活性正离子聚合及原位制备聚醋酸乙烯酯-g-聚四氢呋喃共聚物/纳米银复合材料

通过将烯丙基溴/高氯酸银引发体系引发四氢呋喃活性正离子开环聚合与"grafting onto"合成方法相结合,原位制备了不同接枝密度和接枝链长度的新型聚醋酸乙烯酯-g-聚四氢呋喃接枝共聚物(PVAc-g-PTHF)及其与纳米银(Ag)的复合材料.采用傅里叶变换红外光谱(FTIR)、核磁共振波谱(1H-NMR)和多角度激光光散射-黏度-凝胶渗透色谱仪(MALLS-VIS-GPC)分别表征了该接枝共聚物的化学结构、共聚组成、分子量、分子量分布、接枝支链数目及支化度,采用原子力显微镜(AFM)、示差扫描量热分析(DSC)、偏光显微镜(POM)研究了接枝共聚物中接枝支链数目及支链长度对其微观形态、单端受限链段结晶行为的影响,并探讨了该纳米复合材料的抗菌性能.结果表明:所制备的不同支链数目和支链长度的PVAc-g-PTHF/Ag纳米复合材料,均表现出良好的抗菌性能;接枝共聚物PVAc-g-PTHF的重均分子量可达4.52×10~5,分子分子量较窄(M_w/M_n~1.8),支化因子可达0.19.接枝共聚物PVAc-g-PTHF可形成明显的相分离结构,其微观形态与接枝支链数目有关;相比相同分子量的双端不受限的PTHF链,PVAc-g-PTHF接枝共聚物中单端受限PTHF支链的结晶速率明显降低;在确定接枝支链数目的情况下,随着支链中PTHF链段长度增加,其结晶逐渐增强,结晶熔融温度及熔融焓均稍有增加.     

Nanocrystallization-locked Network of Poly(styrene-b-isobutylene-b-styrene)-g-Polytetrahydrofuran Block Graft Copolymer

Poly(styrene-b-isobutylene-b-styrene) triblock copolymer(SIBS), a kind of thermoplastic elastomer with biocompatibility and biostability containing fully saturated soft segments, could be synthesized via living cationic copolymerization. A novel poly[(styrene-comethylstyrene)-b-isobutylene-b-(styrene-co-methylstyrene)]-g-polytetrahydrofuran(M-SIBS-g-PTHF) block graft copolymer was prepared to increase the polarity and service temperature of SIBS by grafting polar PTHF segments onto SIBS. A series of the above block graft copolymers with average grafting numbers from 2 to 6 and molecular weights of PTHF branches ranging from 200 g·mol~(-1) to 4200 g·mol~(-1) were successfully synthesized via living cationic ring-opening polymerization of tetrahydrofuran(THF) coinitiated by AgClO_4. The introduction of PTHF branches led to an obvious microphase separation due to thermodynamic incompatibility among the three kinds of segments of polyisobutylene(PIB),polystyrene(PS) and PTHF. Moreover, the microphase separation promotes the rearrangement of PTHF branches to form the nanocrystallizationlocked physically cross-linked network after storage at room temperature for 2 months, leading to insolubility of the copolymers even in good solvents. The melting temperature and enthalpy of PTHF nanocrystallization locked in hard domains of M-SIBS-g_5-PTHF~(-1).1 k block graft copolymer increased remarkably up to 153 °C and 117.0 J·g~(-1) by 23 °C and 11.6 J·g~(-1) respectively after storage for long time. Storage modulus(G')is higher than loss modulus(G') of M-SIBS-g-PTHF block graft copolymer at temperatures ranging from 100 °C to 180 °C, which is much higher than those of the SIBS triblock copolymer. To the best of our knowledge, this is the first example of high performance M-SIBS-g-PTHF block graft copolymers containing segments of PIB, PS and PTHF with nanocrystallization-locked architecture.     

