Synthesis and characterization of epoxy resins containing bismuth

The synthesis of epoxy resins in the presence of Bi as bismuth acrylate (BiA₃) showed that the properties such as epoxide equivalent weight (eq/100 g), molecular weight, and viscosity (η_sp) increased; whereas hydrolyzable chlorine content, hydroxyl content, and refractive index decreased in the presence of BiA₃. The metal forms a complex with ether linkage of epoxy resins, as evidenced from infrared spectroscopy. The presence of Bi in epoxy resins has been confirmed by scanning electron microscopy (SEM) and qualitative analysis. The glass transition temperature (T_g) of epoxy resins containing 1.18 × 10⁻⁵ and 2.8 × 10⁻⁵ molar equivalent of BiA₃ is 131.58 and 190°C, respectively, and is greater than that of blank (130°C). The heat of reactions for epoxy resins containing 1.18 × 10⁻⁵ molar equivalent of BiA₃, calculated by differential scanning calorimetry, is 4.75 J g. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1359–1365, 1997     

季铵盐型水性环氧树脂乳化剂的制备及特性研究

以二乙醇胺、环氧E-44树脂等为原料,合成叔胺结构中间体,与溴乙烷反应制得季铵盐型水性环氧树脂乳化剂,以相反转技术乳化环氧树脂E-44.研究了乳化剂合成过程中反应温度、反应时间和环氧基转化率的关系;探讨了乳化剂用量对水性环氧树脂水分散性,稳定性及固化性能的影响.利用红外光谱对产物的结构进行了表征.结果表明:二乙醇胺与环氧E-44树脂在80 ℃反应3 h,环氧基转化率可达98%以上;乳化剂用量为ω=22%时其乳化效果及所制得乳液的稳定性最好.DSC和TG分析结果表明,水性环氧树脂乳液和工业环氧树脂E-44比较,固化后热性能基本一样,分解温度约在350 ℃,但其玻璃化转变温度有所降低,说明其韧性有一定提高.     

Synthesis and characterization of epoxy resins containing arsenic acrylate

The properties of epoxy resins containing arsenic acrylate have been compared with that of a blank epoxy resin (DGEBA). The values of epoxide equivalent, hydroxyl content, hydrolyzable chlorine content, and specific gravity increased, whereas refractive index decreased in the epoxy resins containing arsenic acrylate (AsA₃). This is attributed to a complex formation between an As and an oxygen atom in the resin, as evidenced from IR spectroscopy. The reaction is first order (ER₃) with an activation energy of 53 kJ/mole. The epoxy resin with As cured with polyamide at 30°C, showed chemical resistance and excellent thermal stability compared with blank epoxy resin (epoxy resin without As).     

Synthesis and properties of phosphorus containing advanced epoxy resins

A series of advanced epoxy resins with various epoxy equivalent weights were synthesized from a reactive phosphorus‐containing diol, 2‐(6‐oxido‐6H‐dibenz[c,e][1,2]oxaphosphorin‐6‐yl)‐1,4‐dihydroxy phenylene and diglycidyl ether of bisphenol A and then cured with 4,4′‐diaminodiphenyl sulfone, phenol novolac, or dicyandiamide. The parameters of the polymerization reaction (such as reaction time, catalyst) are discussed in this article. Thermal properties of cured epoxy resins were studied using differential scanning calorimetry, dynamic mechanical analysis, and thermal gravimetric analysis. The flame retardancy of cured epoxy resins was tested by limiting oxygen index. The relations between thermal properties, flame retardancy, and epoxy equivalent weights were also studied. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 429–436, 2000     

非对称双子季铵盐阳离子表面活性剂的合成及性能

以十二烷基二甲基叔胺、盐酸、环氧氯丙烷为原料,合成了中间体N-(3-氯-2-羟丙基)-N,N-二甲基十二烷基氯化铵,后与3种不同烷基链长的长链烷基叔胺反应,得到3种非对称Gemini季铵盐阳离子表面活性剂(Ⅰ～Ⅲ)。通过IR光谱,1HNMR确证了中间体及目的产物的结构。测定了产物的临界胶束浓度cmc及γcmc。cmc分别为1 07×10-3mol·dm-3、1 99×10-3mol·dm-3和9 55×10-3mol·dm-3,γcmc分别为40 9mN·m-1、48 0mN·m-1和50 9mN·m-1。结果表明:所合成的非对称Gemini季铵盐阳离子表面活性剂具有较高的表面活性。     

