CN114075334A - 光响应聚磺酸酯的合成方法及应用 - Google Patents
光响应聚磺酸酯的合成方法及应用 Download PDFInfo
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- CN114075334A CN114075334A CN202110664083.4A CN202110664083A CN114075334A CN 114075334 A CN114075334 A CN 114075334A CN 202110664083 A CN202110664083 A CN 202110664083A CN 114075334 A CN114075334 A CN 114075334A
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Classifications
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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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/24—Polysulfonates
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/04—Sulfonic acids; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
本发明提供了一种温和条件下合成光响应聚磺酸酯的新方法,及聚磺酸酯的光降解、光酸生成性质在荧光多色二维图案、荧光三维图案生成与广谱抗菌中的应用。该聚合路线以简单易得的二炔卤、和廉价的二磺酸为原料,在空气氛围中一锅法室温高效制备聚磺酸酯,无需催化剂,产率高达94%,原子利用率为100%。与传统的光响应聚合物合成方法相比,该方法无需利用光敏单体,反应时间短,操作简单而且条件极其温和。该方法不仅提供了新的光响应聚合物合成策略,还丰富了光响应聚合物的种类。
Description
技术领域
本发明涉及化学、材料、生物领域,特别是涉及一种新型光响应聚磺酸酯的简易合成方法、所得聚合物的性质探索及其应用,如快速光降解及光酸产生,可视化监测光降解,制备荧光二维图案、多色荧光二维图案、荧光三维图案,用于高效广谱快速选择性杀菌,作为聚合物抗菌膜、抗菌喷雾等的应用。
背景技术
光响应聚合物的性质在外界光源刺激下能够快速灵敏地发生改变,这类材料在光电器件、信息储存、生物成像和治疗等领域有着广阔的应用前景。然而,合成上的困难使得光响应聚合物的研究进展受到很大限制。光响应聚合物通常由光敏单体聚合而成,这些单体需要精妙的设计,种类有限且成本高昂。目前用于合成光响应聚合物的方法也十分有限,且大多反应条件严格。
因此,发展一种简易高效地合成光响应聚合物的方法具有重要转化价值。
发明内容
本发明提供一种新型聚磺酸酯合成路线,成功制备出一系列多功能光响应聚磺酸酯。该聚合路线以简单易得的磺酸和炔卤为原料,无需催化剂,在常温下空气氛围中通过一锅法高效制备聚磺酸酯,原子利用率为100%,产率高达94%。与传统的光响应聚合物合成方法相比,该方法无需利用光敏单体,反应时间短,操作简单而且条件极其温和。该方法不仅提供了新的光响应聚合物合成策略,还丰富了光响应聚合物的种类。
在聚合过程中原位生成的磺酸酯基团对白光稳定,但对紫外光非常敏感,所得到的聚合物在紫外(365nm)光照下可迅速降解并产生强酸,同时发光波长明显蓝移。
由于这类聚磺酸酯具有灵敏的光响应性、良好的成膜能力和固态发光的性质,他们是制备荧光二维或三维图案的优异材料,并在先进光电子器件中具有重要潜在应用。聚合物薄膜在短时间紫外光照下发生光降解,长时间紫外光照下被光漂白,因此利用单一聚合物材料便可制备复杂的双色荧光二维图案或者荧光三维图案,同时可以调控聚合物的折光指数。
