超支化聚(胺酯)的分子设计及其制备

以丙烯酸甲酯和二乙醇胺为原料由Michael加成反应制得N ,N 二羟乙基 3 胺基丙酸甲酯单体 ,再用“准一步法”和“发散法”使之与 1 ,1 ,1 三羟甲基丙烷 (核 )反应合成一种新型超支化聚 (胺 酯 ) .以核磁共振和元素分析方法对N ,N 二羟乙基 3 胺基丙酸甲酯单体的分子结构进行了表征 .GPC测定表明合成的超支化聚 (胺 酯 )分子量分布窄 ,具有单分散性 ;粘度小于同分子量的线形分子 ;耐热性能较好 ,失重温度高于2 0 0℃ .     

氟取代聚芳醚酮低温合成及其结构研究

通过傅克酰基化反应合成4,4'-二(4-氟苯甲酰基)二苯醚、4,4'-二(五氟苯甲酰基)二苯醚、4,4'-二(4-氟苯甲酰基)二苯硫醚以及4,4'-二(五氟苯甲酰基)二苯醚4种长链双卤单体,并进一步制备了含二氮杂萘酮聚芳醚酮聚合物.通过多氟取代双卤单体在含二氮杂萘酮聚芳醚酮聚合物主链中引入氟原子.多氟取代双卤单体具有多...     

Synthesis and characterization of the B3-monomer and hyperbranched poly(aryl ether ketone)s

Hyperbranched poly(aryl ether ketone)s were prepared by polymerization of hydroquinone (A₂) and 1,3,5-tris[4-(4-fluorobenzoyl)phenoxy]benzene (B₃). The gelation of hyperbranched poly(aryl ether ketone)s was effectively avoided. Hydroxyl-term inated (HPAEK-OH) and fluoro-terminated (HPAEK-F) hyperbranched poly(aryl ether ketone)s were prepared by using different A₂/B₃ mass ratio. The structure of the B₃ monomer was confirmed by MS, ¹H NMR/IR. The glass transition temperatures of the HPAEK-F and HPAEK-OH are 114°C and 162°C respectively. Thermal stability of HPAEK-F is higher than HPAEK-OH. __________ Translated from Acta Scientianum Naturalium Universitatis Jilinensis, 2005, 5 (in Chinese)     

超支化聚(β-环糊精)的合成与表征

通过硅氢加成反应, 以ABx型功能化β-环糊精大单体为原料, 采用一步法合成出新型超支化聚(β-环糊精)高分子. ABx大单体由单取代对甲苯磺酰化β-CD依次与烯丙基胺、1,1,3,3-四甲基二硅氧烷(含氢双封头)及丙烯酰氯反应得到. 采用1H NMR, 13C NMR, 29Si NMR和飞行时间质谱对ABx大单体及其聚合物的结构进行了表征. 利用凝胶渗透色谱/多角度激光光散射(SEC/MALLS)联用仪得到了超支化聚(β-环糊精)的分子量、分子量分布及本体黏度.     

Synthesis of multiblock hyperbranched‐linear poly(ether sulfone) copolymers

Hyperbranched poly(ether sulfone) was prepared in the presence of an oligomeric linear poly(ether sulfone) to generate multiblock hyperbranched‐linear (LxHB) copolymers. The LxHB copolymers were prepared in a two‐step, one‐pot synthesis by first polymerizing AB monomer to generate a linear block of a desired molecular weight followed by addition of the AB₂ monomer in a large excess (19:1, AB₂:AB) to generate the hyperbranched block. NMR integration analysis indicates that AB₂:AB ratio is independent of the reaction time. Because the molecular weight still increases with reaction time, these results suggest that polymer growth continues after consumption of monomer by condensation into a multiblock architecture. The LxHB poly(ether sulfone)s have better thermal stability (10% mass loss > 343 vs. 317 °C) and lower T_g (200 vs. > 250 °C) than the hyperbranched homopolymer, higher T_g than the linear homopolymer (<154 °C), while little difference in the solubility character was observed between the two polymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4785–4793, 2008     

