Effect of TRITON™ X‐based dispersants bearing a carboxylic terminal group on rheological properties of BAM/ethyl cellulose/terpineol paste

In this study, we attempted to use TRITON? X (or octyl phenol ethoxylate (OPE) of different oxyethylene units (i.e., n = 2, 5, and 10))‐based dispersants containing a carboxylic group in the oxyethylene chain end for the formulation of BAM phosphor paste. Thus, a three‐component system employing OPE‐COOH as a dispersant, terpineol as a solvent, and ethyl cellulose as a binder was compounded with BAM particles, and the rheological properties of the paste were investigated in detail. Among three acidic TRITON X‐based compounds we tested (i.e., [OPE2‐COOH], [OPE5‐COOH], and [OPE10‐COOH]), OPE10‐COOH containing the highest number of oxyethylene units in the backbone was found to be the dispersant showing the lowest viscosity of BAM paste under identical conditions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and characterization of polyanilines doped with several carboxylic acids and with a carboxylic acid equivalent

Polyanilines (PANIs) doped with several organic acids—maleic acid, squaric acid and 2‐propynoic acid—were chemically synthesized in good yields, while PANI doped with 2,6‐dihydroxybenzoic acid did not form under similar polymerization conditions. The resulting PANIs were characterized by spectroscopic and thermal analysis, and it was found that the spectroscopic and thermal properties of these PANIs were affected by the type of dopant ion. Formation of different oxidation states of these PANIs were confirmed by the spectroscopic (UV‐visible and FT‐IR) analysis. Thermogravimetric analysis suggested that PANI doped with maleic acid indicated higher thermal stability than those with the other dopants. The yield and conductivity of PANI doped with maleic acid were found to be higher than those with the other dopants. The PANI doped with 2‐propynoic acid was readily soluble in organic solvents including tetrahydrofuran and dioxane. Copyright © 2005 Society of Chemical Industry     

Synthesis,characterization of new carboxylic acid‐containing benzoxazine and its cocuring behaviors with bisoxazoline

A new benzoxazine‐benzoic acid (BBA) was synthesized and the structure was conformed by ¹H‐NMR, ¹³C‐NMR, FTIR, etc. The cure behavior of BBA and cocure behavior of BBA with phenylene bisoxazoline (1,3‐PBO) were investigated by differential scanning calorimetry (DSC). It was found that BBA showed a single curing exothermic peak at about 217°C. However, all BBA/1,3‐PBO systems exhibited two exothermic peak. One may be attributed to the reaction between carboxyl groups of BBA and 1,3‐PBO. And the other was attributed to the ring‐opening polymerization of oxazine rings and the reaction between phenolic hydroxyl groups generated by the ring opening of benzoxazine ring and 1,3‐PBO. The curing temperature of benzoxazine containing carboxyl groups could be lowered by the copolymerization of 1,3‐PBO. Thermogravimetric analysis showed that the incorporation of ester–amide groups had a significant effect on decreasing thermal stability and char yield of the cured resin. SEM results indicated that 1,3‐PBO could toughen BBA benzoxazine resin. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

皂氨型洁面的开发及性能研究

根据皂氨型洁面的开发需求,首先筛选合适的皂基型表面活性剂和氨基酸型表面活性剂;然后对皂基型表面活性剂和氨基酸型表面活性剂的配比进行优化,得出最优配比;最后将制得的复配皂氨型洁面与市售单一的皂基型洁面和单一的氨基酸型洁面的性能进行对比测试。结果表明,皂氨复配的皂氨型洁面对皮肤刺激性比单一皂基型洁面和单一氨基酸型洁面都小;皂氨复配的皂氨型洁面对油脂的清除率介于单一的皂基型和单一的氨基酸型洁面之间,为90.2%;皂氨型洁面在使用感方面整体上优于单一皂基型洁面和单一氨基酸型洁面。     

Fibrous long‐chain organic acid cellulose esters and their characterization by diffuse reflectance FTIR spectroscopy,solid‐state CP/MAS 13C‐NMR,and X‐ray diffraction

