经γ射线辐照的LLDPE与氢氧化铝体系冲击性能的研究

研究了γ射线剂量率对线性低密度聚乙烯（ＬＬＤＰＥ）氧化与降解的影响和ＬＬＤＰＥ／γ－ＬＬＤＰＥ／ＡＴＨ（氢氧化铝）体系的冲击性能。结果表明，剂量率越低，ＬＬＤＰＥ氧化和降解的程度越高。γ－ＬＬＤＰＥ的加入可明显改善ＬＬＤＰＥ和ＡＴＨ的相容性，提高ＬＬＤＰＥ／ＡＴＨ体系的冲击强度，改善ＡＴＨ在ＬＬＤＰＥ树脂相中的分散性。     

稀土化合物的润滑性能

通过摩擦磨损试验考察了Ｌａ，Ｐｒ，Ｓｍ，Ｅｕ和Ｇｄ的二烷基二硫代磷酸盐（ＲＥＤＤＰ）、二烷基膦酸盐（ＲＥＤＰＥ）和三烷基磷酸盐（ＲＥＴＡＰ）３种类型１５种稀土化合物的抗磨减摩性能。结果表明，稀土化合物具有较好的抗磨减摩性能，润滑性能的优劣顺序为：ＲＥＤＤＰ＞ＲＥＤＰＥ＞ＲＥＴＡＰ，对每一种类型的稀土化合物而言，润滑性能的优劣顺序为：Ｓｍ＞Ｌａ＞Ｐｒ＞Ｇｄ＞Ｅｕ。     

EVA增容PP/HDPE共混体系的形态结构与性能

采用乙烯－醋酸乙烯酯共聚物（ＥＶＡ）作为聚丙烯（ＰＰ）／高密度聚乙烯（ＨＤＰＥ）共混体系的增容剂,通过冲击实验、拉伸实验、示差量热扫描仪（ＤＳＣ）和扫描电镜（ＳＥＭ）,系统地研究了共混体系的性能与其形态结构之间的。结果表明,ＥＶＡ是ＰＰ／ＨＤＰＥ共混物较好物增容剂,ＥＶＡ可以使ＰＰ、ＨＤＰＥ的晶相结构受到一定程度的破坏,增加ＰＰ和ＨＤＰＥ的相容性,同时共混物的冲击韧性明显提高。     

原子簇P12（D3d）的理论研究

利用Ｇａｕｓｓｉａｎ－９２程序在６－３１Ｇ基组下优化Ｐ１２（Ｄ３ｄ）构型，研究了３Ｐ４（Ｔｄ）→Ｐ１２（Ｄ３ｄ）的相对能量，计算结果为△Ｅ＝Ｅｐ１２（Ｄ３ｄ）－３Ｅｐ４（Ｔｄ）＝－７９．８４４ｋＪ／ｍｏｌ，优化Ｐ１２（Ｄ３ｄ）获得的Ｐ－Ｐ键键长接近于实验测得的Ｐ－Ｐ单键键长，并进一步在该基组下计算了Ｐ１２（Ｄ３ｄ）原子簇的振动频率，得到的全部为正频率，表明原子簇Ｐ１２的Ｄ３ｄ构型是位能面上的稳定点     

高密度聚乙烯／低密度聚乙烯／乙烯－醋酸乙烯共聚物共混体系的结晶行为

通过ＤＳＣ和ＷＡＸＤ研究了高密度聚乙烯／低密度聚乙烯／乙烯－醋酸乙烯共聚物（ＨＤＰＥ／ＬＤＰＥ／ＥＶＡ）三元共混体系的热行为和结晶性能。发现当ＨＤＰＥ含量小于４０％时，ＥＶＡ对ＬＤＰＥ起稀释剂作用，促进ＨＤＰＥ、ＬＤＰＥ的晶相分离，使ＨＤＰＥ、ＬＤＰＥ单独结晶．当ＨＤＰＥ含量高于４０％时，ＬＤＰＥ片晶进入ＨＤＰＥ晶相。形成与ＬＤＰＥ在片晶水平上的共晶。     