Synthesis of backbone thermo and pH dual‐responsive hyperbranched poly(amine‐ether)s through proton‐transfer polymerization

Stimuli‐responsive hyperbranched polymers have attracted great attention in recent years because of their wide applications in biomedicine. Through proton‐transfer polymerization of triethanolamine and 1,2,7,8‐diepoxyoctane with the help of potassium hydride, a series of novel backbone thermo and pH dual‐responsive hyperbranched poly(amine‐ether)s were prepared successfully in one‐pot. The degrees of branching of the resulting polymers were at 0.40–0.49. Turbidity measurements revealed that hyperbranched poly(amine‐ether)s exhibited thermo and pH dual‐responsive properties in water. Importantly, these responsivities could be readily adjusted by changing the polymer composition as well as the polymer concentration in aqueous solution. Moreover, in vitro evaluation demonstrated that hyperbranched poly(amine‐ether)s showed low cytotoxicity and efficient cell internalization against NIH 3T3 cell lines. These results suggest that these backbone thermo and pH dual‐responsive hyperbranched poly(amine‐ether)s are promising materials for biomedicine. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

由聚丙二醇二缩水甘油醚和甘油制备温敏性超支化聚合物

由聚丙二醇二缩水甘油醚和甘油通过质子转移聚合(proton transfer polymerization)一步法制备了端羟基的温敏性超支化聚醚.聚合产物的分子量(Mn)在1.76×104~2.43×104之间,玻璃化转变温度(Tg)在-31.5~-26.7℃之间,热分解温度(Td)在367~376℃之间.通过控制聚丙二醇二缩水甘油醚和甘油的投料比,实现了对温敏性超支化聚醚最低临界溶解温度(LCST)的调节,LCST可控制在28.3~39.6℃之间.     

Synthesis and characterization of new semifluorinated linear and hyperbranched poly(arylene ether phosphine oxide)s through B2 + A2 and AB2 approaches

A new phosphorus containing trifluoromethyl-activated bisfluoro B₂ monomer has been synthesized successfully by coupling reaction of 4-methoxyphenylphosphonic dichloride and the Grignard salt of 5-bromo-2-fluorobenzotrifluoride. This monomer was converted to linear poly(arylene ether phosphine oxide)s by nucleophilic displacement of the fluorine atom on the benzene ring with several diphenols. The B₂ monomer was further demethylated to form an AB₂ monomer which on self condensation yielded hyperbranched poly(arylene ether phosphine oxide) with identical phosphorous containing moiety. The products obtained exhibit weight-average molecular weights as high as 600,000 g mol⁻¹ in SEC. These linear and hyperbranched poly(arylene ether phosphine oxide)s showed thermal stability as high as 516 °C for 10% weight loss in TGA in nitrogen and showed glass transition temperatures up to 253 °C in DSC. All the polymers were soluble in a wide range of organic solvents, e.g., CHCl₃, THF, NMP and DMF, however, the hb sample showed a significant lower solution viscosity compared to linear samples of similar molar mass. Transparent thin films of linear poly(arylene ether phosphine oxide)s casted from dichloromethane exhibited tensile strengths up to 50 MPa, a modulus of elasticity up to 0.95 GPa and elongation at break up to 36% depending on their exact repeating unit structures. No free standing films could be prepared from the hb analogue due to the missing entanglements, but stable thin polymer films on silicon wafers with high hydrophobicity were formed which showed water contact angles as high as 91°.     

