CN102516988A - 一类可聚合荧光染料、其制备方法及应用 - Google Patents

一类可聚合荧光染料、其制备方法及应用 Download PDF

Info

Publication number
CN102516988A
CN102516988A CN2011103871458A CN201110387145A CN102516988A CN 102516988 A CN102516988 A CN 102516988A CN 2011103871458 A CN2011103871458 A CN 2011103871458A CN 201110387145 A CN201110387145 A CN 201110387145A CN 102516988 A CN102516988 A CN 102516988A
Authority
CN
China
Prior art keywords
polymerization
optical dye
fluorescent dye
preparation
polymerizable optical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2011103871458A
Other languages
English (en)
Other versions
CN102516988B (zh
Inventor
彭孝军
强新新
樊江莉
宋锋玲
孙世国
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DALIAN FUSIDA SPECIAL CHEMICAL Co Ltd
Dalian University of Technology
Original Assignee
Dalian University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian University of Technology filed Critical Dalian University of Technology
Priority to CN201110387145.8A priority Critical patent/CN102516988B/zh
Publication of CN102516988A publication Critical patent/CN102516988A/zh
Application granted granted Critical
Publication of CN102516988B publication Critical patent/CN102516988B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B5/00Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/02Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic ring being only condensed in peri position
    • C09B5/14Benz-azabenzanthrones (anthrapyridones)
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02Monomers containing only one unsaturated aliphatic radical
    • C08F12/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22Oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02Monomers containing only one unsaturated aliphatic radical
    • C08F12/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/26Nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/22Emulsion polymerisation
    • C08F2/24Emulsion polymerisation with the aid of emulsifying agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52Amides or imides
    • C08F20/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/60Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02Monomers containing only one unsaturated aliphatic radical
    • C08F212/32Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B5/00Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/62Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00Other synthetic dyes of known constitution
    • C09B57/08Naphthalimide dyes; Phthalimide dyes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00Dyes not provided for by a single group of this subclass
    • C09B69/10Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/101Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an anthracene dye
    • C09B69/102Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an anthracene dye containing a perylene dye
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00Dyes not provided for by a single group of this subclass
    • C09B69/10Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/109Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • C08F220/603Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing oxygen in addition to the carbonamido oxygen and nitrogen

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Emergency Medicine (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

一类可聚合荧光染料、其制备方法及应用,所述的可聚合荧光染料具有下述通式的结构:

Description

一类可聚合荧光染料、其制备方法及应用
技术领域
本发明属于有机聚合物材料领域,尤其涉及一类可聚合荧光染料及其应用。
背景技术
功能聚合物纳米微球由于其在材料、荧光传感器、生物医学检测方面的极具潜力的应用而引起人们广泛的研究兴趣。与分子状态的荧光染料相比,荧光微球具有稳定性好、发光效率高的优点;与无机荧光颗粒相比,荧光聚合物微球具有单分散性好、粒度均一、球形度好等特点。因此在标准、计量、免疫医学、生物化学、分析化学、生物医学领域的应用具有良好的前景。
常规方法的荧光微球制备,将荧光染料吸附在载体上[Z.L.Zhang,Y.Long,J.B.Pan and X.M.Yan,Journal of Materials Chemistry 20(2010)1179-1185],这种方法方便快捷,但是吸附的染料分子容易受到外界环境的干扰而脱落,难以功能化,限制了其使用。
另一种方法是硅无机聚合物包埋或单体聚合的方法制备荧光微球[F.Enrichi,G.Canton,R.Ricco,F.Marinello and S.Carmignato,Journal of Nanoparticle Research 13(2011)4349-4356;G.Bosma,C.Pathmamanoharan,E.H.A.de Hoog,W.K.Kegel,A.van Blaaderen and H.N.W.Lekkerkerker,Journal of Colloid and Interface Science 245(2002)292-300],具有无毒的特点,得到了广泛关注,但不耐酸碱,在功能化(如官能团化学交联)时受到了反应条件的限制。
随着荧光微球的应用发展,微球的功能化,如在微球上使用引入羧基、氨基、氯甲基等活性基团满足连接生物分子的要求。但如何在含有荧光的球上同时具有可反应基团,成为难点。
聚苯乙烯和聚丙烯酸作为廉价的聚合体系,可以提供乳化聚合制备微球等有利技术手段,也易于在聚合物上带有可交联的潜在位点。但荧光母体在烯烃自由基聚合过程中,容易对自由基淬灭,起到阻聚剂的终止作用,从而使聚合过程缓慢[Y.J.He andH.Tian,Acta Polymerica Sinica(2000)379-381;潘祖仁.高分子化学[M].化学工业出版社,2007:108]。因此目前报道的体系较少,成为本领域的难点之一。
发明内容
本发明旨在提供一种制备方法简单、可方便地嵌入高分子聚合物中、并且不易脱落的可聚合荧光染料。
本发明首先提供一类可聚合荧光染料,具有通式I的结构:
Figure BDA0000113256800000021
其中:
D是荧光染料母体;
Z为含有可聚合的官能团的连接基团;
n是1或2。
本发明所述的可聚合荧光染料中所述的Z选自Z1、Z2、Z3和Z4
Figure BDA0000113256800000022
其中,虚线键,即X的游离键,为与D连接的键,R1为氢原子或CH3;X为氧原子、CH2或NH。
上述本发明所述的可聚合荧光染料,其特征在于所述的D选自1,8-萘酰亚胺类染料、蒽吡啶酮类染料和苝酰亚胺类染料。
优选的技术方案中,上述本发明的可聚合荧光染料中所述的D选自D1、D2、D3和D4
Figure BDA0000113256800000023
其中,虚线键为与Z连接的键,R2为C1-10的直连烷烃、支链烷烃或环烷烃。
进一步优选,所述的D选自下述化合物:
所述及的D为D1、D2或D3时,本发明所述及的可聚合荧光染料可以通过酰化反应、N烷基化反应或成醚反应制备。本领域的技术人员应当能够从现有技术中得到启示,准确地设计所需反应并确定反应条件。
所述及的D为D4时,本发明所述及的可聚合荧光染料通过化合物i和化合物ii的取代反应得到:
Figure BDA0000113256800000032
所述的化合物i和化合物ii的取代反应体系中,有缚酸剂存在,其选自碳酸钾、碳酸钠、碳酸氢钠或三乙胺。所述反应体系中还有阻聚剂存在,其选自一价铜盐、二价铜盐或碘盐。
本发明再一方面提供一种荧光纳米微球,所述的荧光纳米微球是由上文所述的本发明的可聚合荧光染料与苯乙烯或其衍生物、丙烯酸或其衍生物、甲基丙烯酸或其衍生物中的一种或几种聚合而成。
本发明进一步提供上述荧光纳米微球的制备方法,是乳液聚合的方法,聚合反应以Triton X-100、SDS或二者的混合物为乳化剂,以氧化还原反应体系作为引发体系,反应温度30~55℃,反应时间5~78小时;
其中,乳化剂的用量为聚合单体总质量的1~50%。其中可聚合荧光染料的用量可由本领域技术人员根据对聚合目的产物的荧光当量等具体要求确定,本发明不加以限定。
通过上述本发明的方法制备得到的荧光纳米微球粒径大小为15~300纳米,优选于20~200纳米。
本发明所述的可聚合荧光染料具有光稳定性高、荧光量子产率高的优点,可在激光读取、激光扫描、霓虹灯照射、户外等苛刻条件下使用。所制备得到的荧光纳米微球可广泛应用于生物检测、发光材料、印刷或涂料领域的应用。乳液聚合的制备方法利用烯烃双键自由基聚合反应,可以方便地将荧光染料化学嵌入聚合物中,不脱落,同时引入带有氯化苄乙烯的单体,可以进行形成化学交联位点,通过乳化聚合制备可功能化的荧光纳米微球,可以满足上述需求。
附图说明
本发明附图6幅:
图1是可聚合荧光染料11溶液聚合后的核磁谱图
图2是实施例8制备的纳米聚合物荧光微球的透射电镜图;
图3是实施例8制备的荧光纳米微球的粒径分布;
图4是可聚合荧光染料3及实施例8中制备的荧光纳米微球的光谱图;
图5是实施例10制备的纳米聚合物荧光微球的透射电镜图;
图6是乙醇中可聚合荧光染料3和罗丹明B光降解对比曲线。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明,但不以任何方式限制本发明。
实施例1
可聚合荧光染料3的合成:
Figure BDA0000113256800000051
中间体2的合成:将4-溴-N-甲基蒽吡啶酮(1,4.9g,14.4mmol),无水硫酸铜(0.2g,10mol%)和1,6-己二胺(2g,17.2mmol)溶于100mL乙二醇单甲醚中,加入无水碳酸钾(3g,21.6mmol)作为缚酸剂。回流反应24h后过滤除去碳酸钾及硫酸铜。滤液使用旋转蒸发除去溶剂,得到红色固体。固体用乙醇洗涤,以除去过量的1,6-己二胺。硅胶柱分离(乙酸乙酯∶甲醇=10∶1为洗脱液),产率51%。