官能化聚四氢呋喃-b-聚异丁烯-b-聚四氢呋喃三嵌段共聚物的合成与性能

采用2-氯-2,4,4-三甲基戊烷或对二枯基氯为引发剂和TiCl4或FeCl3为共引发剂,引发异丁烯(IB)可控/活性正离子聚合与官能端基转化,设计合成不同分子量及窄分子量分布的端基官能化聚异丁烯,如双端烯丙基溴官能化聚异丁烯(Br-PIB-Br)或双端烯丙基胺官能化聚异丁烯(H2N-PIB-NH2).采用烯丙基溴/高氯酸银体系引发四氢呋喃(THF)开环聚合,合成聚四氢呋喃活性链(PTHF+).进一步通过将IB可控/活性正离子聚合与THF可控/活性正离子开环聚合2种方法相结合,设计合成2种新型官能化聚四氢呋喃-b-聚异丁烯-b-聚四氢呋喃(PTHF-b-PIB-b-PTHF)三嵌段共聚物:(1)以上述Br-PIB-Br为大分子引发剂,在AgClO4作用下引发THF活性正离子开环聚合,采用水终止活性链端,设计合成双端为羟基的HO-PTHF-b-PIB-b-PTHF-OH三嵌段共聚物(简称:FIBF-OH);(2)以上述合成的PTHF+活性链与H2NPIB-NH2链端胺基发生高效亲核取代反应,设计合成中间链段连接点含―NH―官能基团的PTHF-b-HNPIB-NH-b-PTHF三嵌段共聚物(简称:FIBF-NH).在上述三嵌段共聚物中,极性PTHF链段与非极性PIB链段的热力学不相容,导致其呈现明显的微相分离,且微观形态与共聚组成相关.PTHF均聚物易结晶,在上述共聚物中由于PTHF链段单端受限致其结晶性减弱.三嵌段共聚物分子链的中间连接点含―NH―官能基团,具有更强的氢键作用,促进PTHF链段重排并结晶,易形成更紧密的超分子网络结构,导致即使在PTHF链段相对分子量为0.7 kg·mol^-1时仍具有较强的结晶性,且结晶熔融温度明显提高.此外,由于FIBF-NH中形成超分子网络结构,使材料具有优异的自修复性能,材料表面的切痕在常温下10 min后可以完全自愈合.本文设计合成的新型官能化PTHF-b-PIB-b-PTHF三嵌段共聚物兼具有PTHF与PIB的优良性能,在生物医用、智能修复等功能材料领域具有潜在的应用前景.     

Grafting on polybutadiene with polytetrahydrofuran macroperoxyinitiators. Postpolymerization studies

Grafting reactions of polybutadiene with macro peroxy initiators and postpolymerization were studied. The cationic polymerization of tetrahydrofuran (THF) initiated by the cationic species derived from bis-(4-bromomethylbenzoyl) peroxide (BBP) or bis-(3,5-dibromomethylbenzoyl) peroxide (BDBP) gave the PTHF macroperoxy initiator (MPI). PTHF-b-PMMA macroperoxy initiator (MPIb) was also obtained by the redox polymerization of methyl methacrylate initiated with the hydroxyl ends of PTHF and Ce(IV) salts without decomposing the peroxide groups in the middle. Macroperoxy initiators thermally grafted on cis-polybutadiene (PBD) with thermal curing to yield graft copolymers containing crosslinked and soluble parts, which were separated by the sol-gel analysis. FTIR spectra of the crosslinked samples indicated the characteristic signals of the PTHF, PBD and PMMA blocks. The crosslinked copolymers decomposed at around 470 °C. Postpolymerization of the crosslinked products indicated the increase in crosslinking density which has been followed by measuring the gradual increase of swelling values. Postpolymerization crosslinking was estimated as a first order reaction rate.     

Synthesis of novel tetrahydrofuran‐epichlorohydrin [poly(THF‐b‐ECH)] macromonomeric peroxy initiators by cationic copolymerization and the quantum chemically investigation of initiation system effects

