Characterizations for blends of phosphorus-containing copolyester with poly(ethylene terephthalate)

High molecular weight phosphorus-containing copolyesters, poly(ethylene terephthalate)-co-poly(ethylene DDP) (PET-co-PEDDP)s, were prepared and characterized with the objective of producing a non-halogen flame retardant system for practical applications. The phosphorus-containing copolyester with 30 wt% phosphorus (P30 copolyester) was blended with PET to evaluate their characteristics and flame retardancy. Higher phosphorus content results in lower crystallinity and higher char formation after thermal degradation. The rheological behavior remains similar to that of PET. The P30/PET blend possesses higher crystallization rate than the corresponding phosphorus-containing copolyester containing equal phosphorus content. Thermal and rheological behaviors of P30/PET blends are similar to PET or the phosphorus-containing copolyesters. The P30/PET blends are miscible or compatible base on single T_gs detected by DSC or DMA. The SEM/EDX phosphorus mapping image of the P30/PET blend shows uniform distribution of the phosphorus moieties within the P30/PET matrix, another indication of a compatible or miscible blend between the phosphorus-containing copolyester P30 and PET. Flame retardancy of the P30/PET blend is identical to that of the phosphorus-containing copolyester with identical phosphorus content. Blending of high phosphorus content copolyester with virgin PET provides a feasible method to obtain a flame resistant PET with LOI greater than 28.     

环保型阻燃涤纶全拉伸丝生产工艺探讨

介绍了环保型阻燃涤纶全拉伸丝(FDY)熔融纺丝生产的过程,通过实验确定采用磷系阻燃母粒与聚酯切片共混进行纺丝。该阻燃母粒与聚酯切片共混纺丝时,纤维可纺性良好,热稳定性比较高,断裂强度随阻燃剂加入量的增加而降低,当阻燃母粒的质量分数在5%￣7%时,阻燃FDY强度能达到3.2cN/dtex,织物的极限氧指数超过30%。探讨了阻燃母粒的干燥、聚酯切片的干燥、纺丝温度、纺丝组件及拉伸条件对阻燃FDY长丝生产的影响,通过优化工艺条件可以生产出物理机械性能和阻燃效果良好的阻燃FDY产品。     

无卤阻燃ABS研究进展

从市场化角度综述了近年来无卤阻燃丙烯腈-丁二烯-苯乙烯塑料(ABS)的研究进展和可能市场化的技术方案,结合笔者自身的实验论述了几种常用无卤阻燃剂在ABS中的应用现状,重点介绍了反应型/添加型磷系阻燃剂在无卤阻燃ABS中的应用。展望了未来无卤阻燃ABS的研究方向,指出通过探索不同结构磷系阻燃剂的阻燃效果存在差异的原因从而开发出具有最好阻燃效率结构的磷系阻燃剂,以及将ABS与无卤阻燃聚对苯二甲酸乙二酯共混是无卤阻燃ABS最有可能实现市场化的方向。     

The flame‐retardant properties and mechanisms of poly(ethylene terephthalate)/hexakis (para‐allyloxyphenoxy) cyclotriphosphazene systems

Para‐allyl ether phenol derivative of cyclophosphazene (PACP) was prepared and used as a filler to modify the flame‐retardant properties of poly(ethylene terephthalate) (PET) by melting‐blending. The mechanism of flame‐retardant was discussed and the influences of flame‐retardant contents to the mechanical properties were studied. The results revealed that the incorporation of only 5 phpp PACP (0.37 wt % phosphorus containing) into PET matrix can distinctly increase the flame retardancy of PET/PACP composition, and it has a little effect on the mechanical properties of PET. The high flame‐retardant performance of PET/PACP composite was attributed to the combination of condensed‐phase flame retardant and gas‐phase flame retardant. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42711.     