1H-NMR(400MHz,CDCl3)δ10.49(m,1H,NH),8.46(d,J=7.7Hz,1H,ArH,),8.30(d,J=7.9Hz,1H,ArH),8.20(d,J=7.9Hz,1H,ArH),7.83-7.62(m,4H,ArH,CH2),3.86(s,3H,CH3),1.71-1.60(nb,12H,CH2).MS(TOF MS ES+)calculated for[C23H26N3O2]+:376.2020,measured:376.2022.
中间体2(1g,2.7mmol),甲基丙烯酰氯(2g,19mmol)和5mL三乙胺作为缚酸剂溶于20mL无水THF中0℃反应8h。反应结束后,将反应液倒入饱和食盐水中,过滤并用水洗涤滤饼,干燥后硅胶柱分离(乙酸乙酯作为洗脱液)可得到0.5g红黑色可聚合荧光染料3产品,产率50%。
1H-NMR(400MHz,CDCl3)δ10.45(s,1H,NH),8.46(d,J=7.7Hz,1H,ArH,),8.18(d,J=7.9Hz,1H,ArH),7.80-7.57(m,4H,ArH,CH2),7.14(d,J=9.5Hz,1H,ArH),5.93(s,1H,NH),5.68(s,1H,CH),5.31(s,1H,CH),3.83(s,3H,CH3),3.46-3.25(m,4H,CH2),1.97(s,3H,CH3),1.80(m,2H,CH2),1.59(m,4H,CH2),1.50-1.39(m,2H,CH2).MS(TOF MS ES+)calculated for[C27H30N3O3]+:444.2282,measured:444.2286。
实施例2
可聚合荧光染料5的合成:
以4-溴-1,8-萘酐为起始原料制备可聚合的萘酰亚胺类荧光染料。
Figure BDA0000113256800000061
中间体4的合成:4-溴-1,8-萘酐(5.5g,19.9mmol)和1,6-己二胺(4.6g,39.7mmol)溶于200mL乙二醇单甲醚中,回流5h,有大量黄色固体析出。反应结束后将反应液倒入500mL水中,过滤,滤饼用冷的乙醇洗涤以除去残留的1,6-己二胺。干燥后得到黄色固体5.1g,产率63%,无需进一步提纯可用于染料5的合成。
将中间体4酰胺化可得到染料5,反应步骤参考合成染料3的过程。
1H-NMR(400MHz,CDCl3)δ8.57(d,1H,J=4.0,ArH),8.45(d,1H,J=8.0,ArH),8.29(d,1H,J=8.0,ArH),7.63(t,1H,J=8.0,ArH),6.71(d,1H,J=8.0,ArH),6.03(s,1H,NH),5.83(s,1H,NH),5.71(d,3H,J=4.0,CH,NH),5.34(d,2H,J=12.0,CH),4.18(t,2H,CH),3.42(m,4H,CH),3.32(m,2H,CH),1.98(s,6H,CH),1.82(6H,m,CH),1.68(m,6H,CH),1.43(s,4H,CH).MS(TOF MS ES+)calculated for[C32H43N4O4]+:547.3279,measured:547.32870.
实施例3
可聚合荧光染料8的合成:
中间体6的合成:4-溴-1,8-萘酐(2.7g,10mmol)和3-辛胺(1.5g,12mmol)溶于100mL乙醇溶液中,加热回流反应10h后,TLC检测无原料4-溴-1,8-萘酐,冷却至室温,有大量土黄色固体析出。过滤反应液,滤饼用少量冷的乙醇溶液洗涤至滤液无黄色,干燥后得到土黄色产品3.0g,粗产率88%。
中间体7的合成:中间体6(3.0g,7.7mmol)和无水哌嗪(5.0g,58mmol)溶于100mL乙二醇单甲醚中,升温至100℃,反应液变成黄褐色,继续反应6h后,冷却至室温。将反应液倒入400mL冷水中,乙酸乙酯萃取(3×100mL),合并有机相,蒸出溶剂得黄色固体2.8g,粗产率93%。
取中间体7(0.6g,1.5mmol)、4-氯甲基苯乙烯(0.3g,2.0mmol)和无水碳酸钾(0.5g,3.6mmol)溶于50mL乙腈中回流反应4h,TLC检测物原料点,反应液倒入冰水中,有黄色固体析出,过滤,滤饼干燥后用碱性氧化铝柱分离后(石油醚∶二氯甲烷=1∶1.5~2为洗脱液)得目标产物为黄色固体0.5g,产率65%。
1H-NMR(400MHz,CDCl3)δ8.57(d,1H,ArH,J=8Hz),8.51(d,1H,ArH,J=18Hz),8.40(d,1H,ArH,J=4Hz,),7.685(t,1H,ArH,J=8.4Hz,),7.413(d,2H,ArH,J=8Hz,),7.350(d,2H,ArH,J=8Hz,),7.205(d,1H,ArH,J=8Hz,),6.760(m,1H,CH),5.778(d,1H,CH,J=17.6Hz),5.257(d,1H,CH,J=10.8Hz,),3.648(s,2H,CH2),3.289(s,4H,CH2),2.773(s,4H,CH2)1.949-0.854(m,15H CH,CH2,CH3).MS(TOF MS ES+)calculated for[C33H40N3O2]+:510.3115,measured:510.3117.
实施例4
可聚合荧光染料11的合成:
Figure BDA0000113256800000081
中间体10的合成:对苯二酚(8.8g,80mmol)、4-氯甲基苯乙烯(3.0g,20mmol)、碳酸钾(2.8g,20mmol)溶于75mL丙酮中,回流反应24h后,冷却至室温,过滤,滤饼用丙酮洗涤(3×5mL),合并滤液后蒸出溶剂,加50mL氯仿至残留物中,充分溶解过滤以除去残留的对苯二酚,蒸干滤液,硅胶柱分离(乙酸乙酯∶石油醚=1∶10为洗脱液),得白色固体1.9g,产率43%。
1H-NMR(400MHz,CDCl3)δ7.404(d,2H,ArH,J=10Hz),7.376(d,1H,ArH,J=10Hz),6.834(d,2H,ArH,J=16Hz,),6.756(d,2H,ArH,J=16Hz,),6.708(m,1H,CH),5.778(d,1H,CH,J=21Hz),5.262(d,1H,CH,J=16Hz,),4.988(s,2H,CH2).
