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1.
RAFT聚合制备结构明确的荧光标识聚甲基丙烯酸甲酯   总被引:1,自引:0,他引:1  
以铁氰化钾为氧化剂,通过N-咔唑二硫代甲酸钠的水相氧化制备了高纯度的中间体二硫化双(N-咔唑硫代甲酰)(DTCD),DTCD以晶体的形式从水中析出,提纯简单,性质稳定.通过DTCD与偶氮二异丁腈(AIBN)或偶氮二氰基戊酸(ACVA)的反应合成了2种性能优异的叔丁腈酯基RAFT试剂,N-咔唑二硫代甲酸异丁腈酯(CYCBD)和N-咔唑二硫代甲酸氰基戊酸(CVCBD),新合成工艺的副反应和杂质被大量减少,最终产物的收率可达80%以上.以CYCBD和CVCBD为可逆加成断裂链转移(RAFT)试剂,研究了它们对甲基丙烯酸甲酯(MMA)RAFT聚合的控制能力,结果表明CYCBD和CVCBD是性能优异的RAFT试剂,可以很好地用于制备结构明确、分子量分布窄的链末端咔唑标记的聚甲基丙烯酸甲酯(CPMMA),由它们所制得的CPMMA的PDI小于1.2.研究结果还表明CYCBD和CVCBD及由其合成的CPMMA在四氢呋喃(THF)溶液中具有显著的荧光特性,CPMMA在358nm处有很强的荧光发射峰,而且,在浓度范围为0.1~20μmol/L的THF溶液中,CPMMA的荧光发射强度与其浓度具有良好的线性关系.通过CYCBD和CVCBD可以方便地制备结构明确且具荧光标识的功能聚合物。  相似文献   

2.
总结了近十年来可逆加成一断裂链转移(RAFT)自由基聚合技术在材料表面改性领域的研究进展。主要介绍了相关的四大类改性途径:(1)物理涂覆RAFT聚合物;(2)从表面接枝聚合(graftingfrom),即在表面自由基和溶液中自由RAFT链转移剂存在下进行表面接枝聚合反应;(3)将聚合物接枝到表面(graftingto)...  相似文献   

3.
将γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPS)接枝到凹凸棒土(AT)表面,制得表面带有可聚合碳碳双键的改性粒子AT-MPS;以二硫代苯甲酸氰基异丙酯(CPDB)为链转移剂,采用可逆加成断裂链转移(RAFT)聚合技术,在AT表面进行甲基丙烯酸甲酯(MMA)接枝聚合.通过红外(FTIR)、热失重(TGA)等方法进行了表征,考察了引发剂以及RAFT链转移剂用量对聚合反应动力学和AT表面接枝聚合接枝率的影响.结果表明,PMMA通过RAFT聚合成功接枝在AT表面;基于RAFT过程的接枝聚合比传统自由基接枝聚合具有更长的反应时间和较高的接枝率.本体系相对适宜条件:温度为70℃,[MMA]/[CPDB]/[AIBN]为400/1/0.5.此条件下聚合反应具有很好的可控性,溶液中的聚合物分子量分布指数为1.2~1.3,AT表面PMMA接枝率为16.33%.引发剂和RAFT链转移剂用量过大均会造成接枝率降低.  相似文献   

4.
As a kind of living free radical polymerizations, reversible addition-fragmentation chain transfer (RAFT) has been proved to be an important technique nowadays as it is applicable to a wide range of monomers at a wide range of temperature below 100oC. In …  相似文献   

5.
可逆加成-断裂链转移聚合(RAFT Polymerization)是目前最为常用的活性可控自由基聚合方法之一,因其产物分子量分布较窄、适用单体范围广、反应条件温和等优势得到了不同领域科学家的广泛应用。然而,科学家们在选择RAFT链转移剂(也称RAFT试剂)时,经常会忽略RAFT链转移剂与单体活性的匹配原则,导致在制备高活单体与低活单体的嵌段共聚物方面存在产物分子量分布宽、聚合速率慢,甚至反应无法成功进行的问题。基于此,本文首先综述聚合中RAFT链转移剂的选用原则,随后介绍近几年开发的一类同时适用于高/低活性单体聚合的通用型RAFT链转移剂(Universal/Switchable RAFT agent)的作用原理及适用条件,并着重探讨了基于通用型RAFT链转移剂制备高/低活性单体的嵌段共聚物的最新进展及应用。  相似文献   

