CN116444977B - 聚氨酯弹性体及利用其制备抛光磨块的方法 - Google Patents
聚氨酯弹性体及利用其制备抛光磨块的方法 Download PDFInfo
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- CN116444977B CN116444977B CN202310712771.2A CN202310712771A CN116444977B CN 116444977 B CN116444977 B CN 116444977B CN 202310712771 A CN202310712771 A CN 202310712771A CN 116444977 B CN116444977 B CN 116444977B
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- KVMPUXDNESXNOH-UHFFFAOYSA-N tris(1-chloropropan-2-yl) phosphate Chemical compound ClCC(C)OP(=O)(OC(C)CCl)OC(C)CCl KVMPUXDNESXNOH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
- B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
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- C—CHEMISTRY; METALLURGY
- 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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
本发明公开了聚氨酯弹性体及利用其制备抛光磨块的方法,属于抛光磨块技术领域。其技术方案为:包括A、B、C三组分,A组分由以下质量百分数的原料组成:小分子扩链剂10‑15%、阻燃剂3‑10%、水合硅酸盐79‑86.3%、偶联剂0.5‑0.6%、消泡剂0.08‑0.1%、防沉剂0.085‑0.1%和催化剂0.01‑0.02%;B组分由以下质量百分数的原料聚合而成:聚醚多元醇1.7‑28%、异氰酸酯52‑83.3%和降粘剂15‑20%;C组分由以下质量百分数的磨料组成:硅微粉10‑20%、金刚砂40‑50%和砂子30‑40%。本发明聚氨酯弹性体粘度低、混合磨料后易混匀、不用高温加热预成型、熟化速度快。
Description
技术领域
本发明涉及抛光磨块技术领域,具体涉及聚氨酯弹性体及利用其制备抛光磨块的方法。
背景技术
目前市面上的金刚石弹性磨块用结合剂主要使用三聚氰胺与甲醛反应得到的聚合物—密胺树脂、酚醛树脂、脲醛树脂或环氧树脂等制作,制得的弹性磨块具有机械强度高、耐磨性好、抛光效果均匀等优点。但这些树脂具有交联密度大、刚性强的特点,固化后硬度高但韧性差,树脂本身的结构特征决定了其制备的磨块存在硬而脆的特点,在使用过程中会发生磨料脱落、掉块,进而影响磨块使用效率及使用时间,且打磨后产品表面光亮度也存在一些问题,需要多次或反复打磨来提高光亮度。此外,使用这些树脂制备磨块时,大部分需要加热热压成型,温度最高要到200℃以上,造成大规模生产操作不便与资源的极大浪费。
目前,市面上使用聚氨酯作为结合剂制备弹性抛光磨块鲜见报道。聚氨酯作为一种新型高分子聚合物材料,其有“液体橡胶”之称,具有高耐磨、高撕裂强度、高承载力及优良的耐低温、耐油污、耐老化等性能。其与目前常用的酚醛树脂、脲醛树脂、密胺树脂及环氧树脂具有较大的差异,通过配方设计制作的弹性磨块兼具高的强度与韧性,抛光打磨表面光洁度效果更佳,且其本身为液体,不需要高温高热即可快速成型,制备工艺简单,操作方便,原料环保无污染,制备的弹性磨块更适合大批量、规模化、低成本生产。因此针对以上问题,需要开发出一种打磨产品的表面光亮度高、不用高温加热预成型且操作工艺简单,易于大规模工业化生产的聚氨酯弹性体结合剂。