取染料9(0.135g,0.19mmol,合成方法参考L.Fan,Y.Xu and H.Tian,TetrahedronLett,46(2005)4443-4447;B.A.Jones,M.J.Ahrens,M.-H.Yoon,A.Facchetti,T.J.Marksand M.R.Wasielewski,Angewandte Chemie International Edition,43(2004)6363-6366)、中间体10(0.175g,0.77mmol)、碳酸铯(0.1g,0.3mmol)和碘化亚铜(0.1g,0.5mmol)溶于15mL甲苯中,回流反应20h后,蒸出溶剂,加二氯甲烷50mL洗涤残留物,过滤,蒸出溶剂后,硅胶柱分离(石油醚∶二氯甲烷=1∶1~1.5为洗脱液),得目标产物为暗红色固体60mg,产率32%。
1H NMR(400MHz,CDCl3):δ9.54(d,2H,ArH,J=8.0Hz),8.55(d,2H,ArH,J=8.4Hz,),8.21(s,ArH,2H),7.41-7.48(m,ArH,8H),7.03-7.12(m,ArH,2H),6.71(m,CH,2H),5.81(d,2H,CH,J=17.6Hz),5.29(d,2H,CH,J=13.2Hz),5.09(s,CH2,4H),4.98(m,CH,2H),2.52(m,4H,CH2),1.89(d,4H,CH2,J=7.2Hz),1.72(d,4H,CH2,J=12.0Hz)1.23-1.57(m,8H,CH,CH2).MS(TOF MS ES+)calculated for[C66H55N2O8]+:1003.3953,measured:1003.3949.
实施例5
可聚合荧光染料13的合成:
Figure BDA0000113256800000091
中间体12的合成:将对苯二酚(2.5g,22.7mmol)、烯丙基溴(1.4mL,5.7mmol)、无水碳酸钾(0.8g,5.8mmol)加至50mL无水乙腈中,回流反应12h后冷却至室温,过滤后,蒸干滤液,加水100mL,乙醚(3×50mL)萃取,有机相无水硫酸钠干燥后减压蒸干,硅胶柱分离(乙酸乙酯∶石油醚=1∶10为洗脱液)得褐色油状物2.7g,产率79%。
荧光染料13的合成步骤与染料11的合成步骤类似。
产率:53%。1H NMR(400MHz,CDCl3):δ9.60(d,2H,ArH,J=8.0Hz),8.64(d,2H,ArH,J=8.0Hz,),8.24(s,2H,ArH),7.10(d,4H,ArH,J=8.8),7.01(d,4H,ArH,J=9.2Hz),6.09(m,2H,CH),5.49(d,2H,CH,J=17.6Hz),5.36(d,2H,CH,J=10.4Hz),4.98(m,2H,CH),4.59(d,4H,CH2,J=8.0Hz),2.52(m,4H,CH),1.90(d,4H,CH2,J=12.0Hz),1.75(d,8H,CH,J=12.0Hz),1.56(s,2H),1.44-1.25(m,2H).MS(TOF MS ES+)calculated for C54H47N2O8:851.3327,measured:851.3329.
实施例6
可聚合荧光染料14的合成:
Figure BDA0000113256800000101
合成方法与实施例1类似,使用丙烯酸作为酰胺化试剂即可得到染料14。
产率:66%。1H-NMR(400MHz,CDCl3)δ10.40(s,1H,NH),8.43(d,J=8.0Hz,1H,ArH),8.19(d,J=12.0Hz,1H,ArH),7.73-7.55(m,4H,ArH,CH2),7.10(d,J=12.0Hz,1H,ArH),6.31(d,J=16.0Hz,1H,CH),6.16(m,1H,CH),5.95(b,1H,NH),5.63(d,J=16.0Hz,1H,CH),3.79(s,3H,CH3),3.40-3.35(m,4H,CH2),1.80-1.46(m,8H,CH2).MS(TOF MS ES+)calculated for[C26H28N3O3]+:430.2125,measured:430.2123.
实施例7
可聚合荧光染料11的溶剂聚合:
可聚合荧光染料11(50mg,0.05mmol),偶氮二异丁腈(5mg,0.03mmol)溶于10mL环己酮中,70℃反应3h,冷却至室温,将反应液倒入100mL甲醇中,有暗红色固体析出,过滤,并用50mL甲醇洗涤,干燥后得聚合物35mg。
聚合物的核磁表征见图1。
实施例8
较小粒径荧光纳米微球的微乳液制备过程:
单体4-氯甲基苯乙烯(0.5g,4.8mmol)、甲基丙烯酸甲酯(1.5g,15mmol)和实施例1所制备的可聚合荧光染料3(5mg,11.3μmol)的微乳液聚合反应在带三口圆底烧瓶中进行。Triton X-100(0.4g,0.62mmol)作为乳化剂溶解于45mL双蒸水中,随后以上混合在一起的单体加入三口瓶中超声波震荡乳化5min,通氮气除氧10min,匀速磁力搅拌。亚硫酸氢钠(10mg,97.1μmol)和过硫酸钾(45mg,0.17mmol)分别溶在5mL双蒸水中依次加入反应瓶中。聚合反应在40℃引发,反应24h。透射电镜测试在JEM-2000EX(JEOL,Tokyo,Japan)上进行,制得的纳米微球透射电镜图片见图2,纳米微球的粒径分布通过Malvern ZS-90激光纳米粒度仪测试获得,其平均粒径为22nm,见图3。
实施例9
光谱性能测试:
取实施例8所制备的纳米微球乳液,配制成一定浓度的水溶液,测定其荧光性能。同时,将实施例4所制备的可聚合荧光染料11配制成6×10-6M,测定其吸收和荧光光谱性能。归一化的谱图见图4。
实施例10
较大粒径荧光纳米微球的合成步骤:
单体苯乙烯(2.5g,24.0mmol)和实施例4所制备的可聚合荧光染料11(5mg,5.0μmol)的乳液聚合反应在带三口圆底烧瓶中进行。十二烷基磺酸钠(SDS,50mg,0.17mmol)作为乳化剂溶解于45mL双蒸水中,随后以上混合在一起的单体加入三口瓶中超声波震荡乳化5min,通氮气除氧10min,匀速磁力搅拌。过硫酸钾(45mg,0.17mmol)分别溶在5mL双蒸水中滴加至反应瓶中。聚合反应在75℃引发,反应7h。透射电镜测试在JEM-2000EX(JEOL,Tokyo,Japan)上进行,制得的纳米微球透射电镜图片见图5,其平均粒径约为150nm。
实施例11
实施例1所制备的可聚合荧光染料3和商品化染料罗丹明B的光稳定性对比:
罗丹明B是一个广泛应用的商品化染料,我们比较了染料3和罗丹明B在乙醇中光稳定性(如图6)。可见,经过500W碘钨灯照射7h后,在各自最大吸收处的百分比染料3比罗丹明B高约10%,说明染料3比商品化的荧光染料罗丹明B有更高的光稳定性。

