Antimony polymers. III. Flame retardant behavior of chloroprene and natural rubber vulcanizates with antimony polymer

The antimony-containing polymer of bisphenol-A (BPA) and triphenyl antimony dinitrate was used as a flame retardant (FR) for chloroprene rubber (CR) and natural rubber (NR). The flame retardancy of this additive was monitored by the limiting oxygen index (LOI) measurements of the rubber vulcanizates and compared with that for antimony trioxide used as a FR additive. The thermogravimetric analysis (TGA) of the vulcanizates has also been studied. A structure flammability relationship has been established. The effect of this FR additive on physical properties of the vulcanizates undergoing heat aging and solvent leaching has also been evaluated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 927–935, 1998     

Development of halogen‐free flame‐retardant thermoplastic elastomer polymer blend

Ethylene‐propylene diene rubber (EPDM) and isotactic polypropylene (iPP) blends have widest industrial applications that require a degree of flame retardancy. Halogen‐free intumescent technology based on phosphorous salt is a significantly advanced approach to make the polymer flame‐retardant. Both ammonium polyphosphate and ethylenediamine phosphate are important intumescent compounds. Their combination with carbonific and spumific agents were studied in binary blends of EPDM/PP. The polymer system was vulcanized online during melt mixing. Intumescent flame‐retardant polymer systems exhibit good flame‐retardancy with optimum comparable physiomechanical, electrical, and fluid resistance properties, including lower smoke emission, which is essential to protect people because the visibility remains unaffected in the event of fire. Pronounced charring and intumescent effect appear to enhance the flame‐retardancy of the polymers. Possible expected intumescent mechanism is proposed based on the nonpyrolysis mechanism for the flame‐retarded polymer and the intumescent components. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 407–415, 2004     

超支化型抗静电剂的合成及其在煤矿PVC阻燃输送带中的应用

合成了一种含有长链烷基的端羟基超支化聚合物,并通过两种方法（外部涂覆法和内部掺加法）将其作为PVC阻燃输送带的抗静电剂,测试了输送带的表面电阻。结果表明,在较低的质量分数下,即可使PVC阻燃输送带的表面电阻降至期望值（107数量级）,达到了理想的抗静电要求。含有超支化型抗静电剂的PVC阻燃输送带经过多次水洗和较长的存储时间,依然保持优良的抗静电性能。经计算,超支化型抗静电剂的生产成本低廉,适合大规模工业生产。     

Surface modification of LDPE with PE‐PEO graft copolymer

Films of LDPE containing 1–10 wt % of various polymeric additives were prepared by different techniques. Three poly(ethylene‐graft‐ethylene oxide)s synthesized by grafting poly(ethylene‐co‐acrylic acid) with poly(ethylene oxide) monomethyl ether (MPEO), and two pure MPEOs having molecular weights 750 and 2000 were used as additives. The additives were mixed with LDPE both by blending in a common solvent and by melt mixing. The blends were then solvent cast from xylene onto glass Petri dishes or compression molded between glass plates. The film surfaces were studied by water contact angle measurements and by X‐ray photoelectron spectroscopy (XPS), and melting points and heats of melting were recorded by differential scanning calorimetry (DSC). The blends had a two‐phase morphology, with enrichment of the graft copolymers at the glass–polymer interface, as shown by contact angle values and XPS spectra. Large differences in the interface accumulation between the different film samples were observed. Films prepared by compression molding of solution‐mixed blends exhibited much lower surface accumulation of graft copolymer at the glass–polymer interface than did the solvent cast or melt‐mixed/compression‐molded samples. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 316–326, 2000     

