用于水性车漆的受阻胺光稳定剂的合成及性能

设计、合成了一种受阻胺光稳定剂（HALS）TM-3。首先,三聚氯氰和N-丁基-2,2,6,6-四甲基-4-哌啶胺通过亲核取代反应合成了N-丁基-4,6-二氯-N-(2,2,6,6-四甲基-4-哌啶基)-1,3,5-三嗪-2-胺（中间体Ⅰ）;中间体Ⅰ再与N,N-双(2,2,6,6-四甲基-4-哌啶基)-1,6-己二胺反应生成了N2,N2’-(己烷-1,6-二基)双[N4-丁基-6-氯-N2,N4-双(2,2,6,6-四甲基哌啶-4-基)-1,3,5-三嗪-2,4-二胺]（中间体Ⅱ）;最后,中间体Ⅱ水解生成目标化合物6,6’-{己烷-1,6-二基双[(2,2,6,6-四甲基哌啶-4-基)氮二基]}双{4-[丁基(2,2,6,6-四甲基哌啶-4-基)氨基]-1,3,5-三嗪-2-醇}（TM-3）。采用1HNMR、13CNMR、HRMS表征了TM-3的结构,通过UV-Vis、TGA考察了其性能,比较了TM-3和双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯（HALS770）在汽车清漆涂料中的光稳定性。结果表明,TM-3在210nm处具有强烈的UV-Vis吸收;热稳定性能良好,在400℃以前能...     

两种杯[4]芳烃化合物对天然橡胶抗热氧老化性能及机理研究

将含乙氧基甲基侧链的杯[4]芳烃-1化合物和含硫醚及正己基侧链的杯[4]芳烃-2化合物作为抗氧剂加入到天然橡胶中,采用加速热氧老化实验研究了其对天然橡胶硫化胶的抗热氧老化性能的影响,并测试了其氧化诱导时间。结果表明,杯[4]芳烃-2对硫化胶的抗热氧老化性能与抗氧剂2246S相当,优于杯[4]芳烃-1,这主要归因于其与硫化胶良好的相容性以及硫醚键与受阻酚基团之间的协同抗氧效应。     

杯芳烃／聚丙烯共混体系耐热氧性能的研究

合成了对叔丁基杯[4]、杯[6]、杯[8]芳烃,并用热重法和烘箱老化评价了共混体系的耐热氧性能。结果表明,杯芳烃能明显提高聚丙烯的耐热氧性能,其耐热氧能力为：对叔丁基杯[6]芳烃＞对叔丁基杯[4]＜2,6－二叔丁基－4－甲基苯酚。     

多功能性二元受阻胺类光稳定剂的合成与性能

以三聚氯氰,2,2,6,6-四甲基哌啶-4-醇为原料得到中间体化合物2,4-二(哌啶-4-氧基)-6-氯-s-三嗪化合物(Ⅱa和Ⅱb),再与2-羟基苯并三唑类衍生物(Ⅲa,Ⅲb和Ⅲc)反应,得到6个二元受阻胺类光稳定剂化合物(Ⅳ)。用1HNMR、IR和ESI-HRMS确定了目标产物的结构。初步研究了其紫外吸收性能、热稳定性能和光稳定性能。结果显示:6个化合物在360 nm左右均有较强的吸收,最大摩尔消光系数ε分别为3.67×105、4.06×105、4.22×105、3.99×105、4.65×105,5.31×105L·mol-1·cm-1;6种光稳定剂的热和光稳定性能良好,其光稳定剂失重1%(质量分数)时的温度依次为:210、225、224、238、181和185℃,当掺杂光稳定剂化合物的样品的质量分解率达到10%的时候,所需要时间大于100 h。     

含金刚烷胺的杯［4］芳烃衍生物的合成及抗菌活性研究

对叔丁基杯[4]芳烃与对甲苯磺酸酯基乙氧基对苯甲醛反应生成对叔丁基杯[4]芳烃-1,3-二醛基衍生物1,对叔丁基杯[4]芳烃-1,3-二醛基衍生物1与金刚烷胺进行分子间缩合反应得到含金刚烷基的新型杯[4]芳烃衍生物,并利用1H NMR,13C NMR,MS和元素分析对目标化合物的结构进行了表征。初步的抗菌试验表明,该化合物表现出较好的抑菌活性。     

