CN102471411A - 具有二丙烯酸酯末端的含氟聚合物 - Google Patents
具有二丙烯酸酯末端的含氟聚合物 Download PDFInfo
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Abstract
本发明公开了遥爪二丙烯酸酯含氟聚合物和用于制造所述含氟聚合物的方法。所述二丙烯酸酯共聚物为式CH2=CR’COO-(CH2)n-R-(CH2)n-OOCCR’=CH2,其中R选自:i)包含偏二氟乙烯和全氟(甲基乙烯基醚)共聚单元的低聚物,ii)包含偏二氟乙烯和六氟丙烯共聚单元的低聚物,iii)包含四氟乙烯和全氟(甲基乙烯基醚)共聚单元的低聚物,和iv)包含四氟乙烯和烯烃共聚单元的低聚物,R’为H或-CH3,n为1-4,并且其中所述低聚物具有1000-25,000道尔顿的数均分子量。
Description
发明领域
本发明涉及式CH2=CR’COO-(CH2)n-R-(CH2)n-OOCCR’=CH2的二丙烯酸酯共聚物,其中R选自:i)包含偏二氟乙烯和全氟(甲基乙烯基醚)共聚单元的低聚物,ii)包含偏二氟乙烯和六氟丙烯共聚单元的低聚物,iii)包含四氟乙烯和全氟(甲基乙烯基醚)共聚单元的低聚物,和iv)包含四氟乙烯和烯烃共聚单元的低聚物,R’为H或-CH3,n为1-4,并且其中所述低聚物具有1000-25,000道尔顿的数均分子量。
发明背景
偏二氟乙烯(VF2)与全氟(甲基乙烯基醚)(PMVE)的双官能低分子量(数均分子量介于1000和25,000道尔顿)共聚物和四氟乙烯(TFE)与PMVE的双官能共聚物已被公开于US 20090105435A1。官能团位于所述共聚物主链的每个末端(有时被称为“遥爪”)。所公开的官能团包括碘、烯丙基、羟基、羧基和腈。
期望具有在US 20090105435 A1中公开的类型的低分子量含氟聚合物,其中聚合物主链的每个末端均具有丙烯酸酯或甲基丙烯酸酯基团。此类含氟聚合物可被用做合成其它含氟聚合物的中间体,并还可被硫化以形成坚韧的涂层、密封、O形环、垫片等。
发明概述
本发明既是1)遥爪二丙烯酸酯低分子量含氟聚合物,并且又是2)用于制造此类共聚物的方法。
因此,本发明的一个方面为式CH2=CR’COO-(CH2)n-R-(CH2)n-OOCCR’=CH2的遥爪二丙烯酸酯共聚物,其中R’为H或-CH3,n为1-4且R为具有1000-25,000道尔顿数均分子量的低聚物,所述低聚物选自:i)包含偏二氟乙烯和全氟(甲基乙烯基醚)共聚单元的低聚物,ii)包含偏二氟乙烯和六氟丙烯共聚单元的低聚物,iii)包含四氟乙烯和全氟(甲基乙烯基醚)共聚单元的低聚物,和iv)包含四氟乙烯和烯烃共聚单元的低聚物。
本发明的另一个方面为用于制造遥爪二丙烯酸酯共聚物的方法,所述方法包括:
A)提供式HO-(CH2)n-R-(CH2)n-OH的二醇,其中n为1-4且R为具有1000-25,000道尔顿数均分子量的低聚物,所述低聚物选自:i)包含偏二氟乙烯和全氟(甲基乙烯基醚)共聚单元的低聚物,ii)包含偏二氟乙烯和六氟丙烯共聚单元的低聚物,iii)包含四氟乙烯和全氟(甲基乙烯基醚)共聚单元的低聚物,和iv)包含四氟乙烯和烯烃共聚单元的低聚物;以及
B)使所述二醇与CH2=CR’COX反应,以形成式CH2=CR’COO-(CH2)n-R-(CH2)n-OOCCR’=CH2的二丙烯酸酯共聚物,其中X为卤化物且R’为H或-CH3。
发明详述
本发明涉及低分子量遥爪二丙烯酸酯含氟聚合物和用于制造所述聚合物的方法。术语“二丙烯酸酯”是指所述含氟聚合物每个聚合物链包含两个丙烯酸酯基团或两个甲基丙烯酸酯基团。所述丙烯酸酯或甲基丙烯酸酯基团位于所述聚合物主链的两端。“主链”是指共聚单体单元的最长链,即非侧链或支链。