发明内容
本发明要解决的技术问题是:克服现有技术的不足,提供聚氨酯弹性体及利用其制备抛光磨块的方法,聚氨酯弹性体具有粘度低、混合磨料后易混匀、不用高温加热预成型、熟化速度快等优点,且操作工艺简单,易于大规模工业化生产。
本发明的技术方案为:
一方面,本发明提供了聚氨酯弹性体,包括A、B、C三组分,A组分由以下质量百分数的原料组成:小分子扩链剂10-15%、阻燃剂3-10%、水合硅酸盐79-86.3%、偶联剂0.5-0.6%、消泡剂0.08-0.1%、防沉剂0.085-0.1%和催化剂0.01-0.02%;B组分由以下质量百分数的原料聚合而成:聚醚多元醇1.7-28%、异氰酸酯52-83.3%和降粘剂15-20%;C组分由以下质量百分数的磨料组成:硅微粉10-20%、金刚砂40-50%和砂子30-40%;A组分、B组分和C组分的质量比为100:(150-250):(200-600)。
优选的,所述A组分中,小分子扩链剂为一缩二丙二醇、乙二醇(EG)或甘油,数均分子量为62-134,官能度为2或3。
优选的,所述A组分中,阻燃剂为三(2-氯丙基)磷酸酯、异丙基化三苯基磷酸酯或磷酸甲苯二苯酯。
优选的,所述A组分中,水合硅酸盐为水合硅酸钠和水合硅酸钾中的一种或两种,密度为1.48-1.56g/cm3,模数为2.5-2.7,波美度为47-52°Be'。
优选的,所述A组分中,偶联剂为KH-550、KH-560、KH-590或KH-570。
优选的,所述A组分中,防沉剂为膨润土或气相白炭黑。
优选的,所述B组分中,聚醚多元醇为聚氧化丙烯多元醇,数均分子量为400-3000,官能度为2或3。
优选的,所述B组分中,异氰酸酯为二苯基甲烷二异氰酸酯和多亚甲基多苯基异氰酸酯中的一种或两种。
优选的,所述C组分中,硅微粉目数为300-600目,金刚砂目数为80-200目,砂子目数为80-1000目。
另一方面,本发明还提供了利用上述聚氨酯弹性体制备抛光磨块的方法,A组分的制备:将A组分中的原料混合后,搅拌均匀后封装,即得A组分;B组分的制备:将水分含量控制在0.05%以下的聚醚多元醇与异氰酸酯和降粘剂,在70-80℃下反应2-3h,得到异氰酸根含量为15-25%的预聚物,抽真空脱除机械泡后封装,即得B组分;C组分的制备:将各磨料搅拌均匀后封装,即得C组分;抛光磨块的制备:将A、B、C三组分混合搅拌均匀,倒入磨具中,室温熟化3-5天或完全硬化后于80-100℃下熟化4-6h,即得抛光磨块。
本发明与现有技术相比,具有以下有益效果:
1. 本发明的聚氨酯弹性体,通过C组分中不同粉体的搭配,加入A、B组分构成的聚氨酯粘合剂,达到粘接粉体骨架的作用,使得制备的抛光磨块具有高硬度的同时还具有更好的韧性及阻燃、耐磨特性。不同种类粉体及粒径搭配使得抛光磨块对物体表面打磨光洁度更高,特别适合需要精打磨的物体表面,如光面瓷砖、金属加工件等,且工艺制作简单,易于大规模工业化生产。
2. 本发明通过选用水合硅酸盐原料,与聚氨酯预聚物B组分搭配使用,即使体系内有水存在,其与异氰酸酯反应生成的CO2也被硅酸盐原料捕捉,生成硬硅酸产物,超越常规聚醚原料体系易发泡特性,使得体系内有水存在的情况下仍旧具有良好的表面平整度及硬度,大大拓展了聚氨酯产品的应用范围与应用场景。
3. 本发明的抛光磨块制备方法简单,借助聚氨酯A、B双组分高活性料反应过程中放热及选取合适的胺类催化剂,使得聚氨酯弹性体不需要前期预加热成型即可快速固化成型,后期室温放置3-5天即可达到最终强度,弥补了酚醛树脂等需要高温100℃以上的预加热成型及后熟化阶段的不足,生产投入小,易于规模化生产,且原料使用安全环保无污染,节约能源与资源。
具体实施方式
为了使本技术领域的人员更好地理解本发明中的技术方案,下面将结合本发明的实施例,对本发明的技术方案进行清楚、完整地描述。