聚丙烯薄膜中抗氧剂与光稳定剂对受阻胺光稳定性能的影响

考察了各种主抗氧剂、辅助抗氧剂及光稳定剂体系对受阻胺化合物双(2,2.6,6-四甲基-4-哌啶基)癸二酸酯在聚丙烯薄膜中光稳定性能的影响。没有一个抗氧剂或光稳定剂与受阻胺化合物产生加和效果。很多情况下发现了反协同效应。讨论了所观察到的影响作用,涉及当前流行的对受阻胺化合物作用机理的理解。     

新型叠氮-均三嗪类含能化合物的合成与表征

以三聚氯氰为前驱体,通过亲核取代反应,得到硝基芳环均三嗪中间体;再将中间体与NaN3反应,得到4种新型叠氮-均三嗪类含能化合物:4,6-二叠氮基-N-(2-硝基苯基)-1,3,5-三嗪-2-胺基、4,6-二叠氮基-N-(3-硝基苯基)-1,3,5-三嗪-2-胺基、4,6-二叠氮基-N-(4-硝基苯基)-1,3,5-三嗪-2-胺基、2,4-二叠氮基-6-(2-(2,4-二硝基苯基)肼基)-1,3,5-三嗪;采用IR、1 H NMR、13 C NMR、MS等对4种化合物的结构进行了表征;采用TG-DSC研究了4种化合物的热力学性能;通过B3LYP/6-311G**方法预估了化合物的理论密度、标准生成焓、爆速和爆压。结果表明,4种化合物具有较好的热稳定性,叠氮基的引入使其具有较高的正生成焓。综合4种叠氮-均三嗪类含能化合物的性能,化合物2,4-二叠氮基-6-(2-(2,4-二硝基苯基)肼基)-1,3,5-三嗪的性能较佳。     

杯[4]芳烃咪唑盐的微波合成及在氟化反应中的应用

以杯[4]芳烃为起始原料,首先制得中间体杯[4]芳烃双溴代烷基衍生物,然后经微波辐射和阴离子交换,共得9种杯[4]芳烃咪唑盐衍生物,化合物的结构与构象经元素分析、IR、1HNMR、19FNMR、31PNMR表征.研究了它们在对氯硝基苯氟化反应中的催化性能以及对K+的萃取性能.结果表明,这9种化合物在氟化反应中的催化效果良好,对氟硝基苯的收率为80.89％～92.67％;同时化合物对K+具有较好的萃取效果,其中以化合物25,27-二[4-(3-甲基咪唑)乙氧基]-26,28-二羟基-5,11,17,23-四叔丁基杯[4]芳烃六氟磷酸盐的萃取效果最好,萃取率可达75.45％.     

聚合型多功能光稳定剂的合成研究

设计并通过以3,5-二叔丁基-4-羟基苯甲醛为原料,经与正丁胺还原胺化,与三聚氯氰取代反应,最后与N,N-双（2,2,6,6-四甲基-四哌啶基）己二胺进行聚合反应,得到了含有受阻胺和受阻酚活性基团的多功能聚合型光稳定剂化合物。     

不同抗氧剂体系对聚丙烯热氧光老化的稳定作用

以受阻酚类抗氧剂与受阻胺类光稳定剂作为聚丙烯(PP)的防老化助剂,从而筛选出对PP具有长效抗氧化作用的助剂;利用混合流变仪和万能试验机进行了流变和力学性能测试,研究了抗氧剂与光稳定剂单独及复配使用对PP老化性能的影响。结果表明,单独使用抗氧剂与PP共混,对PP成型加工时抗氧化能力的提升顺序为受阻酚1076受阻酚3114受阻酚1330受阻酚1010;受阻酚1076与受阻胺944复配使用时,PP的长效抗氧化性能最好,热氧光老化72h和144h后断裂伸长率保持率分别为75.9%、52.8%,螺杆转速为1r/min时的剪切黏度值保持率分别为89.9%、74.1%。     

In‐line analysis of the influence of monomeric and oligomeric hindered amine on the hydrolysis of polycarbonate in a PC/ABS blend