Claims (7)

1.一类可聚合荧光染料,具有通式I的结构:
Figure FDA0000113256790000011
其中:
D是荧光染料母体;
Z为含有可聚合的官能团的连接基团;
n是1或2。
2.权利要求1所述的可聚合荧光染料,其特征在于所述的Z选自Z1、Z2、Z3和Z4
其中,虚线键为与D连接的键,R1为氢原子或CH3;X为氧原子、CH2或NH。
3.权利要求1或2所述的可聚合荧光染料,其特征在于所述的D选自1,8-萘酰亚胺类染料、蒽吡啶酮类染料和苝酰亚胺类染料。
4.权利要求3所述的可聚合荧光染料,其特征在于所述的D选自D1、D2、D3和D4
Figure FDA0000113256790000013
其中,虚线键为与Z连接的键,R1为甲基或氢原子;R2为C1-10的直连烷烃、支链烷烃或环烷烃。
5.权利要求4所述的可聚合荧光染料,其特征在于所述的D选自下述化合物:
6.一种荧光纳米微球,其特征在于是由权利要求1所述的可聚合荧光染料与苯乙烯或其衍生物、丙烯酸或其衍生物、甲基丙烯酸或其衍生物中的一种或几种聚合而成。
7.权利要求6所述的荧光纳米微球的制备方法,是乳液聚合的方法,聚合反应以Triton X-100、SDS或二者的混合物为乳化剂,以氧化还原反应体系作为引发体系,反应温度30~55℃,反应时间5~78小时;
其中,乳化剂的用量为聚合单体总质量的1~50%。
CN201110387145.8A 2011-11-28 2011-11-28 一类可聚合荧光染料、其制备方法及应用 Active CN102516988B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110387145.8A CN102516988B (zh) 2011-11-28 2011-11-28 一类可聚合荧光染料、其制备方法及应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110387145.8A CN102516988B (zh) 2011-11-28 2011-11-28 一类可聚合荧光染料、其制备方法及应用

Publications (2)

Publication Number Publication Date
CN102516988A true CN102516988A (zh) 2012-06-27
CN102516988B CN102516988B (zh) 2014-04-09

Family

ID=46288065

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110387145.8A Active CN102516988B (zh) 2011-11-28 2011-11-28 一类可聚合荧光染料、其制备方法及应用

Country Status (1)