Cationic polymerization of tetrahydrofuran (THF) and epichlorohydrin (ECH) was performed with peroxy initiators synthesized from bis (4,4′‐bromomethyl benzoyl peroxide (BBP) or bromomethyl benzoyl t‐butyl peroxy ester (t‐BuBP) and AgSbF₆ or ZnCl₂ system at 0 °C to obtain the poly(THF‐b‐ECH) macromonomeric peroxy initiators. Kinetic studies were accomplished for poly(THF‐b‐ECH) initiators. Poly(THF‐b‐ECH‐b‐MMA) and poly(THF‐b‐ECH‐b‐S) block copolymers were synthesized by bulk polymerization of methyl methacrylate (MMA) and styrene (S) with poly(THF‐b‐ECH) initiators. The quantum chemical calculations for the block copolymers, the initiating systems of the cationic polymerization of THF and ECH were achieved using HYPERCHEM 7.5 program. The optimized geometries of the polymers were investigated with the quantum chemical calculations. Poly(THF‐b‐ECH) initiators having peroxygen groups were used for graft copolymerization of polybutadien (PBd) to obtain poly(THF‐b‐ECH‐g‐PBd) crosslinked graft copolymers. The graft copolymers were investigated by sol‐gel analysis. Swelling ratio values of the graft copolymers in CHCl₃ were calculated. The characterizations of the polymers were achieved by FTIR, ¹H NMR, GPC, SEM, TEM, and DSC techniques. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2896–2909, 2010     

Synthesis of poly(tetrahydrofuran)‐b‐polystyrene block copolymers from dual initiators for cationic ring‐opening polymerization and atom transfer radical polymerization

A dual initiator (4‐hydroxy‐butyl‐2‐bromoisobutyrate), that is, a molecule containing two functional groups capable of initiating two polymerizations occurring by different mechanisms, has been prepared. It has been used for the sequential two‐step synthesis of well‐defined block copolymers of polystyrene (PS) and poly(tetrahydrofuran) (PTHF) by atom transfer radical polymerization (ATRP) and cationic ring‐opening polymerization (CROP). This dual initiator contains a bromoisobutyrate group, which is an efficient initiator for the ATRP of styrene in combination with the Cu(0)/Cu(II)/N,N,N′,N″,N″‐pentamethyldiethylenetriamine catalyst system. In this way, PS with hydroxyl groups (PS‐OH) is formed. The in situ reaction of the hydroxyl groups originating from the dual initiator with trifluoromethane sulfonic anhydride gives a triflate ester initiating group for the CROP of tetrahydrofuran (THF), leading to PTHF with a tertiary bromide end group (PTHF‐Br). PS‐OH and PTHF‐Br homopolymers have been applied as macroinitiators for the CROP of THF and the ATRP of styrene, respectively. PS‐OH, used as a macroinitiator, results in a mixture of the block copolymer and remaining macroinitiator. With PTHF‐Br as a macroinitiator for the ATRP of styrene, well‐defined PTHF‐b‐PS block copolymers can be prepared. The efficiency of PS‐OH or PTHF‐Br as a macroinitiator has been investigated with matrix‐assisted laser desorption/ionization time‐of‐flight spectroscopy, gel permeation chromatography, and NMR. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3206–3217, 2003     

Synthesis of Well-defined Poly(tetrahydrofuran)-b-Poly(α-amino acid)s via Cationic Ring-opening Polymerization(ROP) of Tetrahydrofuran and Nucleophilic ROP of N-thiocarboxyanhydrides

The synthesis of block copolymers of poly(tetrahydrofuran)-b-poly(α-amino acid)(PTHF-b-PAA) is challenging since it is difficult to combine the two blocks produced via different/conflicting ring-opening polymerization(ROP) mechanisms. In this contribution, the cationic ROP of THF is catalyzed by rare-earth triflate [RE(OTf)_3] and terminated by 2-(t-butyloxycarbonyl-amino) ethanol(BAE). After the deprotection of tbutyloxycarbonyl(Boc) group, the chain end of PTHF is quantitatively changed to amino group which thereafter initiates the nucleophilic ROP ofα-amino acid N-thiocarboxyanhydrides(NTAs). Both polymerizations are well controlled, generating PTHF and PAA segments with designable molecular weights(MWs). PTHF-b-polylysine(PTHF-b-PLys) and PTHF-b-polysarcosine(PTHF-b-PSar) are obtained with MWs between 8.6 and28.7 kg/mol. The above amphiphilic diblock copolymers form micelles in water. PTHF_(40)-b-PSar_(32) acts as a surfactant to stabilize oil-in-water emulsions. Both segments of PTHF-b-PAA are biocompatible and promising in the biomedical application.     

