The effect of the amphiprotic nature of human hair keratin on the adsorption of high charge density cationic polyelectrolytes

Adsorption of the cationic polymers poly(methacrylamidopropyltrimethyl ammonium chloride) (PMAPTAC) and poly(1,1-dimethylpiperidinium-3,5-diallylmethylene chloride) (PDMPDAMC) on human hair was studied by measurements of the amount of polymer adsorbed and by the streaming potential method. Results reflect the amphoteric nature of the keratin surface and show that the excess of anionic sites at pH values above 4 is the main driving force for the adsorption of cationic polyelectrolytes. Lowering the pH below 4 or addition of neutral salt (KCl) reduces the amount of adsorbed polymer. It was shown that the adsorption of cationic polymer in the concentration range 0.01 to 0.1 % and at neutral pH reverses the overall character of the surface from anionic to cationic. Keratin fibers modified in this manner do not exhibit amphoteric character and bear excess positive charge in the pH range 2–9.5. The value of the amount of the polymer adsorbed at saturation concentration (2 mg/g) as well as the lack of molecular weight effect in the range (5 · 10⁴ – 10⁶) on the amount of polymer adsorbed suggest that polymer chains adopt a rather extended conformation on the fiber surface. Some data concerning the formation of a complex between adsorbed cationic polymer and anionic detergents or polyelectrolytes are also presented.     

Synthesis and characterization of segmented liquid crystal poly(azoxy polyester-co-polyoxypropylene)

In this study a series of a segmented copolyester, poly(4,4′-dioxy-2,2′-dimethyl-azoxybenzene dodecanedioyl) (PMABD)-co-polyoxypropylene 400 (POP), was prepared. The chain length of PMABD studied (n) was varied from 7.8-18.2, and that of POP was unchanged. The intrinsic viscosity of the segmented copolyesters was 1.04-1.30, and the number average molecular weight obtained was 2.53 × 10⁴?3.49 × 10⁴ g/mol. The mesophase texture and thermal properties of the segmented copolyesters were measured as functions of n. It was found that the insert of flexible POP between those liquid crystalline domains of PMABD did affect thermotropic properties of PMABD. As the n value was 9.0 and 7.8 (or 7.4 and 8.6% by weight POP) the texture appeared as cholesteric-like oily streaks. The effect could not be attained by simply copolymerizing a mesogenic moiety with a pair of spacers of different lengths. The fluidity and domain structure of the flexible dodecanedioyl-POP-dodcanedioyl segments are taken into account for the obtained results. © 1995 John Wiley & Sons, Inc.     

主链含硅聚芳酯的合成及气体透过性能的研究

以双［对－酰氯苯基］二甲基硅烷和酚酞、四溴酚酞以及双酚Ａ为原料，合成了三种主链含硅聚芳酯，并对聚合物相关的物理性质进行了表征，制成了均质透明的薄膜．采用低真空法测定这些聚合物对Ｈ２、Ｏ２、Ｎ２、ＣＯ２、ＣＨ４的气体透过速率，并计算出气体透过系数、扩散系数、溶解系数、分离系数．从气体透过性能与聚合物分子结构关系的角度，按照气体透过的溶解－扩散机制，对聚合物的气体透过性能进行了研究，而且着重讨论了聚合物的堆积密度对气体扩散系数的影响，以及聚合物主链中极性链段的百分含量对气体溶解系数和溶解选择性的影响。     

A novel hyperbranched polyester acrylate used for microfabrications

A novel hyperbranched polyester acrylate (HPEA) was synthesized based upon ethylenediamine tetraacetic acid as a “core” molecule, 5‐hydroxyisophthalic acid as an AB₂ monomer, and 2‐hydroxyethyl acrylate as an endcapping reagent. The obtained oligomer has an unsaturation concentration of 4.10 mmol_C?C g^?1 measured by nuclear magnetic resonance and a wide molecular weight distribution of 1.64 measured by gel permeation chromatography. The two‐photon absorption (TPA) photopolymerization of HPEA under the exposure of a Ti : sapphire femtosecond laser with a wavelength of 800 nm was investigated through laser exposure dose‐dependant spatial resolutions of its resins. The TPA photopolymerization thresholds at the range 1.6–4.3 × 10⁷ mJ cm^?2, and exposure dose windows at the range 3.4–4.3 for three formulations were determined. A spatial resolution of 0.85 μm was obtained through the TPA photopolymerization of the formulation containing 1 wt% photoinitiator and 0.3 wt% photoinhibitor. A diffraction grating and real three‐dimensional coupled gear wheel created by TPA photopolymerization were described to demonstrate the unique capability of HPEA in microfabrications. Copyright © 2004 John Wiley & Sons, Ltd.     

Nanocomposite materials from latex and cellulose whiskers

Composite materials were processed by casting a mixture of aqueous suspensions of latex and microfibrils. These microfibrils, or whiskers, are extracted from a sea animal and are monocrystals of cellulose, with an aspect ratio around 100 and an average diameter of 20 nm. It has been found that the mechanical properties (shear modulus) are increased by more than two orders of magnitude in the rubbery state of the polymeric matrix, when the whisker content was 6% (w/w). This very large effect is discussed on the basis of different types of mechanical models and it is concluded that these whiskers form a rigid network, probably linked by hydrogen bonds. The formation of this network is assumed to be governed by a percolation mechanism.     