极低密度聚乙烯与其它聚乙烯的共混

从结构角度，用ＤＳＣ，ＷＡＸＤ，ＳＡＸＳ研究了聚乙烯（ＰＥ）家族中极低密度聚乙烯（ＶＬＤＰＥ）与其它ＰＥ的互容性．ＨＤＰＥ／ＶＬＤＰＥ是共晶互容的，以其大量无规部分“溶解”了ＨＤＰＥ的结晶缺陷部分，提高了ＨＤＰＥ的Ｔｃ，Ｔｍ，Ｘｃ，结晶峰半高宽变窄，晶胞参数随组成而有最低值．ＶＬＤＰＥ与ＬＬＤＰＥ结构极为相似，ＤＳＣ及ＷＡＸＤ证明其共混物是共晶相容体系．ＬＤＰＥ／ＶＬＤＰＥ的结晶度符合按组成的计算值，但晶胞参数ａ，ｂ以及晶粒尺寸增大，ＤＳＣ上有分别相应于两组份的两个Ｔｍ；ＶＬＤＰＥ的Ｔｃ，Ｔｍ峰高之和高于按组份的计算值，ＬＤＰＥ的Ｔｍ，Ｔｃ则低于计算值．认为是正如ＬＬＤＰＥ／ＬＤＰＥ，ＬＤＰＥ向充满整个体积的ＶＬＤＰＥ中不断填入，以ＶＬＤＰＥ为晶核而结晶，形成相分离的不相容体系．     

高密度聚乙烯／低密度聚乙烯／乙烯—醋酸乙烯共聚物共混体系的结晶行为

通过ＤＳＣ和ＷＡＸＤ研究了高密度聚乙烯／低密度聚乙烯／乙烯－醋酸乙烯共聚物（ＨＤＰＥ／ＬＤＰＥ／ＥＶＡ）三元共混体系的热行为和结晶性能，发现当ＨＤＰＥ含量小于４０％时，ＥＶＡ对ＬＤＰＥ起稀释剂作用，促进ＨＤＰＥ、ＬＤＰＥ的晶相分离，使ＨＤＰＥ、ＬＤＰＥ单独结晶，当ＨＤＰＥ含量高于４０％时，ＬＤＰＥ片晶入进ＨＤＰＥ晶相，形成与ＬＤＰＥ在片晶水平上的共晶。     

高密度聚乙烯与乙烯丙烯辛烯－1共聚物共混体系的相容性

用ＤＳＣ和ＷＡＸＤ方法研究了高密度聚乙烯／聚（乙烯丙烯辛烯－１）（ＨＤＰＥ／ＥＰＯ）共混体系的结晶性能。共混物的ＤＳＣ曲线皆呈单峰，表明共混体系形成了共晶。晶胞参数ａ及结晶度随共混物组成而变，进一步证明ＨＤＰＥ／ＥＰＯ共混体系的相容性．     

LLDPE／LDPE共混体系的相容性与性能

ＬＬＤＰＥ／ＬＤＰＥ共混体系的相容性与性能杨毓华，花荣，白春霞，于旻李三喜，葛铁军（中国科学院长春应用化学研究所长春１３００２２）（沈阳化工学院高分子系沈阳）关键词ＤＳＣ，ＷＡＸＤ，力学性能，ＬＬＤＰＥ，ＬＤＰＥ，共混，相容性非晶－非晶－结晶共混体系...     

高密度聚乙烯与乙烯丙烯辛烯—1共聚物共混体系的相容性

用ＤＳＣ和ＷＡＸＤ方法研究了高密度聚乙烯／聚（乙烯丙烯辛烯－１）（ＨＤＰＥ／ＥＰＯ）共混体系的结晶性能。共混物的ＤＳＣ曲线皆呈单峰，表明共混体系形成了共晶。晶胞参数ａ及结晶度随共混物组成而变，进一步证明ＨＤＰＥ／ＥＰＯ共混体系的相容性。     

The "missing link": the gas-phase generation of platinum-methylidyne clusters Pt(n)CH+ (n=1, 2) and their reactions with hydrocarbons and ammonia