6.
具有RAFT链转移过程听活性自由基聚合的Monte Carlo模拟   总被引:2,自引:0,他引:2  
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7.
将3-(2-二硫代苯甲酸基丙酰氧基)丙基二甲基甲氧基硅烷化学键合于硅片表面.以甲基丙烯酸甲酯和苯乙烯为单体,在硅片表面进行可逆加成-断裂链转移(RAFT)接枝聚合.X-射线光电子能谱仪证实聚甲基丙烯酸甲酯(PMMA)、聚苯乙烯(PS)、苯乙烯/甲基丙烯酸甲酯的共聚物(poly(MMA-co-St))都接枝到硅片表面.但3个体系表现出不同的性质,甲基丙烯酸甲酯的RAFT聚合可控性差,分子量比设计分子量大得多,分子量分布指数宽,接枝密度仅为0·03chains/nm2;苯乙烯均聚合的活性/可控性好、分子量分布窄,接枝密度提高到0·21chains/nm2;共聚合体系综合了两个均聚体系的优点,分子量分布较窄,接枝密度最高为0·31chains/nm2,聚合物膜厚随转化率、数均分子量基本呈线性增长.  相似文献   

8.
吕飞  张薇 《高分子通报》2014,(10):28-33
可逆加成-断裂链转移(reversible addition-fragmentation chain transfer,RAFT)聚合是一种新型的活性/可控自由基聚合方法,在制备窄分子量聚合物和设计聚合物分子结构方面具有独特的优势。本文首先介绍RAFT活性自由基聚合的机理、体系、特点及链转移(RAFT)试剂的选择,然后总结了近年来国内外利用RAFT聚合技术在设计无规和交替共聚物方面的应用,详细介绍了该方法在制备特殊结构共聚物,如嵌段、梯度、接枝、星形、树形和梳形结构聚合物的新应用,并对RAFT聚合技术在今后的研究重点和应用前景做了展望。  相似文献   

9.
可逆加成-断裂链转移(reversible addition-fragmentation chain transfer,RAFT)聚合是一种有效的可控/活性自由基聚合方法,在功能型高分子的制备中有广泛的应用,RAFT聚合的关键就在于选择合适的RAFT链转移剂。基于环保无害的要求,水溶性RAFT链转移剂的制备就至关重要。本文介绍了RAFT聚合的机理,综述了水溶性RAFT链转移剂的制备及应用进展,探讨出RAFT链转移剂水溶性的作用机理,一方面是极性基团的作用,另一方面是离子键氢键等的作用,这对水溶性RAFT链转移剂的制备有一定的启发。大分子RAFT链转移剂分子中常含有亲水基团和疏水基团,具有一定的分散作用,在水相条件下不仅可以通过扩链反应制备窄分子量分布的嵌段共聚物,还可以制备出微纳米凝胶。  相似文献   

10.
采用Z基团为—CH2C6H5的RAFT试剂为链转移剂,AIBN为引发剂,60℃下进行甲基丙烯酸甲酯/丙烯酸丁酯(MMA/BA)的本体RAFT共聚合,并用GPC法测算不同单体组成下低聚物RAFT的链转移常数(Ctr).实验表明,对BA的均聚合,Ctr高达116,但对MMA的均聚合,Ctr约为0.1.在共聚体系中,Ctr与fMMA之间为非线性关系,随着fMMA的增加呈下降趋势.Ctr随单体组成的变化规律可以很好地解释不同单体组成下RAFT共聚合中分子量及其分布随转化率变化的规律.  相似文献   

11.
A series of polymer chemosensors containing naphthalimide signal moiety and imide recognition moiety for the selective detection of fluoride ions (F) were synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization. The polymer chemosensors display obvious absorption and fluorescence variations upon the addition of F, which can be observed by both naked eyes and optical responses. The polymers showed higher fluorescence enhancement than its monomer, and the polymers with higher molecular weight have higher sensitivity than those with lower molecular weight. Other halide anions are found to hardly induce any variation of either the absorption or fluorescence spectra.

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12.
LI  Yongjun  ZHANG  Sen  FENG  Chun  ZHANG  Yaqin  LI  Qingnuan  LI  Wenxin  HUANG  Xiaoyu 《中国化学》2009,27(11):2261-2266
Amphiphilic block copolymers containing hydrophobic perfluorocyclobutyl‐based (PFCB) polyacrylate and hydrophilic poly(ethylene glycol) (PEG) segments were prepared via reversible addition‐fragmentation chain transfer (RAFT) polymerization. The PFCB‐containing acrylate monomer, p‐(2‐(p‐tolyloxy)perfluorocyclobutoxy)‐phenyl acrylate, was first synthesized from commercially available compounds in good yields, and this kind of acrylate monomer can be homopolymerized by free radical polymerization or RAFT polymerization. Kinetic study showed the 2,2′‐azobis(isobutyronitrile) (AIBN) initiated and cumyl dithiobenzoate (CDB) mediated RAFT polymerization was in a living fashion, as suggested by the fact that the number‐average molecular weights (Mn) increased linearly with the conversions of the monomer, while the polydispersity indices kept less than 1.10. The block polymers with narrow molecular weight distributions (Mw/Mn≦1.21) were prepared through RAFT polymerization using PEG monomethyl ether capped with 4‐cyanopentanoic acid dithiobenzoate end group as the macro chain transfer agent (mPEG‐CTA). The length of the hydrophobic segment can be tuned by the feed ratio of the PFCB‐based acrylate monomer and the extending of the polymerization time. The micellization behavior of the block copolymers in aqueous media was investigated by the fluorescence probe technique.  相似文献   

