新型含萘环/环戊二烯环结构固化剂的合成及性能

A novel novolac curing agent containing both naphthalene and dicyclopentadiene （DCPD） moieties was prepared to produce a highly heat-resistant cured polymer network. The chemical structure was characterized using Fourier transform infrared spectroscopy, nuclear magnetic resonance, mass spectrometry, and gel permeation chromatography analyses. The thermal properties of the resulting polymer from diglycidyl ether of bisphenol A epoxy resin cured with the novel curing agent were evaluated using dynamic mechanical thermal analysis and thermogravimetric analysis. Compared with the conventional curing agent, the resulting polymer cured with naphthalene/DCPD navolac shows considerable improvement in heat resistant properties such as higher glass transition temperature （Tg） and thermal stability. The result also shows better moisture resistance because of the hydrophobic nature of naphthalene/DCPD structure.     

Preparation of aqueous dispersion of epoxy curing agent with specially synthesized phase inversion emulsifier

Generally, the curing agents for aqueous ambient-temperature-cured epoxy resin systems are epoxy-polyamine adduct, which are rendered water-soluble by salting with organic acids, while these acids have adverse influence on film property. It is a trend to develop aqueous dispersion of epoxy curing agent free of organic acids. The conventional surfactants are not suited to act as phase inversion emulsifiers to prepare aqueous dispersion of epoxy-polyamine adduct. So a special phase inversion emulsifier TETADGEPG-EPON834 was synthesized in two steps. Firstly, diglycidyl ether of polyglycol （DGEPG） was used as the chain extender to react with triethylenete tramine （TETA） in propylene glycol methyl ether （PM） at 70℃ for about 4 h. Secondly, epoxy resin （EPON834） was used as the chain extender to react with the adduct of TETA-DGEPG in PM at 65℃ for about 3 h. Then the special phase inversion emulsifier was used to prepare aqueous dispersion of EPON828-TETA adduct terminated by E10. In circumstances of low emulsifier concentration （5%）, phase inversion was not completed at phase inversion point （PIP） （0.35）. While the phase inversion has completely finished at PIP （0.45） in the circumstances of high emulsifier concentration （10%）. A stable aqueous dispersion of EPON828-TETA adduct terminated by E10 was prepared in circumstances of high emulsifier concentration （10%）.     

Preparation and Processing Properties of Nozzle Plate for Aluminum Continuous Strip Casting

The currently used ceramic nozzles for aluminum deep processing continuous hot rolled strips are featured with good integrity,high strength,good processing property,but non-uniform structure caused by the migration of silica sol. In this work,nozzle materials were prepared with aluminum silicate ceramic fiber,kaolin,and aluminum tripolyphosphate as starting materials,silica sol or silica sol- epoxy resin as the binder. After pulping,casting,curing at different temperatures and hot treatment,the prepared materials were analyzed in terms of migration layer thickness,cold modulus of rupture,and microstructure morphology. The results show that( 1) with the same curing temperature,the migration layer thickness of specimens bonded by different binders all decreases with the curing time prolonging; with the same curing time,the migration thickness declines first and climbs then as the curing temperature increases; overall,the specimen cured at 40 ℃ for 120 min has the thinnest migration layer; from the comparison,it is found that the silica sol- epoxy resin bonded specimen has slightly thinner migration layer than the specimen bonded by silica sol only;( 2) the specimen bonded by silica sol and epoxy resin has thinner migration layer,lower cold modulus of rupture and obvious lower bulk density than the silica sol bonded specimen;( 3) the material introduced with epoxy resin has better processing property but slightly lower strength than the material bonded by silica sol.     

