双三羟甲基丙烷磷酸酯盐织物抗静电剂的合成工艺研究

以三氯氧磷（PO）和双三羟甲基丙烷（DTMP）以及氢氧化钾为原料,合成了织物抗静电整理剂双三羟甲基丙烷双磷酸酯钾盐。主要考察了原料配比、反应温度及反应时间对反应过程的影响,确定了最佳反应条件：n（PO）：n（DTMP）=4：1,反应温度为70℃,反应时间为5h,收率为95．04％。     

涤纶织物浸轧用阻燃剂环状磷酸酯的合成

以亚磷酸三乙酯、三羟甲基丙烷和甲基磷酸二甲酯为原料合成了环状磷酸酯,可作为涤纶织物浸轧用的环保型耐久阻燃剂。利用正交实验讨论了反应过程中各因素对结果的影响。结果表明:亚磷酸三乙酯:三羟甲基丙烷:甲基磷酸二甲酯的摩尔比为1.05:1:1.2,自制复合有机酸为酯交换反应催化剂,质量分数为0.1%,反应温度85℃,反应时间3 h,自制复合有机碱为加成反应的催化剂,质量分数为1.0%,反应温度200℃,反应时间8 h,酯交换反应收率95.0%,加成反应收率90.0%。合成的阻燃剂具有良好的阻燃性能和耐洗性能,用量超过100 g/L时,处理的织物经50次水洗可达GB/T5455—1997 B1级。     

离子液体[Bmim]BF4催化合成环状膦酸酯Antiblaze

制备了离子液体[Bmim]BF4,对其催化乙基双环亚磷酸酯与甲基膦酸二甲酯进行聚合反应合成环状膦酸酯进行了考察。正交实验确定了最佳合成路线。结果表明,乙基双环亚磷酸酯与甲基膦酸二甲酯的摩尔比为1∶1.6,催化剂用量为反应物总质量的0.4%,反应温度185℃,反应时间16 h,产率达98%。热重分析显示,500℃时残炭率为7.37%,具有良好的成炭作用。     

氮-磷复合阻燃剂的制备及阻燃性能研究

以双三羟甲基丙烷、三氯氧磷、三聚氰胺为原料,合成膨胀型阻燃剂双三羟甲基丙烷双磷酸酯三聚氰胺盐。主要考察了原料配比、反应温度及反应时间的影响,结果表明,配比为4∶1,反应温度为70℃,反应时间为5h时,可得中间体收率超过95.0%,产物阻燃效果好。产物用红外光谱定性检测。     

三羟甲基丙烷三水杨酸酯的合成与研究

合成了三羟甲基丙烷三水杨酸酯。在N2的保护下,以水杨酸和TMP（三羟甲基丙烷)为原料,采用醇酸直接酯化法合成三羟甲基丙烷三水杨酸酯。通过IR,MS,1H-NMR等手段进行表征,确证了目标产物的结构。考察了反应温度、催化剂种类、反应时间、TMP的羟基与水杨酸羧基的摩尔比对反应的影响,获得适宜的反应条件：水杨酸质量4 %的对甲苯磺酸为催化剂,N2保护下反应温度为160 ℃,反应时间为6 h,n(水杨酸的基)：n(三羟甲基丙烷（TMP）的羟基)=1:0.7,酯化率达99.5 %。并进一步研究了该酯类的抑菌性能,结果表明：该酯类对大肠杆菌具有明显抑菌性能。     

三(壬苯基)亚磷酸酯抗氧剂的合成新工艺

以壬基酚、亚磷酸三乙酯为原料,通过无溶剂催化酯交换反应合成三（壬苯基）亚磷酸酯抗氧剂。考察了催化剂种类及用量、反应温度、反应时间、№流速、原料配比等因素的影响,优化了反应条件。以0．1mol亚磷酸三乙酯为基准,n（壬基酚）：n（亚磷酸三乙酯）为3．2：1．0,反应温度为120℃,反应时间3h,催化剂碳酸钾用量占原料总质量的1．7％,N2流速为15mL／min,产物收率可在76％以上。通过红外、元素分析、核磁氢谱对产品进行结构表征证明为目标产物。     

三羟甲基丙烷三水杨酸酯的合成及抑菌活性研究

在N2保护下,以水杨酸和TMP(三羟甲基丙烷)为原料,采用醇酸直接酯化法合成三羟甲基丙烷三水杨酸酯。通过IR、LC、MS、1H NMR等手段进行表征,确证了目标产物的结构。考察了反应温度、催化剂种类、反应时间、TMP的羟基与水杨酸羧基的摩尔比对反应的影响,获得适宜的反应条件:以占水杨酸质量4%的对甲苯磺酸为催化剂,N2保护下反应温度为160℃,反应时间为6h,n(水杨酸的羧基)∶n〔三羟甲基丙烷(TMP)的羟基〕=1∶0.7,在该条件下,酯化率达99.5%,三羟甲基丙烷三水杨酸酯的产率达83.59%。进一步研究了该酯的抑菌性能,结果表明,抑菌剂质量浓度为0.01g/mL时,抑菌率达到80%。     