Country Link
CN (1) CN102516988B (zh)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013139006A1 (zh) * 2012-03-21 2013-09-26 大连理工大学 一类4位n取代的蒽吡啶酮荧光染料、其制备方法及应用
CN104460233A (zh) * 2014-12-16 2015-03-25 京东方科技集团股份有限公司 一种着色剂组合物及感光性树脂组成物及其应用
CN104877671A (zh) * 2015-05-12 2015-09-02 上海大学 含芴主链非共轭高分子蓝光材料及其制备方法
CN105646766A (zh) * 2016-02-29 2016-06-08 苏州吉人高新材料股份有限公司 一种水性荧光乳胶及其制备方法
CN106699930A (zh) * 2016-12-01 2017-05-24 沈阳化工研究院有限公司 一种油品标记聚合物及制备方法和应用
CN107200709A (zh) * 2017-05-24 2017-09-26 华南理工大学 一类具有聚集诱导发光性质的荧光化合物及其在细胞荧光成像领域中的应用
CN108440711A (zh) * 2018-03-19 2018-08-24 陕西科技大学 一种水性萘酰亚胺荧光聚合物乳液及其制备方法
CN110655603A (zh) * 2019-08-28 2020-01-07 齐鲁工业大学 一种基于萘酐的荧光聚丙烯酸酯的合成方法
KR20200080357A (ko) * 2018-12-14 2020-07-07 문승호 형광 염료를 포함하는 3d 프린팅용 광경화성 수지 조성물
CN111893595A (zh) * 2020-07-09 2020-11-06 上海慧翌新材料科技有限公司 一种兼具荧光和阻燃功能的聚酯纤维及其制备方法
CN112154165A (zh) * 2018-06-26 2020-12-29 荷兰联合利华有限公司 用于增白牙齿的新型聚合物、组合物、方法及套件
CN114539150A (zh) * 2020-11-26 2022-05-27 中国科学院宁波材料技术与工程研究所 一种荧光小分子及其制备方法和应用
CN115677916A (zh) * 2022-11-09 2023-02-03 合肥工业大学 一种环状荧光聚合物、制备方法及其应用

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4326008A (en) * 1976-08-27 1982-04-20 California Institute Of Technology Protein specific fluorescent microspheres for labelling a protein
US4975094A (en) * 1988-08-26 1990-12-04 Sumitomo Chemical Company, Limited Anthrapyridone compounds having vinylsulfone type fiber reactive group through triazinyl bridging group
US6005113A (en) * 1996-05-15 1999-12-21 Molecular Probes, Inc. Long wavelength dyes for infrared tracing
WO2002012402A2 (en) * 2000-08-07 2002-02-14 Eastman Chemical Company Colorant compounds containing copolymerizable vinyl groups
US20050020786A1 (en) * 2003-07-23 2005-01-27 Eastman Kodak Company Polymer microspheres containing latent colorants and method of preparation
WO2005102249A1 (fr) * 2004-03-23 2005-11-03 L'oreal Composition comprenant un compose monomerique a effet optique, procede employant ladite composition, compose monomerique, polymere le comprenant et utilisation
CN1772729A (zh) * 2005-11-14 2006-05-17 武汉大学 可聚合的荧光功能单体及其制备方法和用途
CN101177607A (zh) * 2007-10-26 2008-05-14 中山大学 共聚型交联聚合物荧光微球及其制备方法
EP1975160A1 (en) * 2007-03-30 2008-10-01 Fujifilm Corporation Polymerizable compound, polymer, ink composition, printed articles and inkjet recording method
WO2009023287A1 (en) * 2007-08-16 2009-02-19 Beckman Coulter, Inc. Polymerized nile blue derivatives for plasticizer-free fluorescent ion optode microsphere sensors
JP4294988B2 (ja) * 2002-03-29 2009-07-15 大日本印刷株式会社 光ラジカル重合開始剤及び感光性樹脂組成物
JP2009197171A (ja) * 2008-02-25 2009-09-03 Fujifilm Corp インクジェット用インク組成物、並びに、それを用いたインクジェット記録方法及び印刷物
US7875720B2 (en) * 2000-04-27 2011-01-25 Nalco Company Fluorescent monomers and tagged treatment polymers containing same for use in industrial water systems
CN102093290A (zh) * 2010-12-27 2011-06-15 国家海洋局天津海水淡化与综合利用研究所 一种荧光单体和荧光丙烯酸类聚合物以及制法