原子转移自由基聚合及可控自由基聚合

以作者在原子转移自由基聚合领域的研究成果为主导,结合国内外文献,对近年来出现的颇具影响的可控自由基聚合体系与进行了评述与展望。     

Synthesis of comb‐shaped poly(methyl methacrylate)‐b‐poly(polytetrahydrofuran acrylate) under 60Co γ‐ray irradiation

Comb‐shaped graft copolymers with poly(methyl methacrylate) as a handle were synthesized by the macromonomer technique in two steps. First, polytetrahydrofuran acrylate (A‐PTHF), prepared by the living cationic ring‐opening polymerization of tetrahydrofuran, underwent homopolymerization with 1‐(ethoxycarbonyl)prop‐1‐yl dithiobenzoate as an initiator under ⁶⁰Co γ irradiation at room temperature; Second, the handle of the comb‐shaped copolymers was prepared by the block copolymerization of methyl methacrylate with P(A‐PTHF) as a macroinitiator under ⁶⁰Co γ irradiation. The two‐step polymerizations were proved to be controlled with the following evidence: the straight line of ln[M]₀/[M] versus the polymerization time, the linear increase in the number‐average molecular weight with the conversion, and the relatively narrow molecular weight distribution. The structures of the P(A‐PTHF) and final comb‐shaped copolymers were characterized by ¹H NMR spectroscopy and gel permeation chromatography. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3367–3378, 2002     

聚氯乙烯-g-聚甲基丙烯酸-2-羟乙酯共聚物的合成和表征

聚氯乙烯 (ＰＶＣ)是常用医用高分子材料之一 ,可以制作储血袋、导液管、人工尿道等 .ＰＶＣ亲水性差 ,影响其生物相容性 .采用亲水性单体与ＰＶＣ接枝共聚是提高ＰＶＣ亲水性的重要方法[1] .Ｋｒｉｓｈｎａｎ等[2 ] 对Ｃｏ60 辐照下ＰＶＣ接枝Ｎ 乙烯基吡咯烷酮进行了研究 .Ｓｉｎｇｈ等[3～ 5] 采用辐照引发甲基丙烯酸在ＰＶＣ薄膜的接枝反应 ,对接枝动力学、接枝后薄膜表面形态、溶胀和抗凝血性等进行了研究 .Ｇｏｌｄｂｅｒｇ等[6] 采用辐照引发甲基丙烯酸2 羟乙酯 (ＨＥＭＡ)在ＰＶＣ薄膜上的接枝 .Ｌｅｅ等[7]采用溶液接枝共聚制备了…     

Copper(II) [(4-methylphenyl)sulfonyl]-1H-imino-(2-phenyl-2-oxazoline) complexes

Neutral copper complexes of the deprotonated [(4-methylphenyl)sulfonyl]-1H-imino-(2-phenyl-2-oxazoline) proligands, [HTs-ROz], R = H, 5-Me, 4-Me, 4-Et, 4-ⁱPr, have been prepared by electrochemical oxidation of anodic copper in an MeCN solution of the corresponding proligand. The [Cu(Ts-ROz)₂] complexes were characterised by microanalysis, i.r. and electronic spectroscopies, and by e.p.r. and magnetic measurements. The crystal structures of HTs-5MeOz, [Cu(Ts-Oz)₂], [Cu(Ts-5MeOz)₂] and [Cu(Ts-4MeOz)₂] were determined by X-ray diffraction.     

Synthesis of block copolymers by the transformation of cationic polymerization into reversible atom transfer radical polymerization

Azo-containing polytetrahydrofuran (PTHF) obtained by cationic polymerization was used as a macroinitiator in the reverse atom transfer radical polymerization (RATRP) of styrene and methyl acrylate in conjunction with CuCl₂/2,2′-bipyridine as a catalyst. Diblock PTHF–polystyrene and PTHF–poly(methyl acrylate) were obtained after a two-step process. In the first step of the reaction, stable chlorine-end-capped PTHF was formed with the thermolysis of azo-linked PTHF at 65–70 °C in the presence of the catalyst. Heating the system at temperatures of 100–110 °C started the polymerization of the second monomer, which resulted in the formation of block copolymers. The decomposition behavior of the azo-linked PTHF and the structure of the block copolymers were determined by ¹H NMR and gel permeation chromatography (GPC). Kinetic studies and GPC analyses further confirmed the controlled/living nature of the RATRP initiated by the polymeric radicals. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2199–2208, 2002     