13.
The influence of small C60 additions on thermal and thermal oxidative degradation of polymethyl methacrylate prepared by radical polymerization was studied by differential scanning calorimetry, thermo- gravimetric analysis, differential thermogravimetric analysis, and mass spectrometry.  相似文献   

14.
A new azlactone‐derived trithiocarbonate is prepared and used as a chain‐transfer agent to mediate the reversible addition‐fragmentation chain transfer (RAFT) polymerization of styrene, ethyl acrylate, and N‐isopropyl acrylamide. Well‐defined polymers with controlled molecular weights (M n = 1000–7000 g mol−1) and narrow molecular weight distributions (PDI = 1.05–1.10) are thus obtained that retain the azlactone functionality at the chain end. The ability of the resulting end‐functionalized polymers to react quantitatively at room temperature with a stoichiometric amount of amino groups with retention of the thiocarbonylthio moiety is ascertained by using 4‐fluorobenzylamine and allylamine.  相似文献   

15.
采用等离子体引发的可逆加成-断裂链转移(RAFT)接枝聚合法,以甲基丙烯酸羟乙酯(HEMA)为单体,对聚丙烯(PP)多孔膜表面作了亲水改性.研究了接枝聚合动力学,并以FT-IR、SEM、压汞、水通量等方法研究了改性膜的表面结构形态及孔结构.结果表明,等离子体引发的RAFT接枝聚合速率显著低于普通等离子体引发的接枝聚合速率.表面接枝率随着接枝聚合时间的延长呈线性增长趋势,同时改性膜的孔径和水通量随之减小.  相似文献   

16.
Fractionation data of two poly(methyl methacrylate) samples prepared by suspension polymerization up to limiting conversion, in the presence of different amounts of 1-n-dodecanethiol, indicate that both samples have similar polydispersity factors, although the molecular weight distribution curve for the sample obtained with the highest chain transfer agent concentration is shifted to lower molecular weight values. The results obtained are qualitatively correlated with the high conversion polymerization theory proposed by Cardenas and O'Driscoll.  相似文献   

17.
Summary: Reversible addition fragmentation chain transfer (RAFT) polymerization of pentafluorophenyl methacrylate (PFMA) was carried out in the presence of cumyldithiobenzoate and 4‐cyano‐4‐((thiobenzoyl)sulfanyl)pentanoic acid, respectively. These chain transfer agents with 2,2′‐azoisobutyronitrile (AIBN) as initiator yielded the active ester polymer poly(PFMA) with up to 17 000 g · mol−1 and low polydispersity index ( < 1.2). Kinetic analysis using 19F NMR spectroscopy and gel permeation chromatography (GPC) measurements showed controlled polymerization behavior for both chain transfer agents. Successful preparation of linear diblock copolymers consisting of an active ester block and methyl methacrylate, N‐acryloylmorpholine, or N,N‐diethylacrylamide, respectively, could be demonstrated. These polymers could easily react with amines in a polymer analogous reaction to form multifunctional polymers.

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18.
Coordination binding of polymethyl methacrylate with copper(II) ions was studied by IR spectroscopy and viscometry.  相似文献   

19.
利用自主研发的实时在线监测系统,对不同聚合温度条件下,聚甲基丙烯酸甲酯(PMMA)的本体聚合过程进行实时在线监测,建立"虚拟信号值-反应时间"实时在线监测曲线.通过曲线的变化,可以清晰观察到PMMA本体聚合过程的4个阶段,即诱导期、初期、中期和后期.根据本体聚合"转化率-反应时间"S型曲线的特点,构建"虚拟信号值-反应时间-转化率"关系曲线和聚合物转化率计算公式,并提出PMMA预聚体的预测和实时在线监测方法.方法具有操作简单、实时性强、外界因素影响小和性能稳定等优点,是一种新型的实时在线分析方法.  相似文献   

20.
β-CD存在下MMA细乳液体系的RAFT聚合   总被引:1,自引:2,他引:1  
近年来,活性自由基聚合已成为高分子合成领域中的一个热门课题.Rizzardo研究小组提出了一种新型活性自由基聚合反应,即RAFT(Reversible addition-fragmentation chain transfer)聚合.RAFT反应在传统的自由基聚合中加入了具有高链转移常数和特定结构的链转移剂——双硫酯类化合物.当链转移剂的浓度足够大时,链转移反应由不可逆变为可逆,聚合反应也随之发生质的变化,由不可控  相似文献   

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