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4326008A (en) * 1976-08-27 1982-04-20 California Institute Of Technology Protein specific fluorescent microspheres for labelling a protein
US4975094A (en) * 1988-08-26 1990-12-04 Sumitomo Chemical Company, Limited Anthrapyridone compounds having vinylsulfone type fiber reactive group through triazinyl bridging group
US6005113A (en) * 1996-05-15 1999-12-21 Molecular Probes, Inc. Long wavelength dyes for infrared tracing
US7875720B2 (en) * 2000-04-27 2011-01-25 Nalco Company Fluorescent monomers and tagged treatment polymers containing same for use in industrial water systems
WO2002012402A2 (en) * 2000-08-07 2002-02-14 Eastman Chemical Company Colorant compounds containing copolymerizable vinyl groups
JP4294988B2 (ja) * 2002-03-29 2009-07-15 大日本印刷株式会社 光ラジカル重合開始剤及び感光性樹脂組成物
US20050020786A1 (en) * 2003-07-23 2005-01-27 Eastman Kodak Company Polymer microspheres containing latent colorants and method of preparation
WO2005102249A1 (fr) * 2004-03-23 2005-11-03 L'oreal Composition comprenant un compose monomerique a effet optique, procede employant ladite composition, compose monomerique, polymere le comprenant et utilisation
CN1772729A (zh) * 2005-11-14 2006-05-17 武汉大学 可聚合的荧光功能单体及其制备方法和用途
EP1975160A1 (en) * 2007-03-30 2008-10-01 Fujifilm Corporation Polymerizable compound, polymer, ink composition, printed articles and inkjet recording method
WO2009023287A1 (en) * 2007-08-16 2009-02-19 Beckman Coulter, Inc. Polymerized nile blue derivatives for plasticizer-free fluorescent ion optode microsphere sensors
CN101177607A (zh) * 2007-10-26 2008-05-14 中山大学 共聚型交联聚合物荧光微球及其制备方法
JP2009197171A (ja) * 2008-02-25 2009-09-03 Fujifilm Corp インクジェット用インク組成物、並びに、それを用いたインクジェット記録方法及び印刷物
CN102093290A (zh) * 2010-12-27 2011-06-15 国家海洋局天津海水淡化与综合利用研究所 一种荧光单体和荧光丙烯酸类聚合物以及制法

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
AIBIN WU等: "Novel naphthalimide derivatives as potential apoptosis-inducing agents: Design, synthesis and biological evaluation", 《EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY》, vol. 44, 16 July 2009 (2009-07-16), pages 4674 - 4680 *
CHRISTIAN B. NIELSEN等: "Copolymers of Polyethylene and Perylenediimides through Ring-Opening Metathesis Polymerization", 《MACROMOLECULES》, vol. 41, 12 January 2008 (2008-01-12), pages 1094 - 1103 *
CHUN-SHAN ZHAO等: "The preparation of copolymerized fluorescent microspheres of styrene using detergent-free emulsion polymerization", 《DYES AND PIGMENTS》, vol. 82, 25 December 2008 (2008-12-25), pages 134 - 141 *
JEAN-CLAUDE ALFRED 等: "Facile synthesis of new amine high-loaded poly(meth)acrylamide-based resins for solid phase peptide synthesis", 《MACROMOL. CHEM. PHYS.》, vol. 197, no. 1, 31 January 1996 (1996-01-31), pages 389 - 401 *
何元君 等: "新型可聚合激光染料及双发色团共聚物的合成", 《高分子学报》, no. 03, 30 June 2000 (2000-06-30), pages 379 - 381 *
叶德 等: "含萘酰亚胺生色团的单体及其均聚物荧光性能", 《应用化学》, vol. 26, no. 08, 10 August 2009 (2009-08-10), pages 929 - 934 *
孙德帅 等: "萘酰亚胺类高聚物色素研究进展", 《塑料助剂》, no. 01, 20 February 2008 (2008-02-20), pages 12 - 16 *
陈明强 等: "萘酰亚胺类共聚型聚合色素的合成与表征", 《华东理工大学学报》, vol. 27, no. 02, 25 April 2001 (2001-04-25), pages 195 - 197 *
黄淼 等: "可聚合萘酰亚胺类衍生物的合成及光谱研究", 《波谱学杂志》, vol. 26, no. 04, 31 December 2009 (2009-12-31), pages 524 - 533 *