Synthesis and characterization of a novel hyperbranched polyether

A hyperbranched polyether has been synthesized by a single‐step nucleophilic displacement polymerization technique between cyanuric chloride and the sodium salt of bisphenol‐A. The effects of various reaction parameters on the yield, and molecular weight, as measured by the intrinsic viscosity of the polymer, have been studied. The synthesized polymer has been characterized by FT‐IR, UV and ¹H NMR spectroscopies, elemental analysis, solubility and viscosity measurements. The polymer is soluble in highly polar solvents such as N,N‐dimethylacetamide, N,N‐dimethylformamide and dimethyl sulfoxide, partially soluble in dilute aqueous NaOH solution, methanol, ethanol, chloroform, etc., but insoluble in water and non‐polar hydrocarbon solvents. The solubility parameter of the hyperbranched polymer has also been measured experimentally. Copyright © 2004 Society of Chemical Industry     

纳米氢氧化镁阻燃剂在软质PVC中的应用研究

采用不同改性剂对纳米氢氧化镁进行表面改性,通过切片的TEM电镜照片考察了改性前后的粉体在软质PVC体系中的分散情况。研究了纳米氢氧化镁粉体对该体系阻燃性能和机械力学性能的影响,并与微米氢氧化镁粉体进行了比较。实验结果表明：改性后的纳米氢氧化镁粉体在软质PVC体系中有较好分散性;在不同改性剂中,以硬脂酸锌的改性效果较好;改性纳米氢氧化镁的阻燃性能和机械力学性能要优于微米级氢氧化镁;添加量为40克(以100克PVC为基准)时体系的综合性能较好,氧指数可增加8．6％;加入阻燃协效剂,体系的阻燃性能有大幅度的提高,氧指数可增加19.6％。     

Design and UV-curable behaviour of boron based reactive diluent for epoxy acrylate oligomer used for flame retardant wood coating

Difunctional boron-containing reactive flame retardant for UV-curable epoxy acrylate oligomer was synthesized from phenyl boronic acid and glycidyl methacrylate. The synthesized reactive diluent was utilized to formulate ultraviolet (UV)-curable wood coatings. The weight fractions of reactive diluent in coatings formulation was varied from 5 to 25 wt % with constant photoinitiator concentration. The molecular structure of reactive flame retardant was confirmed by Fourier-transform infrared, Nuclear magnetic resonance (NMR) and ¹¹B NMR spectral analysis. Further, the efficacy of flame retardant behaviour of coatings was evaluated using limiting oxygen index and UL-94 vertical burning test. Thermal stability of cured coatings films were estimated from thermogravimetric and differential scanning calorimetry analysis. The effects of varying concentration of reactive diluent on the viscosity of coatings formulation along with optical, mechanical and chemical resistance properties of coatings were also evaluated. The coatings gel content, water absorption behaviour, contact angle analysis and stain resistance were also studied.     

Preparation and evaluation of two kinds of solid polymer electrolytes made from crosslinked poly(ether urethane) elastomers consisting of a comb‐like and a hyperbranched polyether

Two novel polyethers, one comb‐like and another hyperbranched, were synthesized by the cationic ring‐opening polymerization of 3‐(methoxy(triethylenoxy))methyl‐ and 3‐(hydroxy‐(triethylenoxy))methyl‐3′‐methyloxetane, respectively. The former reacted with a multifunctional isocyanate and the latter with a difunctional isocyanate to give rise to the corresponding crosslinked poly(ether urethane) elastomers, PCEU and PHEU. Accordingly, two kinds of solid polymer electrolytes (SPEs) were prepared from these two elastomers in situ in the presence of lithium salt trifluoromethanesulfonimide. It was found that the PCEU‐based SPEs shows a higher ionic conductivity than that PHEU‐based ones due to its more mobile pendent chains and appropriate crosslinking density in the polymeric network. The maximum ionic conductivities of 1.4 × 10^?5 S/cm at 30°C and 3.5 × 10^?4 S/cm at 80°C were attained at the molar ratio of O/Li = 7.5. The DSC measurements clearly demonstrated that PCEU indeed possesses the more flexible chain motion ability than PHEU. The electrochemical stability window of PCEU, which is 1.7–4.0 V was measured by cyclic voltammogram. Additionally, the significantly high decomposition temperature as evidenced by TGA analyses endowed these SPEs a good safe performance. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nano‐scaled ordering of hyperbranched and star‐hyperbranched polymers