Electrospray ionization (ESI) of tetrameric platinum(II) acetate, [Pt(4)(CH(3)COO)(8)], in methanol generates the formal platinum(III) dimeric cation [Pt(2)(CH(3)COO)(3)(CH(2)COO)(MeOH)(2)](+), which, upon harsher ionization conditions, sequentially loses the two methanol ligands, CO(2), and CH(2)COO to form the platinum(II) dimer [Pt(2)(CH(3)COO)(2)(CH(3))](+). Next, intramolecular sequential double hydrogen-atom transfer from the methyl group concomitant with the elimination of two acetic acid molecules produces Pt(2)CH(+) from which, upon even harsher conditions, PtCH(+) is eventually generated. This degradation sequence is supported by collision-induced dissociation (CID) experiments, extensive isotope-labeling studies, and DFT calculations. Both PtCH(+) and Pt(2)CH(+) react under thermal conditions with the hydrocarbons C(2)H(n) (n=2, 4, 6) and C(3)H(n) (n=6, 8). While, in ion-molecule reactions of PtCH(+) with C(2) hydrocarbons, the relative rates decrease with increasing n, the opposite trend holds true for Pt(2)CH(+). The Pt(2)CH(+) cluster only sluggishly reacts with C(2)H(2), but with C(2)H(4) and C(2)H(6) dihydrogen loss dominates. The reactions with the latter two substrates were preceded by a complete exchange of all of the hydrogen atoms present in the adduct complex. The PtCH(+) ion is much less selective. In the reactions with C(2)H(2) and C(2)H(4), elimination of H(2) occurs; however, CH(4) formation prevails in the decomposition of the adduct complex that is formed with C(2)H(6). In the reaction with C(2)H(2), in addition to H(2) loss, C(3)H(3)(+) is produced, and this process formally corresponds to the transfer of the cationic methylidyne unit CH(+) to C(2)H(2), accompanied by the release of neutral Pt. In the ion-molecule reactions with the C(3) hydrocarbons C(3)H(6) and C(3)H(8), dihydrogen loss occurs with high selectivity for Pt(2)CH(+), but in the reactions of these substrates with PtCH(+) several reaction routes compete. Finally, in the ion-molecule reactions with ammonia, both platinum complexes give rise to proton transfer to produce NH(4)(+); however, only the encounter complex generated with PtCH(+) undergoes efficient dehydrogenation of the substrate, and the rather minor formation of CNH(4)(+) indicates that C-N bond coupling is inefficient.     

2-取代的6-溴甲基-4(3H)-喹唑啉酮的合成

2-取代的6-溴甲基-4(3H)-喹唑啉酮的合成;4(3H)-喹唑啉酮;苯并噁嗪酮;N-溴代琥珀酰亚胺; 合成     

选择性接聚乙烯醇枝聚醚氨酯的合成及其血液相容性

合成了α－甲基，ω－（２，３－环氧丙基）－聚乙二醇醚（Ⅱ）．经水解得到悬挂聚乙二醇（ＰＥＧ）枝的丙二醇－２，３（Ⅲ）．用二元醇（Ⅲ）为扩链剂制得了在硬链段上接有ＰＥＧ枝的聚醚氨酯（Ｈ－ＰＥＵ）．以四氢呋喃与少量大分子单体（Ⅱ）进行正离子开环共聚合制得每个链接有约１．３个ＰＥＧ枝的聚丁二醇（Ⅳ），用以合成了在软链段上接有ＰＥＧ枝的聚醚氨酯（Ｓ－ＰＥＵ）．ＥＳＣＡ及抗凝血性研究结果表明，不同位置接枝的ＰＥＵ，其表面都有明显的聚醚链段富集．Ｓ－ＰＥＵ抗凝血复钙时间只比未接枝者增长约２０％，而Ｈ－ＰＥＵ则增约一倍，比Ｓ－ＰＥＵ增约６０％．随ＰＥＧ最增大，复钙时间增长．     

Separation of homologues and isomers of linear alkylbenzenesulfonates by capillary electrophoresis with sodium dodecyl sulfate,carboxylic acids and bile salts

