计,所述助剂添加量为0.1~2%,优选0.5~1%。
本发明还提供了所述高耐热易溶解TPU的制备方法,可采用一步法将多元醇、二异氰酸酯、扩链剂、交联剂、催化剂及任选的助剂等各原料按配方比例混合均匀,在双螺杆挤出机中反应后挤出,造粒,干燥制得;
优选地,所述反应温度为120~200℃,优选140~180℃;
所述造粒温度为5~30℃,优选10~20℃;
所述干燥温度为30~50℃。
本发明所述高耐热易溶解TPU,具有良好的耐热性,耐温可达90~100℃。
本发明所述高耐热易溶解TPU,具有良好的溶解性,不但可以溶解于酮类、DMF、THF等溶剂中,而且在低极性溶剂例如甲苯、乙酸乙酯、二氯甲烷等中也具有很好的溶解性。
本发明所述高耐热易溶解TPU,可以用于制备胶粘剂,应用于鞋材、服装、纺织、家具、汽车等领域;还可用于制备油墨、底漆等领域。
与现有技术相比,本发明技术方案有益效果在于:
本发明通过引入一定量山梨糖醇酐衍生物作为交联剂,在与其他交联剂及组分协同作用下,得到兼具高耐热,易溶解性的TPU树脂,并且还同时具有高粘结强度、耐湿热的特点,可用于制备胶粘剂、油墨、底漆等,由其制备成的胶液广泛适用于鞋材、服装、纺织、家具、汽车等领域。
具体实施方式
现结合具体实施方式对本发明作如下说明。这里需要说明的是实施例只是用于对本发明作进一步的说明,而不能理解为对本发明保护范围的限定,凡根据本发明的内容对其做出非实质性的改进和调整均属于本发明保护之列。
本发明实施例和对比例中使用的试剂原料来源如下,其余试剂原料如无特别说明,均为普通市售产品:
六亚甲基二异氰酸酯、4,4-二苯基甲烷二异氰酸酯、4,4-二环己基甲烷二异氰酸酯:万华化学集团股份有限公司;
聚己二酸丁二醇酯:数均分子量1000g/mol,2000g/mol,3000g/mol,万华化学集团股份有限公司;
聚丁二酸丙二醇酯:数均分子量2000g/mol,万华化学集团股份有限公司;
聚己内酯(NPG起始剂):数均分子量2000g/mol,日本大赛璐有机合成公司;
聚四氢呋喃醚二醇:数据分子量1000g/mol,德国BASF公司;
1,4-丁二醇:新疆美克化工有限公司;
1,6-己二醇:德国BASF公司;
1,3-丙二醇:美国杜邦公司;
三羟甲基丙烷:瑞典帕斯托特殊化学品公司;
季戊四醇:瑞典帕斯托特殊化学品公司:
三羟甲基丙烷-聚己内酯(300g/mol):日本大赛璐有机合成公司;
山梨糖醇酐衍生物(R’,R”,R”’为羟基,R为C11,C15,C17烷基)分别对应山梨糖醇酐单月桂酸酯、山梨糖醇酐十六酸酯、山梨糖醇酐十八酸酯:美国Sigma-Aldrich公司;
1,4-山梨醇酐(结构如式2):美国Sigma-Aldrich公司;
二月桂酸二丁基锡:美国Momentive公司。
实施例1
一种高耐热易溶解TPU,其原料组成如下:
聚己二酸丁二醇酯85wt%,数均分子量2000g/mol;
六亚甲基二异氰酸酯12wt%;
1,4-丁二醇2.85wt%;
山梨糖醇酐衍生物(R’,R”,R”’为羟基,R为C11烷基)0.1wt%;
二月桂酸二丁基锡0.05wt%;
采用一步法将上述原料混合均匀,在双螺杆机中160℃反应挤出,10℃造粒,30℃干燥制得TPU。
对上述TPU产品分别进行耐热性、粘结性、溶解性、耐湿热性测试,结果如表1所示。
实施例2
一种高耐热易溶解TPU,其原料组成如下:
聚己二酸丁二醇酯90wt%,数均分子量3000g/mol;
4,4-二苯基甲烷二异氰酸酯9.2wt%;