神经二肽N-乙酰天门冬氨酰谷氨酸的合成

The synthesis process of N-acetyl-aspartyl-glutamate (NAAG) was studied, in which L-aspartic acid was used as the raw material, and the dipeptide was first prepared by esterification,acylation and the reaction with L-glutamic acid, and then the product NAAG was finally obtained by hydrolyzation and purification.The product and the intermediate were analyzed and identified by melting point measuring, elemental analysis, polarimeter and IR analysis.The effects of mixture ratio of raw materials, reaction temperature and reaction time were investigated.The results showed that the total yield was 50.02% when the esterification temperature was controlled at 20℃, esterification time 10 h, acylation temperature 70℃, acylation time 2 h, and DCC was used as the addition reagent to synthesize dipeptide.The hydrolization temperature was 60℃, the hydrolization time was 4 h.The product was purified by ion-exchange resin.The purity detected by HPLC was 97.5%.     

新型环氧大豆油增韧酚醛树脂的合成与性质

A novel epoxidized soybean oil-toughened-phenolic resin（ESO-T-PR）has been synthesized by etheri- fication graft and multi-amine curing ESO.Fourier transform infrared spectroscopy（FTIR）was adopted to investi- gate its molecular structure and scan electron microscope（SEM）was used to observe the micro morphology of its impact fracture surface.This ESO-T-PR was adopted as the matrix resin to prepare paper copper clad laminate （P-CCL）and the properties of resulting P-CCL are found superior to the related Chinese National Standard.The toughing mechanism was investigated by comparing the impact strength,solderleaching resistance,flexural strength, peeling strength and morphology of this ESO-T-PR with those of other two ESO modified phenolic resins.It is demonstrated that during the synthesizing process of ESO-T-PR,the phenol hydroxyl is etherified by ESO or ESO epoxy resin prepolymer（ESO chain extension polymer）and the long ESO epoxy resin chain segments enhance the crosslink density of ESO-T-PR and consequently improve the impact toughness and solderleaching resistance of P-CCL made of ESO-T-PR.The ESO-T-PR is a cheap matrix resin with excellent properties to make P-CCL（elec- tric guide board）.     

Synthesis of Chelating Resin PETU and Its Adsorption to Ag(I)

A novel chelating resin (PETU) with thiourea groups in its main chain was synthesized by the reaction of O,O'-butane-1,4-diyl dicarbonisothiocyanatidate and triethylene tetraamine. The adsorption of Ag(I) on PETU was investigated by batch tests. The results showed that adsorption data fitted Boyd's diffusion equation of liquid film and the adsorption was controlled by liquid film diffusion. Under the temperatures between 15~60℃, the adsorption capacity decreased with the increase of temperature, and increased with the increase of initial concentration of Ag(I). The experimental data fitted Langmuir and Freundlich equations, and the correlation coefficients for Langmuir equation were between 0.9965~0.9998, and those for Freundlich equation were between 0.8211~0.9810, and increased with the adsorption temperature. DH, DG and DS calculated by thermodynamic formulae were all negative, which meant that the adsorption process was exothermic and spontaneous, and the entropy decreased during the process. XPS results showed that N, S and O atoms were the electron donors to coordinate with Ag.     

Synthesis of Chelating Resin PETU and Its Adsorption to Ag(I)

A novel chelating resin (PETU) with thiourea groups in its main chain was synthesized by the reaction of O,O'-butane-1,4-diyl dicarbonisothiocyanatidate and triethylene tetraamine. The adsorption of Ag(I) on PETU was investigated by batch tests. The results showed that adsorption data fitted Boyd's diffusion equation of liquid film and the adsorption was controlled by liquid film diffusion. Under the temperatures between 15～60 ℃, the adsorption capacity decreased with the increase of temperature, and increased with the increase of initial concentration of Ag(I). The experimental data fitted Langmuir and Freundlich equations, and the correlation coefficients for Langmuir equation were between 0.9965～0.9998, and those for Freundlich equation were between 0.8211～0.9810, and increased with the adsorption temperature. △H, △G and △S calculated by thermodynamic formulae were all negative, which meant that the adsorption process was exothermic and spontaneous, and the entropy decreased during the process. XPS results showed that N, S and O atoms were the electron donors to coordinate with Ag.     