Synthesis and block‐specific complexation of poly(ethylene oxide)–poly(tetrahydrofuran)–poly(ethylene oxide) triblock copolymers

Well‐defined ABA triblock copolymers in which A stands for poly(ethylene oxide) (PEO) and B for poly(tetrahydrofuran) (PTHF) were synthesized by end‐capping bifunctionally living PTHF with different polyethylene glycol–monomethylethers. Differential scanning calorimetry analysis of these copolymers showed two melting points: one around 55 °C due to the PEO blocks, and one around 30 °C due to the PTHF segments, demonstrating that these block copolymers show extensive phase separation. Upon addition of sodium thiocyanate, crystalline complexes with PEO were formed and as a consequence, the melting points of the PEO segments had shifted to approximately 170 °C, whereas the melting points of the PTHF segments decreased slightly. The obtained materials behave as thermoplastic elastomers up to 160–175 °C. The influence of the relative lengths of the PEO and the PTHF segments on the thermal and mechanical properties of the materials have been investigated. Copyright © 1999 John Wiley & Sons, Ltd.     

Polybutadiene Modification: Reactions of Halogen-Containing Polybutadienes with Organolithium Compounds

Polybutadiene (PB) can be easily halogenated by reaction with iodine chloride or bromine in tetrahydrofuran. The resulting glassy polymers were reacted with n-butyllithium, sec-butyl-lithium, and polystyryllithium in THF. Iodochlorinated PB gave a polybutadiene with a different cis/trans ratio with n-BuLi. The reformation of PB was accompanied by partial crosslinking. The reaction probably involved a halogen-metal exchange followed by intra- and intermolecular elimination of Li halide. With brominated PB, both coupling and elimination took place. With sec-BuLi, an allylic iodine derivative was obtained from iodochlorinated PB, probably by dehydrochlorination. The iodinated intermediate can easily undergo a coupling reaction with further sec-BuLi. Both iodochlorinated and brominated polybutadienes gave graft copolymers by reaction with polystyryllithium in THF. Grafting was always accompanied by gel formation.     

Novel poly(l‐lactide)/poly(d‐lactide)/poly(tetrahydrofuran) multiblock copolymers with a controlled architecture: Synthesis and characterization

Novel poly(l ‐lactide) (PLLA)/poly(d ‐lactide) (PDLA)/poly(tetrahydrofuran) (PTHF) multiblock copolymers with designed molecular structure were synthesized by a two‐stage procedure. Well‐defined PDLA‐PLLA‐PTHF‐PLLA‐PDLA pentablock copolymers were prepared by sequential ring opening polymerization of l ‐ and d ‐lactides starting from PTHF glycol, with the length of the (equimolar) PLLA and PDLA blocks being varied. Then, these dihydroxyl‐terminated pentamers were transformed into multiblock copolymers by melt chain‐extension with hexamethylene diisocyanate–being the first time that the coupling of pentablock units is reported. The successful formation of macromolecular chains with a multiblock and well‐defined architecture was demonstrated by ¹H NMR spectroscopy. The thermal properties and structuring of the resulting materials were investigated by means of DSC and WAXD measurements and DMA analysis. Stereocomplexation was found to be promoted during solution and melt crystallization. This approach affords materials combining the high rigidity and strength (other than improved thermal resistance) of the hard stereocomplex crystallites with the flexibility imparted by the soft block, whereby their properties can be finely tailored through the composition of the basic pentablock units without limitations on the final molecular weight. The adopted reaction conditions make this process highly appealing in view of the possibility to perform it in extruder. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3269–3282     

Controlled grafting of ethyl cellulose with azobenzene‐containing polymethacrylates via atom transfer radical polymerization