The polycarbonate/polyacrylonitrile butadiene styrene (PC/ABS) blends lose mechanical properties when exposed to outdoor conditions. This is due to the ultraviolet (UV) induced photo‐oxidation of the PC phase and the polybutadiene portion of the ABS. It is known that ABS can be stabilised against terrestrial light by the use of hindered amine in combination with a UV absorber. However, such hindered amine cannot be used when PC is present in a multi component polymer blend. The hydrolysis of PC is accelerated when a small amount of hindered amine light stabilisers (HALS) is incorporated in the resin and is exposed to elevated temperature. In this article the effect of monomeric and oligomeric hindered amine on the hydrolysis of PC during the compounding of PC/ABS blend in a twin screw extruder at 240°C is observed by means of in‐line UV‐vis spectroscopy. Tinuvin 765 was used as monomeric hindered amine and Tinuvin 622 as oligomeric hindered amine. The molecular weight of the compounded sample was determined by gel permeation chromatography (GPC) and the rheological properties were observed using an online viscometer. It was found that the extent of hydrolysis induced by the oligomeric hindered amine is less compared to monomeric amine. It was also observed that polymeric hindered amine imparts better dispersion of the ABS phase into the polymer blend. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

“Off-On-Off” fluorescent proton switch synthesized by RAFT polymerization

A polymeric chemosensor (PNa) containing naphthalimide signal moiety and piperazinyl ring recognition moiety for the detection of proton was synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization, which can guarantee narrow molecular weight distribution, high purity and precise polymeric structure. PNa and its corresponding monomer (Na) showed both fluorescence enhancement in low proton concentration and fluorescence suppression in high proton concentration, which can be observed by both naked eyes and optical responses. Quarternization of the alkylated amine of Na (NaI) can better support the “Off-On-Off” mechanism shown by PNa and Na. In addition, PNa displayed better sensitivity than Na. The effect of proton on thin PNa film was also investigated, and the addition of proton led to a decrease of the fluorescence intensity.     

UHMWPE/流动改性剂共混物的流动性能与冲击性能研究

以超高分子量聚乙烯(UHMWPE)／烯烃类流动改性剂(FM4)为共混改性的研究对象,讨论了不同含量的FM4对共混物性能的影响。结果表明,在高剪切速率下FM4对共混物的流动性能有很大的改善,使共混物的挤出成型成为可能;UHMWPE／FM4配比为85／15的共混物有非常优异的冲击性能,接近于纯UHMWPE。     

立构嵌段聚丁二烯的研制Ⅳ．立构二嵌段与三嵌段共混聚丁二烯的研究

在以ｎ－Ｂｕｌｉ为引发剂，环己烷为溶剂，二哌啶乙烷和二乙基锌为调节剂的丁二烯负离子聚合过程中，采用高分子设计，分别以二甲基二氯硅烷、苯甲酸乙酯和乙酸乙酯为偶联剂，合成了不同分子量、不同嵌段比及共混比的１，４－１，２／１，４－１，２－１，４及１，２－１，４／１，２－１，４－１，２立构嵌段聚丁二烯（ＰＢ），考察了共混物的微观相分离、流变性及屈服强度。结果表明，嵌段共混ＰＢ的分子量、嵌段比、共混比值只有在一定范围时，共混物才产生微观相分离，分相的嵌段共混ＰＢ具有较好的流变性、加工性，较小的冷流性和较高的屈服强度。     

高流动性聚丙烯的制备及其热稳定性能研究

采用过氧化物作为聚丙烯(PP)的分子量调节剂,高分子量受阻胺作为PP的热稳定剂,制备了高流动性PP(HFRPP)。研究了过氧化物含量对HFRPP流动性能和冲击性能的影响,并通过氧化诱导期试验、热氧老化试验及流变性能测试研究了高分子量受阻胺热稳定剂对HFRPP性能的影响。结果表明,添加质量分数为0.04%的过氧化物,经过一次和二次双螺杆挤出后,能够实现PP优异的流动性能并保持其适当的缺口冲击强度。高分子量受阻胺能够有效稳定过氧化物催化降解PP体系后所残留的活性中心,提高HFRPP热老化寿命且不影响其流动性能。     

Theoretical influence of polyester molecular weight distribution variation on melt viscosity during injection molding and extrusion as influenced by ester‐ester interchange

In this study Flory's initial molecular weight derivation involving polyester polymerization and ester‐ester interchange was expanded to address two types of blends relative to both the number average molecular weight and the weight average molecular weight. First, an add blend was considered where the numbers of molecules of the same length were simply added together to calculate new number and weight average molecular weights. Second, the complete transesterification blend was calculated using Flory's most probable distribution with the same number average as the add blend but with a very different weight average molecular weight. The ratio of the weight averages of the add blend to the transesterification blend were found to be significantly larger if the initial blending molecular weights were significantly different from one another. This ratio was also found to go through a maximum that occurred at approximately 50% by weight if the two different molecular weights had the same monomer molecular weight. If the monomer molecular weights were different, the location of this maximum could be quite different from 50% by weight. Since melt viscosity is proportional to the weight average molecular weight to a power ranging from 1 to 3.4, a very large ratio between weight average molecular weight of the add blend and the ester‐ester interchange blend was found to have a significant influence on the melt viscosity. A polyester blend mixture of micro‐domains of both a nearly pure add blend and a nearly complete ester‐ester interchange blend was used to explain how a short shot could be followed a few shots later with a part that flashed the mold in an injection molding application.     