A free-standing superhydrophobic film for highly efficient removal of water from turbine oil

A free-standing superhydrophobic film is prepared by sequentially dip-coating a commercially available filter paper with nano SiO2 suspension, epoxy emulsion, and octyltrimethoxysilane solution. A surface with micro- or nano-roughness is formed because SiO2 nanoparticles are uniformly and firmly adhered on the backbone of the filter paper by the cured epoxy resin. Furthermore, the surface energy is significantly reduced because of introducing octytrimethoxysilane. Such a surface structure makes the prepared film a superhydrophobic material. Due to its free-standing nature, this superhydrophobic film can be used to remove water from turbine oil by filtration. The efficiency of water removal is high (up to 94.1%), and the filtration process is driven solely by gravity without extra energy consumption. Because of the facile fabrication process and the high efficiency of water removal, this free-standing superhydrophobic film may find application in power industry.     

非均相羰基氧化一步合成碳酸二苯酯的研究(Ⅴ)筛选催化剂及优化合成条件

Pd/LaxPbyMnOz, Pd/C, Pd/molecular sieve and Pd-heteropoly acid catalysts for direct synthesis of diphenyl carbonate (DPC) by heterogeneous catalytic reaction were compared and the results of DPC synthesis indicated that the catalyst Pd/LaxPbyMnOz had higher activity. The Pd/LaxPbyMnOz catalyst and the support was characterized by XRD, SEM and TEM, the main phase was Lao.szPbo.asMnOa and the average diameter could be about 25.4nm. The optimuna conditions for synthesis of DPC with Pd/LasPbyMnOz were determined by orthogonal experiments and the experimental results showed that reaction temperature was the first factor of effect on the selectivity and yield of DPC, and the concentration of O2 in gas phase also had significant effect on selectivity of DPC. The optimum reaction conditions were catalyst/phenol mass ratio l to 50, pressure 4.5MPa, volume concentration of O2 25%, reaction temperature 60℃ and reaction time 4 h. The maximum yield and average selectivity could reach 13% and 97% respectively in the     

燃烧法制备二氧化钛催化剂的条件对其可见光催化性能的影响

Titania catalysts were synthesized by a solution combustion method （SCM）. Photodegradation of 4-chlorophenol （4-CP） using the synthesized catalysts was studied under both visible light （λ≥420nm） and sunlight irradiation. The effect of preparation conditions on photocatalytic activities of the synthesized catalysts was investigated. The optimal photocatalytic activity of the catalyst （denoted as A1 ） was obtained under the following synthesis conditions： ignition temperature of 350~C, fuel ratio （ φ） of 1 and calcination time of lh. The degradation and mineralization ratio of 4-CP were 78.2% and 53.7% respectively under visible light irradiation for 3h using catalyst A1. And the catalyst A1 also showed high photocatalytic activity under sunlight irradiation.     

Characteristics of epoxy resin cured with in situ polymerized curing agent

In order to improve the heat resistance of a cured epoxy resin together with reducing the viscosity of the resin composition, an epoxy resin was cured with a curing agent formed from the radical copolymerization of vinyl monomers during the cure process of the epoxy resin. N-phenylmaleimide and p-acetoxystyrene were used as vinyl monomers of the curing agent. The epoxy resin was cured by the insertion reaction of the ester group of the in situ polymerized curing agent and the epoxy group of the epoxy resin. In the cure system of the epoxy and the phenol resins, reduction of the viscosity of the resin composition was achieved by replacing some or all of the phenol resin with these monomers. When all phenol resins were replaced by these monomers, the viscosity of resin composition (0.01 Pa s at 70 °C) decreased by about 1/2000 compared with that of the system with only phenol resin (21 Pa s at 70 °C). The glass transition temperature (T_g) of the cured resin with no phenols was 174 °C, an improvement of 17 °C compared with that of the system cured with only phenol resin. The flexural strength of the new resins remained unchanged.     