Hyperbranched polystyrenes (HPS) were prepared by living radical polymerization of 4‐vinylbenzyl N,N‐diethyldithiocarbamate (VBDC) as an inimer under UV irradiation. These HPS exhibited large amounts of photofunctional diethyldithiocarbamate (DC) groups on their outside surfaces. We derived star‐HPS (SHPS) by grafting from such HPS macroinitiator with methyl methacrylate (MMA) or ethyl methacrylate (EMA). The ratios of radius of gyration to hydrodynamic radius R_g/R_h for HPS and SHPS in tetrahydrofuran (THF) were in the range of 0.74–0.90 and 1.05–1.12, respectively. HPS and SHPS behaved in a good solvent as hard and soft spheres, respectively. We demonstrated the structural ordering of both branched polymers in THF through small‐angle X‐ray scattering (SAXS), by varying the polymer concentration. As a result, HPS and SHPS formed face‐centered‐cubic (fcc) and body‐centered‐cubic (bcc) structures, respectively, near the overlap threshold (C*). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3340–3345, 2006     

Synthesis of s‐triazine‐based hyperbranched polyurethane for novel carbon‐nanotube‐dispersed nanocomposites

s‐Triazine‐based hyperbranched polyurethanes (HBPUs) with different hard segments were synthesized by A₂ + B₃ approach. Various kinds of multiwalled carbon nanotube (MWNT) nanocomposites with HBPU were prepared to investigate an impact of hyperbranched polymer on dispersion of MWNTs in the polymer matrix and the resulting properties of nanocomposites. Synthesized HBPUs were characterized using FTIR and NMR measurements. The highly branched structures were found very effective in enhancing the pristine MWNT dispersion in the polymer matrix. As a result, the MWNT‐reinforced HBPU nanocomposites showed a steep increase in the yield stress and modulus and enhanced shape memory effect with an increase of hard segment and MWNT loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

HDPE/MRP共混物阻燃与力学性能研究

用微胶囊化红磷(MRP)作为阻燃剂,利用双螺杆挤出机制备了阻燃高密度聚乙烯(HDPE)/MRP共混物,并首次使用点燃氧指数和燃烧氧指数来表征它们的阻燃性能。MRP的添加有利于HDPE材料的阻燃,但却使其力学性能下降。     

Environmental Stress‐Cracking Resistance of LDPE/EVA Blends

Blends of low‐density polyethylene with random copolymers of ethylene and vinyl acetate (PE/EVA) are studied with respect to their environmental stress‐cracking resistance (ESCR) using the Bell‐telephone test. This system shows the shortest time to failure in the ESCR test after annealing at 50 °C in a stress‐cracking agent (Igepal solution) compared with that in the tests conducted at 30 and 70 °C. The increase of the time to failure at 70 °C as compared with that at 50 °C is probably the result of the semicrystalline proportion of EVA melting. Transmission electron microscopy images (see Figure) reveal that EVA particles are molten and deformed in bending direction of the sample at 70 °C in contrast to samples annealed at 50 and 30 °C. TEM pictures of a failed sample during the test conducted at 50 °C indicate that EVA particles can stop crack propagation.

TEM image of PE/EVA‐5.4 after 1 000 h in ESCR test conditions at 70 °C.     