本发明所述二丙烯酸酯含氟聚合物具有式CH2=CR’COO-(CH2)n-R-(CH2)n-OOCCR’=CH2,其中R’为H或-CH3,n为1-4(优选2或3)且R为具有1000-25,000道尔顿,优选1200-12,000道尔顿,最优选1500-5000道尔顿数均分子量的低聚物。低聚物R选自:i)包含偏二氟乙烯和全氟(甲基乙烯基醚)共聚单元的低聚物,ii)包含偏二氟乙烯和六氟丙烯共聚单元的低聚物,iii)包含四氟乙烯和全氟(甲基乙烯基醚)共聚单元的低聚物,和iv)包含四氟乙烯和烯烃共聚单元的低聚物。烯烃包含乙烯(E)和丙烯(P)。任选地,低聚物R可进一步包含至少一种不同于其它两种共聚单体的附加共聚单体。此类附加共聚单体的实例包括但不限于偏二氟乙烯(VF2)、六氟丙烯(HFP)、四氟乙烯(TFE)和全氟(甲基乙烯基醚)(PMVE)。
可在本发明的含氟聚合物(和用来制备它们的二醇)中使用的低聚物的具体的实例包括但不限于TFE/PMVE、VF2/PMVE、VF2/TFE/PMVE、TFE/PMVE/E、VF2/HFP、VF2/HFP/TFE、TFE/P和TFE/P/VF2。
本发明的二丙烯酸酯含氟聚合物可通过以下方法制得,所述方法包括A)提供式HO-(CH2)n-R-(CH2)n-OH的二醇,其中n和R如上文所定义;以及B)使所述二醇与CH2=CR’COX反应,其中X和R’如上文所定义,以形成式CH2=CR’COO-(CH2)n-R-(CH2)n-OOCCR’=CH2的遥爪二丙烯酸酯共聚物。
式HO-(CH2)n-R-(CH2)n-OH的二醇可由多步方法制得,所述方法以相应的式I-R-I的α,ω-二碘低聚物开始,所述I-R-I一般按照U.S.20090105435A1中所述来制备。所述二碘低聚物可通过在基团自由基引发剂的存在下与乙烯(或烯丙醇,随后通过所述碘原子的选择性还原)的反应而被乙烯化(或烯丙基化)。然后所得的低聚物可被水解以形成所述二醇。
本发明的含氟聚合物可用于形成具有优良的柔韧性、耐化学品性和耐热特性的交联的含氟聚合物网络。
实施例
测试方法
数均分子量(Mn)通过尺寸排阻色谱法(SEC)确定。样品被溶解于THF中。用Spectra-Physics色谱仪进行分析,所述色谱仪配备有两根得自Polymer Laboratories的PLgel 5μm Mixed-C柱,和Spectra Physics SP8430折射率(RI)和UV检测器。使用四氢呋喃(THF)作为洗脱液,具有0.8mLmin-1的流量。标准品为单分散的聚苯乙烯(PS)或聚(甲基丙烯酸甲酯),购自Polymer Laboratories或其他供应商。
含氟聚合物和低聚物组合物和微观结构通过19F和1H NMR测定。在Bruker AC 200、AC 250和AC 400(200、250和400MHz)仪器上记录NMR共振谱,使用氘代丙酮作为溶剂,并用四甲基硅烷(TMS)(或CFCl3)作为1H(或19F)核的基准。偶合常数和化学位移分别以Hz和ppm为单位给出。1H(或19F)NMR谱的实验条件如下:回转角90°(或30°),采集时间4.5秒(或0.7秒),脉冲延迟2秒(或5秒),扫描次数16(或64)次,并且对于19F NMR的脉冲宽度为5微秒。
实施例1
在该实施例中,本发明的含氟聚合物CH2=CHCOO-(CH2)2-R-(CH2)2-OOCCH=CH2通过本发明的方法制得,其中R为聚(偏二氟乙烯-共聚-全氟(甲基乙烯基醚)[即,聚(VF2-共聚-PMVE)]。
在所述含氟聚合物制造方法中所用的二醇低聚物由多步方法制得,以式I-(VF2-共聚-PMVE)-I遥爪二碘低聚物开始。后者用公开于U.S.20090105435 A1中的方法制得。该二碘低聚物包含73.2mol%的VF2和26.8mol%的PMVE且具有2450道尔顿的数均分子量。
所述二碘低聚物的乙烯化:
配备有入口阀和出口阀,压力计和安全隔膜的160mL Hastelloy合金(HC-276)高压釜被脱气并用30巴的氮加压以检查裂漏。然后操作0.5mm Hg的真空5分钟并随后应用氩气氛。重复五次该高压釜脱气程序。在真空下,5.0g(2.87×10-2摩尔)的过氧化新戊酸叔丁酯(TBPPi)、50mL的叔丁醇和100.0g(0.077摩尔)的上述遥爪二碘低聚物被转移到所述高压釜中。将6.0g的乙烯(0.214摩尔)引入到所述高压釜中。然后,将所述高压釜逐步加热至75℃。观察到约10℃的放热和从15巴至18巴的压力的增加,随后压力经过16小时降至14巴。反应后,将高压釜置于冰浴中约60分钟,并缓慢释放出0.5g未反应的乙烯。在打开高压釜后,将反应混合物溶解于100mL丁酮,并分别用蒸馏水(2×100mL)、Na2S2O5液(100mL)和盐水(100mL)在分液漏斗中洗涤。然后,所述有机相经过MgSO4干燥并通过多孔玻璃(G4)过滤。在40℃下减压至10mm Hg,通过旋转真空蒸发器移除有机溶剂。所得的浅黄色粘稠液体在40℃,0.01mbar真空下被干燥至恒重。反应的收率为91%。所述产物通过1H NMR和19F NMR光谱进行分析。缺乏对应于所述末端-CF2I(大约-39ppm)的信号表明向所述乙烯化的低聚物的定量转变。
将乙烯化的共聚物水解成遥爪二醇:
向一个配备有回流冷凝器和磁力搅拌器的250mL的两颈圆底烧瓶中充满61.6g(0.044摩尔)的上文合成的乙烯化产物和80.4g(1.1摩尔)的DMF。然后将所述混合物用氮气吹扫20分钟并通过隔膜加入4.0g的水。将反应加热至120℃并搅拌过夜。14小时后,冷却粗产物(反应混合物)至室温并且滴加在甲醇(70g)中的H2SO4(25g)的混合物。将所述反应保持在室温24小时。然后,所述反应混合物在分液漏斗中用蒸馏水(3×100mL)和乙酸乙酯(200mL)洗涤。所述有机相经过MgSO4干燥并通过多孔玻璃(G4)过滤。通过旋转真空蒸发器(40℃/20mm Hg)移除所述乙酸乙酯和痕量的DMF。所得的棕色粘稠液体在40℃和0.01毫巴下被干燥至恒重。通过1H NMR和19F NMR光谱来分析所述产物(收率74重量%)。
用于水解乙烯化共聚物的可供选择的方法:
向一个配备有回流冷凝器和磁力搅拌器的50mL的两颈圆底烧瓶中充满3.1g(0.0021摩尔)的乙烯化共聚物和16g(0.22摩尔)的DMF。该混合物在氮气氛下被搅拌30分钟。然后通过隔膜滴加1g的水。将所述反应加热到100℃并保持搅拌36小时。在冷却至室温后,加入50mL的丁酮且所得的混合物用水(3×50mL)洗涤。所述有机层经过MgSO4干燥并通过多孔玻璃(G4)过滤。使用旋转真空蒸发器(40℃/20mm Hg)移除所述溶剂。所得的棕色粘稠液体在40℃和0.01毫巴下被干燥至恒重。通过1H NMR、19FNMR来分析所述产品(收率54重量%),证明存在二醇和二甲酸酯两者。
二甲酸酯的皂化:
向一个配备有Claisen冷凝器和磁力搅拌器的100mL两颈圆底烧瓶中充满1.39g(上文制备的)水解的二加合物,0.05g(0.29摩尔)对甲苯璜酸和50mLCH3OH。加热所述反应直至甲醇开始滴下。然后,用水(2×50mL)洗涤反应混合物,加入CH2Cl2(3×30mL)和盐水(50mL)以有利于分离。所述有机层经过MgSO4干燥并通过多孔玻璃(G4)过滤。通过旋转真空蒸发器(40℃/20mm Hg)移除所述CH2Cl2和痕量的MeOH。所得的棕色粘稠液体在40℃和0.01mbar下被干燥至恒重。通过1H NMR和19F NMR来分析所述产物(收率81重量%),从而证明存在二醇。
转化成二丙烯酸酯:
向一个配备有回流冷凝器和磁力搅拌器的250mL两颈圆底烧瓶中充满25.0g(19.2mmol)溶解于100mLTHF(干燥的)上文合成的二醇,和12g聚乙烯基吡啶。在氮气氛下将所述反应混合物冷却至0℃并加入20mg(0.18mmol)的对苯二酚。在6小时间隔内,以四个随后的剂量(分别为4g、4g、2g、4g)用注射器通过隔膜加入丙烯酰氯。向所述反应混合物中加入附加的10g聚乙烯基吡啶。在加入第一个剂量的丙烯酰氯以后,在48小时期间保持反应温度在40℃。通过多孔玻璃G4过滤来移除聚乙烯基吡啶。然后加入丁酮/水(1/1)混合物并随后用水洗涤。所述有机层经过MgSO4干燥然后通过多孔玻璃(G4)过滤。使用旋转真空蒸发器(40℃/20mm Hg)移除所述溶剂和过量的丙烯酰氯。所得的棕色粘稠的液体在40℃,0.01mbar真空下被干燥至恒重。通过1H和19F NMR来分析产物(收率81%)。