Unsaturated and saturated organic acids with 11 and 18 carbon atoms, respectively, were used in a heterogeneous esterification reaction in the pyridine/toluene sulfonyl chloride system to prepare fibrous cellulose esters with different degrees of substitution. Highly bleached sulfite cellulose fibers were esterified during a 1‐ or 2‐h reaction time with the following organic acids: undecylenic acid, undecanoic acid, oleic acid, and stearic acid. In all cases, the heterogeneous esterification yielded partially substituted cellulose esters retaining their fibrous structure. The substitution reaction was confirmed by diffuse reflectance infrared spectroscopy and the chemical structures of cellulose esters were identified by solid‐state CP/MAS ¹³C‐NMR (75.3 MHz). X‐ray diffraction analyses showed broadening of the diffraction peaks with a higher degree of substitution of cellulose esters, which suggests structural changes within the cellulose fibers. Because the broadening peaks of X‐ray spectra or the unassigned C‐4 region of substituted cellulose chains in NMR spectra do not allow the calculation of dimensional changes of cellulose crystallites in cellulose esters, the lateral dimensions of crystallites in only cellulose fibers were calculated. The value derived from NMR (4.6 nm) differs by about 11% when compared with the value calculated from X‐ray diffraction data (4.1 nm). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1354–1365, 2000     

Electron‐beam irradiation of low‐density polyethylene in the presence of phenolic stabilizer,carboxylic acid stabilizer,or both

The effects of Irganox 1010 and citric acid as antioxidants and modifiers of the network structure and mechanical and thermal properties of low‐density polyethylene (LDPE) during electron‐beam crosslinking with different irradiation doses (up to 120 kGy) were investigated. The results showed that the addition of these stabilizers had a retarding effect on the gel fraction of LDPE within the investigated range of electron‐beam‐irradiation doses. However, a noticeable effect on the gel fraction was found for the LDPE formulations compounded with citric acid alone or with its mixture with Irganox 1010 (in an equal ratio), as illustrated by a study of the gel‐fraction/dose relationships. Tensile testing measurements showed that the addition of both stabilizers caused a slight reduction in the stress at break and an increase in the strain at break. On the other hand, the thermal properties of the LDPE batches crosslinked with electron‐beam irradiation were greatly improved as a result of the compounding with these stabilizers, as shown by thermogravimetric analysis studies. In this respect, the temperatures at different weight losses, the temperatures of the maximum rate of thermal decomposition, and the activation energies indicated that compounding with citric acid was more effective for stabilization against thermal decomposition than compounding with Irganox alone or a mixture. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1275–1286, 2005     

长链羧酸铕四元配合物的合成及其发光性质

合成了铕与长链羧酸、二苯甲酰甲烷、邻菲啰啉形成的四元配合物,用元素分析、红外光谱、核磁共振氢谱和紫外光谱对所合成的铕四元配合物进行了表征。由于长链羧酸的引入,铕配合物在氯仿等挥发性有机溶剂中具有良好的溶解性,这为今后与高分子基体复合创造了条件。铕配合物在342nm光波激发下,发出以铕的特征发射谱线612nm左右为主的强荧光。     

Synthesis and physico‐chemical properties of novel dialkyl diphosphate gemini surfactants based on octadecanol

A series of dialkyl diphosphate gemini surfactants has been synthesized using C₁₈ as hydrophobic chains and phosphate as head groups. Three flexible spacers have been used. In the present study, an attempt has also been made to synthesize mono octadecyl phosphate (MOP) at 35°C, which was used as an intermediate in the synthesis of geminis. This long chain of MOP has been effectively converted to gemini surfactants and subsequently converted to their disodium salts. The effect of reaction variables like temperature, duration, molar ratios of reactants, catalyst and spacer on the yield of dialkyl diphosphate gemini surfactant has also been reported. The MOP, gemini surfactants and disodium salt of gemini surfactants were characterized using FT‐IR and ¹H‐NMR. Surface active and physico‐chemical properties of synthesized gemini surfactants and their monomer were also determined. The results revealed that the yield of dialkyl diphosphate gemini surfactants ranged from 80 to 90%. Among all synthesized dialkyl diphosphate gemini surfactants D, S‐1,6‐GSOD had maximum anionic content, i.e. 80.7%, showed highest foaming ability and superior dispersing ability, whereas D, S‐1,8‐GSOD showed low cmc values, i.e. 0.00012 mM/L; minimum surface tension and interfacial tension, i.e. 39.1 and 36.3 mN/m, respectively.     