利用聚磺酸酯光降解时产生强酸的性质,这类聚合物材料还可被用于广谱杀菌。此外,由于这些聚磺酸酯重复单元中含有Br,I等卤素取代基,他们可以通过后修饰进一步扩大光响应聚磺酸酯的功能和种类。
附图说明
图1示出P1a/2a的光降解及光酸生成:(a)P1a/2a在THF、THF/水(体积比1:99)、薄膜、薄膜浸水条件下,不同光照时间的分子量;(b)P1a/2a在水/THF(体积比1:99,浓度1mg/mL)中,不同光照时间的pH值;(c)P1a/2a悬浮液光照前后的发射光谱;(d)本发明提出的聚磺酸酯光降解机理。
图2示出光响应聚磺酸酯P1a/2a的荧光光刻图案与折光指数:(a-b)P1a/2a薄膜制作的荧光二维图案;(c-d)双色荧光二维图案的制作过程与荧光照片;(e)荧光三维图案的制作过程与荧光照片;(f)荧光显微镜下的荧光三维图案;(g)原子力显微镜下观察的三维形貌;(h)在不同光照时间下的薄膜折光指数变化。
图3示出利用聚磺酸酯P1a/2a的光酸生成性质进行可控广谱杀菌;(a)大肠杆菌(E.coli)、金黄色葡萄球菌(SA)、绿脓杆菌(PA)在P1a/2a加光照以及不同对照组下的存活率;(b)用扫面电子显微镜观察不同实验条件下三种细菌的形貌;(b)用透射电镜观察不同实验条件下三种细菌的形貌;(d)对照组与实验组的细菌放置15天后的琼脂板照片;(e)建立聚合物抗菌涂层与聚合物喷雾两种模型,在光照下可以快速100%杀灭细菌;(f)聚合物抗菌涂层与聚合物喷雾两种模型的杀菌效果与对照组对比。
具体实施方式
下面详细描述本发明的实施方案。下面描述的实施方案是示例性的,仅用于解释本发明,而不能理解为对本发明的限制。实施方案中未注明具体技术或条件的,按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规产品。
定义和一般术语
现在详细描述本发明的某些实施方案,其实例由随附的结构式和化学式说明。本发明意图涵盖所有的替代、修改和等同技术方案,它们均包括在如权利要求定义的本发明范围内。本领域技术人员应认识到,许多与本文所述类似或等同的方法和材料能够用于实践本发明。本发明绝不限于本文所述的方法和材料。在所结合的文献、专利和类似材料的一篇或多篇与本申请不同或相矛盾的情况下(包括但不限于所定义的术语、术语应用、所描述的技术,等等),以本申请为准。
应进一步认识到,本发明的某些特征,为清楚可见,在多个独立的实施方案中进行了描述,但也可以在单个实施例中以组合形式提供。反之,本发明的各种特征,为简洁起见,在单个实施方案中进行了描述,但也可以单独或以任意适合的子组合提供。
除非另外说明,本发明所使用的所有科技术语具有与本发明所属领域技术人员的通常理解相同的含义。本发明涉及的所有专利和公开出版物通过引用方式整体并入本发明。
除非另外说明,应当应用本文所使用的下列定义。出于本发明的目的,化学元素与元素周期表CAS版,和《化学和物理手册》,第75版,1994一致。此外,有机化学一般原理可参考“Organic Chemistry”,Thomas Sorrell,University Science Books,Sausalito:1999,和“March's Advanced Organic Chemistry”by Michael B.Smith and Jerry March,JohnWiley&Sons,New York:2007中的描述,其全部内容通过引用并入本文。
除非另有说明或者上下文中有明显的冲突,本文所使用的冠词“一”、“一个(种)”和“所述”旨在包括“至少一个”或“一个或多个”。因此,本文所使用的这些冠词是指一个或多于一个(即至少一个)宾语的冠词。例如,“一组分”指一个或多个组分,即可能有多于一个的组分被考虑在所述实施方案的实施方式中采用或使用。
术语“包含”为开放式表达,即包括本发明所指明的内容,但并不排除其他方面的内容。
另外,需要说明的是,除非以其他方式明确指出,在本发明中所采用的描述方式“各…独立地为”与“…各自独立地为”和“…独立地为”可以互换,均应做广义理解,其既可以是指在不同基团中,相同符号之间所表达的具体选项之间互相不影响,也可以表示在相同的基团中,相同符号之间所表达的具体选项之间互相不影响。
