可交联含氟聚醚醚酮的合成

聚醚醚酮 (PEEK)是一种耐热等级高、耐化学药品、耐辐射并有优异的电性能及机械性能的特种工程塑料 .由于其综合性能优异 ,PEEK在航空航天、通信、电子和机械化工等领域获得成功应用 [1] .含氟芳香聚合物以其独特的性能而成为低介电常数微电子和低损耗光波导器件极具潜力的材料 [2 ] .聚合物良好的溶解性虽对光电集成电路的加工十分重要 ,但也要满足多层化操作过程 ,还要考虑器件成型后的抗化学药品性 .因而 ,在聚合物中引入可交联组分是必要和可行的方法 .另外 ,交联后的聚合物将有更高的玻璃化转变温度 (Tg)、更好的尺寸稳定性和防开…     

聚合物电光调制器包覆层材料研究

随着信息技术的飞速发展 ,利用光作为信息传输、存储、处理工具的光电子信息技术将得到广泛的应用 .电光调制器是将电信号调制到光束上的电光器件 ,在光通讯领域有十分重要的应用背景[1～ 5] .与通常基于无机材料 (如 ,LiNbO3 、KH2 PO4晶体等 )的电光调制器相比 ,基于聚合物材料的电光调制器具有非线性光学系数大、能量损耗低 (聚合物材料的介电常数很低 )和制作方法简单等优点[6,7] .因此 ,可应用于聚合物电光调制器的新材料是最近一、二十年来研究的热点和前沿 ,受到人们的广泛关注 .通常Mach Zehnder聚合物电光调制器具有“三明治”…     

低表面能侧基含氟聚合物*

含氟聚合物材料具有优异的热稳定性、极低的表面能、强化学稳定性和生物相容性等,在功能涂料、织物整理、微电子、汽车以及航空航天等领域具有很好的应用前景。本文综述了侧基含氟聚合物的主链、全氟烷基链、主链与全氟烷基链段间连接基团的结构对聚合物表面性能的影响,并总结了环境友好型低表面能侧基含氟聚合物的研究进展。     

溶胶-凝胶法制备氧化铝光学薄膜

氧化铝薄膜性能优异,具有较高的介电常数、高热导率、抗辐照能力强、抗碱离子渗透能力强以及在很宽的波长范围内透明等性能。因此,氧化铝薄膜广泛地应用于微电子器件、电致发光器件、光波导器件以及抗腐蚀涂层等众多领域[1]。特别是氧化铝光学薄膜具有高的抗激光损伤阈值[2],用     

含氟聚芳醚酮的合成与性能研究

研究了含氟基团的引入对聚醚醚酮(PEEK)的介电常数、溶解性、结晶性和力学性能等的影响.结果表明,这种含氟聚芳醚酮在保持PEEK良好机械性能的条件下,介电常数达到2.7,且频率依赖性小,成膜性能好,成本比相应的含氟PI低5～10倍,有望成为一种极有实用价值的电子封装材料.同时利用合成的含氟单体合成了一系列不同-CF₃取代基含量的聚芳醚酮共聚物,研究了聚芳醚酮共聚物的介电常数与聚合物结构单元中-CF₃取代基含量的关系.结果表明,聚芳醚酮共聚物的介电常数随聚合物结构单元中-CF₃取代基含量的增加而线性降低.     

联苯并环丁烯的制备及其聚合物的热稳定性

苯并环丁烯树脂具有优异的综合性能,可作为微电子器件中的高性能介电薄膜材料。其优异的性能满足大规模集成电路(MCM)、微电机系统(MEMS)、液晶显示器等器件的苛刻性能要求,在微电子领域有着极为重要的应用且前景广阔[1,2,3]。苯并环丁烯单体的种类较多,其聚合物大多具有优异的     

含氟侧基聚芳醚酮的合成与表征

聚芳醚酮具有优异的化学、物理和机械性能 ,被广泛用于结构材料、高分子膜、航空航天和电子工业中所需的涂敷材料 [1,2 ] .传统的聚芳醚酮由于主链的规整性和刚性 ,使其难熔难溶 ,给加工和应用带来一定的困难 .许多研究者对其进行了大量的改性研究 [3,4 ] .氟元素具有较强的电负性 ,尺寸较小 ,可以形成强化学键和具有较好的电性能等 ,使其在化学物质的分子设计中成为极有价值的取代基 .含氟聚合物可以影响聚合物的溶解性、阻燃性、热稳定性、玻璃化转变温度、颜色、结晶性、介电常数和吸水性等性能 [5,6 ] .为了改善聚芳醚酮的溶解性、结晶…     

纳米Hg2Cl2/Al2O3有序阵列体系的制备和表征

纳米结构材料由于其独特的物理化学性质以及在微电子器件、光开关等方面的应用而备受关注. 多孔氧化铝由于具有孔径分布较窄、取向一致和孔密度高等优点而广泛用于模板制备纳米结构材料. 在多孔氧化铝中可以组装金属纳米粒子[1]、半导体纳米粒子[2]、导电高分子[3]以及碳纳米管[4]等.     