Synthesis and characterization of emulsion‐type curing agent of water‐borne epoxy resin

Self‐emulsified water‐borne epoxy curing agent of nonionic type was prepared using triethylene tetramine (TETA) and derivative of epoxy resin as a capping agent, which was synthesized by liquid epoxy resin (E51) and polyethylene glycol (PEG), and the curing agent possessed emulsification and curing properties at the same time. The curing agent with good property of emulsifying liquid epoxy resin could be obtained under the condition of the molar ratio of PEG : E51 : TETA as 0.8 : 1 : 3.5 at 80°C for 5 h. The mean particle size of the emulsion liquid was about 220 nm with the prepared curing agent and epoxy resin at the mass ratio of 1 : 3. The structure of the emulsion‐type curing agent was confirmed by FTIR and ¹H NMR spectra, and the mechanism of cured film formation was also analyzed by SEM photographs. The cured film prepared by the emulsion‐type curing agent and epoxy resin under ambient cure conditions showed good properties even at high staving temperature. This study provides useful suggestions for the application of the water‐borne epoxy resins in coating industry. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2652–2659, 2013     

聚双胍/环氧树脂体系潜伏性固化过程

用己二胺与双氰胺熔融缩聚, 合成了一种新型潜伏性环氧树脂固化剂, 并研究了其与环氧树脂的固化过程。用FTIR、XPS、¹H NMR分析了固化剂的结构;用DSC分析得到了固化剂与环氧树脂的适宜配比、固化体系的适宜固化温度及固化动力学参数;通过XRD分析了固化物的相结构;通过TG分析了固化物的热稳定性。结果表明, 与双氰胺环氧树脂固化体系相比, 固化温度降低近70℃, 同时潜伏性能良好, 30 d内固化度少于10%, 热稳定性能良好, 热分解温度超过300℃。     

水性环氧树脂/双氰胺体系的研究

多官能团酚醛环氧树脂F-51与适量二乙醇胺反应,制得一种分子中含环氧基和亲水基团的改性F-51环氧树脂,该树脂成盐后具有良好亲水性。以双氰胺为固化剂,对体系的反应性及固化物主要性能进行研究,结果表明固化反应起始温度显著降低,固化膜的硬度达6H,并具有很强的附着力。     

Room Temperature Curing Epoxy Adhesives for Elevated Temperature Service

Room Temperature curing compositions of epoxy resins with high temperature service capability (95-120°C) were formulated and evaluated. The compositions were based on selected high functionality atomatic epoxy polymers and multicomponent poly amine curing agent systems. Toughening was achieved by addition of a rubbery phase either by prereaction of the epoxy resin with carboxyl terminated (CTBN) or by amine terminated (ATBN) poly butadiene acrylonitrile. The latter elastomeric component served as a part of the poly amine curing agent.

Best results were achieved with an adhesive formulation comprising tetra glycidyl-4-4'-diaminodiphenylmethane (TGDDM) and triglycidyl ether of p-aminophenol with triethylenetetramine and addition of ATBN with a felt carrier.

Lap shear strengths of aluminum/aluminum specimens primed by silane coupling agent in the order of 22 MPa at 25°C and 11 MPa at 120°C with T-Peel strengths of 1.6N/mm at 25°C and 0.52 N/mm at 120°C, were obtained.

The thermal behaviour and transitions, the chemical and mechanical properties, the microstructure and morphology of the selected adhesive formulation were studied, using DSC, Gehman, FTIR, mechanical testing and SEM analysis, respectively.

Experimental results showed that the selected compositions could develop good high temperature (120°C) properties while cured at room temperature. Furthermore, their high temperature performance compares favorably or even exceeds that of commercially available room-temperature-curing adhesive compounds, and are competitive with elevated temperature cured film adhesives.     