在本说明书的各部分,本发明公开化合物的取代基按照基团种类或范围公开。特别指出,本发明包括这些基团种类和范围的各个成员的每一个独立的次级组合。例如,术语“C1-18烷基”包括甲基、乙基、C3烷基、C4烷基、C5烷基和C6烷基。
本发明使用的术语“烃基”包括芳香族烃基和脂肪族烃基。脂肪族烃基包括“烷基”或“烷基基团”,烯基和炔基,它们可以是饱和或不饱和的直链或支链二价烃基基团。所述烃基可以任选地被一个或多个本发明描述的取代基所取代。在本发明的一个实施方案中,烷基基团含有1-18个碳原子。在另一实施方案中,烷基基团含有1-12个碳原子;在又一实施方案中,烷基基团含有1-6个碳原子;再一实施方案中,烷基基团含有1-4个碳原子;还在一实施方案中,烷基基团含有1-3个碳原子。
烷基基团的实例包含,但并不限于,C1-12烷基,如甲基,乙基,正丙基,异丙基,正丁基,异丁基,仲丁基,叔丁基,正戊基,2-戊基,3-戊基,2-甲基-2-丁基,3-甲基-2-丁基,3-甲基-1-丁基,2-甲基-1-丁基,正己基,2-己基,3-己基,2-甲基-2-戊基,3-甲基-2-戊基,4-甲基-2-戊基,3-甲基-3-戊基,2-甲基-3-戊基,2,3-二甲基-2-丁基,3,3-二甲基-2-丁基,正庚基,正辛基,等等。
术语“烯基”表示碳原子的直链或支链一价烃基,其中至少有一个不饱和位点,即有一个碳-碳sp2双键,其中,所述烯基基团任选地被一个或多个本发明所描述的取代基所取代,其包括“cis”和“tans”的定位,或者"E"和"Z"的定位。在一实施方案中,烯基基团包含2-8个碳原子;在另一实施方案中,烯基基团包含2-6个碳原子;在又一实施方案中,烯基基团包含2-4个碳原子。烯基基团的实例包括,但并不限于,乙烯基、烯丙基等等。
术语“炔基”表示碳原子的直链或支链一价烃基,其中至少有一个不饱和位点,即有一个碳-碳sp三键,其中,所述炔基基团任选地被一个或多个本发明所描述的取代基所取代。在一实施方案中,炔基基团包含2-8个碳原子;在另一实施方案中,炔基基团包含2-6个碳原子;在又一实施方案中,炔基基团包含2-4个碳原子。炔基基团的实例包括,但并不限于,乙炔基、炔丙基、1-丙炔基等等。
术语“羧基”,无论是单独使用还是和其他术语连用,如“羧烷基”,表示-CO2H;术语“羰基”,无论是单独使用还是和其他术语连用,如“氨基羰基”或“酰氧基”,表示-(C=O)-。
术语“卤素”和“卤代”是指氟(F)、氯(Cl)、溴(Br)或碘(I)。
术语“芳香族基团”包括从芳香环中去掉两个氢原子从而与其他基团直接连接的基团。优选地,芳香族基团在成环原子中具有至少一个杂原子,例如N、O或S。
术语“芳香族环烃基”包括单环、双环和三环的芳基,其中,至少一个环体系是芳香族的,其中每一个环体系包含6-18个原子组成的环。芳基基团通常,但不必须地通过芳基基团的芳香性环与母体分子连接。术语“芳基”可以和术语“芳香环”或“芳环”交换使用。芳基基团的实例可以包括苯基、联苯基、萘基和蒽。所述芳基基团任选地被一个或多个本文所描述的取代基所取代。
在本发明中,取代基可以选自卤原子、羟基、醛基、羧基、氨基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18烯基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18炔基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的的C1-C18烷基或烷氧基、成环碳原子6-18的芳香族环烃基、成环碳原子5-18的芳香族杂环基、巯基、氰基和硝基中的至少一者。
芳香族环烃基和芳香族杂环基的例子包括(例如)苯基、萘基、苯基、萘基、蒽基、菲基、并四苯基、芘基、苯并[c]菲基、苯并菲基、芴基、苯并芴基、二苯并芴基、联苯基、三联苯基、四联苯基、荧蒽基、吡咯基、吡嗪基、吡啶基、嘧啶基、三嗪基、吲哚基、异吲哚基、咪唑基、呋喃基、苯并呋喃基、异苯并呋喃基、二苯并呋喃基、二苯并噻吩基、喹啉基、异喹啉基、喹喔啉基、咔唑基、菲啶基、吖啶基、菲咯啉基、吩嗪基、吩噻嗪基、吩噁嗪基、噁唑基、噁二唑基、呋咱基、噻吩基、苯并噻吩基、二氢吖啶基、氮杂咔唑基、喹唑啉基等。