水分散体系中甲基丙烯酸甲酯和丙烯酸八氟戊酯嵌段共聚物的合成与表征

在聚合物链上引入氟元素可以赋予聚合物很多优异的性能 ,如良好的热稳定性、化学稳定性、生物相容性和憎水憎油性等 .含氟单体与一般单体共聚是合成含氟共聚物的重要途径 .通过原子转移自由基聚合 (ATRP)不仅可以实现多种单体的控制 (共 )聚合 ,而且可以合成出具有预定分子量、窄分子量分布以及结构明晰聚合物[1] ,我们曾报道了溶液体系中用ATRP方法合成含氟嵌段共聚物[2～ 4] .众所周知 ,大多数含氟聚合物都是通过乳液或悬浮聚合反应合成的 .然而 ,普通的乳液或悬浮聚合难以合成结构和组成可控的聚合物 ,如嵌段共聚物 ,所以近年来 ,水…     

高性能双极性聚合物半导体材料与晶体管器件

有机聚合物半导体材料与晶体管器件是融合了化学、材料、半导体以及微电子等学科的前沿交叉研究方向.聚合物半导体材料分子是该领域研究的重要内容,其中双极性聚合物分子半导体材料,兼具了电子和空穴的双重载流子输运能力而受到学术界的广泛关注.本文总结了双极性聚合物半导体材料与器件的研究进展,重点介绍了我们在D-A型双极性聚合物分子半导体材料设计、加工技术与器件制备以及功能应用方面的研究工作,并论述了双极性聚合物分子半导体材料与器件研究过程中存在的科学问题及发展方向.     

New block copolymers—III. Synthesis,characterization and crosslinking studies of an (A-B)n type block copolymer

A new block copolymer was prepared by low temperature polycondensation between (acid chloride)-terminated poly(trimethylene terephthalate), as the hard block, and amine-terminated butadiene/acrylonitrile rubber, as the soft block. The polymer was characterized by elemental (nitrogen) analysis, i.r. and NMR spectroscopy. The analysis of the content of the block in the copolymer was carried out by the NMR peak area integration method. The polymer is soluble in polar aprotic solvents. X-ray study reveals that the crystallinity in the polymer is due to the presence of the hard block. The polymer behaves like a thermoplastic elastomer between ambient temperature and 125°. Above 150°, particularly around 200°, the residual unsaturation of the soft block results in crosslinking. Crosslinking and thermal behaviour of the polymer are also reported.     

Polymerization of Dioxolane by Triethyloxonium Hexafluorophosphate

Abstract

The polymerization of dioxolane by triethyloxonium hexafluorophosphate in methylene chloride has been studied with a view to determine the nature of the active center. NMR studies of solutions of the initiator with low ratios of monomer led to little reaction of the initiator over long times. Analysis of normal reaction mixtures showed that only a small amount of the initiator was consumed during the reaction. The polymer was studied by GPC, UV spectroscopy, and NMR. The polymer appears to consist largely of high molecular weight material with M_w/M_n less than 2, and also low molecular weight material perhaps formed by a different mechanism. The high molecular weight material appears not to have been formed by a simple linear trialkyloxonium ion, from end-group studies, and it is suggested the active center is a secondary oxonium ion on a large cyclic polymer.     

NMR study of polymer surfactant interaction in the system HPMC/SDS/water

The interaction between the nonionic water soluble polysaccharide hydroxypropylmethyl cellulose (HPMC) and the low molecular weight amphiphile sodiumdodecyl sulphate (SDS) has been studied by NMR¹H-chemical shift measurements and by self-diffusion NMR measurements. The polymer concentration has been kept sufficiently dilute to avoid coil overlap and the SDS composition range goes from zero up to well above the normal CMC point. Although a different fraction was used, the present results agree well with previous results for the same system obtained by techniques other than NMR and show very clear break points that can be related to the polymer surfactant interaction. Furthermore, it can be inferred from the chemical shift measurements that the structure of the micellar clusters are similar whether polymer is present or not. From a combination of chemical shift and self diffusion measurements it is also found that neither the size nor the shape of the clusters seem to change significantly in the composition interval investigated.     

Cationic polymerization of styrene by acetyl perchlorate. II. Steric structure of the polymer and nature of the propagating species

Cationic polymerization of styrene initiated by acetyl perchlorate in CH₂Cl₂ yields a polymer having a bimodal molecular weight distribution. The high molecular weight and the low molecular weight portions of the polymer were separated by thin-layer chromatography, and the steric structure of these separated polymers was investigated by ¹³C NMR spectra. The high molecular weight polymer had a larger racemic dyad content than the low molecular weight material. From the dependence of the steric structure of the polymer on the polarity of a solvent, it was estimated that the propagating species producing the high molecular weight material was a loose ion pair or a free ion, and that producing the high molecular weight material was a loose ion pair or a free ion, and that producing the low one was a nondissociated species.     