1,4-丁二醇0.6wt%;
山梨糖醇酐衍生物(R’,R”,R”’为羟基,R为C15烷基)0.15wt%;
二月桂酸二丁基锡0.05wt%;
采用一步法将上述原料混合均匀,在双螺杆机中170℃反应挤出,15℃造粒,35℃干燥制得TPU。
对上述TPU产品分别进行耐热性、粘结性、溶解性、耐湿热性测试,结果如表1所示。
实施例3
一种高耐热易溶解TPU,其原料组成如下:
聚己二酸丁二醇酯84wt%,数均分子量1000g/mol;
4,4-二苯基甲烷二异氰酸酯13wt%;
1,4-丁二醇2.6wt%;
三羟甲基丙烷-聚己内酯0.05wt%,数均分子量300g/mol;
山梨糖醇酐衍生物(R’,R”,R”’为羟基,R为C17烷基)0.3wt%;
二月桂酸二丁基锡0.05wt%;
采用一步法将上述原料混合均匀,在双螺杆机中170℃反应挤出,15℃造粒,40℃干燥制得TPU。
对上述TPU产品分别进行耐热性、粘结性、溶解性、耐湿热性测试,结果如表1所示。
实施例4
一种高耐热易溶解TPU,其原料组成如下:
聚己二酸丁二醇酯79wt%,数均分子量1000g/mol;
4,4-二环己基甲烷二异氰酸酯17wt%;
1,4-丁二醇3.5wt%;
季戊四醇0.1wt%;
山梨糖醇酐衍生物(R’,R”,R”’为羟基,R为C15烷基)0.3wt%;
二月桂酸二丁基锡0.1wt%;
采用一步法将上述原料混合均匀,在双螺杆机中190℃反应挤出,10℃造粒,50℃干燥制得TPU。
对上述TPU产品分别进行耐热性、粘结性、溶解性、耐湿热性测试,结果如表1所示。
实施例5
一种高耐热易溶解TPU,其原料组成如下:
聚己内酯(NPG起始剂)74wt%,数均分子量2000g/mol;
4,4-二环己基甲烷二异氰酸酯20wt%;
1,4-丁二醇5.5wt%;
山梨糖醇酐衍生物(R’,R”,R”’为羟基,R为C11烷基)0.4wt%;
二月桂酸二丁基锡0.1wt%;
采用一步法将上述原料混合均匀,在双螺杆机中200℃反应挤出,15℃造粒,50℃干燥制得TPU。
对上述TPU产品分别进行耐热性、粘结性、溶解性、耐湿热性测试,结果如表1所示。
实施例6
一种高耐热易溶解TPU,其原料组成如下:
聚丁二酸丙二醇酯80wt%,数均分子量2000g/mol;
4,4-二苯基甲烷二异氰酸酯13wt%;
1,6-己二醇6.7wt%;
山梨糖醇酐衍生物(R’,R”,R”’为羟基,R为C17烷基)0.1wt%;
三羟甲基丙烷0.1wt%
二月桂酸二丁基锡0.1wt%;
采用一步法将上述原料混合均匀,在双螺杆机中190℃反应挤出,20℃造粒,50℃干燥制得TPU。
对上述TPU产品分别进行耐热性、粘结性、溶解性、耐湿热性测试,结果如表1所示。
实施例7
一种高耐热易溶解TPU,其原料组成如下:
聚四氢呋喃醚二醇88wt%,数均分子量1000g/mol;
六亚甲基二异氰酸酯8wt%;
1,3-丙二醇3.65wt%;
山梨糖醇酐衍生物(R’,R”,R”’为羟基,R为C15烷基)0.25wt%;
二月桂酸二丁基锡0.1wt%;
采用一步法将上述原料混合均匀,在双螺杆机中180℃反应挤出,15℃造粒,40℃干燥制得TPU。
对上述TPU产品分别进行耐热性、粘结性、溶解性、耐湿热性测试,结果如表1所示。
对比例1
参照实施例1方法制备TPU,不同之处仅在于交联剂山梨糖醇酐衍生物替换为等质量的三羟甲基丙烷,其他原料及用量不变,制得TPU。
对上述TPU产品分别进行耐热性、粘结性、溶解性、耐湿热性测试,结果如表1所示。