Graft copolymers of ethyl cellulose with azobenzene‐containing polymethacrylates were synthesized through atom transfer radical polymerization (ATRP). The residual hydroxyl groups on ethyl cellulose were first esterified with 2‐bromoisobutyryl bromide to yield 2‐bromoisobutyryloxy groups, which was then used to initiate the polymerization of 6‐[4‐(4‐methoxyphenylazo)phenoxy]hexyl methacrylate (MMAzo) in the presence of CuBr/N,N,N′,N″,N″‐pentamethylenetriamine (PMDETA) as catalyst and anisole as solvent. The graft copolymers were characterized by gel permeation chromatography (GPC) and ¹H‐NMR. The molecular weights of the graft copolymers increased relatively to the macroinitiator, and the polydispersities were narrow. The thermal and liquid crystalline property of the graft copolymers were investigated by differential scanning calorimeter (DSC) and polarizing optical microscope (POM). Photoresponsive property was studied under the irradiation of UV–vis light in THF solution. The graft copolymers have potential applications, including sensors and optical materials. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1653–1660, 2007     

四氢呋喃开环均聚以及四氢呋喃和环硫氯丙烷共聚新催化体系

研究发现无水稀土氯化物 ５０％发烟硫酸体系是四氢呋喃（ＴＨＦ）均聚和四氢呋喃与环硫氯丙烷（ＣＭＴ）共聚合的优良新催化体系．考察了ＴＨＦ均聚反应特征，在合适条件下，ＴＨＦ聚合以６５％转化率制得粘均分子量达１０，０００～１５，０００的白色聚四氢呋喃（ＰＴＨＦ）固体．端羟基分析法测得聚合物的分子链两端均为羟基．考察了影响ＴＨＦ ＣＭＴ共聚合反应诸因素，如聚合温度和时间、两单体的比例等，制得数均分子量为１，０００左右的淡黄色粘性固体共聚物．     

Controlled grafting of acetylated starch by atom transfer radical polymerization of MMA

Graft copolymers of acetylated starch oligomer (AS) and poly(methyl methacrylate) (PMMA) were polymerized by atom transfer radical polymerization (ATRP). AS was converted to an ATRP macroinitiator by converting a part of the hydroxyl groups of AS to 2-bromoisobutyryl groups. Macroinitiators with varying degrees of substitution for the 2-bromoisobutyryl group were prepared. The polymerizations were conducted using CuBr/BiPy catalyst system, either in bulk or in 1:1 v/v THF solution. They proceeded with first-order kinetics and the molecular weights of the polymers increased linearly with conversion. Graft copolymers with different graft densities and graft lengths were prepared in a controlled manner. The hydrophobicity of these copolymers was studied by contact angle measurements.     

聚谷氨酸苄酯-g-(聚四氢呋喃-b-聚异丁烯)共聚物的微观结构与形态

通过可控/活性离子聚合方法设计合成一系列不同共聚组成的聚谷氨酸苄酯-g-(聚四氢呋喃-b-聚异丁烯)的新型嵌段接枝共聚物,即PBLG-g-(PTHF-b-PIB),研究共聚物中支链(PTHF-b-PIB)长度及接枝密度对主链PBLG玻璃化转变温度、α-螺旋二级结构及其转变的影响,研究支链中PTHF链段长度对其双端受限的玻璃化转变及凝聚态结构的影响.结果表明:PBLG-g-(PTHF-b-PIB)共聚物中刚性主链保持α-螺旋二级结构;随着支链长度增加或接枝密度增加,主链PBLG的α-螺旋二级结构特征峰逐渐减弱,玻璃化转变温度逐渐提高,α-螺旋结构发生转变的焓值逐渐增大;在确定接枝密度的情况下,随着支链中PTHF链段长度增加,共聚物中双端受限的PTHF链段结晶逐渐增强,结晶熔融温度及熔融焓均增加;在确定支链中PTHF链段长度的情况下,随着接枝密度增大,支链间链段相互排斥,PTHF链段结晶逐渐减弱.     

三苯基吡啶-芴交替共轭聚合物的合成与光致发光性能研究

通过Suzuki偶合反应得到了两种间位连接的三苯基吡啶同分异构体和9,9-二辛基芴的交替共聚物PFOTPP1和PFOTPP2.并对它们的紫外-可见吸收光谱、光致发光光谱以及电化学性能等进行了初步研究.结果表明,将间位连接的三苯基吡啶基引入聚芴主链能使聚合物的LUMO能级降低,光致发光光谱发生蓝移,得到了两种有望应用于电致炼光发光器件的共轭聚合物蓝光发光材料.