以下实施例中的原料,未做特殊说明,均为市购或通过现有方法制备得到。
实施例中所用材料如下:
PPG400:数均分子量为400,官能度为2,羟值为280±15(mg KOH/g),聚氧化丙烯二醇;
MN500:数均分子量为500,官能度为3,羟值为340±10(mg KOH/g),丙二醇与环氧丙烷合成的聚醚多元醇;
PPG3000:数均分子量为3000,官能度为为2,羟值为38±2(mg KOH/g),聚氧化丙烯二醇;
水合硅酸钠:密度为1.48g/cm3,模数为2.7,波美度为47°Bé;
水合硅酸钾:密度为1.56g/cm3,模数2.5,波美度52°Bé;
小分子扩链剂:分子量为93,官能度为3,纯度99.5%甘油(KG-03);分子量为62,官能度为2,乙二醇(EG);分子量为134,官能度为2,一缩二丙二醇(DPG);
异氰酸酯:二苯基甲烷二异氰酸酯(MDI-50)、多亚甲基多苯基异氰酸酯(PM200);
降粘剂:2,2,4-三甲基-1,3-戊二醇双异丁酸酯(TXIB)、对苯二甲酸二辛脂(DOTP);
催化剂:胺类催化剂(TX-1);
消泡剂:BYK-066;
防沉剂:气相白炭黑(XH-201)、膨润土(P-070);
阻燃剂:异丙基化三苯基磷酸酯(IPPP50)、三(2-氯丙基)磷酸酯(TCPP)、磷酸甲苯二苯酯(CDP);
偶联剂:KH-590、KH-570、KH-550、KH-560;
磨料:硅微粉300-600目、金刚砂80-200目、砂子80-1000目。
实施例1
本实施例利用聚氨酯弹性体制备抛光磨块的方法如下:
A组分的制备:数均分子量为93的小分子扩链剂KG-03 10%、液体阻燃剂IPPP505%、水合硅酸钠84.3%、偶联剂KH-590 0.5%、消泡剂BYK-0660.08%、防沉剂XH-201 0.1%,催化剂TX-1 0.02%;各原料混合后,使用高速分散机1500r/min充分搅拌均匀后封装,得到A组分。
B组分的制备:水分含量控制在0.05%以下的聚醚多元醇PPG400 1.7%、降粘剂TXIB15%与异氰酸酯PM20083.3%,在温度70℃条件下反应2.5h,得到异氰酸根含量为25%的预聚物,抽真空脱除机械泡后封装,得到B组分。
C组分的制备:将硅微粉10%、金刚砂50%、砂子40%充分搅拌均匀后封装,得到C组分。
抛光磨块的制备:A组分、B组分和C组分的质量比为100:150:400,室温条件下使用1500r/min高搅机将三组分搅拌均匀,倒入磨具中,室温熟化3天,得到硬度为邵D85的抛光磨块。
实施例2
本实施例利用聚氨酯弹性体制备抛光磨块的方法如下:
A组分的制备:数均分子量为134的小分子扩链剂DPG 15%,液体阻燃剂IPPP50 5%,水合硅酸钾79.3%、偶联剂KH-550 0.5%、消泡剂BYK-0660.1%、防沉剂P-070 0.085%,催化剂TX-1 0.015%;各原料混合后,使用高速分散机1500r/min充分搅拌均匀后封装,得到A组分。
B组分的制备:水分含量控制在0.05%以下的聚醚多元醇PPG3000 16%、降粘剂DOTP20%与异氰酸酯PM20064%,在温度75℃条件下反应3h,得到异氰酸根含量为19%的预聚物,抽真空脱除机械泡后封装,得到B组分。
C组分的制备:将硅微粉20%、金刚砂40%、砂子40%充分搅拌均匀后封装,得到C组分。
抛光磨块的制备:A组分、B组分和C组分的质量比为100:250:600,室温条件下使用1500r/min高搅机将三组分搅拌均匀,倒入磨具中,室温熟化5天,得到硬度为邵D75的抛光磨块。
实施例3
本实施例利用聚氨酯弹性体制备抛光磨块的方法如下:
A组分的制备:数均分子量为62的小分子扩链剂EG 10%,液体阻燃剂TCPP 3%,水合硅酸钠86.3%、偶联剂KH-560 0.5%、消泡剂BYK-0660.08%、防沉剂XH-201 0.1%,催化剂TX-10.02%;各原料混合后,使用高速分散机1500r/min充分搅拌均匀后封装,得到A组分。