The ability of several anionic compounds, including carboxylic and dicarboxylic acids, sodium dodecyl sulfate (SDS), and sodium deoxycholate (SDC) and other bile salts, to separate the C(10)-C(13) homologues and the corresponding 20 positional isomers of linear alkylbenzenesulfonates (LAS) by capillary electrophoresis was studied. Up to 19 peaks and a shoulder were observed with a background electrolyte (BGE) containing 10 mM phosphate (pH 6.8), 30% acetonitrile and 40 mM SDS, and 18 peaks were obtained with a BGE containing 10 mM borate (pH 9), 40% ethanol and 40 mM palmitic acid (PA). Resolution increased with the alkyl chain length of the carboxylic acid. Dicarboxylic acids with a short alkyl chain, as azelaic acid, were useful to separate the homologues without distinguishing between the isomers. Up to 16 peaks and a shoulder were distinguished with SDC. Resolution decreased with the other bile salts. The 6-C(11)/5-C(11) isomer pair was better resolved with SDC than with SDS, and the 2-C(12) isomer was isolated using both PA and SDC, but not with SDS. Only the 7-C(13)/6-C(13) pair could not be resolved with any of the discriminating agents used.     

Oxidation by oxygen and sulfur of Tin(IV) derivatives containing a redox-active o-amidophenolate ligand

Oxidation of tin(IV) o-amidophenolate complexes [Sn(ap)Ph(2)] (1) and [Sn(ap)Et(2)(thf)] (2) (ap=dianion of 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-iminobenzoquinone (ImQ)) with molecular oxygen and sulfur in toluene solutions was investigated. The reaction of oxygen with 1 at room temperature forms a paramagnetic derivative [Sn(isq)(2)Ph(2)] (3) (isq=radical anion of ImQ) and diphenyltin(IV) oxide [{Ph(2)SnO}(n)]. Interaction of 1 with sulfur gives another monophenyl-substituted paramagnetic tin(IV) complex, [Sn(ap)(isq)Ph] (4), and the sulfide, [Ph(3)Sn](2)S. The oxidation of 2 with oxygen and with sulfur proceeds through the derivative [Sn(isq)(2)Et(2)] (7), which undergoes alkyl elimination to give two new tin(IV) compounds, [Sn(ap)(isq)Et] (5) and [Sn(ap)(EtImQ)Et] (6) (EtImQ=2,4-di-tert-butyl-6-(2,6-diisopropylphenylimino)-3-ethylcyclohexa-1,4-dienolate ligand), respectively, along with the corresponding alkyltin(IV) oxide and sulfide. Complexes 3-5 and 7 were studied by EPR spectroscopy. The structures of 3, 4 and 6 were investigated by X-ray analysis.     

MEKC determination of vanadium from mineral ore and crude petroleum oil samples using precapillary chelation with bis(salicylaldehyde)tetramethyl‐ethylenediimine

An analytical procedure has been developed for the separation of Cu(II), Ni(II), Co(II), Fe(II), Pd(II), Th(IV), V(IV), and determination of Fe(II), Co(II), Ni(II), and V(IV) by MEKC after chelation with bis(salicylaldehyde)tetramethylethylenediimine (H₂SA₂Ten). Uncoated fused silica capillary was used with an applied voltage of 30 kV with photo‐diode array detection at 228 nm. SDS was added as micellar medium at pH 8.2 with sodium tetraborate buffer (0.1 M). Linear calibrations were established within 0.015–1000 μg/mL of each element with LOD within 5–67 ng/mL. The method was applied for the determination of vanadium from crude oil and ore samples in the range 0.34–2.40 and 114.2–720.7 μg/g with RSD 1.7–3.8 and 0.98–2.30% (n = 3), respectively. Fe, Ni, and Co present in crude oil and ore samples were also determined with RSD 1.3–2.8, 1.1–4.1, and 1.2–3.5% (n = 3), respectively. The results were compared with that of supplier's specifications and atomic absorption spectrometry (AAS). Method was evaluated by standard addition technique.     