实施例2
在该实施例中,本发明的含氟聚合物,CH2=CHCOO-(CH2)3-R-(CH2)3-OOCCH=CH2通过本发明的方法制得,其中R为聚(偏二氟乙烯-共聚-全氟(甲基乙烯基醚)[即,聚(VF2-共聚-PMVE)]。所述遥爪I-(VF2-共聚-PMVE)-I低聚物原料与在实施例1中所用的相同。
转变成二碘醇:
向一个配备有回流冷凝器和磁力搅拌器的100mL两颈圆底烧瓶中充满10.5g(6mmol)的I-(VF2-共聚-PMVE)-I,2.05g(34.4mmol)的烯丙醇和50mL的CH3CN。然后将烧瓶加热至80℃。用30分钟的添加间隔以10个剂量(每次20mg)加入AIBN(2,2’-偶氮二异丁腈)。所述反应在氮气氛80℃下进行21小时。在冷却至室温后,通过棉花过滤反应混合物,然后在旋转真空蒸发器(40℃/20mm Hg)上移除溶剂和过量的烯丙醇。所得的浅黄色粘稠液体被干燥(40℃/0.01mbar)至恒重。通过1H和19F NMR和FT-IR光谱来分析所述产物(收率93%)。
将所述二碘醇还原成双丙醇:
向一个配备有回流冷凝器和磁力搅拌器的250mL三颈圆底烧瓶中充满11.5g(6.6mmol)的上文制备的二碘醇,4.8g(16.5mmol)Bu3SnH和50mLCH3CN。然后将烧瓶加热至70℃。用介于添加之间60分钟的间隔以10个剂量(每次55mg)加入AIBN。所述反应在氮气氛,70℃下进行12小时。在冷却至室温后,0.6g的KF与50mLEt2O一起被加入。然后所述反应在约25℃下搅拌24小时。反应混合物通过多孔玻璃(G5)过滤以移除白色固体,如Bu3SnK、Bu3SnF或Bu3SnI。在旋转真空蒸发器(40℃/20mm Hg)上移除所述溶剂。将粗产物溶解于50mL的丁酮中并用水(2×50mL)洗涤。所述有机层经过MgSO4干燥,其然后通过多孔玻璃(G4)过滤。在旋转真空蒸发器上部分移除丁酮,并且残余物从戊烷中沉淀。在4℃冷却12小时以后,通过滗析,仔细从沉淀出的产物中移除戊烷。通过旋转真空蒸发(40℃/20mm Hg)移除残余的溶剂。所得的浅黄色粘稠液体被干燥(40℃/0.01mbar)至恒重。通过1H和d 19F NMR和FT-IR光谱来分析所述产物(总收率91%)。滗析的戊烷也被蒸发以提供期望的二醇的低分子量组分。
二醇的酰化作用:
向一个配备有回流冷凝器和磁力搅拌器的100mL三颈圆底烧瓶中充满5.03g(3.33mmol)上文制备的双丙醇,25mLTHF,4.5g聚乙烯基聚吡咯烷酮,5mg(0.045mmol)对苯二酚并冷却至0℃。然后以三个剂量(2mL、1mL和1mL)滴加丙烯酰氯(4.456g,4mL,50mmol)。在第一次添加丙烯酰氯之后,将反应温度升至40℃;经过5和22小时的运行时间后,完成两个随后的添加。然后向所述反应混合物中加入附加量的聚乙烯聚吡咯烷酮(4.5g)。所述反应在氮气氛和在40℃下进行48小时。在冷却至室温后,通过多孔玻璃(G4)过滤反应混合物以移除聚乙烯聚吡咯烷酮。用THF洗涤过滤的聚乙烯聚吡咯烷酮。通过旋转蒸发部分移除所述溶剂,并且残余物从戊烷中沉淀。在4℃下12个小时后,仔细滗析戊烷,留下沉淀出的产物。通过旋转真空蒸发(40℃/20mm Hg)移除残余的溶剂。所得的淡黄色粘稠液体被干燥(40℃/0.01mbar)至恒重。通过1H和19F NMR来分析所述产品(总收率91%)。滗析的戊烷也被蒸发并回收低收率(7%)的期望的聚合物低分子量组分。
Claims (10)