B组分的制备:水分含量控制在0.05%以下的聚醚多元醇MN500 10.4%、降粘剂TXIB20%与异氰酸酯PM20055.6%、异氰酸酯MDI-50 14%,在温度75℃条件下反应2h,得到异氰酸根含量为19%的预聚物,抽真空脱除机械泡后封装,得到B组分。
C组分的制备:将硅微粉10%、金刚砂50%、砂子40%充分搅拌均匀后封装,得到C组分。
抛光磨块的制备:A组分、B组分和C组分的质量比为100:200:500,室温条件下使用1500r/min高搅机将三组分搅拌均匀,倒入磨具中,完全硬化后放入80℃烘箱中熟化6h后,得到硬度为邵D82的抛光磨块。
实施例4
本实施例利用聚氨酯弹性体制备抛光磨块的方法如下:
A组分的制备:数均分子量为93的小分子扩链剂KG-03 10%,液体阻燃剂CDP 10%,水合硅酸钠79.2%、偶联剂KH-570 0.6%、消泡剂BYK-0660.1%、防沉剂XH-201 0.09%、催化剂TX-1 0.01%;各原料混合后,使用高速分散机1500r/min充分搅拌均匀后封装,得到A组分。
B组分的制备:水分含量控制在0.05%以下的聚醚多元醇PPG3000 28%、降粘剂DOTP20%与异氰酸酯PM20052%,在温度80℃条件下反应3h,得到异氰酸根含量为15%的预聚物,抽真空脱除机械泡后封装,得到B组分。
C组分的制备:将硅微粉20%、金刚砂50%、砂子30%充分搅拌均匀后封装,得到C组分。
抛光磨块的制备:A组分、B组分和C组分的质量比为100:250:200,室温条件下使用1500r/min高搅机将三组分搅拌均匀,倒入磨具中,完全硬化后放入100℃烘箱中熟化4h后,得到硬度为邵D70的抛光磨块。
对比例1(中国发明专利CN115338786A中的实施例1)
一种浇注弹性磨块的制备方法,包括如下步骤:
S1.按重量份计,取9份金刚石,8.5份氧化锌,10份聚乙烯醇,10份碳化硅,18份聚酰胺,31份环氧树脂,挤压成型后得到片状的树脂金刚石;
金刚石为片状金刚石,得到的树脂金刚石的厚度为0.3mm;
S2.按重量份计,将315份环氧树脂、215份聚酰胺、10份硅烷偶联剂、55份聚乙烯醇、80份氧化锌和98份碳化硅混合后搅拌17min,再静置30min得到混合树脂;
所述环氧树脂的环氧值为0.5,所述聚酰胺的胺值为215mgKOH/g,所述硅烷偶联剂为亚烷基缩水甘油醚;
S3.将若干个树脂金刚石竖向、间隔0.7mm插设在浇注模具内,将混合树脂倒入浇注模具中浇注成型,静置9.2h;
S4.置于干燥设备进行二次固化,其中,二次固化的温度为125℃,且保温4h,得到所述浇注弹性磨块。
对比例2(中国发明专利CN113492365A中的对比例1)
酚醛树脂弹性磨块的制备:称取50份酚醛树脂粉、15份金刚石磨料和25份铜粉、15份氧化铝辅助填料,经高速混合机混合分散1h后,装入模具。在热压成型机中以150℃、压力15MPa压制0.5h进行预固化后,预成型后的磨具经160℃/1h+160℃/0.5h干燥箱后固化,得到酚醛树脂弹性磨块。
对比例3(中国发明专利CN113146488B中的实施例1)
聚醚多元醇30份(官能度2,分子量为2000)、聚酯多元醇20份(官能度3,分子量为4000)、TDI 25份、三亚乙基二胺0.035份、1,4-丁二醇4份、水0.6份、江苏美思德化学股份有限公司商品号M-7742的稳泡剂0.2份、黑碳化硅120份(粒度为80#-1000#)、滑石粉7份、铬绿0.7份。制备抛光轮时,将各组分原料浇注到模具中,模具加温到35-45℃,模具中的材料自然发泡成型,然后进行脱模;加热烘烤使聚氨酯树脂固化得到抛光轮半成品;固化中烘烤温度为80-120℃,烘烤时间为1-3小时,固化后需要达到聚氨酯树脂完全硬化,硬度到达92-98A邵氏硬度;抛光轮半成品通过胶黏剂与橡胶圈粘接,再次烘烤对胶黏剂进行固化,得到抛光轮成品;固化中烘烤的温度为80-100℃,烘烤时间为2-6小时;固化需要达到抛光轮与橡胶圈粘结牢固,其验收指标是:胶水完全固化,粘结力牢固,不脱胶,不离层。