取代基的例子包括:
本发明开发出一种新型聚磺酸酯合成路线(如下式I所示),成功制备出一系列多功能光响应聚磺酸酯。该聚合路线以简单易得的磺酸和炔卤为原料,无需催化剂,在常温下空气氛围中一锅法高效制备聚磺酸酯,原子利用率为100%,产率高达94%。与传统的光响应聚合物合成方法相比,该方法无需利用光敏单体,反应时间短,操作简单而且条件极其温和。该方法不仅提供了新的光响应聚合物合成策略,还丰富了光响应聚合物的种类。
在聚合过程中原位生成的磺酸酯基团对白光稳定,但对紫外光非常敏感,所得到的聚合物在紫外(365nm)光照下可迅速降解并产生强酸,同时发光波长明显蓝移。
由于这类聚磺酸酯具有灵敏的光响应性、良好的成膜能力和固态发光的性质,他们是制备荧光二维或三维图案的优异材料,并在先进光电子器件中具有重要潜在应用。聚合物薄膜在短时间紫外光照下发生光降解,长时间紫外光照下被光漂白,因此利用单一聚合物材料便可制备复杂的双色荧光二维图案或者荧光三维图案,同时可以调控聚合物的折光指数。
利用聚磺酸酯光降解时产生强酸的性质,这类聚合物材料还可被用于广谱杀菌。此外,由于这些聚磺酸酯重复单元中含有Br,I等卤素取代基,他们可以通过后修饰进一步扩大光响应聚磺酸酯的功能和种类。如下式2示出含卤素聚磺酸酯的后修饰路线示意图。
例子
提供下述的例子来示意性描述以帮助本领域技术人员理解本发明。然而,本发明的以下例子不应被构建为不适当地限制本发明。在不脱离本发明发现的范围的情况下,本领域普通技术人员可以对所讨论的例子进行变化和修改。
通用方法
所得的聚合物的重均分子量(Mw)和数均分子量(Mn)以及多分散性指数(Mw/Mn)是通过Waters 1515凝胶渗透色谱系统估计而得的。THF溶液以1mL/min的流速用作洗脱剂。分子量范围为103-107g/mol的一组单分散聚苯乙烯用作分子量校准的标准。有关样品制备和实验设置的详细信息可以在我们之前的论文中找到。FT-IR光谱和高分辨率质谱(HRMS)分别记录在Bruker Vertex 70FT-IR光谱仪(KBr盘)和GCT Premier CAB 048质谱仪上。1H和13C谱图是用CD2Cl2,CDCl3或DMSO-d6做溶剂通过Bruker ARX 400NMR波谱仪获得。用CDCl3的δ7.26ppm(1H NMR)和δ77.16ppm(13C NMR),CD2Cl2的δ5.32ppm(1H NMR)和δ53.84ppm(13CNMR)和DMSO-d6的δ2.50ppm(1H NMR)和δ39.52ppm(13C NMR)作为内部参照来校准化学位移。TGA和DSC测量分别在氮气下以10℃/min的加热速率在TA TGA Q5000和TA InstrumentsDSC Q1000进行。紫外-可见光谱和PL光谱分别在Milton Ray Spectronic 3000阵列分光光度计和PerkinElmer LS 55分光光度计测量。RI值由Woollam椭偏仪上使用Alpha-SE模型确定,波长可调范围为380至900nm。荧光照片图案在紫外光源(330-380nm)下由荧光光学显微镜(Nikon Eclipse的80i)拍摄而得。将聚合物的1,2-二氯乙烷溶液(~10mg mL-1)以600rpm(6秒)、1000rpm(60秒)的速度旋涂在硅片上,然后在真空烘箱中室温下干燥2h,制成用于RI测量的薄膜。通过在室温下在空气中通过光掩模对聚合物薄膜进行紫外线照射来生成光图案。具有网格图案的光掩模在正方形区域涂有铜,而网格线是透明的玻璃板。通过激光打印机将有“二维码”等图案的光掩模印刷在不透明的纸上。用Oriel Mercury弧光灯的紫外线在25cm的距离下进行光照过程。入射光强度为~18.5mW cm-2,汞弧光灯的施加功率为180W。
为了进行生物学实验,从Sigma-Aldrich购买Luria-Bertani(LB)培养基,LB琼脂和生理盐水(0.85%NaCl)。所有其他化学品均购自Sigma-Aldrich和国药集团化学试剂有限公司,无需进一步纯化即可直接使用。通过Milli-Q系统(德国密理博)制备超纯水(18.0MΩcm),并在整个过程中使用。