咪草烟分子印迹聚合物的制备及其选择性吸附性能的研究

以丙烯酸为聚合单体,TMPTA为交联剂,AIBN为引发剂,咪草烟为模板分子,采用在低温光聚合的方法,制备了对咪草烟分子具有选择性识别能力的分子印迹聚合物．通过IR和HPLC表征,咪草烟分子印迹聚合物对咪草烟分子具有良好的识别作用．     

主链含双层倍半硅氧烷的C_2-对称双脯氨酰胺手性聚合物催化剂的合成及在不对称Aldol反应中的应用

以双夹板形的笼型倍半硅氧烷(DDSQ)和叔丁基氧羰基(Boc)保护的C2-对称双脯氨酰胺为底物,通过硅氢加成反应和脱Boc反应,制得主链含DDSQ的C2-对称双脯氨酰胺手性聚合物催化剂;对其化学结构、分子量及热失重性能进行了表征.将制备的聚合物催化剂应用于催化不对称Aldol反应,探讨了其催化性能.结果表明,催化产物均具有较高的产率和立体选择性,且该催化剂便于分离纯化,循环使用6次后催化活性未见明显下降.     

Hydration of synthetic polypropylenephosphate (PPP) — a simplified model for natural teichoic acids Part 3. Bound (nonfreezing) water in PPP gels by the pulsed Fourier transform NMR method

The structure and properties of bound water, nonfreezing at low temperature, in polypropylenephosphate (PPP) gels have been studied by the pulsed Fourier transform NMR method. The amount of hydrate water in gels depends strongly on the type of counterions. For PPP in acid and magnesium salt forms this amount was found to be three and eight moles per one mole of phosphate groups, respectively. The shape of a resonance line of bound water protons at low temperature was approximated by the curve of the system of proton pairs of statistically distributed orientations. The distance between two interacting protons in a pair, calculated from NMR spectrum, corresponds to the H-H distance in an isolated water molecule. This means that hydrate water molecules are fixed at hydration sites of polymer phosphate groups at a distance limiting intermolecular proton-proton interaction. The analysis of the NMR signal shape confirms that the structures of the primary hydration layer of phosphodiester groups, proposed in our previous theoretical studies, exist in PPP gels.     

Ion and polymer dynamics in polymer electrolytes PPO-LiClO4. I. Insights from NMR line-shape analysis

We investigate ion and polymer dynamics in polymer electrolytes PPO-LiClO4 performing 2H and 7Li NMR line-shape analysis. Comparison of temperature dependent 7Li and 2H NMR spectra gives evidence for a coupling of ion and polymer dynamics. 2H NMR spectra for various salt concentrations reveal a strong slowdown of the polymer segmental motion when the salt content is increased. The 2H NMR line shape further indicates that the segmental motion is governed by dynamical heterogeneities. While the width of the distribution of correlation times G(log tau) is moderate for low and high salt content, an extremely broad distribution exists for an intermediate salt concentration of 15:1 PPO-LiClO4. For the latter composition, a weighted superposition of two spectral components, reflecting the fast and the slow polymer segments of the distribution, describes the 2H NMR line shape over a broad temperature range. Analysis of the temperature dependent relative intensity of both spectral components indicates the existence of a continuous rather than a discontinuous distribution G(log tau). Such continuous distribution is consistent with gradual fluctuations of the local salt concentration and, hence, of the local environments of the polymer segments, whereas it is at variance with the existence of large salt-depleted and salt-rich domains featuring fast and slow polymer dynamics, respectively. Finally, for all studied PPO-LiClO4 mixtures, the 2H NMR line shape strongly depends on the echo delay in the applied echo-pulse sequence, indicating that the structural relaxation of the polymer segments involves successive rotational jumps about small angles gamma < 20 degrees .     

Preparation and properties of a POSS-containing organic-inorganic hybrid crosslinked polymer

A novel POSS-containing organic-inorganic hybrid crosslinked polymer was prepared by hydrosilylation reaction of octahydridosilsesquioxane (T8H8) with 4,4'-bis(4-allyloxybenzoyloxy)phenyl (diene A). Its structure and property was character-ized by FTIR, 29Si NMR, TGA and ellipsometer, respectively. The results show that the hybrid polymer possesses high thermal stability and low dielectric constant of 1.97 at optical frequencies.     

Nanoporous structure of ultrahigh-molecular-weight polyethylene reactor powder

The influence of the catalyst system and synthesis conditions on the morphology and molecular dynamics of reactor (nascent) powders of ultrahigh-molecular-weight PE synthesized over supported Ziegler-Natta catalysts in laboratory reactors was studied by means of electron microscopy and ¹H broadline NMR spectroscopy. For comparison, commercial reactor powders were studied as well. The type of the catalyst system and the temperature of slurry polymerization have a substantial effect on the supermolecular structure of the nascent polymer. The proton NMR spectra of the reactor powders synthesized at low temperatures display a narrow component. An analysis of its behavior at low temperatures and different humidities led to the conclusion that the signal is due to water localized in nanopores of 2–4 nm in size in the nascent polymer. The role of nanopores in the sintering of reactor particles is discussed.