超支化聚(胺酯)的合成及其光固化性能研究

采用甲基丙烯酸酐直接改性和先以丁二酸酐或邻苯二甲酸酐酯化再以甲基丙烯酸缩水甘油酯改性所得到的甲基丙烯酸酯化超支化聚 (胺 酯 )齐聚物在光引发剂存在时紫外光辐照下发生快速聚合反应 ;反应速率和双键转化率随超支化分子的结构不同而变化 ;高度交联的涂膜具有较好的热学性能     

pH and thermo responsive aliphatic tertiary amine chromophore hyperbranched poly(amino ether ester)s from oxa-Michael addition polymerization

In this research, we developed a novel and facile strategy to prepare aliphatic tertiary amine chromophore hyperbranched poly(amino ether ester)s with pH and thermo responsiveness via phosphazene base (t-BuP₂) catalyzed oxa-Michael addition polymerization of triethanolamine with ethylene glycol diacrylate at room temperature. UV–vis and fluorescence analyses results showed that the tertiary amine at branching point for hyperbranched poly(amino ether ester)s is very important to retain strong blue fluorescence of tertiary amine chromophore. Moreover, the hyperbranched poly(amino ether ester)s exhibit an aggregation caused quenching (ACQ) fluorescence, solvent induced red-shifted emission, molecular weight, and temperature dependent emission characters. More interestingly, the hyperbranched poly(amino ether ester)s show extreme acid induced quenching fluorescence phenomenon, and also display good water solubility, specific recognition of Fe³⁺ ion, low cytotoxicity, and bright cell imaging, which could serve as a microenvironment-responding fluorescent probe for application in chemical sensing, cell imaging, drug delivery, or disease diagnostics. This research provides a versatile method for the preparation of stimuli-responsive aliphatic tertiary amine chromophore polymers, and supplies ideas for researchers to explore other unconventional fluorescent polymers for application.     

新型含萘含氟聚芳醚酮的合成与表征

聚芳醚酮是一类具有独特的耐热性、耐疲劳性、耐辐射性、化学稳定性和介电性等诸多优异性能的工程塑料,广泛应用于航天、军事、电子、信息、核能和精密仪器等领域中．氟元素的引入可以降低材料的介电常数、折光率和吸水率,增加材料透明度,因此这类聚合物在光电子、光学和微电子等应用领域的研究备受关注．     

Synthesis and Characterization of a Novel Poly(aryl ether) Containing 4-Chloro-2,5-diphenyloxazole

4-Chloro-2,5-bis(4-fluorophenyl)oxazole monomer has successfully been synthesized using cyclization reaction of 4-fluorobenzoyl cyanide with 4-fluorobenzaldehyde. This monomer was converted to poly(aryl ether)s by nucleophilic substitution of the fluorine atoms on the benzene rings of oxazole monomer with bisphenol A. The influence of the reaction time on the molecular weight had been investigated. The polymers were identified by FT-IR,¹H-NMR and TGA. The products exhibited weight-average molar masses up to 2.81 x 10⁴g mol⁻¹ in GPC. These poly(aryl ether)s showed very high thermal stability up to 363 °C for 5 % weight loss in TGA under N₂.     

Synthesis and properties of hyperbranched poly(ether sulfone)s prepared by self‐polycondensation of novel AB2 monomer

Hyperbranched poly(ether sulfone)s were prepared by the self‐polycondensation of the novel AB₂ monomer, 4‐(3,5‐hydroxyphenoxy)‐4′‐fluorodiphenylsulfone. The high‐molecular‐weight polymers were isolated in good yields. The degree of branching (DB) of the resulting polymers was investigated by the preparation of dendritic and linear model compounds. The DB determined by gated decoupling ¹³C NMR measurements was in the range 0.17–0.41 and was dependent on the base used for the self‐polycondensation. It was found that cesium fluoride was an effective base to form the polymer having the DB of 0.41. The resulting hyperbranched poly(ether sulfone)s showed good solubility in organic solvents. The solubility and the glass transition temperature of the polymers were influenced by the terminal functional groups. The unique thermal crosslinking phenomenon was observed during the DSC measurements of the hydroxyl‐terminated hyperbranched poly(ether sulfone) under air condition. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Reduction‐cleavable hyperbranched polymers with limited intramolecular cyclization via click chemistry