X‐ray diffraction characterization of the structure of zein–Oleic acid films

Wide‐angle (WAXS) and small‐angle X‐ray scattering (SAXS) studies of dry granular zein, zein fibers, zein–oleic acid resin, and zein–oleic acid films are reported. WAXS patterns showed two diffuse rings for these samples indicative of noncrystalline structures. Measured d‐spacings of ∼ 4.6 Å and ∼ 10.5 Å were found for zein–oleic acid resins and films, consistent with the presence of α‐helical segments. The granular zein and zein fibers had ∼ 4.6‐Å and ∼ 9.5‐Å spacings. Neither the films nor the fibers showed evidence of orientation of the molecular axes. SAXS studies of zein–oleic acid films indicated that the structure of the films was affected by preparation method. Biaxially drawn resin films showed periodicities of ∼ 170 Å along the film surface direction and ∼ 135 Å in the thickness direction, while the cast films had weaker intensity periodicities of ca. 80 Å for all beam directions; a weak, diffuse 45‐Å spacing was also observed for both samples. The 170‐Å periodicity was present in the resin before deformation and following uniaxial deformation. No SAXS periodicity was observed for the granular zein or zein fibers. Several structural models are presented for the resin films that are consistent with reports in the literature that zein, in solution, consist of prism‐like particles consisting of four or more molecules. ? 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1267‐1281, 1999     

Synthesis and characterization of side‐chain liquid‐crystalline ionomers containing quaternary ammonium salt groups

A series of thermotropic side‐chain liquid‐crystalline ionomers (LCIs) containing 4‐(4‐alkoxybenzyloxy)‐4′‐allyloxybiphenyl (M) as mesogenic units and allyl triethylammonium bromide (ATAB) as nonmesogenic units were synthesized by graft copolymerization upon polymethylhydrosiloxane. The chemical structures of the polymers were confirmed by IR spectroscopy. DSC was used to measure the thermal properties of these polymers. The mesogenic properties were characterized by polarizing optical microscopy, DSC, and X‐ray diffraction. Homopolymers without ionic groups exhibit smectic and nematic mesophases. The nematic mesophases of the ionomers disappear and the mesomorphic temperature ranges decrease with increasing concentration of ionic units. The influence of the alkoxy chain length on clearing temperature (T_c) values of ionomers clearly shows an odd‐even effect, similar to that of other side‐chain liquid‐crystalline polymers. The mesomorphic temperature ranges increase with increasing alkoxy chain length when the number of alkoxy carbon is over 3. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2879–2886, 2003     

Synthesis and characterization of azo‐based methacrylate polymers with methoxy and nitro end groups for nonlinear optical applications

One new and three already described azobased methacrylate monomers with methoxy and nitro end groups and spacer length 2 and 6 were synthesized. These monomers were copolymerized with methyl methacrylate and the monomers as well as copolymers were characterized by classical spectroscopy techniques (FTIR, NMR, and UV‐VIS), gel permeation chromatography (GPC), elemental analysis and thermal analysis (TGA and DSC). The glass transition temperature of the polymers was found to be above room temperature and thermal decomposition temperatures above 100°C. All the polymers were amorphous in nature and formed excellent homogeneous films with good optical transparency. The polymer films coated on indium tin oxide glass slides were poled and their order parameters were calculated to check the stability of oriented dipoles. Few samples were also studied for their second harmonic generation properties. Temporal stability, checked up to 120 h at room temperature, was found to be quite satisfactory. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3497–3504, 2007     