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013139006A1 (zh) * 2012-03-21 2013-09-26 大连理工大学 一类4位n取代的蒽吡啶酮荧光染料、其制备方法及应用
CN104460233A (zh) * 2014-12-16 2015-03-25 京东方科技集团股份有限公司 一种着色剂组合物及感光性树脂组成物及其应用
CN104877671A (zh) * 2015-05-12 2015-09-02 上海大学 含芴主链非共轭高分子蓝光材料及其制备方法
CN105646766A (zh) * 2016-02-29 2016-06-08 苏州吉人高新材料股份有限公司 一种水性荧光乳胶及其制备方法
CN105646766B (zh) * 2016-02-29 2018-02-23 苏州吉人高新材料股份有限公司 一种水性荧光乳胶及其制备方法
CN106699930A (zh) * 2016-12-01 2017-05-24 沈阳化工研究院有限公司 一种油品标记聚合物及制备方法和应用
CN107200709A (zh) * 2017-05-24 2017-09-26 华南理工大学 一类具有聚集诱导发光性质的荧光化合物及其在细胞荧光成像领域中的应用
CN107200709B (zh) * 2017-05-24 2020-04-28 华南理工大学 一类具有聚集诱导发光性质的荧光化合物及其在细胞荧光成像领域中的应用
CN108440711B (zh) * 2018-03-19 2020-08-07 陕西科技大学 一种水性萘酰亚胺荧光聚合物乳液及其制备方法
CN108440711A (zh) * 2018-03-19 2018-08-24 陕西科技大学 一种水性萘酰亚胺荧光聚合物乳液及其制备方法
CN112154165A (zh) * 2018-06-26 2020-12-29 荷兰联合利华有限公司 用于增白牙齿的新型聚合物、组合物、方法及套件
KR20200080357A (ko) * 2018-12-14 2020-07-07 문승호 형광 염료를 포함하는 3d 프린팅용 광경화성 수지 조성물
KR102146616B1 (ko) 2018-12-14 2020-08-20 문승호 형광 염료를 포함하는 3d 프린팅용 광경화성 수지 조성물
CN110655603A (zh) * 2019-08-28 2020-01-07 齐鲁工业大学 一种基于萘酐的荧光聚丙烯酸酯的合成方法
CN110655603B (zh) * 2019-08-28 2021-09-24 齐鲁工业大学 一种基于萘酐的荧光聚丙烯酸酯的合成方法
CN111893595A (zh) * 2020-07-09 2020-11-06 上海慧翌新材料科技有限公司 一种兼具荧光和阻燃功能的聚酯纤维及其制备方法
CN111893595B (zh) * 2020-07-09 2022-09-23 上海慧翌新材料科技有限公司 一种兼具荧光和阻燃功能的聚酯纤维及其制备方法
CN114539150A (zh) * 2020-11-26 2022-05-27 中国科学院宁波材料技术与工程研究所 一种荧光小分子及其制备方法和应用
CN114539150B (zh) * 2020-11-26 2023-12-01 中国科学院宁波材料技术与工程研究所 一种荧光小分子及其制备方法和应用
CN115677916A (zh) * 2022-11-09 2023-02-03 合肥工业大学 一种环状荧光聚合物、制备方法及其应用

Also Published As

Publication number Publication date
CN102516988B (zh) 2014-04-09

Similar Documents

Publication Publication Date Title
CN102516988B (zh) 一类可聚合荧光染料、其制备方法及应用
CN107011469A (zh) 一种具有聚集诱导发光性能的侧链型液晶高分子及其制备方法
CN111875811B (zh) 一种超分子聚合物及其制备方法和应用
CN108504348B (zh) 一种双荧光聚合物量子点材料的制备和应用
CN102725299A (zh) 光致发光纳米粒子及其制备方法与应用
CN103755928B (zh) 一种水溶性卟啉共轭聚合物及其制备方法与应用
CN107365254B (zh) 一种聚合物微球在拉曼检测中的应用
CN103601856A (zh) 一种负载手性催化剂的聚合物微球及其制备方法和应用
CN108772027B (zh) 一种超分子有机凝胶及其金属凝胶的制备和应用
CN108181288B (zh) 一种检测细胞内pH值的聚合物纳米荧光探针及其制备方法以及应用
CN105733504B (zh) 一种具有液晶性质的近红外吸波材料
CN105440065A (zh) 一种萘酰亚胺-氟硼二吡咯荧光分子np-bodipy及其制备方法和应用
CN113214144B (zh) 基于偶极有机配体的金属有机框架材料、合成方法及其应用
CN103755634A (zh) 9-氨基吖啶衍生物及其合成方法
Shao et al. Photostable, hydrophilic and functional near infrared quaterrylenediimide-cored dendrimers for biomedical imaging
US5900490A (en) Preparation of perylene-3, 4-Dicarboxylic acid anhydrides
CN104387790B (zh) 一种含噻吩基团的苯并吲哚盐染料及其制备方法和用途
CN112940708B (zh) 一种瞬态荧光变色超分子共组装体的制备方法
CN107090191A (zh) 一类罗丹明荧光染料及其制备方法
CN103666453A (zh) 一种含三氟甲基芴蓝色荧光材料及其制备方法
CN110003449B (zh) 含吡咯并吡咯烷酮构筑单元的荧光共轭高分子、制备方法及应用
CN113527364A (zh) 一种Mn(II)配合物多光子吸收材料及其制备方法和用途
CN110156762A (zh) 含有喹啉和香豆素功能团的聚集诱导发光材料及制备方法
CN110143907A (zh) 一种9,10-二吡咯基蒽荧光化合物及其制备方法和应用
CN108586387A (zh) 一种基于苯基桥联和羧基封端的D-A-π-A型苯并噻二唑衍生物及其制备方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
ASS Succession or assignment of patent right

Owner name: DALIAN FUSIDA SPECIAL CHEMICALS CO., LTD.

Effective date: 20140126

C41 Transfer of patent application or patent right or utility model
TA01 Transfer of patent application right

Effective date of registration: 20140126

Address after: 116024 Dalian high tech park, Liaoning Ling Road, No. 2

Applicant after: Dalian University of Technology

Applicant after: Dalian Fusida Special Chemical Co., Ltd.

Address before: 116024 No. 2 Ling Road, hi tech Development Zone, Liaoning, Dalian

Applicant before: Dalian University of Technology

C14 Grant of patent or utility model
GR01 Patent grant