对比例2
参照实施例1方法制备TPU,不同之处在于交联剂山梨糖醇酐衍生物替换为等质量的季戊四醇,其他原料及用量不变,制得TPU。
对上述TPU产品分别进行耐热性、粘结性、溶解性、耐湿热性测试,结果如表1所示。
对比例3
参照实施例1方法制备TPU,不同之处在于交联剂山梨糖醇酐衍生物替换为具有如式2的1,4-山梨糖醇酐,其他原料及用量不变,制得TPU。
对上述TPU产品分别进行耐热性、粘结性、溶解性、耐湿热性测试,结果如表1所示。
对比例4
参照实施例1方法制备TPU,原料不变,不同之处在于组分含量按如下配比,制得TPU。
聚己二酸丁二醇酯50wt%,数均分子量2000g/mol;
六亚甲基二异氰酸酯30.85wt%;
1,4-丁二醇19wt%;
山梨糖醇酐衍生物(R’,R”,R”’为羟基,R为C11烷基)0.1wt%;
二月桂酸二丁基锡0.05wt%。
对上述TPU产品分别进行耐热性、粘结性、溶解性、耐湿热性测试,结果如表1所示。
表1 TPU产品耐热性、粘结性、溶解性、耐湿热性测试结果
Claims (10)
1.一种高耐热易溶解TPU,其特征在于,其原料质量百分含量组成包括:
多元醇70~95wt%,优选80~90wt%;
二异氰酸酯5~20wt%,优选7~14wt%;
扩链剂0~10wt%,优选3~6wt%;
交联剂0.03~0.5wt%,优选0.05~0.3wt%;
催化剂0~0.1wt%,优选0.02~0.05wt%;
所述交联剂,以交联剂总质量计,其中含有50~100wt%的山梨糖醇酐衍生物,所述山梨糖醇酐衍生物结构如式1所示:
式中,R为线性或支化的C1-C17烷基、线性或支化的C2-C6烯基,优选为C11-C17烷基、乙烯基;
R'、R″、R″'分别独立的为羟基、线性或支化的C1-C6烷羟基,优选为羟基、羟乙基。
2.根据权利要求1所述的高耐热易溶解TPU,其特征在于,所述山梨糖醇酐衍生物为山梨糖醇酐单月桂酸酯、山梨糖醇酐十六酸酯、山梨糖醇酐十八酸酯中的任意一种或至少两种的组合。
3.根据权利要求1或2所述的高耐热易溶解TPU,其特征在于,所述多元醇数均分子量为1000~5000g/mol,优选为2000-4000g/mol。
4.根据权利要求1-3任一项所述的高耐热易溶解TPU,其特征在于,所述多元醇选自聚酯多元醇、聚醚多元醇、聚己内酯多元醇中的任意一种或至少两种的组合;
优选地,所述聚酯多元醇是由己二酸与二元醇聚合反应制得;其中,所述二元醇选自乙二醇、二乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、一缩二乙二醇、一缩二丙二醇、新戊二醇、3-甲基-1,5-戊二醇、甲基丙二醇中的任意一种或至少两种的组合,优选为聚己二酸丁二醇酯、聚己二酸乙二醇酯、聚己二酸己二醇酯中的任意一种或至少两种的组合,更优选聚己二酸丁二醇酯;
优选地,所述聚醚多元醇是以含活泼氢化合物作为起始剂与环氧化合物开环聚合制得;其中,所述含活泼氢化合物选自乙二醇、二乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇中的任意一种或至少两种的组合,优选为乙二醇、二乙二醇、1,2-丙二醇中的任意一种或至少两种的组合;所述环氧化合物选自环氧丙烷、四氢呋喃、环氧乙烷中的任意一种或至少两种的组合,优选聚四氢呋喃醚二醇;