Synthesis and characterization of biodegradable lactic acid‐based polymers by chain extension

BACKGROUND: Poly(lactic acid) (PLA), coming from renewable resources, can be used to solve environmental problems. However, PLA has to have a relatively high molecular weight in order to have acceptable mechanical properties as required in many applications. Chain‐extension reaction is an effective method to raise the molecular weight of PLA. RESULTS: A high molecular weight biodegradable lactic acid polymer was successfully synthesized in two steps. First, the lactic acid monomer was oligomerized to low molecular weight hydroxyl‐terminated prepolymer; the molecular weight was then increased by chain extension using 1,6‐hexamethylene diisocyanate as the chain extender. The polymer was characterized using ¹H NMR analysis, gel permeation chromatography, differential scanning calorimetry and Fourier transform infrared spectroscopy. The results showed that the obtained polymer had a M_n of 27 500 g mol^?1 and a M_w of 116 900 g mol^?1 after 40 min of chain extension at 180 °C. The glass transition temperature (T_g) of the low molecular weight prepolymer was 47.8 °C. After chain extension, T_g increased to 53.2 °C. The mechanical and rheological properties of the obtained polymer were also investigated. CONCLUSION: The results suggest that high molecular weight PLA can be achieved by chain extension to meet conventional uses. Copyright © 2008 Society of Chemical Industry     

Synthesis and characterization of coordination polymers of polyesters with pendant amino groups

Oligomeric polyester, namely, poly(tetramethylene aspartate) (PTMA), was synthesized from D ,L -aspartic acid and 1,4-butanediol by a melt-condensation technique. Polyester–metal complexes were synthesized by the reaction of PTMA with hydrated acetates of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II), Mg(II), Ca(II), Pb(II), and Ce(IV) in DMSO. The polyester–metal complexes were characterized by elemental analysis, IR spectral studies, magnetic susceptibility measurements, and thermogravimetry. The metal ions were found to be six-coordinated with two water molecules as additional ligands besides oxygen and nitrogen atoms of polyester repeating units. Thermogravimetric analysis (TGA) showed that coordination polymers are thermally more stable than is polyester. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 751–759, 1998     

Synthesis of rosin‐based imidoamine‐type curing agents and curing behavior with epoxy resin

Rosin is an abundantly available natural product. The characteristic fused ring structure of rosin acids is analogous to that of some aromatic compounds in rigidity, and makes rosin and its derivatives potential substitutes for those aromatic compounds. In the study reported, the synthesis of biobased curing agents containing imide structure using rosin and the cure reaction were investigated. Rosin‐based imidoamine‐type curing agents were synthesized, and the chemical structure was confirmed using ¹H NMR, Fourier transform infrared and electrospray ionization spectroscopy. The curing behavior with diglycidyl ether of bisphenol A epoxy was studied using differential scanning calorimetry. The thermal mechanical properties and thermal stability of the cured epoxy resins were evaluated using dynamic mechanical analysis and thermogravimetry, respectively. The results indicate that the curing behavior of the rosin‐based curing agents is similar to that of curing agents with analogous structures. Cured products have good thermal stability due to the presence of the imide group and the bulky hydrogenated phenanthrene ring structure. Rosin acids have a great potential in the synthesis of epoxy curing agents as replacements for some of the current commercial aromatic or cycloaliphatic analogues. Copyright © 2010 Society of Chemical Industry     

Synthesis,characterization, and thermal properties of tris (3‐aminophenyl) phosphine oxide‐based nadimide resins