Synthesis,characterization, and properties of silicone–epoxy resins

Silicone–epoxy (SiE) resins were synthesized through the hydrolytic condensation of 2‐(3,4‐epoxycyclohexylethyl) methyldiethoxysilane (EMDS) and the cohydrolytic condensation of EMDS with dimethyldiethoxysilane. Structural characterization was carried out by ¹H‐NMR, ²⁹Si‐NMR, and mass spectrometry analysis; the resins were linear oligomers bearing different numbers of pendant epoxy groups, and the average number of repeat Si O units ranged from 6 to 11. Methyhexahydrophthalic anhydride was used to cure the SiE resins to give glassy materials with high optical clarity. The cured SiE resins showed better thermal stability and higher thermal and UV resistances than a commercial light‐emitting diode package material (an epoxy resin named CEL‐2021P). The effect of the epoxy value on the thermal and mechanical properties and the thermal and UV aging performances of the cured SiE resins were investigated. The SiE resins became more flexible with decreasing epoxy value, and the resin with the moderate epoxy value had the highest thermal and UV resistances. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis,characterization, thermal and flame-retardant properties of silicon-based epoxy resins

A new silicon-containing oxirane triglycidyl phenyl silane oxide (TGPSO) and its corresponding silicon-containing epoxy resins are synthesized and characterized. The activation energies of TGPSO curing reaction with various curing agents, including 4,4-diaminodiphenylmethane, 4,4-diaminodiphenylsulfone, and dicyanodiaminde, are found to be 180, 196.5, and 154 kJ/mol. The curing reaction of TGPSO with diamines is determined to be a first-order reaction through means of Arrhenius plots. The introduction of the silicon-containing group results in higher curing reactivity. This silicon-containing resin possesses higher char yield as well as higher limiting oxygen index (LOI = 35) than the commercial epoxy resins, confirming the usefulness of these silicon-containing epoxy resins as flame retardants. Char yields and LOI measurements demonstrate that incorporating silicon into epoxy resins is able to improve their flame retardancy. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1231–1238, 1999     

Preparation, surface-active and antielectrostatic properties of multiple quaternary ammonium salts

A series of new cationic surfactants, bis-quaternary ammonium salts and tris-ammonium salts, were prepared from N,N-dimethyldodecylamine and a product of the reaction of epichlorohydrin with ethyl-, propyl-, butyl-, pentyl-, hexyl-, and octylamine (in the xase of bis-ammonium salts) or the hydrochloride of diethyl-, dipropyl-, dibutyl-, or dihexylamine (in the case of tris-ammonium salts). The obtained multiple salts were examined with respect to their surface-active properties: Critical micelle concentrations (CMC), effectiveness of surface tension reductions (γ_CMC), and adsorption efficiencies (pC₂₀) were measured. All these surfactants showed good water solubility and low CMC of more than one order of magnitude lower than those of corresponding monoalkylammonium salts. They also showed good foaming properties, but worse wetting capability. The obtained multiple salts showed excellent antielectrostatic properties.     

Synthesis and antibacterial activity of immobilized quaternary ammonium salts

Quaternary ammonium salts were immobilized on hydrophilic gels based on sucrose methacrylates (SM) and tested for their antibacterial properties. The cross-linked polymers were prepared by copolymerization of monomer–SM mixtures with 4-vinylpyridine and subsequent quaternization with 1-bromoctane and 1-bromoctadecan and by esterification of SM gels with 3-pyridine carboxylic acid chloride and quaternization. In addition, immobilized quaternary salts bonded by hydrophobic as well as by hydrophilic spacers were synthesized by esterification of SM gels with 11-bromundecanoic acid chloride and the tetraethylene glycol-based acid chloride 13c , respectively, and subsequent reaction of the halogen-substituted gels with tertiary amines. Suspension tests for antibacterial properties of the immobilized bactericides against Escherichia coli, Staphylococcus aureus, and Micrococcus luteus demonstrated high activity of the quaternary salts bonded by the hydrophobic spacer. Advantageously, these insoluble bactericides can be applicated without contamination of the substrate; they can be removed easily and used repeatedly. © 1994 John Wiley & Sons, Inc.     

乙氧基化三酯基季铵盐的合成与性能

以硬脂酸和三乙醇胺为原料合成硬脂酸三乙醇胺三酯,对该酯先进行乙氧基化改性,再进行季铵化反应得到了不同平均EO数的乙氧基化三酯基季铵盐——乙氧基化三硬脂酸乙酯基甲基硫酸甲酯铵(3EQDMS-nEO)。采用IR和1HNMR对产物结构进行了表征。考察了不同平均EO数的乙氧基化三酯基季铵盐的柔软性、再润湿性、去污力和对织物白度的影响等性能,并与硬脂酸乙酯基羟乙基甲基硫酸甲酯铵(EQDMS)进行了对比。结果表明,3EQDMS-6EO是一种性能良好的新型柔软剂,其柔软性与EQDMS相近,再润湿性优于EQDMS,多次处理后对织物白度影响不大,具有EQDMS所不具备的去污力。     

