新型杂萘联苯聚醚砜酮及其应用

介绍瓣型杂萘联苯聚醚砜酮的制备，性能和应用，研究表明该树脂各项性能优异，是一种优良的绝缘材料，将其作用漆包线漆，操作工艺性好，且属于Ｈ级漆包线漆。     

杂萘联苯聚醚砜超滤膜的研制

以杂萘联苯聚醚砜(PPES)为膜材料,N-甲基-2-吡咯烷酮(NMP)为溶剂,采用相转化法制备了非对称超滤膜.结果表明,聚合物浓度的变化、添加剂含量的变化、凝胶浴温度或停留蒸发时间的改变都会影响超滤膜的性能,所制得的PPES超滤膜在0.1 Mpa的操作压力下对PEG10000的截留率高于95%,纯水通量可达632 L·m-2·h-1.     

耐高温新型含杂萘联苯聚醚砜嵌段共聚物的性能

将氯端基聚醚醚砜齐聚物和杂萘联苯类双酚羟端基齐聚物通过溶液缩聚,成功地合成了一系列新型聚醚醚砜-聚醚砜(PEES-PPES)嵌段共聚物,并用IR、DSC、TGA、X-WAXD等测试手段对聚合物进行了表征。结果表明:PEES-PPES具有较高的热稳定性,较好的溶剂溶解性;砜基比例的变化对PEES-PPES的热性能有较大的影响,表明砜基对杂萘联苯聚醚砜改性效果明显。     

含二氮杂萘酮联苯结构双马来酰亚胺的合成

由含二氮杂萘联苯酮结构的芳香族二元胺4-[4-(4-氨基苯氧基)苯基]-2-(4-氨基苯基)二氮杂萘-1-酮(DHPZ-DA)与顺丁烯二酸酐(MA)反应得到了含二氮杂萘酮联苯结构的双马来酰亚胺预聚物(DHPZ-BMI),并对其进行了FT-IR红外及1H-1H COSY NMR核磁表征。对其溶解性的研究表明,DHPZ-BMI易溶或部分溶解于一些常见低沸点极性溶剂,如氯仿、丙酮。利用示差扫描量热仪(DSC)对DHPZ-BMI热行为进行了研究,结果表明该预聚物的熔点较高,熔融和固化过程的温度范围在低升温速率下有所重叠。为此,加入不同含量的2,2′-二烯丙基双酚A(DABPA)改善其工艺性,并采用DSC对其热性能进行了初步研究,结果表明DABPA的加入,可明显改善树脂的固化行为。     

杂萘聚芳酰胺的合成与性能

由自制的1,2-二氢-2-(4-氨基苯基)-4-[4-(4-氨基苯氧基)-苯基]-二氮杂萘-1-酮(DHPZ—DA)、4,4’-二氨基二苯甲烷(DAPM)、对苯二胺与对苯二甲酸进行缩聚合,改变不同二胺的配比,制成一系列高相对分子质量的聚芳酰胺,其特性粘数为0．81-2.38dL／g。用傅里叶变换红外光谱和核磁共振氢谱分柝了聚合物的结构,利用差示扫描量热法和热重分析研究了聚合物的耐热性能,结果表明：聚芳酰胺的玻璃化转变温度在220℃以上,氮气气氛中．5％热失重温度在450℃以上;当DHPZ—DA的摩尔分数与DAPM的摩尔分数之和超过70％时,聚合物能溶于非质子极性溶剂中。     

含杂萘酮联苯结构耐高温聚氨酯胶粘剂的合成

采用本体聚合,将自制的含有4-(4’-羟基苯基)-2,3-二氮杂萘—1-酮(DHPz)作为单体引入双组分聚氨酯的固化剂中,合成一类新型的含杂萘类联苯结构的聚氨酯胶粘剂。DHPz的杂萘类联苯结构提高了胶粘剂的结构刚性和耐高温性能。常温剪切强度不低于20MPa,而且具有较强的耐酸、耐水解性能。以FT-IR、DSC、TGA等分析手段研究了聚合物的结构和耐热性能。结果表明,新型的聚氨酯胶粘剂具有较高的玻璃化转变温度(Tg＝170—200℃),在氮气氛围中10％热失重温度为300℃,250℃无失重。该胶粘剂可在较高温度下使用。     

磺化杂萘联苯聚醚砜纳滤膜用于海水预处理

采用纳滤对海水进行预处理,初步考察了不同操作压力、回收率、温度条件对水通量的影响和膜对海水中主要离子的脱除效果。当水的回收率控制在30%时,在0.5～1.3 MPa压力范围内,膜对各主要离子的脱除率随着压力的升高逐渐增大。当固定操作压力为1.3 MPa,增大回收率时,膜对各主要离子的脱除呈下降趋势。当回收率为7%时,渗透出水的Langelier饱和指数(LSI)为-0.03<0,无结垢倾向。在20～90℃范围内,随着操作温度升高膜对各离子的脱除率略有降低,而水通量逐渐增大。     