Comparison of different reactive organophosphorus flame retardant agents for cotton: Part I. The bonding of the flame retardant agents to cotton

N-Methylol dimethylphosphonopropionamide (MDPA), known as “Pyrovatex CP” and “Pyrovatex CP New” commercially, has been one of the most commonly used durable flame retardant agents for cotton for many years. In our previous research, we developed a flame retardant finishing system for cotton based on a hydroxy-functional organophosphorus oligomer (HFPO) in combination with a bonding agent such as trimethylolmelamine (TMM) and dimethyloldihydroxyethyleneurea (DMDHEU). In this research, we investigated the bonding of these two flame retardant finishing agents to cotton. We found that the majority of MDPA is bound to cotton by its N-methylol group and that the use of TMM as a co-reactant modestly increases the fixation of MDPA onto cotton. For HFPO, however, the use of a bonding agent is necessary to form a covalent linkage between HFPO and cotton. Both the fixation of HFPO on cotton and its laundering durability are influenced by the effectiveness and concentration of the bonding agent. The commercial product of HFPO contains approximately 33% more phosphorus than that of MDPA and the percent fixation of HFPO on cotton is also moderately higher than that of MDPA. The bonding between MDPA and cotton is significantly more resistant to hydrolysis during multiple launderings than that between HFPO and cotton. The selection of catalyst also plays a significant role in influencing the bonding of the flame retardant agents to cotton.     

聚碳酸酯改性聚酯型热塑性聚氨酯弹性体的合成与性能

以聚碳酸１，６－已二醇酯（ＰＣ）、聚己二酸－１，４－丁二醇酯（ＰＢＡＧ）、４，４－二苯基甲烷二异氰酸酯（ＭＤＩ）和１，４－丁二醇（ＢＤＯ）为原料，合成线型聚碳酸酯改性聚酯型热塑性聚氨酯弹性体（ＴＰＣＺＥ）．对其玻璃化转变温度Ｔｇ、力学性能、耐水解性能和流变特性进行了研究。实验结果表明：随ＰＣ二醇含量的增加，弹性体的贮能模量下降，Ｔｇ则向高温方向（从－７．８℃到＋２．６℃）移动。水解后的强度保持率从８５．４％提高到９９，７％和１１７％，熔体的表现粘度降低，加工性能得到改善。     

Electrospun cellulose acetate fibers: effect of solvent system on morphology and fiber diameter

This paper reports an investigation of the effects of solvent system, solution concentration, and applied electrostatic field strength (EFS) on the morphological appearance and/or size of as-spun cellulose acetate (CA) products. The single-solvent systems were acetone, chloroform, N,N -dimethylformamide (DMF), dichloromethane (DCM), methanol (MeOH), formic acid, and pyridine. The mixed-solvent systems were acetone–DMAc, chloroform–MeOH, and DCM–MeOH. Chloroform, DMF, DCM, MeOH, formic acid, and pyridine were able to dissolve CA, forming clear solutions (at 5% w/v), but electrospinning of these solutions produced mainly discrete beads. In contrast, electrospinning of the solution of CA in acetone produced short and beaded fibers. At the same solution concentration of 5% (w/v) electrospinning of the CA solutions was improved by addition of MeOH to either chloroform or DCM. For all the solvent systems investigated smooth fibers were obtained from 16% (w/v) CA solutions in 1:1, 2:1, and 3:1 (v/v) acetone–DMAc, 14–20% (w/v) CA solutions in 2:1 (v/v) acetone–DMAc, and 8–12% (w/v) CA solutions in 4:1 (v/v) DCM–MeOH. For the as-spun fibers from CA solutions in acetone–DMAc the average diameter ranged between 0.14 and 0.37 μm whereas for the fibers from solutions in DCM–MeOH it ranged between 0.48 and 1.58 μm. After submersion in distilled water for 24 h the as-spun CA fibers swelled appreciably (i.e. from 620 to 1110%) but the physical integrity of the fibrous structure remained intact.     

Comparison between self-reinforced composites based on ultra-high molecular weight polyethylene fibers and isotropic UHMWPE

1. Download : Download high-res image (140KB)
2. Download : Download full-size image

     

Self-ordering process of phenanthrene polyesters observed by the simultaneous DSC-XRD method

Phase transition behavior of polyesters derived from 2,7-phenanthrene dicarbonic acid diethylester and alkanediols with even methylene carbon number was investigated by the simultaneous DSC-XRD method. The smectic A phase was observed on cooling from the molten state. The transition entropy from the isotropic state to the smectic A phase was about 9.0 J mol^-1 K^-1, which depended on the methylene carbon number. The linear expansion coefficients, based on the (001) spacing of the crystalline phase at room temperature, were 1.3·10^-4 K^-1 (crystalline phase), 5.7·10^-4 K^-1 (crystallization region), 1.7·10^-3 K^-1 (smectic A phase) during cooling, and 1.5·10^-4 K^-1 (crystalline phase), and 1.0·10^-3K^-1(melting region) on heating. This revised version was published online in July 2006 with corrections to the Cover Date.