1.式CH2=CR’COO-(CH2)n-R-(CH2)n-OOCCR’=CH2的遥爪二丙烯酸酯共聚物,其中R’为H或-CH3,n为1-4且R为具有1000-25,000道尔顿数均分子量的低聚物,所述低聚物选自:i)包含偏二氟乙烯和全氟(甲基乙烯基醚)共聚单元的低聚物,ii)包含偏二氟乙烯和六氟丙烯共聚单元的低聚物,iii)包含四氟乙烯和全氟(甲基乙烯基醚)共聚单元的低聚物,和iv)包含四氟乙烯和烯烃共聚单元的低聚物。
2.权利要求1的遥爪二丙烯酸酯共聚物,其中n为2或3。
3.权利要求1的遥爪二丙烯酸酯共聚物,其中所述低聚物具有1200-12,000道尔顿的数均分子量。
4.权利要求3的遥爪二丙烯酸酯共聚物,其中所述低聚物具有1500-5000道尔顿的数均分子量。
5.权利要求1的遥爪二丙烯酸酯共聚物,其中所述低聚物包含共聚单元,所述共聚单元选自:i)偏二氟乙烯、四氟乙烯和全氟(甲基乙烯基醚);ii)四氟乙烯、全氟(甲基乙烯基醚)和乙烯;iii)偏二氟乙烯、六氟丙烯和四氟乙烯;和iv)四氟乙烯、偏二氟乙烯和丙烯。
6.用于制造遥爪二丙烯酸酯共聚物的方法,所述方法包括:
A)提供式HO-(CH2)n-R-(CH2)n-OH的二醇,其中n为1-4且R为具有1000-25,000道尔顿数均分子量的低聚物,所述低聚物选自:i)包含偏二氟乙烯和全氟(甲基乙烯基醚)共聚单元的低聚物,ii)包含偏二氟乙烯和六氟丙烯共聚单元的低聚物,iii)包含四氟乙烯和全氟(甲基乙烯基醚)共聚单元的低聚物,和iv)包含四氟乙烯和烯烃共聚单元的低聚物;以及
B)使所述二醇与CH2=CR’COX反应,以形成式CH2=CR’COO-(CH2)n-R-(CH2)n-OOCCR’=CH2的二丙烯酸酯共聚物,其中X为卤化物且R’为H或-CH3。
7.权利要求6的用于制造遥爪二丙烯酸酯共聚物的方法,其中n为2或3。
8.权利要求6的用于制造遥爪二丙烯酸酯共聚物的方法,其中所述低聚物具有1200-12,000道尔顿的数均分子量。
9.权利要求8的用于制造遥爪二丙烯酸酯共聚物的方法,其中所述低聚物具有1500-5000道尔顿的数均分子量。
10.权利要求6的用于制造遥爪二丙烯酸酯共聚物的方法,其中所述低聚物包含共聚单元,所述共聚单元选自:i)偏二氟乙烯、四氟乙烯和全氟(甲基乙烯基醚);ii)四氟乙烯、全氟(甲基乙烯基醚)和乙烯;iii)偏二氟乙烯、六氟丙烯和四氟乙烯;和iv)四氟乙烯、偏二氟乙烯和丙烯。
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US8394870B2 (en) * | 2009-07-16 | 2013-03-12 | E.I. Du Pont De Nemours And Company | Crosslinked fluoropolymer networks |
KR101730802B1 (ko) * | 2015-10-21 | 2017-04-28 | (주)켐옵틱스 | 광경화형 레진 조성물 및 이를 이용한 패턴의 형성방법 |
EP4317214A3 (en) | 2018-03-01 | 2024-05-01 | Daikin Industries, Ltd. | Method for manufacturing fluoropolymer |
KR102325037B1 (ko) * | 2018-04-27 | 2021-11-12 | 주식회사 엘지에너지솔루션 | 리튬 이차 전지 및 이의 제조방법 |
US20220002531A1 (en) | 2018-11-19 | 2022-01-06 | Daikin Industries, Ltd. | Production method of modified polytetrafluoroethylene and composition |