含二氮杂萘酮结构环氧树脂胶粘剂的研制

以双氰胺 (DCDA)为固化剂 ,以咪唑 (MZ)为固化促进剂 ,研制了一种含二氮杂萘酮结构的环氧树脂 (ER)胶粘剂 ,其成分为ER∶DCDA∶MZ∶SiO2 ∶Al=10 0∶7∶1∶3∶60 ,固化工艺为 12 0℃下固化 40min时 ,拉伸剪切强度为 17.8MPa ,有良好耐热性     

注塑级含二氮杂萘酮联苯结构的聚醚酮/聚四氟乙烯共混物的性能研究

通过熔融共混制备了聚四氟乙烯质量分数低于30%的注塑级含二氮杂萘联苯结构聚醚酮/聚四氟乙烯(PPEK/PTFE)共混物,并对其摩擦性能、力学性能、热性能和密度进行了研究。PTFE的加入,使得共混物的摩擦性能比纯PPEK得到大幅度的改善,且随着PTFE含量的增加,共混物的摩擦性能逐步提高;共混物的力学性能则随PTFE含量的增加有所降低,但依然处于较高的水平;不同配比共混物的耐热性能则与纯PPEK相当,热变形温度大约为244℃;共混物的密度随PTFE含量的增加而呈线性增大趋势。     

无机杂化倍半硅氧烷／磺化杂萘联苯聚醚酮质子导电复合膜

通过磺化反应制备了一系列不同磺化程度的磺化杂萘联苯聚醚酮（SPPEK）,采用共混法将无机杂化倍半硅氧烷（POSS）掺杂到IEC值为1．60的SPPEK中,通过溶液浇铸制得复合膜。对SPPEK／POSS复合膜进行了FTIR、TGA分析和SEM表观形貌观察。研究了SPPEK／POSS复合膜的吸水性、溶胀度和质子导电性,并与Nation 117进行对比。随着POSS的加入,复合膜的吸水性、溶胀度和氧化稳定性提高。SPPEK／POSS复合膜的室温电导率达到0．75×10^-2S·cm^-1,接近Nafion 117膜相同条件下的电导率（1．08×10^-2S·cm^-1）。随着温度升高,SPPEK／POSS复合膜的电导率逐渐增大。采用不同测试方法分别对复合膜的膜平面方向和厚度方向上的电导率进行了测试,表明在两个方向上的电导率相差较大,SPPEK／POSS复合膜室温下膜平面方向上的电导率达到2．1×10^-2S·cm^-1。     

新型间甲基取代杂萘联苯型聚芳酰胺的研制

采用间甲基取代杂萘联苯型类双酚4-(2-甲基-4-羟基苯基)-2,3-二氮杂萘-1-酮与对氯苯腈反应制得二腈化合物,进一步水解为二酸,以此新型二酸与三种二胺聚合制得的三种新型聚芳酰胺均具有较高的耐热性能,其玻璃化转变温度在287～317℃,且易溶于非质子极性溶剂中,聚合物的特性粘数为1.62～1.83 dL/g,拉伸强度为87～98 MPa,断裂伸长率为6.4％～8.4％,拉伸模量为0.7～1.3 GPa,表面电阻系数为10~(14)Ω,体积电阻系数达10~(17)Ω·cm。     

Synthesis and cross-linking of bifunctional monomers containing carbazole moieties

New bifunctional carbazolyl-containing monomers were synthesized and their cationic photo-initiated polymerization investigated. The monomers containing two reactive groups such as epoxy, oxetanyl and vinyloxyethyl, were prepared from commercially available 9-(2,3-epoxypropyl)carbazole. The kinetics of UV curing of the monomers was monitored by real-time FT-IR technique. The type of functionality was found to have a considerable influence on the photo-curing rate, but has not an evident effect on the final reactive group conversion. The cross-linked systems were found to have low glass transition temperatures ranging from 7 to 10 °C. Electron photoemission spectroscopy revealed ionization potentials of 5.75–5.8 eV for the thin cross-linked layers of the monomers.     

一步法合成四丁基锡

该文对格氏试剂合成四丁基锡的工艺进行了研究,提出了混合溶剂一步法合成工艺。采用正交实验及单因素法研究了合成过程中反应时间、反应温度、反应物用量等因素对四丁基锡收率的影响,获得了控制反应过程的最佳参数,并用气相色谱法对产物的成分进行了定量分析。研究结果表明,采用混合溶剂一步法合成工艺,当四氯化锡加入量达到理论量的90%时,产物中四丁基锡的质量分数大于97%,收率大于97%;用该工艺在500t/a规模的工业装置上生产时,产品四丁锡质量分数为87.2%~96.2%,收率为85.8%~94.3%。     

Synthesis and characterization of fully disulfonated poly(arylenethioethersulfone)s containing hexafluoroisopropylidene moiety