主链含酰亚胺环和炔基的聚酰亚胺型聚氨酯弹性体的合成及阻燃性能

以均苯四甲酸酐、 D,L-苯丙氨酸和1,4-丁炔二醇为原料合成了一种含有酰亚胺环和炔基的二醇, 并以其为扩链剂, 采用预聚体法, 与4,4-二苯基甲烷二异氰酸酯(MDI)和聚四氢呋喃醚二醇(PTMG)反应, 合成了不同硬段含量的主链含有酰亚胺环和炔基的热塑性聚酰亚胺型聚氨酯弹性体. 用红外光谱(FTIR)、 电子拉力机、 热失重分析(TG)、 广角X射线衍射(XRD)、 UL-94垂直燃烧和极限氧指数对聚酰亚胺型聚氨酯弹性体进行了表征. 结果表明, 这种聚氨酯呈现出无定形结构; 其拉伸强度随着硬段含量的增加而增大; 与传统的热塑性聚氨酯相比, 酰亚胺环和炔基改性的聚酰亚胺型聚氨酯弹性体的热分解过程非常缓慢, 呈现出较好的热稳定性; 不同硬段含量的聚酰亚胺型聚氨酯弹性体的UL-94垂直燃烧均达到V-2级别; 其极限氧指数随着硬段含量的增加而增大.     

Synthesis of trimethylammoniumphenylthio-substituted phthalocyanines with different pattern of substitution

The base-catalyzed cyclotetramerization of 3-, 4- and 4,5-dimethylaminophenylthio phthalonitriles with zinc(II)acetate afforded 1(4),8(11),15(18),22(25)- and 2(3),9(10),16(17),23(24)-tetrasubstituted and 2,3,9,10,16,17,23,24-octasubstituted Zn(II)phthalocyanines, respectively. The statistical mixed condensation of the same phthalonitriles with 1,2-dicyanobenzene gave the corresponding mono- and disubstituted derivatives. Methylation of such products afforded a series of cationic Zn(II)phthalocyanines with different pattern of substitution, with potential use as photodynamic agents in microbial infections.     

A cleaner and simple spectrophotometric micro-fluidic procedure for copper determination using nitroso-R salt as chromogenic agent

A cleaner and simple spectrophotometric method using microflow analysis (muFA) was performed. It consisted of a T-junction with microcoil on a polymethyl methacrylate (PMMA) chip which was fabricated by laser ablation and a molded polydimethylsiloxane (PDMS) as top plate. The fabricated PMMA chip was integrated with light emitting diode (LED) as light source and spectrometer as detector. The proposed device was applied to determining copper in water samples using nitroso-R salt as chromogenic reagent at 495nm. It was found that the proposed muFA system was with less reagents and samples consumption with tiny waste generation. The relative standard deviation (R.S.D.) was less than 2% (n=11) with the percentage recovery of 98.0+/-1.7% (n=7). The linear range for determination of copper in water samples was over the range of 0.05-3.0mugmL(-1) with a correlation coefficient (r(2)) of 0.999. The limit of detection (3sigma) was 47ngmL(-1) with a sample throughput of 30h(-1).     

第五、六族元素的有机化合物在有机合成中应用的研究 XVII.胂叶立德与氟代烯烃的反应

Reaction of perfluoropropylene (2a) with cyanomethylene- triphenylarsorane (1b) gave cyano-2, 3, 3, 3-tetrafluoropropionylmethylene-triphenylarsorane (4b), and with benzoylmethylene-(1c) and acetylmethylene-triphenylarsorane (1d) gave benzoyl-(3c) and acetyl-(trans-perfluoropropen-1-yl)- methylene-triphenylarsorane (3d), respectively 3c and 3d could be converted to benzoyl-(4c) and acetyl-2, 3, 3, 3-tetrafluoropropionyl -methylene triphenylarsorane (4d), respectively by refluxing with moist benzene. Reaction of carbomethoxymethylene- triphenylphosphorane (1e) with perfluoropropylene was similar to that of arsorane. However, benzoylmethylene-and acetylmethylene- triphenylphosphorane were unreactive towards perfluoropropylene. Reaction of carbomethoxymethylene-triphenylarsoraen (1a) with trifluorochloroethylene gave carbomethoxyfluoroacetylmenthylene- triphenylarsorane (4f) in low yield. when the residue was treated with methanol, difluorotriphenylarsorano and methyl- fluorochloroacetate (8) were obatined. The structures of the aforementioned products are ascertained by elemental analyses, IR, ^1H NMR, ^1^9F NMR and mass spectra.