浅色水滑石/红磷复合阻燃剂的制备及性能

采用白磷插层进入水滑石层间后再转化为红磷的方法制得红磷插层水滑石,从而得到了用于环氧树脂体系的浅色水滑石/红磷复合阻燃剂。考察了白磷和水滑石配比对转化率的影响及红磷含量对丙氨酸交换量的影响,并研究了白磷插层水滑石阻燃剂用于环氧树脂的阻燃性能。结果表明转化后红磷在水滑石中的含量与转化前白磷与水滑石的配比之间符合一定的线性关系,即y=-8.44373+0.72491x;丙氨酸的交换量随着红磷含量的增大而减小;以插层水滑石为阻燃剂,阻燃效果优于水滑石/红磷混合物,且颜色较浅,亨特白度为30.13,大于直接混合的23.93;当水滑石、红磷质量分数分别为5%、1.48%时,环氧树脂的阻燃性能就达到FV-0级。     

Influence of gel preparation concentration on statistical mechanics of poly(dialkylaminoethyl methacrylate) gels on the basis of scaling concept: Toward tunable elasticity and thermomechanical parameters

In order to evaluate the scaling parameters of weakly cationic crosslinked network structures, poly(dialkylaminoethyl methacrylate)-based hydrogels were synthesized via free-radical crosslinking in aqueous solution varying systematically concentration of pregel solution. Based on the gel-preparation concentration, variation in structural properties, effective crosslinking density, average molecular weight of polymer chains, and thermodynamic parameters from combined swelling and elasticity results were discussed using the scaling theory to predict various exponent identities. The concentration dependence of compressive elastic modulus as-prepared state was described by a power-law relationship with the exponent of m = 3.55 indicating the importance of the trapped entanglements. Two structural characteristics, the network chain length N and the average molecular weight of polymer chains have inverse dependence on the gel-preparation concentration in the matrix, while the compressive moduli and effective crosslinking density show completely direct dependence. Experimentally determined N values of PDMAEMA hydrogels first decrease with increasing up to 0.2972 and the dependence of N on the gel-preparation concentration gives the relation with a scaling parameter n = −1.80, which coincides with the prediction of scaling theory. Acceptable agreement was found between the estimate of crosslink density fluctuations deduced from mechanical measurements and the results derived from independent swelling observations. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48350.     

Development of internal structure of polymer-modified asphalts via transformations of the reduced frequency

The independent variable of dynamic material functions and corresponding master curves, the reduced angular frequency , was transformed into the apparent molecular weight MW*. As a function of MW*, the normalized master phase angle represented an apparent cumulative molecular weight. This function's numerical differentiation yielded the probability density function of the apparent molecular weight, f(MW*). While this procedure is unproblematic in conventional (straight run) asphalts, it is yielding peaks of negative MW* in polymer modified asphalts. Thus reduced frequency was also transformed to the temperature, which allowed us to determine that the apparent glass transition temperature as the maximum on the master curve of loss modulus G"(T). The master curve of the normalized phase angle as a function of temperature helped to explain the phenomenon associated with the probability density function in modified asphalts. The results presented in this article were obtained numerically, without the use of rheological models.     

新型磷／氮协同阻燃环氧树脂的合成与性能

以双酚A环氧树脂E－51与DOPO（9,10-dihydrooxa-20－phosph henanthrene－10-oxide）合成含磷环氧树脂（ED）,以三聚氰胺与苯酚反应制备含氮的酚醛固化剂MFP。采用红外光谱对产物进行分析表征,采用热失重分析和UL94V垂直燃烧测试考查树脂的热性能和阻燃性能,同时探讨了阻燃环氧树脂的力学性能。结果表明,随着含磷量的增加,环氧树脂的热稳定性和阻燃性能得到改善,当含磷量为3％时,环氧树脂的初始分解温度高达330℃以上,在700℃下的残炭率达到30％以上,阻燃性能均达到了UL－94 V—0级。而试样的力学性能则随含磷量的增加而降低。     

Correlation between clay type and performance of swelling inhibitors based on polyetherdiamine in aqueous fluids

In this work, the linear swelling of four samples of natural clays was evaluated, using poly(propylene glycol) bis(2-aminopropyl ether) ~230 g mol⁻¹ (PEDA-230) and ~400 g mol⁻¹ (PEDA-400) as shale inhibitors for water-based drilling fluids, in comparison to a commercial shale inhibitor. The swelling kinetics was described by a semiempirical equation. A correlation was found between the cation exchange capacity of the clays and the diffusion kinetic constant of the inhibitors. Increased molar mass of PEDA favored swelling inhibition. The swelling inhibition was also evaluated by rheology, and the results were in agreement with the linear swelling tests. Scanning electron microscopy demonstrated the occurrence of microfractures on the clay surface after water contact, as well as the adsorption of the different shale inhibitors on the clay surfaces after contact with the aqueous inhibited fluid. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47661.     