乙氧基化酯基季铵盐的合成与性能研究

以硬脂酸与三乙醇胺反应制备了硬脂酸三乙醇胺酯,对该酯先进行乙氧基化改性,再进行季铵化反应得到了一种乙氧基化酯基季铵盐乙氧基化硬脂酸乙酯基羟乙基甲基硫酸甲酯铵(EQDMS-2EO)。采用IR和1HNMR对产物结构进行了表征,考察了EQDMS-2EO的生物降解性、柔软性、抗静电性、再润湿性和对织物白度的影响等性能,并与硬脂酸乙酯基羟乙基甲基硫酸甲酯铵(EQDMS)和传统织物柔软剂双十八烷基二甲基氯化铵(D1821)进行了对比研究。结果表明,EQDMS-2EO的生物降解性优于D1821,柔软性与D1821相近,抗静电性和再润湿性优于EQDMS和D1821,多次处理后对织物白度影响不大。     

Synthesis, characterization and properties of tetramethyl stilbene-based epoxy resins for electronic encapsulation

Two novel tetramethyl stilbene-based novolac (II and IV) were synthesized from 2,6-dimethyl phenol and chloroacetaldehyde dimethylacetal or chloroacetone, and then the resulted novolacs were epoxidized to tetramethyl stilbene-based epoxy resins (III and V). The proposed structures were confirmed by FTIR, elemental analysis, mass spectra, NMR spectra and epoxy equivalent weight titration. The synthesized tetramethyl stilbene-based epoxy resins were cured with 4,4-diaminodiphenyl methane (DDM) and 4,4-diaminodiphenyl sulfone (DDS). Thermal properties of cured epoxy resins were studied using dynamic mechanical analyzer, differential scanning calorimeter, thermal expansion analyzer and thermal gravimetric analyzer (TGA). These data were compared with that of the commercial tetramethyl biphenol (TMBP) epoxy system. According to the experimental data, the order of T_g for cured epoxy system is III>TMBP>V. The order of moisture absorption for cured epoxy system is V<III<TMBP. According to TGA, the 5% degradation temperatures in nitrogen atmosphere were in the range 370-377 and 397-412 °C for DDM and DDS curing systems, respectively. In air atmosphere, the 5% degradation temperatures were in the range 372-385 and 410-411 °C for DDM and DDS curing systems, respectively. The CTE is in inverse order with T_g, therefore, III/DDS<TMBP/DDS<V/DDS.     

Synthesis and characterization of quaternary ammonium ionomers

The cationic monomers, MPDMAC₁₆ and MPDMAC₁₈, were obtained by quaternization of methacrylamidopropyl–N,N′‐dimethylamine with n‐alkyl iodides (1‐iodohexadecane and 1‐iodooctadecane) in ethyl acetate. Hydrophobic ionomers of MPDMAC₁₆ and MPDMAC₁₈ with N‐substituted acrylamides were prepared at 60 ± 0.1°C in DMF using AIBN initiator. The cationic monomers and ionomers were characterized by ¹H‐ and ¹³C‐NMR spectroscopy. The copolymer composition was evaluated from elemental analysis data using carbon/nitrogen (C/N) ratio. The molecular weight distributions of ionomers were obtained from GPC analysis. Both the dilute solution and concentrated solution properties of ionomers were studied by viscometry at 30°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1100–1105, 2005     

三头基型季铵盐表面活性剂的合成及表面性能研究

以甲胺醇溶液、环氧氯丙烷、十二胺、十六胺、十八胺为主要原料,合成出一种新型的表面活性剂BHMDn,(n=12,16,18,代表两端烷基链的碳原子个数),考察其的表面活性以及盐对其表面活性的影响。结果表明,目标产物水溶液的cmc分别为1×10-4,6×10-5,5×10-5 mol/L;临界胶束浓度下的表面张力rcmc分别为27.4,21.5,19.6 mN/m。目标物与十二烷基苯磺酸钠(SDBS)复配产生了较好的协同效应。     

Synthesis and antimicrobial activities of acrylamide polymers containing quaternary ammonium salts on bacteria and phytopathogenic fungi

