改性双马来酰亚胺的研究

本文研究了双马来酰亚胺与烯丙基化合物形成的改性树脂体系的固化和热性能，讨论了单体配比、增韧剂、催化剂对性能的影响。     

BIOFUMIGANT COMPOUNDS RELEASED BY FIELD PENNYCRESS (<Emphasis Type="Italic">Thlaspi arvense</Emphasis>) SEEDMEAL

Defatted field pennycress (Thlaspi arvense L.) seedmeal was found to completely inhibit seedling germination/emergence when added to a sandy loam soil containing wheat (Triticum aestivum L.) and arugula [Eruca vesicaria (L.) Cav. subsp. sativa (Mill.) Thell.] seeds at levels of 1.0% w/w or higher. Covering the pots with Petri dishes containing the soil-seedmeal mixture decreased germination of both species at the lowest application rate (0.5% w/w), suggesting that the some of the phytotoxins were volatile. CH₂Cl₂, MeOH, and water extracts of the wetted seedmeal were bioassayed against wheat and sicklepod (Senna obtusifolia (L.) H. S. Irwin & Barneby) radicle elongation. Only the CH₂Cl₂ extract was strongly inhibitory to both species. Fractionation of the CH₂Cl₂ extract yielded two major phytotoxins, identified by gas chromatography–mass spectrometry and NMR as 2-propen-1-yl (allyl) isothiocyanate (AITC) and allyl thiocyanate (ATC), which constituted 80.9 and 18.8%, respectively, of the active fraction. When seeds of wheat, arugula and sicklepod were exposed to volatilized AITC and ATC, germination of all three species was completely inhibited by both compounds at concentrations of 5 ppm or less. In field studies, where seedmeal was applied at 0.50, 1.25, and 2.50 kg/m² and tarped with black plastic mulch, all of the treatments significantly reduced dry weight of bioassay plants compared to the tarped control, with the highest seedmeal rate decreasing dry matter to less than 10% of the control 30 d after seedmeal application. Field pennycress seedmeal appears to offer excellent potential as a biofumigant for high-value horticultural crops for both conventional and organic growers.Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may also be suitable.     

2-羟基-3-烯丙氧基丙磺酸钠的合成

采用新方法合成了2-羟基-3-烯丙氧基丙磺酸钠。先由环氧氯丙烷和亚硫酸氢钠合成中间体3-氯-2-羟基丙磺酸钠，然后中间体再与丙烯醇在氢氧化钠催化下生成目标产物2-羟基-3-烯丙氧基丙磺酸钠。2步反应总收率在70％左右，中间体和产物分别进行了光谱表征。     

基于吲哚类半花菁染料的钯比率荧光探针

利用6-羟基萘-2-醛和碘化N-乙基-2,3,3-三甲基-3H-吲哚啉季铵盐的缩合反应生成的羟基半花菁染料2与氯甲酸烯丙酯的反应合成了荧光比率型钯探针1.研究表明:在含水介质中,探针1对钯(Pd0和Pd2+)显示出很高的敏感性、选择性和抗干扰性,其荧光比率增强大约72倍,对Pd2+的最低检测极限为0.23μmol/L.探针1对钯的作用机理是钯催化碳酸烯丙酯断裂导致比率荧光变化.     

Properties of novel diallyl phthalate resin modified with sulfur‐containing allyl ester compounds

Sulfur‐containing allyl ester, which reacts with diallyl phthalate (DAP) resin to have allyl groups, was synthesized by the reaction of allyl phthalic acid with bisphenol having sulfur atoms. The sulfur‐containing allyl ester compound was blended with DAP resin to improve the adhesive properties to copper. By modification with sulfur‐containing allyl ester compound, the T‐peel adhesive strength and the lap shear adhesive strength to copper was improved. In particular, the adhesive strength was greatly improved when the resin was modified with the allyl ester compound having a disulfide bond (?S?S?) (DADS). It is concluded that this result is due to the improvement of the interfacial adhesive strength because the sulfur atom was found to be located in the surface of the copper by Fourier transform infrared (FTIR) analysis. The glass transition temperature (T_g) and the thermal decomposition temperature (T_d) of the cured DAP resin modified with DADS slightly decreased with increasing concentration of DADS. The lowering of T_g is because the crosslinking density of the DAP resin modified with DADS is smaller than that of DAP resin. Moreover, from thermogravimetric analysis, the lowering of Td of the DAP resin modified with DADS is because DADS is likely to pyrolyze. © 2013 Society of Chemical Industry     

烯丙基酚氧树脂改性双马来酰亚胺体系的优化

通过环氧树脂与二烯丙基双酚A合成了一种烯丙基酚氧树脂,用以增韧双马来酰亚胺。在单因素试验的基础上,根据Box-Benhnken的中心组合试验设计原理,选取改性树脂体系组分为影响因子,应用响应面法进行3因素3水平的18组的设计试验,改性树脂性能(弯曲强度,冲击强度,热变形温度)为响应值,对改性树脂组分配比进行优化。结果表明,改性树脂组分配比BMI、DDS、APO、DABPA、DAP为2∶1∶0.2∶0.84∶0.1(物质的量比)时,综合2性能最好,此时改性双马树脂体系的冲击强度可达到21.4 k J/m,弯曲强度为200.5 MPa,热变形温度为195.8℃。     

Mechanical and dynamic properties of graft polyurethane/allyl novolac resin simultaneous interpenetrating network