磷系涤纶共聚阻燃剂的性能探析

对自制的磷系涤纶共聚阻燃剂的热性能、阻燃性能进行了测定,并初步考察了该阻燃剂对聚酯切片质量指标及热性能的影响。结果表明：该阻燃剂分解温度为２５８℃,在聚酯中的添加量为３．２％时,氧指数为２９。用该阻燃剂研制的阻燃聚酯切片与普通切片的特性粘数、端羧基含量、二甘醇含量、加工流变性能等指标相同     

Preparation and characterization of poly(ethylene terephthalate) copolyesters modified with sodium‐5‐sulfo‐bis‐(hydroxyethyl)‐isophthalate and poly(ethylene glycol)

Two types of poly(ethylene terephthalate) (PET) copolyesters were successfully prepared with sodium‐5‐sulfo‐bis‐(hydroxyethyl)‐isophthalate (SIPE) and poly(ethylene glycol) (PEG) units with different molecular weights named as cationic dyeable polyester and easy cationic dyeable polyester. Their chemical and crystalline structures were characterized by the nuclear magnetic resonance (NMR), wide angle X‐ray diffraction (WAXD), and small angle X‐ray scattering measurement, and their thermal properties were tested by differential scanning calorimetry and thermogravimetric analysis, respectively. NMR experimental results showed that the actual molar ratio of comonomers was basically consistent with the correlative feed ratio. WAXD results indicated that the crystalline structures of prepared copolyesters were similar to that of PET. Moreover, the glass transition temperature, melting temperature, and thermal degradation temperature were found to decrease with the reduction of the of PEG units as the incorporation of lower of PEG units brought more ether bonds into molecular chains, which increased the irregularity of molecular chain arrangement and led to lower crystallinity. In addition, because the incorporation of PEG units with lower molecular weight led to more ether bonds and hydroxyl end‐groups in molecular chains, the value of contact angle of PET copolyesters dropped, manifesting PET copolyesters had better hydrophilicity with the decreasing molecular weight of PEG units.© 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39823.     

Shear rheology and scaling of semiflexible polymers: Effect of polymer-solvent interactions in the semidilute regime

Semiflexible polymers and their assemblies are important in biology as cross-linked networks of semiflexible polymers form a major structural component of tissue and living cells. This research used shear rheology to demonstrate the tuning from worm-like to rod-like conformation in semiflexible polymers by polymer-solvent interactions. The conformation was assessed by the persistence length l_p, and its influence, in the semidilute regime, was assessed by the scaling of zero-shear viscosity η_o with concentration c and molecular weight . The polymers were poly n-butyl and poly n-octyl isocyanate (PBIC and POIC, respectively). PBIC exhibited the largest l_p in chlorinated solvents, and the solutions obeyed the scaling law . However, when PBIC was dissolved in benzene the l_p was greatly reduced and the scaling law now was , consistent with a worm-like conformation. On the other hand, POIC dissolved in chlorinated and benzenic solvents exhibited a worm-like conformation and the scaling was . These results were contrasted with those of hydroxypropyl cellulose (HPC) aqueous solutions, which exhibit worm-like conformation, the solutions obeyed the scaling η_o ∝ c^2.5 . Finally, the shear viscosity of the polyisocyanates and HPC obeyed the Saito scaling, valid for anisotropic particles in solution.     