(-)反式-4R(4-氟苯基)-3S-羟甲基-1-甲基哌啶的合成

亚磷酸三乙酯与氯乙酸乙酯进行缩合、重排、脱氯乙烷合成磷酸酯,再与对氟苯甲醛经Knoevenagel反应合成肉桂酸酯,肉桂酸酯与丙二酸二乙酯胺解合成的N-甲胺基羰基乙酸乙酯环合得到哌啶二酮,环化物用硼氢化钾复合还原剂还原得±4-(4-氟苯基)-3-羟甲基-1-甲基哌啶,把混旋体进行手性拆分得目标产物(-)反式-4R(4-氟苯基)-3-羟甲基-1-甲基哌啶。选择自制硅胶酸载催化剂Cat1#、醋酸-乙二胺催化剂Cat2#、复合相转移催化剂Cat3#为各步催化剂,反应收率分别为89.1%、96.3%、86.5%、76.3%、87.2%、43.7%,总收率24.3%,比旋光度-36￣-38°,纯度大于99%。     

制备绿色润滑剂三羟甲基丙烷酯的催化酯化新工艺

以油酸和三羟甲基丙烷(TMP)为原料,用SnCl2.2H2O作催化剂,通过减压酯化的方法合成了三羟甲基丙烷油酸酯。反应的优化条件如下:n(油酸)n∶(TMP)=3.11∶,催化剂用量4%,反应温度170℃,反应时间4h,真空度0.09MPa。优化条件下TMP的酯化率达到94%。产物结构经IR光谱证实。     

膨胀型阻燃剂三羟甲基丙烷磷酸酯三聚氰胺盐的合成

以三羟甲基丙烷、磷酸、三聚氰胺为原料,用乙二醇作为分散剂,采用两步法合成了氮磷膨胀型阻燃剂三羟甲基丙烷磷酸酯三聚氰胺盐。对反应温度、反应时间、物料配比和分散剂等条件作了工艺考察。结果表明,第一步反应时间3 h、反应温度为60℃;第二步反应时间1.5 h,反应温度为60℃,分散剂为乙二醇;物料最佳摩尔比n(三羟甲基丙烷)∶n(磷酸)∶n(三聚氰胺)=1∶1∶1,该条件下阻燃剂剩炭率可达41%。通过红外光谱和热重分析对阻燃剂进行了表征,分别表明该阻燃剂具有N-H、C=N、P-O-C等特征峰,能够在有效的温度区间内发生热分解,起到阻燃作用。     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

Novel polyurethane coating technology through glycidyl carbamate chemistry

Glycidyl carbamate chemistry combines the excellent properties of polyurethanes with the crosslinking chemistry of epoxy resins. Glycidyl carbamate functional oligomers were synthesized by the reaction of polyfunctional isocyanate oligomers and glycidol. The oligomers were formulated into coatings with several amine functional crosslinkers at varying stoichiometric ratios and cured at different temperatures. Properties such as solvent resistance, hardness, and impact resistance were dependent on the composition and cure conditions. Most coatings had an excellent combination of properties. Studies were carried out to determine the kinetics of the curing reaction of the glycidyl carbamate functional oligomers with multifunctional and model amines. Detailed kinetic analysis of the curing reactions was also undertaken. The results indicated that the glycidyl carbamate functional group is more reactive than a glycidyl ether group. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.     

Highly moisture-proof polysilsesquioxane coating prepared via facile sol-gel process

A highly moisture-proof polysilsesquioxane coating was obtained from a new bis-silylated precursor, which was synthesized from 3-aminopropyltriethoxysilane (APTES) and m-xylylene diisocyanate (m-XDI) in tetrahydrofuran (THF) and verified by ¹H MAS NMR. For direct comparison purposes, an SiO₂ coating was also prepared by the Stöber method using tetraethoxysilane (TEOS) as the reactant. Interestingly, the coating obtained from the polysilsesquioxane sol exhibited a much higher moisture resistance capability than its counterpart, which was attributed to its more compact feature between nanoparticles as characterized by N₂ absorption experiment and transmission electron microscopy (TEM). Furthermore, its high transparency of about 92% showed potential for application in the protection of optical crystals.