样品制备:制备浓度为100mg/mL的聚磺酸酯的THF储备溶液,并将其存储在4℃的冰箱中。LB培养基和LB琼脂根据产品说明书中的方案制备。在用细菌接种之前,将所有培养基在121℃下灭菌20分钟。
细菌培养:将LB琼脂平板上的单个细菌菌落(大肠杆菌,金黄色葡萄球菌或铜绿假单胞菌)转移到5mL LB培养基中,并在37℃下摇动生长过夜。细菌的浓度通过测量600nm(OD600)的光密度来确定。通过以7000rpm离心2分钟收获细菌,并用生理盐水洗涤两次。除去上清液后,将剩余的细菌重悬于生理盐水中,并以约1×109CFU/mL的浓度稀释至光密度1.0(OD600=1.0)。
平板菌落计数法测定抗菌效果:收集的细菌用生理盐水(OD600=1.0)重悬,并用生理盐水稀释1×103倍。在黑暗中将所得细菌与聚磺酸酯(2mg/mL)孵育5分钟。接下来,将细菌悬浮液暴露于365nm(40mW/cm2)的紫外线辐射下30分钟。同时,将在没有聚磺酸酯或没有光照射的情况下处理的细菌悬浮液用作对照组。经过各种处理后,将细菌悬浮液直接稀释100倍。将50μL稀释的细菌细胞铺展在固体LB琼脂平板上,然后在集落形成单位(CFU)计数并拍照之前,在37℃下培养14-24h。通过细菌菌落的数量评估细菌的生存力。对每个样品进行一式三份的分析,并且每个实验一式两份进行。
为了测试聚磺酸酯对大肠杆菌,金黄色葡萄球菌和铜绿假单胞菌的毒性,将细菌悬浮液与聚磺酸酯(2mg/mL)在自然光下孵育30分钟。并通过平板菌落计数法评估细菌的生存力。
扫描电子显微镜(SEM)分析:随后进行抗菌实验,将得到的细胞悬浮液滴到新鲜的硅片上,以在空气中进一步干燥。干燥后,使用0.1%的戊二醛固定细菌细胞1小时,然后添加更高浓度的戊二醛(2.5%)固定2h。用无菌水洗涤后,通过按梯度系列(30%,50%,70%,80%,90%,95%和100%)添加乙醇使样品脱水,每次6分钟,然后与叔胺温育-丁醇在4℃下过夜。进一步冷冻干燥1-2小时后,将样品涂上金,用SEM S-4800(日本日立)进行SEM分析。
透射电子显微镜(TEM)分析:随后进行抗菌实验,将细菌用2.5%戊二醛固定12小时。将样品沉积在铜栅支撑的碳膜上,并用TEM H-7650(日本日立)进行表征。
抗菌涂料的制备,应用及性能评价:为了制备抗菌涂层,将含有聚磺酸酯(2mg/mL)的THF溶液涂在玻璃上,并在室温下于空气中干燥。对于抗菌应用,将准备好的抗菌涂层用金黄色葡萄球菌悬浮液(OD600=1.0)覆盖,在室温下温和干燥,然后在365nm的紫外线下照射30分钟(40mW/cm2)。为了比较,分别在潮湿环境和普通环境中进行UV照射。同时,没有聚磺酸酯涂层的玻璃也用作对照组。为了评估上述涂层的抗菌性能,将残留的细菌洗涤到新鲜的LB琼脂平板中,并在37℃下孵育14-24h。
抗菌喷雾剂的制备,应用及性能评价:通过制备含有2%THF的聚磺酸酯水悬浮液(2mg/mL)获得抗菌喷雾剂。对于抗菌应用,将准备好的抗菌喷雾剂喷在覆盖活金黄色葡萄球菌细胞的载玻片上,然后在365nm的紫外线下照射30分钟(40mW/cm2)。同时,将未经喷雾或UV辐射处理的细胞用作对照组。为了评估上述喷雾剂的抗菌性能,将残留的细菌洗至新鲜的LB琼脂平板中,并在37℃下孵育14-24小时。
合成及表征
聚合物合成
在所有聚合反应中均采用标准Schlenk技术,下面以P1a/2a(表1,条目4)的合成步骤为例。向15mL Schlenk管中加入4,4’-联苯二磺酸2a(0.1mmol),二卤代炔烃1a(0.1mmol)和0.5mL的六氟异丙醇/二氯甲烷(体积比为1∶8)。加入六氟异丙醇后溶液立即变黑。将所得溶液在室温搅拌2小时。完成后,通过加入30mL水洗涤未反应的磺酸单体,然后用二氯甲烷萃取3次。随后收集有机层并浓缩,将溶液滴加到100mL正己烷中,过滤后最终收集沉淀物,用正己烷洗涤并在室温下真空干燥至恒重。结构表征的结果如下。
