蓖麻油基巯烯基紫外光固化胶粘剂的研制与性能研究

以异佛尔酮二异氰酸酯(IPDI)、蓖麻油(CO)、丙烯酸羟丙酯(HPA)为原料,采用熔融缩聚法合成出端丙烯酸酯基预聚体;同时以CO和3-巯基丙酸(3-MPA)为原料采用酯化反应合成出端巯基光引发单体。将端不饱和双键聚氨酯丙烯酸酯预聚体与所制备巯基丙酸酯按一定比例复合,加入光引发剂,在紫外光照射下,预聚体中双键与光引发单体中巯基发生巯基-烯点击反应,制得聚氨酯丙烯酸酯固化膜。采用核磁共振氢谱(1 HNMR)、红外光谱(FT-IR)、热重分析(TG)和光量热系统(Photo-DSC)等手段对合成预聚体、巯基丙酸酯及固化膜结构和性能进行了分析表征。结果表明:在紫外光辐照下,预聚体中不饱和双键与巯基化合物中巯基间发生了自由基加成反应,固化时间在60s以内,且所制备UV固化膜具有良好的机械性能和热稳定性。     

光敏树脂合成及3D打印的综合实验教学设计与实践

针对综合实验的特点,结合创新性、趣味性等特性,设计了光敏树脂合成及3D打印综合实验。实验用1,6-己二异氰酸酯(HDI)三聚体和丙烯酸羟乙酯反应,以丙烯酰吗啉(ACMO)为活性溶剂,合成可紫外光固化的预聚体树脂。通过对预聚体树脂的—NCO测定、红外光谱、核磁共振,分析了HDI三聚体和丙烯酸羟乙酯的反应程度,表征预聚体树脂的结构及评价光固化性能,并与其他光固化单体和光引发剂配合制备黏度适宜的光敏树脂。用405 nm波长的桌面级3D打印机打印出测试样条和展示样品,通过对样条性能测试,表明该光敏树脂打印的样条具有较好的力学性能。本实验开设在本科四年级的综合教学实验中,其可以使本科生学到光固化树脂的制备方法,了解化学材料与数字模型及3D打印技术的结合,体会聚合物结构与性能的关系,增强本科生对数据的分析处理能力以及拓展本科生对其他学科的知识水平。     

氟硅协同改性丙烯酸树脂的合成与防污性能研究

以甲基丙烯酸十二氟庚酯(FMA)、甲基丙烯酸聚二甲基硅氧烷基酯(SMA)、甲基丙烯酸甲酯、丙烯酸正丁酯、甲基丙烯酸正丁酯和丙烯酸乙酯为共聚单体,通过溶液聚合反应合成出侧链含有机氟、有机硅的丙烯酸树脂.通过核磁共振氢谱(1H-NMR)、核磁共振氟谱(19F-NMR)、红外光谱(FTIR)对聚合物的结构进行了表征.通过扫描电镜(SEM)、接触角测试和生物评价等方法,探讨了FMA、SMA含量对树脂涂膜性能的影响.结果表明氟硅改性的丙烯酸树脂比单独含氟或含硅改性的丙烯酸树脂具有更低的表面能,而且氟硅改性的丙烯酸树脂涂膜比商业化的聚硅氧烷涂膜具有更好的防污性能.     

紫外光固化聚氨酯丙烯酸酯树脂的流变行为

合成了一系列紫外光因化聚氨酯丙烯酸酯聚合物,研究了分子量、原料配比、反应方式、含水量、溶剂等对其流变行为的影响。实验表明,控制剂聚物分子量,干燥原料,以ＨＥＡ先与异氰酸酯反应的加料方式合成的树脂,流动性较好。在此基础上合成了较好流动性和光固化性能的蓖麻油紫外光固化树脂。     

苯乙炔封端的BTDA系列酰亚胺预聚体的研究

合成了具有苯侧基的二胺单体1,4-双(4'-氨基苯氧基)-2-(苯基)苯(p-TPEQ), 并与3,3',4,4'-苯酮四羧酸二酐(BTDA)进行缩聚反应, 分别以4-苯乙炔苯酐(PEPA)和4-苯乙炔-1,8-萘二甲酸酐(PENA)作为封端剂, 合成了两个系列的苯乙炔封端的酰亚胺预聚体. DSC测试结果表明, 此类预聚体具有比PETI-5更宽的加工窗口; 利用所合成的预聚体制成了具有较高热分解温度热固性交联PI薄膜. 结果表明, PI预聚体加工性能良好, 其交联后具有优异的力学和热学性能; 同时PEPA封端的预聚体树脂具有比PENA封端的树脂更为优异的综合性能.     