皮芯复合阻燃疏水纤维的制备工艺

采用有机膦系G-77阻燃剂对聚对苯二甲酸乙二醇酯(PET)进行共混改性用作芯层料,赋予纤维阻燃性能,采用聚偏氟乙烯(PVDF)和共聚阻燃母粒对自制阻燃母粒进行改性用作皮层料,赋予纤维一定的阻燃性和疏水性;将改性后皮芯料通过皮芯复合纺丝制得多功能阻燃疏水纤维;探讨了芯层料和皮层料阻燃加入量对其阻燃性能的影响,研究了皮芯复合阻燃疏水纤维的制备工艺及其原丝的力学性能。结果表明:当芯层料中的G-77阻燃剂与PET的质量比为7.25/100时,其极限氧指数(LOI)为27.8%;当皮层料中的PVDF的质量分数为6%,自制阻燃母粒与共聚阻燃母粒质量比为7.0/3.0时,其与水的接触角为83.4°,LOI为26.3%;当皮芯复合比为20.0/40.5,卷绕速度为1 200 m/min,拉伸倍数为3.75时,皮芯复合阻燃疏水纤维的可纺性较好,原丝的线密度为2.15 dtex,断裂强度为4.52 cN/dtex。     

A Novel Phosphorus‐Containing Polymer as a Highly Effective Flame Retardant

Summary: A novel phosphorus‐containing polymeric retardant, WLA‐3, was synthesized from phenylphosphonic dichloride (PPD) and 2‐(6‐oxido‐6H‐dibenz〈c,e〉〈1,2〉oxaphosphorin‐6‐yl) 1, 4‐benzenediol (ODOPB). The flame‐retardant element, phosphorus, was bonded both in the main chains and in the pendant chains of flame‐retardant polymer molecules, and reached a content of 13.8%. The high phosphorus content and rich aryl group structures of WLA‐3 contribute an excellent flame retardancy to poly(ethylene terephthalate) (PET) without a considerable decrease of mechanical properties. WLA‐3 is also very effective in improving flame retardancy of epoxy resin and unsaturated polyester.

     

A green resin acid ester surfactant from colophony and xylitol: Synthesis,self-assembly in nonaqueous solvents,and thermodynamics

An environmental friendly oil-soluble surfactant colophony xylitol ester (CXE) is first synthesized from natural colophony and xylitol with the use of hot-compressed water and subcritical CO₂ in a steel autoclave. In this solvent-free system, the conversion of the reaction was up to 90.30% in 4 h. Thermal gravimetric analysis determine that its thermal stability was as high as 310°C. CXE is effective in reducing the surface tension of six different organic solvents. The greatest effect of surface tension reduction by CXE is in the case of dimethyl sulfoxide, the surface tension of the surfactant solution was as low as 36.26 mN/m at its critical micelle concentration value of 7.49 mM; The greatest effect of interfacial tension reduction by CXE is in the case of turpentine and water, the interfacial tension low to 1.51 mN/m. Furthermore, transmission electron microscope and particle size measurement showed that CXE is successfully self-assembled into micelles, vesicles, and heteromorphic vesicles in six kinds of organic solvents. Finally, the critical micelle concentration curves at different temperatures provided the thermodynamic parameters of the aggregate formation, found that , , and are negative and increased as the temperature increased.     

Regeneration and utilization of waste phenolic formaldehyde resin: A performance investigation

Recycled thermosetting phenolic formaldehyde (RPF) resins were pulverized to micron-sized powders and successfully reused as an effective component by reactive-injecting with neat phenolic formaldehyde (PF) and/or trioxymethylene (TOX) to prepare regenerated phenolic formaldehyde (i.e., and ). Tensile strength (σ_f), impact strength (I_s), and density (ρ) of and specimens were reduced as RPF concentrations or average particle sizes increased. It is worth emphasizing that σ_f, I_s, and ρ of each reaction-injected series having a fixed RPF concentration and average particle size improved to a maximum value, as TOX concentrations reached a corresponding optimal value. This is the first investigation to report that σ_f and I_s of proper regenerated PF/RPF/TOX specimens using ≦20 wt % RPF waste were ≥ 95% of those of the virgin reaction-injected PF. Possible reasons accounting for these improved mechanical properties were proposed based on results from their Fourier transform infrared analysis (FTIR). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47445.     