High molecular weight sulfonated poly(arylenethioethersulfone) homopolymer containing hexafluoroisopropylidene moiety (6F-SPTES-100) was synthesized from the monomers 3, 3′-disulfonated-4, 4′-difluorodiphenylsulfone and 4, 4′-(hexafluoroisopropylidene) diphenylthiol, using 4-fluorobenzophenone as the end-capping agent in polar aprotic solvents at temperatures up to 180 °C to provide the desired polymeric composition for utilization as proton exchange membrane (PEM) in fuel cells applications. Tough, ductile freestanding membranes were fabricated from N, N-dimethylacetamide (DMAc) by solvent-casting. The end-capped 6F-SPTES-100 polymer was fully characterized and the membrane was found to have proton conductivity as high as 180 mS/cm which was measured at 85 °C and 65% relative humidity. The proton conductivity of 6F-SPTES-100 was approximately two and half times higher than that of Nafion-117 under comparable conditions. The swelling and solubility characteristics of the 6F-SPTES-100 polymer in water are directly related to the high degree of sulfonation of the polymer backbone.     

一种新型共聚酰亚胺的合成与表征

以3,3’-二氨基二苯砜（DDS）和4,4’-二氨基二苯醚（ODA）作为共缩聚二胺单体,与3,3’,4,4’-二苯酮四羧酸二酐（BTDA）进行缩合聚合,合成了一系列具有一定溶解性的共聚酰亚胺。采用升温红外光谱监控了聚酰胺酸热环化为聚酰亚胺的过程,对所得产物的热稳定性和力学性能进行研究,发现二胺单体的组成对共聚酰亚胺的性能产生较为明显的影响。     

Synthesis and characterization of vinyl ester networks containing phthalonitrile moieties

A new styrenic monomer, 4-vinylphenoxyphthalonitrile, was synthesized by nucleophilic aromatic substitution of 4-vinylphenolate onto 4-nitrophthalonitrile. The new monomer was reacted with dimethacrylate-styrene resins (so-called vinyl esters) via free radical copolymerization at 90, then 120 °C with benzoyl peroxide as the initiator to form networks. The networks were further post-cured at 220, 240, or 260 °C for 4 h to convert the last portion of the methacrylates, and to partially cross-link the pendent phthalonitrile groups. A dimethacrylate-styrene network containing 30 wt% of the phthalonitrile-functional monomer exhibited a 70% reduction in peak heat release rate by cone calorimetry measured at an incident heat flux of 50 kW m⁻² relative to control vinyl ester networks. This still remains somewhat higher than peak heat release rates exhibited by brominated vinyl ester networks, but the CO/CO₂ ratio in the smoke is much lower for these non-halogenated materials.     

Humid aging of polyetherimide. I. Water sorption characteristics

The sorption and desorption kinetics of water into polyetherimide (ULTEM 1000) were studied at various temperatures ranging from 20 to 100°C. The water equilibrium concentration increases slightly with temperature from 1.39% (by weight) at 20°C to 1.50% at 100°C. The solubility coefficient, S, calculated from these data, and the water vapor pressure decrease with temperature. The calculated heat of dissolution H_s is close to −43 kJ mol⁻¹, which explains the low effect of temperature on the equilibrium concentration. The diffusion coefficient, D, varies from about 1.10⁻¹² m² · s⁻¹ at 20°C to about 16.10⁻¹² m² · s⁻¹ at 100°C. The apparent activation energy of diffusion, E_D, and the heat of dissolution, H_s, of water in the polymer have opposite values (respectively, +43 and −42 kJ · mol⁻¹). From this observation and a comparison of these data with water diffusion characteristics in other glassy polar polymers, it is hypothesized that the transport rate of water is kinetically controlled by the dissociation of water–polymer complexes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1439–1444, 2000     

一步法制备含羟基聚氨酯水分散体

以甲苯二异氰酸酯(TD I)、聚酯二醇和二羟甲基丙酸(DMPA)等为原料,采用一步法工艺制备了含羟基聚氨酯水分散体,探讨了聚酯二醇的种类、DMPA含量和NCO/OH摩尔比、中和剂及用量等对水分散体稳定性的影响,利用红外和粒度分析等方法表征了该体系的结构和胶粒尺寸。实验结果表明,随着亲水性离子用量增加,水分散体的粒径变小,稳定性增强,且在同样条件下采用不同的聚酯二醇制备的分散体粒径有一定的差异;采用JS307-110和JS308-110为原料时,最佳的NCO/OH摩尔比分别为0.91和0.85左右,其分散体粒径分别为60 nm和90 nm;采用三乙胺为中和剂,中和度为90%~100%时可得到稳定的水分散体。     

乙基纤维素的一步法合成与表征

采用纤维素与过量的氯乙烷及氢氧化钠反应 ,以甲苯为稀释剂 ,用一步法成功地合成了乙基纤维素。通过元素分析、红外光谱和核磁共振氢谱对产物的分子结构进行表征 ,确定所合成的化合物即为目标产物。该法所得乙基纤维素产品的乙氧基含量为 4 3 98%。