WPU预聚体中羧基含量及其位置对树脂的粒径及其耐水性之影响的研究

本文先将马来酸酐与多元醇作用，然后再与其它单体反应，合成了含有羧基的聚氨酯预聚体，并用丁酮稀释后，在普通搅拌条件下使预聚体分散于三乙醇胺的水溶液中，合成出以水为分散介质的聚氨酯分散体系（WPU）。并通过改变羧基在预聚体中的含量和位置，发现随着羧基含量的增加，WPU的粒径减小，而耐水性下降。同时发现，在一定的羧基含量下，同侧羧基相比，端羧基更有利于预聚体的乳化，制得的WPU不仅颗粒较小，而且树脂耐水性明显优于侧基羧预聚体制备的WPU，从而提出羧基的运动自由度是影响羧基乳化活性和树脂耐水性的重要因素。     

偶联剂对丙烯酸酯改性聚氨酯聚合物接枝率和乳液性能的影响

合成了含双羟基的甲基丙烯酸甘油酯(GM)并将其作为偶联剂用于聚丙烯酸酯(PAC)对水基聚氨酯(PU)的改性.采用核磁共振、红外光谱和气相色谱等对GM进行了表征.分别以该双羟基GM和单羟基的丙烯酸羟乙酯(HEA)与异氰酸酯基(NCO)封端的PU预聚体进行反应以在PU分子链上引入双键,然后再与丙烯酸酯类单体通过自由基聚合制...     

可循环回收利用的本征导热聚六氢三嗪树脂研究

采用多聚甲醛(PFA)和含有芳香酰胺特殊结构的4,4'-二氨基苯酰替苯胺(DABA)为原料,通过利用分子链间氢键强相互作用向树脂固化网络中引入局域微观有序结构增大声子传播自由程,合成一种新型本征导热聚六氢三嗪热固性树脂(DABA-PHT).通过对树脂预聚过程和机理、固化工艺、导热性能、降解性能及循环回收利用性能的研究表明:水能够作为催化剂有效加速预聚反应、大幅缩短预聚时间,且酰胺N-H键未参与交联反应;DABA-PHT树脂易于合成和加工,且具有良好的力学、耐热、降解和循环回收利用性能,热导率达到0.38 W·m~(-1)·K~(-1),接近普通环氧树脂的2倍,有望用来制备可循环回收利用的高热导率热固性树脂基复合材料.     

新型乙炔封端聚酰亚胺的制备及性能

用双酚A型二醚二酐(BPADA)和3-乙炔基苯胺(m-APA)进行缩聚反应合成了乙炔基封端的聚酰亚胺预聚体, 并对预聚体的熔体黏度、稳定性和热性能等进行研究. 结果表明, 此类预聚体具有较宽的加工窗口和较低的加工温度, 适合模压成型工艺制备树脂基复合材料. 预聚体经250 ℃固化后显示了优异的热性能, 动态力学分析显示其玻璃化转变温度为363 ℃, 在氮气和空气气氛下5%热失重温度分别为490和492 ℃.     

含氟丙烯酸酯共聚物表面性能的稳定化研究

为提高传统含氟丙烯酸酯乳胶膜表面性能的稳定性,以γ-(甲基丙烯酰氧基)丙基三甲氧基硅烷(MPS)作为可交联单体,采用细乳液聚合法合成了MPS改性的含氟丙烯酸酯共聚物,利用DLS、TEM、IR对聚合物进行表征,研究了MPS对合成乳液的稳定性、涂膜性能和膜表面接触角稳定性的影响。结果表明,细乳液聚合法适合用于对水敏感单体的聚合,合成的纯丙烯酸酯乳胶为球形结构,平均粒径为92 nm,而氟丙乳胶和含3%MPS的含硅氟丙乳胶形成了典型的核壳结构,平均粒径分别增大至107 nm和103 nm,含硅氟丙聚合物中存在Si-O-Si的交联结构。涂膜性能测试表明,MPS的引入增加了共聚物膜的硬度、耐溶剂性和耐水性。接触角测试表明,随MPS用量的增加,乳胶膜对水的初始接触角和动态接触角随时间的降低值均呈先增大后减小的趋势,共聚体系中加入适量MPS,通过含氟链段与MPS链段的协同作用,可显著提高涂膜表面性能的稳定性。     