In this contribution, we present new reduction‐cleavable hyperbranched disulfide bonds‐containing poly(ester triazole)s with limited intramolecular cyclization, which can be synthesized by the Cu(I)‐catalyzed azide–alkyne cycloaddition (CuAAC) of A₂ monomer of dipropargyl 3,3′‐dithiobispropionate and B₃ monomer of tris(hydroxymethyl)ethane tri(4‐azidobutanoate). The hyperbranched poly(ester triazole)s possess numerous terminal groups and weight‐average molecular weight up to 20,400 g mol^?1 with a polydispersity index in the range 1.57–2.17. The CuAAC introduces rigid triazole units into the backbones of hyperbranched poly(ester triazole)s and reduces intramolecular cyclization, which is proved by topological analysis and ¹H NMR spectroscopy. The disulfide bonds on backbones endow the reduction‐cleavable feature to the hyperbranched poly(ester triazole)s at the presence of dithiothreitol. It gives a novel and convenient methodology for the synthesis of reduction‐responsive functional polymer with controlled topologies, and the reduction‐cleavable hyperbranched poly(ester triazole)s with limited intramolecular cyclization are expected to possess potential in the application of stimuli‐responsive anticancer drug nanocarriers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2374–2380     

Polyaryläther-Kondensationsprodukte des 4,4′-bis(chloromethylphenyl) äthers mit manchen diphenolen

Poly(aryl ethers) as products of the polycondensation of 4,4′-bis(chloromethylphenyl) ether with sodium salts of various phenols have been prepared in the Williamson reaction. The reaction was carried out at three different temperatures (78, 140, and 185°C.) in ethanol, xylene, and tetralin, respectively. The effect of the polycondensation and the nature and composition of initial components on the properties of the products has been studied. The molecular weights and the melting temperature of the synthesized resins increased with increasing reaction temperature. The structure and molecular weight have a pronounced effect on the properties of the resins. Resins prepared from 4,4′-dihydroxydinaphthyl had the highest melting temperature and were practically insoluble, while the resins prepared from 2,2′-dihydroxydinaphthlmethane had the lowest melting temperature and were soluble in practically all organic solvents. On the basis of the experimental data a reaction scheme appropriate for the synthesis of poly(aryl ethers) from the phenolates as well as from the free phenols in the presence of NaOH has been proposed. Some thermal and mechanical properties of poly(aryl ethers) have been determined. Thermal treatment of the resins above theri softening temperature resulted in an elevated softening point too. This is explained by the supplementary condensation of both chlorine or hydroxyl endgroups in the molten resins.     

Preparation of polyvinylpyrrodione microspheres by dispersion polymerization

The preparation of polyvinylpyrrolidone (PVP) microspheres in ethyl acetate by dispersion polymerization with N-vinylpyrrolidone (NVP) as initial monomer, poly(N-vinylpyrrolidone-co-vinyl acetate) (P (NVP-co-VAc)) as dispersant, and 2, 2′-azobisisobutyronitrile(AIBN) as initiator is reported. The influences of monomer concentration, dispersant concentration and initiator concentration on the size of PVP microspheres as well as the monomer conversion were studied. The structure and properties of PVP microspheres were analyzed. The results show that the prepared PVP microspheres have a mean diameter of 3-4 μm. With an increase in NVP concentration, the size and the molecular weight of the PVP microspheres as well as the monomer conversion all increase. With increasing P(NVP-co-VAc) concentrations, the PVP molecular weight and monomer conversion both increase while the size of the microspheres becomes smaller. As the concentration of AIBN increases, the microsphere size and monomer conversion increase whereas the PVP molecular weight decreases. The PVP prepared by dispersion polymerization has a crystal structure, and its molecular weight is lower compared to that prepared by solution polymerization. __________ Translated from Acta Polymerica Sinica, 2007, 11 (in Chinese)     

Synthesis and characterization of water‐soluble hyperbranched poly(ester amine)s from diacrylates and diamines