Structure‐property relationships of blends of polycarbonate

Three grades of bisphenol‐A polycarbonate—high molecular weight linear, high molecular weight branched and low molecular weight linear—and their blends have been studied by GPC, DMTA, DSC, rheometry and impact measurements. The molecular weight distribution of the blends agred with that predicted from the component's distributions, indicating that no transesterification reactions had occurred during melt blending. The T_g of the blends varied with blend composition according to the Fox equation and was related to the reciprocal molecular weight predicted by the Flory‐Fox equation. The low shear rate viscosity of the blends agreed with a logarithmic rule of mixtures and showed power‐law dependence on the weight average molecular weight. At higher shear rates, shear thinning was observed. The steady shear viscosity correlated well with the dynamic viscosity, as suggested by the Cox‐Merz relation. The stress relaxation behavior of the melt was very sensitive to the blend composition and molecular weight and correlated well with the real modulus. Temperature studies of the dart impact energy showed that only the low molecular weight polymer underwent a brittle‐duetile transition at ea ?30°C and that all the blends were tough at room temperature. The enhanced stress triaxiality inherent in the notched lzod test caused the impact strenght at room temperature to decrease almost linealy with blend composition.     

Influence of different types of UV absorber/UV stabilizer combination on the photodegradation of PC/ABS blend

The polycarbonate/poly(acrylonitrile butadiene styrene) blends, (PC/ABS), are mainly degraded by sunlight known as photodegradation when exposed to outdoor conditions. It is the ultraviolet (UV) radiation that is responsible for the degradation of the blend. To stabilize against the harmful UV radiation and to scavenge the radical species which arise from UV or thermally induced degradation of the PC or the ABS, UV absorbers, and UV stabilizers are used. In this article three different UV absorbers namely, Tinuvin 1577—hydroxyphenyl triazine type, Cyasorb 5411—benzotriazole type, Uvinul 3030—cyanoacrylate type, and two different UV stabilizers, Tinuvin 765—monomeric hindered amine type, Tinuvin 622—oligomeric hindered amine were compounded in different combinations with PC/ABS blend at 240°C using a twin screw extruder. Accelerated aging of the compounded sample was done by Atlas Suntest apparatus. The photodegradation studies were done using UV–vis, attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy, and Yellowing index measurement. The molecular weight of the compounded sample before aging was determined by gel permeation chromatography (GPC). It was found that samples protected with hydroxyphenyl triazine type UV absorber and oligomeric hindered amine show the best result for decreasing the degradation products, oxidation rate, and yellowing of the PC/ABS blend. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

High-impact poly(ethylene terephthalate) blends

Rubbers of different kind were tested as toughening agents of poly(ethylene terephthalate) (PET), noting significant morphological and mechanical differences. In particular, good results were obtained by using an ethylene–ethyl acrylate–glycidyl methacrylate copolymer. The resulting blend evidenced good particle distribution, and the latter was related to chemical interactions between the rubber epoxy groups and PET terminal groups, including the effect of low molecular weight and polymeric amine catalysts, and to extrusion conditions. © 1995 John Wiley & Sons, Inc.     

PAHs in Sediments Contaminated by the Haven Oil Spill. (Genoese Bay)

Sediment samples were collected 40 months after the wreckage of the HAVEN off shore Arenzano, facing the Genoese coast, at 300 to 500 m depth, (wreckage zone) and analysed by UV fluorescence spectroscopy and CG/MS. PAHs as alkylated naphtalene, fluorene, phenanthrene, dibenzothiophene series have been studied. Analytical results reveal – 1° – a great alteration of alkylated homologues compared to parent compounds - 2° - the appearance of anthracene (absent in the original crude oil) in samples – 3° – a relative increase of high molecular weight PAHs (4–5 rings and more) as benzo(ghi)perylene and indeno(cd)pyrene. These changes result from the partial burning of the contaminant oil. A beginning of biodegradation is observed for alkylated phenanthrenes.