Two series of polyurethane (PU)/allyl novolac resin simultaneous interpenetra ing networks (SINs) were synthesized. The PU components were prepared by reacting 4,4′-diphenyl methane diisocyanate with poly(tetramethylene oxide) (PTMO), whose molecular weight range was 600–700 (for convenience, this polymer was called UT1), 900–1050 (UT2) and 1900–2100 (UT3), respectively. The phenolic resin component was synthesized by substituting the hydroxy groups of the phenolic resin with the allyl group. To prove that the alkene group can be applied as a binding element between the networks to improve the network compatibility, trimethylol propane monoally ether (TMPME) with a double bond was chosen as the PU chain extender in one series of the PU/allyl novolac resin SINs (designated TUT1, TUT2 and TUT3 for different molecular weights of PTMO used as PU soft segments). After a detailed study of the thermal, mechanical, and dynamic properties and morphology, the extent of phase mixing of the graft PU/allyl novolac resin SINs (TUT series SINs) was significantly improved over that of UT series SINs. This result is consistent with the loss tangent shift in dynamic mechanical analysis measurements and with transmission electron microscope micrographs. The mechanical properties of the graft SINs (TUT series) were lower than those of the original SINs (UT series) because TMPME with bulky structure was used as the chain extender of PU.     

甘油直接制备丙烯醇的催化剂和反应工艺研究进展

丙烯醇是一种十分重要的中间体和化学原料。近年来,以甘油为原料直接制备丙烯醇的研究引起了许多科学家的关注。本文参考了最近十年来发表的文献,详细介绍了均相甲酸诱导的甘油脱氧脱水反应、催化剂作用下的甘油脱氧脱水反应、液固相甘油氢解反应和气固相甘油氢转移反应等过程制备丙烯醇的相关工艺、反应机理和催化剂的研究进展及发展趋势,并对比了上述工艺的优缺点。其中,均相甲酸诱导的甘油脱氧脱水工艺比较成熟,已经在实验室中得到验证和应用,但是甲酸的消耗量大,整个过程的原子经济性很差。 甘油脱氧脱水反应和液固相甘油氢解反应不仅需要采用价格昂贵的铼基催化剂,而且丙烯醇的选择性较低。 铁基催化剂作用下的气固相甘油氢转移反应制备丙烯醇,由于催化剂的价格低廉、制备工艺简单、产品分离容易等优势而备受关注,是最近五年的研究热点。在文献基础上,认为今后研究应该重点关注催化剂的酸碱性、氢转移能力及其与速率控制步骤的匹配,并有针对性地对催化剂进行优化和改进。     

双活性基固色剂的合成及应用

以二甲基二烯丙基氯化铵(DMDAAC)和烯丙基缩水甘油醚(AGE)为原料,过硫酸钠为引发剂,合成了一种环保型双活性基固色剂P(DMDAAC-AGE).通过FT-IR、TG-DTA和SEM等表征了固色剂的结构和性能.讨论了影响固色剂P(DMDAAC-AGE)性能的主要因素.合成P(DMDAAC-AGE)的优化工艺条件为:单体n(AGE)∶n(DMDAAC)=1∶2,在水相介质中,反应混合液中总单体初始质量分数为30%,引发剂0.75%(对单体质量),引发剂和原料AGE的加料方式为连续滴加,80℃保温反应6 h.将合成的固色剂用于活性染料染棉织物的固色,湿摩擦牢度可达4级,干摩擦牢度可达4～5级,皂洗沾色牢度可达4级.     

Combined effect of high pressure treatment and anti-microbial bio-sourced materials on microorganisms' growth in model food during storage

Antimicrobial bio-sourced films based on poly(lactic acid) containing either carvacrol or allyl isothiocyanate (AITC) were prepared and their antimicrobial properties were assessed on Botrytis cinerea during storage and after a high pressure (HP) “pasteurisation-like” treatment (up to 800 MPa at ambient temperature). A dry process (extrusion + thermomoulding) was used to shape the material. The high temperature encountered during film processing dramatically decreased the carvacrol and AITC content in the film, leading to a less efficient antimicrobial activity. The use of β-cyclodextrin (β-CD) to encapsulate the active compounds before film processing proved to be efficient to protect the AITC against thermal degradation and to control its release from the films during its use. PLA-based films containing either AITC or β-CD encapsulated AITC showed a significant activity against B. cinerea. An effective combination between the antimicrobial activity of AITC-based films and the high pressure treatment was observed on a model food system (PDA) inoculated with N × 10⁴ (N ~ 1–9) conidia of B. cinerea. An HP treatment of only 300 MPa associated with an antimicrobial PLA/β-CD system providing an initial quantity of active agents equivalent to 4 mg of AITC/L of air (i.e. almost 2 folds lower than the minimal inhibition concentration of the active packaging used alone, which was determined to be equal to 10 mg/L of air in the same conditions) was found more efficient (total inhibition of B. cinerea growth during 10 days) than an 800 MPa HP treatment used alone (increase of the lag phase growth of 3.3 days).

Industrial relevance

The consumer demand for “fresh like” product containing reduced amount of preservatives without compromising human and environmental safety needs the development of new preservation strategies. As a consequence, the concept of “hurdle technologies” has risen up. The combined effect of HP treatment and volatile antimicrobial packaging allowed the use of lower individual treatment intensities to inhibit B. cinerea growth. Combining such “hurdles” is of relevance in the context of development of low-cost and eco-friendly food technologies.