Polystyrene resins cross-linked with di- or tri(ethylene glycol) dimethacrylates as supports for solid-phase peptide synthesis

Polystyrene resins cross-linked with di(ethylene glycol) dimethacrylate (DEGDMA) and tri(ethylene glycol) dimethacrylate (TEGDMA), DEGDMA-PS and TEGDMA-PS, were synthesized by suspension copolymerization. Four functionalized resins, chloromethyl resin, 4-hydroxymethylphenoxymethyl resin (Wang resin), 4-methylbenzhydrylamine resin (MBHA resin) and 2-chlorotrityl chloride resin, were prepared from DEGDMA-PS and TEGDMA-PS. DEGDMA-PS and TEGDMA-PS showed high reactivity in the functionalization reactions in comparison with Merrifield resin (polystyrene cross-linked with divinylbenzene, DVB-PS). DEGDMA-PS-Wang resin and TEGDMA-PS-Wang resin were used as the solid-phase support for the synthesis of a difficult sequence, the fragment of acyl carrier protein 65-74. The yields of the crude peptide synthesized using DEGDMA-PS-Wang resin, TEGDMA-PS-Wang resin and DVB-PS-Wang resin were 92.3%, 91.6% and 78.8%, respectively. The purities of the crude peptides were 85.7%, 88.1% and 73.3%, respectively.     

Anion-exchange resin modified with bismuthiol-II, as a new functional resin for the selective collection of selenium(IV)

A functional resin for the collection of selenium(IV) has been prepared simply by the conversion of a common ion-exchange resin with bismuthiol-II which has three functional properties, namely the capabilities of selective reaction with selenium(IV), ion-exchange reaction with ion-exchange resin and strong physical sorption to the ion-exchange resin matrix. The binding ratio of selenium(IV) to bismuthiol-II on the resin was confirmed to be 1:4. The reaction was represented as follows: 4RSH + H(2)SeO(3)--> R-S-Se-S-R + R-S-S-R + 3H(2)O. Highly selective sorption of selenium(IV) was achieved, based on the formation of stable selenotrisulphide on the resin. Selenium(IV) sorbed on bismuthiol-II resin was eluted effectively with 8-13M nitric acid or some thiols, such as cysteine and penicillamine. In the cases of thiols, the elution of selenium was found to be also based on the formation of selenotrisulphide, and the bismuthiol-II resin was regenerated. Satisfactory results were obtained when this resin was applied to the determination of selenium(IV) in river, estuarine or sea water samples.     

Microwave Assisted Benign Method of Chelating Resin Synthesis Having Different Thermal and Ion Exchange Properties

Summary: Microwave irradiation method was used for synthesis of chelating ion exchange resin derived fom Salicylicacid-Formaldehyde-Resorcinol (SFR-M). The resin was characterized by Elemental analysis, FTIR, TGA and SEM. The Broido and Horowitz-Metzger method were used to calculate the energy of activation (Ea) from TGA. The microwave assisted chelating resin has different thermal behaviour as compared to conventional resin (SFR-C). The sorption capacities of microwave SFR resin for transition metal ions are higher than conventional SFR resin. The separation of binary mixtures [Cu (II) and Zn (II)] in brass and [Ni (II) and Cd (II)] were successfully carried out using Kd value.     

Adsorption properties of ionic species on cross-linked chitosans modified with catechol and salicylic acid moieties.

Catechol-type chitosan resin and salicylic acid-type chitosan resin were easily synthesized for use in estimating the adsorption behavior of 34 elements at pH 1 - 7 in aquatic media. The catechol-type chitosan resin could adsorb Cu(II) at pH 3 - 7, In(III) at pH 4 - 6, Pb(II) and lanthanoids at pH 5 - 7, and U(VI) at pH 4 - 7 more effectively than the salicylic acid-type chitosan resin and the cross-linked chitosan resin (base material). Adsorption ability was in the order: catechol-type chitosan resin > salicylic acid-type chitosan resin > cross-linked chitosan resin.     