环氧树脂胺加成物的合成及其固化性能研究

研究了环氧树脂二乙撑三胺加成物的合成、性能，结果表明合成温度宜为75－85℃，在控制反应热释放的条件下可向胺中直接加入环氧树脂。加成物能在室温快速固化E51环氧树脂并得到综合性能良好的固化产物，邻苯二甲酸二丁酯对固化反应活性的影响有化学控制与扩散控制2个方面。     

New type of phenolic resin: Curing reaction of phenol‐novolac based benzoxazine with bisoxazoline or epoxy resin using latent curing agent and the properties of the cured resin

In this study, we aimed to reduce the cure time, and to lower the cure temperature of the benzoxazine compound. Therefore, curing reaction of benzoxazine with bisoxazoline or epoxy resin using the latent curing agent and the properties of the cured resins were investigated. The cure behavior of benzoxazine with bisoxazoline or epoxy resin using the latent curing agent was monitored by differential scanning calorimetry and measurements for storage modulus (G′). The properties of the cured resin were estimated by mechanical properties, electrical insulation, water resistance, heat resistance, and flame resistance. As a result, it was confirmed that by using the latent curing agent, cure time of benzoxazine and bisoxazoline or epoxy resin was reduced, and cure temperature was lowered. And it was found that the curing reaction using phenol‐novolac based benzoxazine (Na) as the benzoxazine compound could proceed more rapidly than that using bisphenol‐A based benzoxazine (Ba) as the benzoxazine compound. However, the cured resins from Ba and bisoxazoline or epoxy resin using the latent curing agent showed good heat resistance, flame resistance, and mechanical properties compared with those from Na and bisoxazoline or epoxy resin using the latent curing agent. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

CARDURAE-10改性水性环氧固化剂及其室温固化机理

用具有多支链柔韧性链段的C12～14叔碳酸缩水甘油酯(CARDURAE-10)对环氧-胺加成物EPON828-TETA进行封端改性。CARDURAE-10改性后的水性环氧固化剂与液体环氧树脂在室温下固化所形成的涂膜性能良好。采用傅立叶转换红外光谱法(FT-IR)对其室温固化过程和机理进行了研究。     

硫脲改性胺环氧树脂固化剂的合成及性能研究

对硫脲改性胺(3,3′-二乙基4,4′-二氨基二苯基甲烷和二元脂肪胺A)固化剂固化环氧树脂进行了系统研究,分析了合成反应时间、反应温度和单体配料比对固化剂性能的影响,并进一步考察了固化剂与环氧树脂的最佳掺量比以及固化产物的热性能和力学性能。实验结果表明:反应时间为2.5 h,反应温度为130℃,3,3′-二乙基4,4′-二氨基二苯基甲烷与硫脲和二元脂肪胺A的物质的量比为1∶0.5∶0.4时,合成的固化剂以1∶3加入环氧树脂中,体系能在室温环境下1 h左右凝胶,该体系经室温固化再以100℃的温度后固化之后具有较好的耐热性能和冲击韧性。     

对甲基苯胺改性双氰胺环氧固化剂的合成及性能

用对甲基苯胺对双氰胺进行改性,制备了一种新型的改性双氰胺固化剂,对合成条件进行了优化,并对其固化环氧树脂条件进行了研究。结果表明,对甲基苯胺改性双氰胺的较佳工艺条件为对甲苯胺和水的物质的量比定为1∶1.5,双氰胺和苯胺的物质的量比为1∶1,转速为一档,于90℃,反应3h,收率85%。通过测试涂层硬度来考察固化工艺与性能。作为环氧树脂固化剂单独使用时,固化温度为110℃,比双氰胺体系固化温度160℃降低了近50℃,对甲基苯胺改性双氰胺固化温度高于120℃时,涂膜硬度大于双氰胺固化温度为160℃时涂膜硬度。