Synthesis of flame retardant polyester‐urethanes and their applications in nanoclay composites and coatings

This paper describes the synthesis of phosphorus‐containing polyester‐urethanes and their applications in nanoclay composites and coatings. Polyester was prepared by the reaction of bis(bisphenol‐A) monophenyl phosphonate, maleic anhydride and phthalic anhydride. The polyester was reacted with various diols such as ethylene glycol, diethylene glycol and propylene glycol to obtain polyester polyols. Synthesized polyester polyols were characterized by chemical analysis and instrumental analysis and was used further to react with different isocyanates to develop polyester‐urethanes. The synthesized polyester‐urethanes were blended with organo‐modified montmorillonite nanoclay (1 wt%, 3 wt% and 5 wt%) and were cast in a mold and coated on mild steel panels. The thermal stability of neat polyester‐urethane and the nanoclay composites was determined by thermogravimetric analysis. The flame retardant properties of cast films and their composites were determined by the limiting oxygen index and UL‐94 test methods. The physical and mechanical properties of coatings such as pot life, drying properties, scratch hardness, pencil hardness, impact resistance, adhesion and flexibility were investigated. The chemical resistance properties of the coatings were also determined in different reagents. The data reveal that the polyester‐urethane nanoclay composites with 3 wt% clay hold promise for use in effective flame retardant coatings. © 2013 Society of Chemical Industry     

Influence of the degree of exfoliation of an organoclay on the flame‐retardant properties of cross‐linked ethylene‐co‐Propylene‐co‐diene monomer‐g‐Maleic anhydride‐based composites

Layered montmorillonite was synthesized by hydrothermal method, progressively modified by an alkylammonium and thoroughly characterized by elemental, thermal, and X‐ray diffraction (XRD) analysis. Pristine and modified clays were introduced in maleic anhydride‐modified ethylene‐co‐propylene‐co‐diene monomer matrix. XRD and transmission electron microscopy investigations showed microcomposite as well as intercalated or exfoliated nanocomposites morphologies depending on the organic content of the clay. The inhibitor character of the pristine clay on peroxides as crosslinking agent for rubbers was then demonstrated and overcome by using electron beam irradiation for specimens containing unmodified clay. Dynamic mechanical analyses and swelling measurements showed that it is possible to obtain the same degree of crosslinking of the polymer matrix by electron beam irradiation of the composites based on pristine clay specimens and conventional peroxide curing of modified‐clay‐based ones. Finally, flame‐retardant properties of different clays‐based composites showed a direct dependence on the degree of exfoliation. It was observed that the better the exfoliation, the higher is the flame retardancy. POLYM. COMPOS., 38:966–973, 2017. © 2015 Society of Plastics Engineers     

Dispersion and flame retardancy of ethylene vinylacetate/layered silicate nanocomposites using the masterbatch approach for cable insulating material

Ethylene vinylacetate (EVA) copolymer-based nanocomposites with maleic anhydride-grafted ethylene-vinylacetate (EVAgMA) and organically modified clay (o-clay) were prepared in a twin screw extruder by following a two-step melt compounding method. EVAgMA/o-clay masterbatches with various clay contents up to 50 wt% were examined, after which the masterbatch with the highest clay content was melt compounded with EVA for the preparation of EVA/o-clay nanocomposites containing specific amounts of clay. Further morphological dispersion of the clay particles by highly polar EVA and shearing was confirmed in the EVA/o-clay nanocomposites by X-ray diffraction (XRD) and transmission electron microscopy (TEM). These morphologies led to increased thermal properties in air as well as a considerable decrease in heat release rate (HRR). EVA/o-clay/MDH nanocomposites were also prepared using a high clay-bearing masterbatch to confirm the synergistic flame retardancy of clay as a co-additive in EVA/MDH composites. EVA/o-clay/MDH nanocomposites prepared by substituting o-clay for MDH showed significantly lower and wider HRR during combustion compared to EVA/MDH composite.     

Preparation and characterization of polyurethane flame‐retardant coatings using pyrophosphoric lactone‐modified polyesters/isophorone diisocyanate–isocyanurate

Pyrophosphoric lactone‐modified polyester containing two phosphorous functional groups in one structural unit of base resin was synthesized to prepare a nontoxic, reactive flame‐retardant coatings. Then, the pyrophosphoric lactone‐modified polyester was cured at room temperature with isocyanate and isophorone diisocyanate (IPDI)–isocyanurate to get a two‐component polyurethane flame‐retardant coatings (TAPPU). Comparing the physical properties of the films of TAPPU with the film of nonflame‐retardant coatings, no deterioration of physical properties was observed with the incorporation of a flame‐retarding component into the resin. Three kinds of flame retarding tests were conducted, including the 45° Meckel burner method, limiting oxygen index method (LOI method), and oxygen combustion method with Cone calorimeter. It was observed that the char lengths were 3.1～4.5 cm and LOI values were 27～30%. These results indicate that the prepared coatings are good flame‐retardant ones. It was also found that the flame retardancy of those coatings was increased with the contents of phosphorous. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2316–2327, 2001     