阻燃吸湿改性PET的制备及性能研究

在聚对苯二甲酸乙二醇酯(PET)合成过程中添加不同配比的共聚单体2-羧乙基苯基次磷酸(CEP-PA)、间苯二甲酸双羟乙酯-5-磺酸钠(SIPE)及聚乙二醇(PEG),制得阻燃吸湿改性PET;分析了改性PET的热性能、结晶行为、阻燃和吸湿性能等。结果表明:采用CEPPA为阻燃剂合成阻燃PET过程中,添加SIPE,改性PET的结晶速率和结晶度下降,含水率提高,耐热性及极限氧指数(LOI)降低;同时引入CEPPA和PEG,改性PET的结晶速度、阻燃性和吸湿性都得到提高;添加了CEPPA、SIPE和PEG的改性PET的含水率为0.61%,LOI为25%,具有良好的阻燃性能。     

Fluorosilicone resin as a high ultraviolet transmittance optical material

In this study, hydrofluorosilicone oil with a cyclic structure () and tetramethyl-tetravinylcyclotetrasiloxane () are synthesized through a hydrosilylation reaction with platinum as the catalyst to obtain high ultraviolet transmittance fluorosilicone. The curing process of fluorosilicone resin is monitored by Fourier transform infrared spectroscopy. The effects of different A values (the molar ratio of Si─H to vinyl) on the curing process, mechanical properties, glass transition temperature, crosslinking density, hydrophobicity, and UV transmittance are studied. The results demonstrate that with the increase in the A value, the initial curing temperature and the temperature at the completion of curing decrease, the tensile strength initially increases and then decreases, and the glass transition temperature and crosslinking density increase. Furthermore, the contact-angle and UV transmittance initially increase and subsequently decrease, the maximum contact-angle is 107.61°, which shows good hydrophobicity, and the maximum UV transmittance at 351 nm reaches 93.66%.     

Synthesis,thermal, dielectric,and microwave reflection loss properties of nickel oxide filler with natural fiber-reinforced polymer composite

Fabrication of hybrid composite of nickel oxide (NiO) combined with oil palm empty fruit bunch (OPEFB) reinforced with polycaprolactone (PCL) has been done by using thermal Haake blending machine, which ensured mixture homogeneity. All hybrid composites' characterizations were carried out using X-ray diffraction (XRD), Fourier transform infrared spectrometry, differential thermogravimetry, thermogravimetric analysis, and scanning electron microscopy. The results showed that the XRD profile patterns of the composites clearly changed as the filler loading amount was increased. Fourier transform infrared spectra illustrated a slight change in the frequencies and positions of the peaks after adding NiO, indicating that some interactions occurred between C=O and O–H or among the fiber, NiO, and PCL. The microwave electromagnetic properties, such as reflection loss (dB), relative complex permittivity (ε_r =–j), and permeability (−j) were calculated at various microwave frequencies in the X-band (8–12 GHz) range. It was observed that the thermal stability, magnetic, and dielectric properties of NiO:OPEFB:PCL composites were modified significantly with NiO addition. This enables the new hybrid composites to be used as engineering materials in the microwave applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46998.     

Correlation between the mechanical and dielectric responses in polymer films by a fractional calculus approach

A fractional calculus approach was used to study the correlation between the complex elastic modulus and the complex relative permittivity for a polystyrene (PS) film with thickness of ~80 μm. Experimental measurements were carried out using dynamic mechanical analysis and dynamic dielectric analysis. Experimental results show the mechanical and dielectric manifestations of the main relaxation (glass transition process), whose molecular mobility was analyzed by two innovative models: a mechanical fractional model and a dielectric fractional model. Parameters of fractional models show that, when temperature increases, the molecular mobility of the main relaxation also increases, but the cooperativity of mobility decreases. Besides, molecular mobility is greater in the mechanical manifestation of the main relaxation than in the electric manifestation. From theoretical results obtained from fractional models for the isochronal mechanic storage modulus, E′(T) , and the isochronal relative permittivity, , a correlation model for mechanical and dielectric properties of PS film was obtained. This correlation model describes in function of E′(T) . These results suggest that this correlation model can be used to study molecular mobility of mechanical and dielectric dynamic properties of the polymer films samples and predict changes in their behavior by modifying ambient conditions.