This article describes the synthesis, characterization, and thermal properties of nadimides obtained by reacting endo‐5‐norbornene‐2,3‐dicarboxylic acid anhydride (nadic anhydride) (NA), 4,4′‐oxodiphthalic anhydride (ODA), 1,4,5,8‐naphthalene tetra carboxylic dianhydride (NTDA) in glacial acetic acid/DMF. Structural characterization of the resins was done by elemental analysis, IR, ¹H‐NMR, and ¹³C‐NMR. The DSC scan showed the endothermic transition in the temperature range of 120–270°C. Multistep decomposition was observed in the TG scan of uncured resins in nitrogen atmosphere. Isothermal curing of the resins was done at 250 and 300°C for 1 h in an air atmosphere. These cured resins were stable to (350 ± 30)°C and decomposed in a single step above this temperature. This may be due to the retro Diels Alder (RDA) reaction. The char yield of the resins increased significantly on curing. The char yield was highest for P‐2N resin and this could be due to the presence of rigid skeleton i.e. naphthalene. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of styrene–N-butyl maleimide copolymers using iniferters containing thiyl end groups

The radical homopolymerization of styrene or copolymerization of styrene (S) with N-butyl maleimide (I) initiated by tetraethylthiuram disulfide was used to prepare macroinitiators having thiyl end groups. The S–I copolymers from the feeds containing 30–70 mol % I showed approximately alternating composition. The rate of copolymerization and molecular weights decreased with increasing maleimide derivative concentration in the feed; homopolymerization of I alone did not proceed. The macroinitiators served for synthesis of further S–I copolymers. Using polystyrene macroinitiator and the S–I copolymer with thiyl end groups in the polymerization of S–I mixture and styrene, respectively, the copolymers containing blocks of both polystyrene and alternating S–I copolymer were obtained. The copolymerization of S–I mixture initiated with the S–I copolymer bearing thiyl end groups led to the extension of macroinitiator chains by the blocks of alternating copolymer. The presence of the blocks in the polymer products was corroborated using elemental analysis, size exclusion chromatography, and differential scanning calorimetry. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 755–762, 1998     

Synthesis of copolyesters having tertiary amine groups or zwitterion moieties in the main chain

Copolyesters having tertiary amine groups or zwitterion moieties in the main chain were prepared from terephthaloyl chloride (TPC) and mixtures of bisphenol A and aliphatic diols such as N-ethyldiethanolamine (EDA), N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES) and N,N-bis(2-hydroxyethyl)glycine (BHG) by a liquid/solid biphase polycondensation in trimethyl phosphate (TMP) as well as a water phase/organic phase interfacial polycondensation. The composition of copolymers obtained by the biphase polycondensation is close to that of the feeds. The nucleophilicity of hydroxyl groups of these aliphatic diols is increased in TMP and the solvent TMP participates in the reaction. In the water phase/organic phase interfacial polycondensation, the copolyester (P1) from EDA has a higher aliphatic diol residue content than P2 and P3 from BES and BHG, because the self-nucleophilic catalysis of the tertiary amine groups of the resulting polymer occurs in the organic phase. The copolyesters (P2 and P3) having pendant hydrophilic groups contain very few aliphatic diol residues because the self-nucleophilic catalysis of the tertiary amine groups takes place in the water phase and the extensive hydrolysis of the intermediate occurs, which results from TPC with the tertiary amine groups during the reaction.     

Kinetic behavior of photo‐polymerization of UV‐curable resins with carboxylic acid and amino groups

Photo‐polymerization behaviors of bisphenol‐A epoxy diacrylate (EPA) and six kinds of EPA‐derived resins containing different amounts of carboxylic acid, urethane, amide, and imide groups were studied by a photo differential scanning calorimetry. The dark polymerization was performed and pseudo‐steady state assumption of growing radicals was made to obtain the kinetic constants for propagation, bimolecular termination, monomolecular termination, and the concentration of growing radicals of different resins as a function of extent of reaction. Compared with EPA, it was found that the rate of polymerization and kinetic constants of the six resins were relatively small because the mobility of reacting species in resins was restricted by carboxylic acid, urethane, amide, and imide groups. Finally, three different photo‐initiators were used to initiate the polymerization, and their kinetic behaviors were compared. The effect of tertiary amine group of photo‐initiator on the rate of polymerization of resins having carboxylic acid group and the initiator efficiency were discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010