优选地,所述聚己内酯多元醇是以小分子醇作为起始剂与ε-己内酯开环聚合制得;其中,所述小分子醇起始剂选自乙二醇、二乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、一缩二乙二醇、一缩二丙二醇、新戊二醇、3-甲基-1,5-戊二醇、甲基丙二醇中任意一种或至少两种的组合,优选为乙二醇、1,4-丁二醇、新戊二醇中任意一种或至少两种的组合。
5.根据权利要求1-4任一项所述的高耐热易溶解TPU,其特征在于,所述二异氰酸酯选自芳香族异氰酸酯、脂肪族异氰酸酯中的任意一种或至少两种的组合;
优选地,所述芳香族二异氰酸酯选自4,4-二苯基甲烷二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、对苯二异氰酸酯中任意一种或至少两种的组合,更优选4,4-二苯基甲烷二异氰酸酯;
优选地,所述脂肪族二异氰酸酯选自六亚甲基二异氰酸酯、4,4-二环己基甲烷二异氰酸酯、异氟尔酮二异氰酸酯、环己烷二亚甲基二异氰酸酯中任意一种或至少两种的组合,更优选六亚甲基二异氰酸酯。
6.根据权利要求1-5任一项所述的高耐热易溶解TPU,其特征在于,所述扩链剂选自乙二醇、二乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、一缩二乙二醇、一缩二丙二醇、新戊二醇、3-甲基-1,5-戊二醇、甲基丙二醇中的任意一种或至少两种的组合,优选1,4-丁二醇和/或1,6-己二醇;和/或
所述交联剂,包括任选的三羟甲基丙烷、丙三醇、季戊四醇中的任意一种或至少两种的组合,优选三羟甲基丙烷;或者
所述交联剂,包括任选的以三羟甲基丙烷、丙三醇或季戊四醇作为起始剂由ε-己内酯反应制得的低分子量聚己内酯多元醇;其中,所述起始剂优选三羟甲基丙烷;
优选地,所述低分子量聚己内酯多元醇,其分子量为300~1000g/mol,优选400~800g/mol;和/或
所述催化剂选自叔胺类化合物、有机锡类化合物、有机重金属盐类化合物的中的任意一种或至少两种的组合;其中,所述叔胺类化合物选自三乙胺、三亚乙基二胺、二甲基环己胺中的任意一种或至少两种的组合,所述有机锡类化合物选自二月桂酸二丁基锡、辛酸亚锡、二(十二烷基硫)二丁基锡、二乙酸二丁基锡中的任意一种或至少两种的组合,所述有机重金属盐类化合物选自异辛酸铅、乙酸苯汞、异辛酸锌、异辛酸锌铋中的任意一种或至少两种的组合;
优选地,所述催化剂为二月桂酸二丁基锡。
7.根据权利要求1-6任一项所述的高耐热易溶解TPU,其特征在于,所述高耐热易溶解TPU,其原料中包括任选的助剂,所述助剂选自抗氧剂、耐uv剂;
优选地,以高耐热易溶解TPU总质量为100%计,所述助剂添加量为0.1~2%,优选0.5~1%。
8.根据权利要求1-9任一项所述高耐热易溶解TPU,其特征在于,所述高耐热易溶解TPU,耐温90~100℃;
所述高耐热易溶解TPU,能够溶解于低极性溶剂例如甲苯、乙酸乙酯、二氯甲烷中。
9.权利要求1-8任一项所述高耐热易溶解TPU的制备方法,其特征在于,采用一步法将多元醇、二异氰酸酯、扩链剂、交联剂、催化剂及任选的助剂混合均匀,在双螺杆挤出机中反应后挤出,造粒,干燥制得;
优选地,所述反应温度为120~200℃,优选140~180℃;
所述造粒温度为5~30℃,优选10~20℃;
所述干燥温度为30~50℃。
10.权利要求1-8任一项所述高耐热易溶解TPU或者由权利要求9所述方法制备的高耐热易溶解TPU在胶粘剂、油墨、底漆领域的应用。
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