表1聚磺酸酯合成的条件优化及不同单体的聚合结果
a除特别说明外,聚合反应均在空气中室温下进行2小时,[1]=[2]。b反应时间为4小时。c反应时间为8小时。d在线性聚苯乙烯校正的基础上由在THF中的GPC估算而得。
P1a/2a的表征数据:黄色粉末;83%.Mn:12,100;Mw:27,600;Mw/Mn:2.3(GPC,聚苯乙烯校正).IR(KBr),ν(cm-1):1710,1678,1664,1604,1500,1492,1442,1391,1240,1190,1136,1047,1001,848,821,761,729,700,619,572cm-1.1H NMR(400MHz,CD2Cl2),δ(ppm):7.88,7.66,7.30-6.74(芳香环质子),6.47(烯烃质子).13C NMR(100MHz,CD2Cl2),δ(ppm):148.11,145.18,144.42,143.13,141.78,141.11,136.07,131.67,131.59,131.42,131.13,129.57,128.19,127.34,121.05,101.41.
P1b/2a的表征数据:黄色粉末;94%.Mn:7,800;Mw:11,900;Mw/Mn:1.5(GPC,聚苯乙烯校正).IR(KBr),ν(cm-1):1716,1672,1629,1598,1554,1494,1442,1386,1267,1238,1190,1138,1049,999,850,819,759,731,700,619,572,563cm-1.1H NMR(400MHz,CD2Cl2),δ(ppm):7.96,7.87,7.62-7.03(芳香环质子),6.44(烯烃质子).13C NMR(100MHz,CD2Cl2),δ(ppm):148.10,145.17,143.47,142.99,141.51,136.08,131.57,131.42,129.56,128.57,128.29,127.19,101.48.
P1c/2a的表征数据:黄色粉末;91%.Mn:7,400;Mw:9,500;Mw/Mn:1.3(GPC,聚苯乙烯校正).IR(KBr),ν(cm-1):1716,1674,1627,1600,1558,1490,1442,1384,1267,1238,1190,1137,1049,999,860,819,761,731,700,621,574,563cm-1.1H NMR(400MHz,CD2Cl2),δ(ppm):7.96,7.85,7.61-6.93(芳香环质子),6.56(烯烃质子).13C NMR(100MHz,CD2Cl2),δ(ppm):149.70,145.49,145.06,142.90,141.52,136.23,131.70,131.57,131.44,131.09,129.50,129.34,129.10,128.98,128.56,128.26,127.38,127.31,127.17,71.11.
P1d/2a的表征数据:黄色粉末;80%.Mn:7,500;Mw:12,800;Mw/Mn:1.7(GPC,聚苯乙烯校正).IR(KBr),ν(cm-1):1595,1558,1485,1465,1413,1382,1305,1267,1238,1190,1157,1137,1097,1047,1014,1001,869,819,729,619,578,543cm-1.1H NMR(400MHz,CD2Cl2),δ(ppm):7.81-6.80(芳香环质子),6.59(烯烃质子),1.55-1.11(CH3).13C NMR(100MHz,CD2Cl2),δ(ppm):154.55,154.26,153.91,149.05,148.70,148.53,145.03,144.92,141.01,139.88,135.90,135.72,131.63,130.72,129.89,129.43,128.99,128.74,128.29,126.91,126.69,123.58,123.30,120.47,103.79,102.18,47.36,26.88.