两亲性超支化聚（胺-酯）对PVC／PP共混体系的增容作用

研究了两亲性超支化聚（胺-酯）（A-HPAE）对PVC／PP共混体系的增容作用，讨论了其用量对PVC／A-HPAE／PP共混体系力学性能和复数黏度的影响。结果表明，在PVC／PP共混物中加入2份（质量份，下同）A-HPAE时，能很好地改善共混体系的相容性，使共混物的拉伸强度和断裂伸长率分别达到26．18mPa和18．72％，比未加的分别提高了107．67％和34．68％；共混体系的绝对复数黏度随着A-HPAE用量的增大而降低；扫描电子显微镜分析表明，A-HPAE增强了PVC和PP之间的界面黏结作用，减小了共混体系中分散相的尺寸。     

Synthesis and properties of novel 4,4′‐biphenylene‐bridged flame‐retardant cyanate ester resin

The bisphenol‐containing 4,4′‐biphenylene moiety was prepared by the reaction of 4,4′‐bis(methoxymethyl) biphenyl with phenol in the presence of p‐toluenesulfonic acid. The bisphenol was end‐capped with the cyanate moiety by reacting with cyanogen chloride and triethylamine in dichloromethane. Their structures were confirmed by Fourier transform infrared spectroscopy, ¹H‐NMR, and elemental analysis. Thermal behaviors of cured resin were studied by differential scanning calorimetry, dynamic mechanical analysis, and TGA. The flame retardancy of cured resin was evaluated by limiting oxygen index (LOI) and vertical burning test (UL‐94 test). Because of the incorporation of rigid 4,4′‐biphenylene moiety, the cyanate ester (CE) resin shows good thermal stability (T_g is 256°C, the 5% degradation temperature is 442°C, and char yield at 800°C is 64.4%). The LOI value of the CE resin is 42.5, and the UL‐94 rating reaches V‐0. Moreover, the CE resin shows excellent dielectric property (dielectric constant, 2.94 at 1 GHz and loss dissipation factor, 0.0037 at 1 GHz) and water resistance (1.08% immersed at boiling water for 100 h). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Waste and Virgin LDPE/PET Blends Compatibilized with an Ethylene‐Butyl Acrylate‐Glycidyl Methacrylate (EBAGMA) Terpolymer, 1

Summary: This work is aimed at studying the morphology and the mechanical properties of blends of low density polyethylene (LDPE) and poly(ethylene terephthalate) (PET) (10, 20, and 30 wt.‐% of PET), obtained as both virgin polymers and urban plastic waste, and the effect of a terpolymer of ethylene‐butyl acrylate‐glycidyl methacrylate (EBAGMA) as a compatibilizer. LDPE and PET are blended in a single screw extruder twice; the first extrusion to homogenize the two components, and the second to improve the compatibilization degree when the EBAGMA terpolymer is applied. Scanning electron microscopy (SEM) analysis shows that the fractured surface of both the virgin polymer and the waste binary blends is characterized by a gross phase segregation morphology that leads to the formation of large PET aggregates (10–50 µm). Furthermore, a sharp decrease in the elongation at break and impact strength is observed, which denotes the brittleness of the binary blends. The addition of the EBAGMA terpolymer to the binary LDPE/PET blends reduces the size of the PET inclusions to 1–5 µm with a finer dispersion, as a result of an improvement of the interfacial adhesion strength between LDPE and PET. Consequently, increases of the tensile properties and impact strength are observed.

SEM micrographs of the fracture surface of a waste 70/30 LDPE/PET blend (R30) and of its blend with 15 pph of EBAGMA (R30C). Magnification × 1 000.     

Correlation between limiting oxygen index and phosphorus/nitrogen content of cotton fabrics treated with a hydroxy‐functional organophosphorus flame‐retarding agent and dimethyloldihydroxyethyleneurea

The combination of a hydroxyl‐functional organophosphorus flame‐retarding agent (FR) and dimethyloldihydroxyethyleneurea (DMDHEU) was used as a durable flame‐retardant finish system for cotton fabrics. DMDHEU functions as a binder between FR and cotton cellulose, thus making this flame‐retarding system durable to home laundering. DMDHEU also provides nitrogen to this system, therefore enhances its performance. Limiting oxygen index (LOI) is one of the most commonly used parameters to indicate the flammability of textiles and other polymeric materials. In this research, we investigated the correlation between LOI and phosphorus/nitrogen content on the cotton fabric treated with that durable flame‐retardant system. Phosphorus concentration on the fabric was analyzed by inductively coupled plasma atomic emission spectroscopy, whereas the nitrogen content was determined indirectly by measuring the carbonyl band intensity in the infrared spectra of the treated fabric. We developed a statistical model to predict LOI of the cotton fabric treated with FR and DMDHEU based on the phosphorus concentration and the intensity of carbonyl band of DMDHEU on cotton. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1885–1890, 2003     