US20220010118A1 (en) | 2018-11-19 | 2022-01-13 | Daikin Industries, Ltd. | Composition and stretched body |
CN109553526B (zh) * | 2018-12-18 | 2022-07-05 | 杭州盛弗泰新材料科技有限公司 | 一种丙烯酰氯的连续生产方法 |
JP7389366B2 (ja) | 2019-04-26 | 2023-11-30 | ダイキン工業株式会社 | フルオロポリマー水性分散液の製造方法、排水の処理方法、及び、フルオロポリマー水性分散液 |
WO2020218621A1 (ja) | 2019-04-26 | 2020-10-29 | ダイキン工業株式会社 | 水の処理方法および組成物 |
EP4026855A4 (en) | 2019-09-05 | 2023-09-20 | Daikin Industries, Ltd. | COMPOSITION AND PRODUCTION PROCESS THEREOF |
WO2021045165A1 (ja) | 2019-09-05 | 2021-03-11 | ダイキン工業株式会社 | パーフルオロエラストマーの製造方法および組成物 |
EP4063404A4 (en) | 2019-11-19 | 2023-12-06 | Daikin Industries, Ltd. | METHOD FOR PRODUCING FLUROPOLYMERS, METHOD FOR PRODUCING POLYTETRAFLUORETHYLENE, METHOD FOR PRODUCING PERFLUORELASTOMER AND COMPOSITION |
CN111253512A (zh) * | 2020-03-05 | 2020-06-09 | 苏州世华新材料科技股份有限公司 | 四氟乙烯-丙烯酸烷基酯-全氟烷基乙烯基醚分散树脂及其制备的微多孔膜 |
CN111548437A (zh) * | 2020-06-28 | 2020-08-18 | 盐城工学院 | 一种丙烯酸改性液体氟聚合物的制备方法 |
EP4249516A1 (en) | 2020-11-19 | 2023-09-27 | Daikin Industries, Ltd. | Method for producing polytetrafluoroethylene, and composition containing polytetrafluoroethylene |
WO2022107890A1 (ja) | 2020-11-19 | 2022-05-27 | ダイキン工業株式会社 | パーフルオロエラストマー水性分散液の製造方法、組成物、架橋性組成物および架橋物 |
WO2022107891A1 (ja) | 2020-11-19 | 2022-05-27 | ダイキン工業株式会社 | 含フッ素エラストマー水性分散液の製造方法および組成物 |
EP4053166A1 (en) | 2021-03-05 | 2022-09-07 | Arkema France | Method for making telechelic fluoride-based polymers |
EP4306553A1 (en) | 2021-03-10 | 2024-01-17 | Daikin Industries, Ltd. | Coating composition, coating film, layered product, and coated article |
WO2022244784A1 (ja) | 2021-05-19 | 2022-11-24 | ダイキン工業株式会社 | フルオロポリマーの製造方法、ポリテトラフルオロエチレンの製造方法および組成物 |
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