含三乙烯二胺强弱碱功能基阴离子交换树脂的制备及其吸附性能

含三乙烯二胺强弱碱功能基阴离子交换树脂的制备及其吸附性能;三乙烯二胺; 强弱碱基阴离子交换树脂; 滴定曲线; 苯甲酸; 吸附性能     

二甲胺修饰戊二醛交联壳聚糖树脂的制备及性能

研究了在均匀水相介质条件下，采用戊二醛稀溶液制备交联壳聚糖树脂的方法，并以三聚氯氰为活化剂，合成了二甲胺修饰戊二醛交联壳聚糖树脂．研究了该树脂的红外光谱及吸附性能．该树脂对铜(Ⅱ)和牛血清白蛋白(BSA)的吸附容量分别为42mg／g(干)和940mg／g(干)，其吸附行为均符合Freundlich等温吸附模型．该树脂制备工艺简单，机械强度较好，可作为金属离子或蛋白质分离纯化的吸附剂和色谱填料．     

Synthesis and properties of a chelating resin containing triazolethiol groups

A macroreticular poly(acrylic acid)-based resin with triazolethiol as the functional group has been synthesized. The stability of the resin in acidic media and the behaviour in sorption and desorption of various metal ions have been investigated and compared with those of the acylthiosemicarbazide resin which is an intermediate in synthesis of the triazolethiol resin. Both resins show high affinity for copper(II) silver, cadmium and mercury(II), and high selectivity for silver and mercury(II) at low pH (1–2), and even at pH 7 if EDTA is present. The triazolethiol resin sorbs metal ions faster than the acylthiosemicarbazide resin does and sorbs mercury(II) from high concentrations of acids and neutral salt solutions. This resin has been applied to the concentration of silver and mercury(II) from sea-water samples by column operation.     

Preparation of magnetic anion exchange resin and their adsorption kinetic behavior of reactive blue

Magnetic anion exchange resin(MD-1) was prepared from quaternization of magnetic copolymeric resin(glycidyl methacrylate -eo-divinylbenzene).For comparison,magnetic resin MD-0 without quaternization and non-magnetic resin(D-1) were also synthesized for the adsorption process.It was found that the adsorption was mainly contributed to the chemical interaction between quaternary ammonium groups and reactive blue RXHC.Due to the smaller size,MD-1 had faster adsorption and desorption kinetics than D-1.Coupled with the advantage of easy separation,the magnetic anion exchange resin was considered to be superior to common anion exchange resin in removal of reactive dye.     

Novel toughened cyanate ester resin with good dielectric properties and thermal stability by copolymerizing with hyperbranched polysiloxane and epoxy resin

A novel toughened cyanate ester (CE) resin with good dielectric properties and thermal stability was developed by copolymerizing 2,2′‐bis(4‐cyanatophenyl)iso‐propylidene (BCE) with a combined modifier (HBPSiEP) made up of hyperbranched polysiloxane (HBPSi) and epoxy (EP) resin. HBPSi was synthesized through the hydrolysis of 3‐(trimethoxysilyl)propyl methacrylate. The effect of differing stoichiometries of HBPSiEP on the curing characteristics and performance of BCE resin is discussed. Results show that the incorporation of HBPSiEP can not only effectively promote the curing reaction of BCE, but can also significantly improve the toughness of the cured BCE resin. In addition, the toughening effect of HBPSiEP is greater than single EP resin. For example, the impact strength of modified BCE resin with 30 wt% of HBPSiEP is 23.3 KJ/m², which is more than 2.5 times of that of pure BCE resin, while the maximum impact strength of EP/BCE resin is about 2 times of pure BCE resin. It is worthy to note that HBPSiEP/BCE resins also exhibit improved thermal stability, dielectric properties, and flame retardancy, suggesting that the novel toughened CE resins have great potentiality to be used as a matrix for advanced functional composites or electronic packing resins. Copyright © 2009 John Wiley & Sons, Ltd.     

Solid-phase synthesis of 7-acylamino-1,4-benzodiazepine-2,5-diones

A method for the synthesis of polymer-bound 7-acylamino-benzodiazepine-2,5-diones is described. The amino group of an alpha-amino acid is linked to polystyrene or TentaGel resin via reductive amination of polymer-bound 4-alkoxy-2,6-dimethoxybenzaldehyde. Acylation with unprotected 5-nitroanthranilic acid is followed by base-catalyzed ring closure. Reduction of the nitro group yields enantiomerically pure 7-aminobenzodiazepin-2,5-dione attached via the N-4 atom to the resin. Acylation of the amino group on the aromatic ring with acid chlorides in N-methylpyrrolidone (no DMF, no base!) followed by cleavage from the resin using TFA/Me(2)S/water (90:5:5) provides the acylated benzodiazepinones in 52-69% (PS resin) and 41-48% (TG resin) yield (based on the theoretical loading) and >70% purity (HPLC, 210 nm). Using Fmoc-protected tyrosine fluoride in NMP gives the amino acid-coupled benzodiazepinones in 24% (PS resin) and 31% (TG resin) yield.