对比例4
与实施例1的区别在于:C组分中不添加金刚砂,以硅微粉等量替代。
对比例5
与实施例1的区别在于:A组分中不添加水合硅酸钠,以等量聚醚多元醇PPG400替代。
实施例1-4及对比例1-5制备得到的抛光磨块的性能测试结果如表1所示:
表1 实施例1-4及对比例1-5制备得到的抛光磨块的性能测试结果
由表1可以看出,与实施例1-4相比,采用对比例1的方法制备的浇注抛光磨块制备温度需要高温110℃以上,且其制备的抛光磨块打磨时光洁度要偏低一些,抛光磨块使用时间也大大缩短,这是由于其制备的抛光磨块使用环氧树脂固化,其原料特性决定了制备的磨块偏脆、偏硬,锐利度偏高、韧性偏差,导致使用过程中易掉块,不耐用。由对比例2可知,使用酚醛树脂作为胶合剂制备的抛光磨块需要更高的160℃热压及后熟化温度,但是其抗弯强度偏差,导致其耐用度同样不高。由对比例3可知,单纯使用多元醇结合TDI体系制备抛光磨块,极易出现发泡现象,进而使得其抗弯强度下降,耐用度大大降低。由对比例4可知,体系中不添加金刚砂,虽然体系硬度变化不大,但其制备的抛光磨块使用过程中光洁度下降、耐用度下降,这是由于金刚砂比硅微粉打磨效果更佳,刚性及锐利度更强所致。进一步地,由对比例5可知,当A组分不添加水合硅酸钠时,在其他相同原料体系下,制备的抛光磨块更易起鼓,内部密实度不够导致其打磨光洁度下降,磨块可使用时间大大缩短。
Claims (6)
1.聚氨酯弹性体,其特征在于,包括A、B、C三组分,A组分由以下质量百分数的原料组成:小分子扩链剂10-15%、阻燃剂3-10%、水合硅酸盐79-86.3%、偶联剂0.5-0.6%、消泡剂0.08-0.1%、防沉剂0.085-0.1%和胺类催化剂0.01-0.02%;B组分由以下质量百分数的原料聚合而成:聚醚多元醇1.7-28%、异氰酸酯52-83.3%和降粘剂15-20%;C组分由以下质量百分数的磨料组成:硅微粉10-20%、金刚砂40-50%和砂子30-40%;A组分、B组分和C组分的质量比为100:(150-250):(200-600);
所述B组分中,聚醚多元醇为聚氧化丙烯多元醇,数均分子量为400-3000,官能度为2或3;
所述B组分中,异氰酸酯为二苯基甲烷二异氰酸酯和多亚甲基多苯基异氰酸酯中的一种或两种;
所述C组分中,硅微粉目数为300-600目,金刚砂目数为80-200目,砂子目数为80-1000目;
所述A组分中,水合硅酸盐为水合硅酸钠和水合硅酸钾中的一种或两种,密度为1.48-1.56g/cm3,模数为2.5-2.7,波美度为47-52°Be'。
2.如权利要求1所述的聚氨酯弹性体,其特征在于,所述A组分中,小分子扩链剂为一缩二丙二醇、乙二醇或甘油,数均分子量为62-134,官能度为2或3。
3.如权利要求1所述的聚氨酯弹性体,其特征在于,所述A组分中,阻燃剂为三(2-氯丙基)磷酸酯、异丙基化三苯基磷酸酯或磷酸甲苯二苯酯。
4.如权利要求1所述的聚氨酯弹性体,其特征在于,所述A组分中,偶联剂为KH-550、KH-560、KH-590或KH-570。
5.如权利要求1所述的聚氨酯弹性体,其特征在于,所述A组分中,防沉剂为膨润土或气相白炭黑。
6.利用如权利要求1-5任一项所述的聚氨酯弹性体制备抛光磨块的方法,其特征在于,A组分的制备:将A组分中的原料混合后,搅拌均匀后封装,即得A组分;B组分的制备:将水分含量控制在0.05%以下的聚醚多元醇与异氰酸酯和降粘剂,在70-80℃下反应2-3h,得到异氰酸根含量为15-25%的预聚物,抽真空脱除机械泡后封装,即得B组分;C组分的制备:将各磨料搅拌均匀后封装,即得C组分;抛光磨块的制备:将A、B、C三组分混合搅拌均匀,倒入模具中,室温熟化3-5天或完全硬化后于80-100℃下熟化4-6h,即得抛光磨块。
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