P1e/2a的表征数据:黄色粉末;88%.Mn:5,100;Mw:11,500;Mw/Mn:2.3(GPC,聚苯乙烯校正).IR(KBr),ν(cm-1):1683,1597,1558,1485,1448,1384,1303,1238,1190,1132,1037,1016,999,962,864,837,821,759,729,617,572cm-1.1H NMR(400MHz,CD2Cl2),δ(ppm):7.96-6.60(芳香环质子),6.40-6.30(烯烃质子).13C NMR(100MHz,CD2Cl2),δ(ppm):149.61,147.78,145.07,142.25,135.70,132.03,129.43,128.51,128.36,127.78,124.69,124.04,120.91,120.42,104.27,101.97,66.18.
P1b/2a的表征数据:黄色粉末;75%.Mn:8,700;Mw:27,000;Mw/Mn:3.1(GPC,聚苯乙烯校正).IR(KBr),ν(cm-1):1710,1679,1656,1598,1500,1442,1402,1274,1244,1226,1190,1151,977,908,839,794,769,698,661,613,568,528,466cm-1.1H NMR(400MHz,CD2Cl2),δ(ppm):7.88,7.64,7.30-6.99(芳香环质子),6.47(烯烃质子).13C NMR(100MHz,CD2Cl2),δ(ppm):143.40,142.00,141.28,131.64,128.91,128.18,127.24,100.54.
P1c/2a的表征数据:黄色粉末;69%.Mn:8,500;Mw:16,200;Mw/Mn:1.9(GPC,聚苯乙烯校正).IR(KBr),ν(cm-1):1679,1597,1494,1442,1400,1276,1180,1163,1107,1072,1018,856,837,815,759,698,621,574cm-1.1H NMR(400MHz,CD2Cl2),δ(ppm):7.73,7.46-7.06(芳香环质子),6.75(烯烃质子),4.45.13C NMR(100MHz,CD2Cl2),δ(ppm):148.55,143.09,141.31,132.03,131.54,128.66,128.31,127.48,101.81,31.98。
Claims (10)
2.根据权利要求1所述的方法,其特征在于,所述聚合反应在室温、空气的环境下进行;所述聚合反应在溶剂和无催化剂存在的条件下进行,溶剂为六氟异丙醇与二氯甲烷的混合物。
3.根据权利要求1所述的方法,其特征在于,所述卤素原子包括F、Cl、Br和I;所述聚集诱导发光基团选自下列基团中的至少一者:
以及其中,所述聚集诱导发光基团可以具有取代基或者不具有取代基,在具有取代基的情况下,取代基选自羟烷基、烷氨基、烷基、不饱和烃基、环烃基、杂烃基、芳基和杂芳基的至少一个氢被选自卤原子、羟基、醛基、羧基、氨基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18烯基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18炔基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的的C1-C18烷基或烷氧基、成环碳原子6-18的芳香族环烃基、成环碳原子5-18的芳香族杂环基、巯基、氰基和硝基中的至少一者。
4.一种根据权利要求1-3所述的方法合成的聚磺酸酯。
5.根据权利要求4所述的聚磺酸酯,其特征在于,所述聚磺酸酯具有聚集诱导发光现象,聚集态与固态有强荧光。
6.根据权利要求4所述的聚磺酸酯,其特征在于,所述聚磺酸酯具有高折光指数,其折光指数对365纳米紫外光照敏感。
7.根据权利要求4所述的聚磺酸酯,其特征在于,所述聚磺酸酯在紫外光照下可迅速被光降解并伴随光酸生成,发光波长有明显蓝移,可肉眼监测光降解过程。
8.一种根据权利要求1-3所述的方法合成的聚磺酸酯在制备均匀的聚合物膜中的应用。
9.根据权利要求8所述的应用,其特征在于,所述聚合物膜用于制备荧光二维图案、多色荧光二维图案、荧光三维图案。
10.一种根据权利要求1-3所述的方法合成的聚磺酸酯在快速选择性杀菌的应用。
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