Three series of acrylamide monomers/polymers containing quaternary ammonium salts (QASs), i.e., acrylamide QAS monomers (QDs), homopolymers of QDs (PQDs) and copolymers of QDs with acrylate monomer (PQDCs), were synthesized and employed in antimicrobial tests against both bacteria (Escherichia coli (E. coli) and Staphylococcus albus (S. albus)) and phytopathogenic fungi (Rhizoctonia solani (R. solani) and Fusarium oxysporum f. sp. cubense race 4 (Foc4)). The antibacterial activity of the QASs was evaluated by determining the minimum inhibitory concentration (MIC) against E. coli and S. albus by the TTC coloration method, and the antifungal activity was measured by mycelia growth inhibition as well as MIC and the minimum fungicidal concentration (MFC) values. The results indicated that PQD homopolymers and PQDC copolymers showed far better antimicrobial activities than QD monomers. PQDC copolymers by incorporating hydrophobic acrylate units into the main chain of polyacrylamide backbone displayed even better antimicrobial activities, depending on QAS structure and hydrophobic content. Moreover, polymers with benzyl group attached to nitrogen atom showed better inhibitory effect on bacteria and phytopathogenic fungi. The results could assist understanding and development of future design of antimicrobial polymers as potential fungicide agents to control plant disease.     

聚苯胺季铵盐的合成及其性能研究

以邻氨基苯甲酸为原料,与氯乙醇反应生成2-氨基苯甲酸氯乙酯,然后用三乙胺季铵化合成了苯胺季铵盐,并将其聚合,通过红外光谱、紫外-可见光谱、X-射线衍射、循环伏安法和热重分析等对其结构与性能进行了研究。     

季铵盐型单偶氮染料的合成及其应用

通过重氮化偶合法合成了1个新的季铵盐型单偶氮弱酸性染料,可按照传统的染色法上染羊毛纤维,上染率达到70%,但染色牢度较低.该染料水溶液具有较低的抗菌活性.并同时测试了前期工作中合成的另3个含不同长度烷烃链的阳离子型染料的染色性能和抗菌活性.     

Multifunctional epoxy resins: Synthesis and characterization

The tetrafunctional epoxy resins were prepared starting from diaminodiphenylmethane, diaminodiphenylether, and diaminobibenzyl. The obtained resins were characterized by IR and ¹H‐NMR spectroscopy, rheological and thermal techniques. The polymerization reaction was investigated by viscosimetry. The flow activation energy and the polymerization activation energy were evaluated from the rheological data and from the critical parameters (critical time and critical viscosity at gel point). The viscosity measurements and gel time determination showed slight differences between the synthesized resins. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2430–2436, 2000     

Synthesis,characterization, and properties of multifunctional naphthalene-containing epoxy resins cured with cyanate ester

Multifunctional naphthalene-containing epoxy resins derived from 2,7-dihydroxylnaphthalene were synthesized and the intermediates were characterized by Fourier transform infrared spectroscopy, elemental analysis, and mass spectrometry. The cured products from naphthalene-containing epoxy resin and the dicyanate ester of bisphenol A (DCBA) exhibited a better T_g and a lower coefficient of thermal expansion than those of the commercial epoxy system. The glass transition temperature, thermal stability, and moisture absorption were found to increase with the epoxy functionality when naphthalene-containing epoxy resins were cured with DCBA. Thermogravimetric analyses revealed that the DCBA-cured system had a better thermal stability than that of the 4,4′-diaminodiphenylsulfone (DDS)-cured system. The addition of a metallic catalyst into the epoxy resin/cyanate ester system not only facilitated the cyclotrimerization of the cyanate ester but also the polyetherification of the epoxy resin. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1611–1622, 1999     

Synthesis and properties of novel phosphorus‐containing bismaleimide/epoxy resins

A novel soluble phosphorus‐containing bismaleimide (BMI) monomer, bis(3‐maleimidophenyl)phenylphosphine oxide (BMIPO), was synthesized by the imidization of bis(3‐aminophenyl) phenylphosphine oxide, in which its structural characterization was identified with ¹H‐NMR, ¹³C‐NMR, and Fourier transform infrared spectra. The BMIPO resin, with five‐membered imide rings and high phenyl density, was an excellent flame retardant with a high glass‐transition temperature (T_g), onset decomposition temperature, and limited oxygen index. In phosphorus‐containing BMI/epoxy/4,4′‐methylene dianiline (DDM)‐cured resins, homogeneous products were obtained from all proportions without phase separation. Because of the higher reactivity of BMIPO/DDM relative to that of 4,4′‐bismaleimidodiphenylmethane (BMIM)/DDM, the increase in the BMIPO/BMIM ratio in this blending resin increased the recrosslinking hazards of the postcuring stage and so lowered the T_g value and thermal stability. The thermal stability of the BMI/epoxy‐cured system was lower than that of the epoxy‐cured system because of the introduction of a phosphide group into BMIPO, whereas for the T_g value and flame retardancy, the former was significantly higher than the latter: the higher the BMIPO content in the blend, the higher the flame retardancy. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2080–2089, 2002; DOI 10.1002/app.10607