Various water‐soluble hyperbranched poly(ester amine)s were synthesized by the direct polyaddition of diamines to diacrylates in the absence of a catalyst. Each diamine contained a secondary amino group and a primary amino group such as 1‐(2‐aminoethyl)piperazine, N‐methyl‐1,3‐propanediamine, or N‐ethylethylenediamine. When the ratio of diacrylate to diamine was 1/1, no gelation was observed throughout the polymerization. When the ratio of diacrylate to diamine was 3/2, no crosslinking occurred in the diluted solution, whereas an insoluble network formed in the concentrated solution. Fourier transform infrared and mass spectrometry were used to investigate the reaction procedure. The secondary amino group of diamine reacted faster with the vinyl group of diacrylate; this resulted in the formation of the intermediate with an acrylate group and two active hydrogen atoms attached to a nitrogen atom. Further self‐polyaddition of the intermediate, a kind of AB₂‐type monomer, gave the hyperbranched poly(ester amine). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2340–2349, 2002     

Linear and Hyperbranched Poly(arylene ether)s from a New Semifluorinated AB Monomer

A new trifluoromethyl-activated AB monomer has been successfully synthesized by Pd-initiated coupling of 4-bromo anisole with 4-fluoro-3-trifluoromethylphenylboronic acid followed by demethylation. The monomer leads to a semifluorinated poly(arylene ether) by nucleophilic displacement polymerization reaction. The AB monomer has been further copolymerized with a corresponding AB ₂ monomer to form the corresponding semifluorinated hyperbranched (hb) poly(arylene ether). The resulting linear and hb poly(arylene ether)s exhibited weight average molecular weight of 75700 and 144100 g/mol, respectively. The hb copolymer exhibited better solubility in different organic solvents compared to the linear poly(arylene ether). The polymers showed excellent thermal stability up to 522°C at 10% wt loss in air and glass transition temperatures as high as 187°C. The mechanical properties of the linear poly(arylene ether) film 1a exhibited tensile strength at break of 89 MPa, elongation at break of up to 3% and a Young’s modulus value of 2.66 GPa. The films of the polymers were hydrophobic in nature and showed water contact angle as high as 93.6°.     

NOVEL HYPERBRANCHED POLY（PHENYLENE OXIDE）S WITH PHENOLIC TERMINAL GROUPS： EFFECTS OF REACTION TIME AND CORE MOLECULES ON THE MOLECULAR WEIGHT AND POLYDISPERSITY

A novel hyperbranched poly（phenylene oxide） （HPPO） with phenolic terminal groups was prepared from 4-bromo-4＇,4＂-dihydroxytriphenylmethane as AB2 monomer in dimethylsulfoxide （DMSO） via a modified Ullmann reaction. The molecular weight and polydispersity （PD） of the resulting polymers increased with increasing reaction time. In the presence of core molecules （bisphenol A and 1,3,5-trihydroxybenzene）, which have the similar molecular backbones to the reactive monomer, the molecular weight could be controlled by varying the core-to-monomer ratio. Incorporation of a very small amount of core molecules could lead to a higher molecular weight as compared with that without the addition of core molecules. However, when the core content reached certain extent, the molecular weight would decrease with the further increase in the core content. A new similar behavior of control over the PD was also obtained. The resulting polymers were characterized by ^1H-NMR, ^13C-NMR, FT-IR, and GPC.     

Effect of substituents on the thermal decomposition of diazirines: experimental and computational studies

The thermal decomposition of phenylchlorodiazirine (1), phenyl-n-butyldiazirine (2), and 2-adamantane-2,3'-[3H]diazirine (3) has been studied in solution in the presence of C(60). The C(60) probe technique indicates that in the decomposition diazirine 1 yielded exclusively phenylchlorocarbene, diazirine 2 yielded mainly a diazo intermediate, and diazirine 3 yielded a mixture of carbene and diazo compound. In the case of diazirine 2, 13% of (E)-1-phenyl-1-pentene resulted from the direct thermal rearrangement of diazirine without the participation of a carbene. As well, the thermal decomposition of these diazirines has been studied theoretically with ab initio and density functional methods. The experimental results are broadly in agreement with the theoretical predictions. The calculations further indicate that the rebound reaction between carbene and molecular nitrogen leading to the formation of a diazo intermediate is an important reaction in the gas-phase decomposition of diazirine.