硅氮系阻燃黏胶纤维的结构与性能研究

分析了硅氮系阻燃黏胶纤维的结构与性能,探讨其阻燃机制。通过扫描电子显微镜、X射线衍射、力学性能以及极限氧指数等测试,分析了硅氮系阻燃剂含量对纤维阻燃性能、热性能和力学性能等的影响。结果表明:当阻燃剂质量分数为20%时,纤维的干态断裂强度为2.1 cN/dtex,极限氧指数为28%,在满足纺织服用需求的同时,达到国家阻燃标准,兼具安全环保与良好的阻燃性能。     

Synthesis,thermal properties,and flame retardancy of phosphorus containing polyimides

Phosphorus containing polyimides were prepared via phosphorylation of organosoluble polyimides. This was achieved by phenoxaphosphine oxide ring formation reaction or esterification with diethylchlorophosphate. The phosphorylation was confirmed by infrared, ³¹P nuclear magnetic resonance, and elemental analysis for phosphorus. Polyimides containing phosphorus of 8.3 and 5.4% by weight were found. Thermal characteristics and decomposition behavior of the resulting polyimides were investigated by differential scanning calorimetry and thermogravimetric analysis. Introduction of phosphorus into polyimides slightly reduced their initial weight loss temperatures and led to high char yields at temperatures higher than 800°C. Limiting oxygen index values higher than 48 were found for the phosphorylated polyimides. Such properties make these polymers useful in flame retardant applications. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 875–882, 1997     

聚磷酸铵的合成及其在聚丙烯阻燃中的应用

聚丙烯具有易燃性,限制其进一步应用。以磷酸二氢铵、五氧化二磷、尿素为原料合成聚磷酸铵,然后将其应用于聚丙烯中考察其阻燃性。在氨气压力为0.5 MPa、温度295℃下反应1.5 h,停止加热,降温至150℃,得到聚磷酸铵。红外光谱和X-衍射线表明合成聚磷酸铵是I型和II型混合型。当聚丙烯复合材料中膨胀型阻燃剂质量分数为30%,极限氧指数达30.8%,通过UL-94测试。结果表明,应用聚磷酸铵为原料的阻燃剂具有较好的阻燃性能。     

Effects of compatibilizer type and rubber‐wood sawdust content on the mechanical,morphological, and thermal properties of PVC/LDPE blend

This article aimed to investigate the mechanical, morphological and thermal properties of PVC/LDPE blend with and without the addition of compatibilizers. The effects of LDPE content, compatibilizer type and rubber‐wood sawdust loading on the properties of the blend were evaluated. The experimental results suggested that as the LDPE content was increased the mechanical properties of PVC‐LDPE blend progressively decreased due to poor interfacial adhesion. The continuity and compatibility between PVC and LDPE phases could be improved through three different types of compatibilizers which included chlorinated polyethylene (CPE) poly(methyl‐methacrylate‐co‐butyl acrylate) (PA20) and poly(ethylene‐co‐methacrylate) (Elvaloy). The PA20 was found to be the most suitable compatibilizer for the blend. A radical transfer reaction was proposed in this work to explain the structure and thermal changes of the PVC in PVC‐LDPE blend. The decomposition temperature of PVC in the blend decreased with the loading of the PA20 and the wood sawdust. As the sawdust content was increased the tensile and flexural moduli increased with considerable decreased in the tensile, flexural and impact strength, a slight improvement being achieved if the PA20 was incorporated in the composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 598–606, 2006