光敏性含磷聚氨酯丙烯酸酯(P-PUA)阻燃预聚物的合成与性能

合成了4种不同结构的光敏性含磷聚氨酯丙烯酸酯阻燃预聚物,并对其结构进行了表征。研究了以所制预聚物为基料的光固化涂料的柔韧性、附着力、硬度等基本物理性能和耐热防火性能。结果表明,该涂料能达到市售PUA涂料的基本物理性能,并具有较高的分解温度,800℃下形成的炭渣能达到涂层原重的20%左右,具有一定的耐热防火性能;以结构相似的阻燃预聚物为基料的涂层,其耐热防火性能随含磷量的增加而提高;预聚物主链中芳环含量也影响涂层的耐热防火性能,相对分子质量相近的预聚物,其主链上的芳环数量增加一倍,涂层在800℃下w(炭渣)能增加5个百分点。     

膨胀型阻燃剂/二乙基次磷酸铝阻燃改性不饱和树脂基复合材料

采用密胺包覆聚磷酸铵（APP）、季戊四醇（PER）和三聚氰胺（MEL）作为膨胀型阻燃剂（IFR）对不饱和树脂（UP）进行改性,研究了APP、PER和MEL不同复配比例及用量对不饱和树脂基复合材料阻燃性能和力学性能的影响。基于IFR最佳用量,以二乙基次磷酸铝（ADP）为协效剂,研究了ADP用量对IFR/UP阻燃复合材料阻燃性能、力学性能及热稳定性的影响。结果表明,当APP∶PER∶MEL复配比例为4∶1∶1,IFR添加量为15 %（质量分数,下同）时,复合材料综合性能最佳,其极限氧指数为27.4 %,UL 94垂直燃烧达到V?1等级,弯曲强度和冲击韧性分别为100.3 MPa和6.3 kJ/m²;ADP的引入能够进一步提高IFR/UP复合材料阻燃性能,且随着ADP质量分数的增加而增强;当ADP质量分数为2 %时,IFR?ADP/UP复合材料极限氧指数为28.5 %并达到V?0阻燃等级,弯曲强度和冲击韧性分别为110 MPa和7.8 kJ/m²,与IFR/UP复合材料相比,分别提高了9.7 %和23.8 %;ADP能够促进IFR/UP复合材料表面成炭,缓解基体的热降解。     

Boron containing UV-curable epoxy acrylate coatings

In the present work boron acrylate monomer was synthesized by esterification reaction. UV-curable boron containing epoxy acrylate coatings were prepared and applied on plexiglass substrates to obtain thermally and mechanically stable coatings. The physical and mechanical properties of UV-cured coatings were investigated such as gel content, solvent resistance, hardness, flexibility and tensile tests. The thermal behavior of coatings was also evaluated. It was observed that the tensile properties and thermal stabilities of boron modified epoxy coatings mainly depend on the boron content.     

Photo‐curable highly water‐repellent nanocomposite coatings

Modification and use of natural products have gained a lot of interest in recent years due to their environmental friendliness and their availability from different sources. In this study, (castor oil)‐based photo‐curable highly hydrophobic coatings were prepared and characterized. Castor oil was first modified with 3‐isocyanatopropyltriethoxysilane and then hydrolyzed prior to the coating preparation. The resulting precursor was mixed with norbornyl acrylate and hexanediol diacrylate, and highly roughened hydrophobic coatings were prepared with the aid of fluorinated/nonfluorinated alkoxysilane coupling agents and hydrophobic fumed nanosilica particles. The coatings were applied on borofloat glass. The addition of fluorine and nanosilica showed a significant impact on the properties of the coatings. As the fluorine and nanosilica contents were increased in the formulations, flame retardancy and the contact angle values of the coatings increased. The surface roughness of the coatings increased with the addition of hydrophobic fumed nanosilica particles. Also, the relation between the surface energy and the contact angle values of the coatings was investigated. J. VINYL ADDIT. TECHNOL., 19:31–38, 2013. © 2013 Society of Plastics Engineers     

Construction of thermoplastic cellulose esters matrix composites with enhanced flame retardancy and mechanical properties by embedding hydrophobic magnesium hydroxide

Biomass-based composites with renewability and biodegradability have attracted extensive researches, but their applications are hindered by poor mechanical properties and flame retardancy. Cellulose ester matrix composites (CEMC), a kind of biomass-based composites, were prepared with inorganic crystals as flame retardant and reinforcement. Cellulose acetate oleate (CAO) prepared by mechanical activation-assisted solid-phase reaction was used as thermoplastic matrix. Hydrophobic oleate-magnesium hydroxide (O-MH), which was surface-modified with oleic acid, was embedded into CAO to prepare O-MH/CAO composites by hot pressing. The introduction of oleoyl contributed to favorable thermoplasticity of cellulose ester, resulting in enhanced thermal stability and mechanical properties of CEMC. The uniform dispersion of O-MH in the CAO matrix via metal–organic coordination increased the mechanical properties and flame retardancy of O-MH/CAO composites, ascribing to the toughening effect and combustion inhibition effect induced by O-MH. This study provides a feasible technology for fabricating the CEMC with outstanding thermal stability and mechanical properties.     

纳米锌/硫化钠/环氧丙烯酸酯涂层的阻燃性能研究

为探讨纳米锌与硫化钠对环氧丙烯酸酯(EA)涂层的阻燃效果,以乙酸锌和苜蓿粉为原料,利用植物还原法制备了纳米锌,将其与硫化钠及EA配合,经紫外光固化制备纳米锌/硫化钠/EA阻燃涂层。通过红外、紫外、差示扫描量热仪及力学分析仪对其阻燃、透光率、热稳定性及硬度等性能进行测定。结果表明:当纳米锌质量分数为10%时,纳米锌/硫化钠/EA涂层阻燃性能最佳,涂层残余率达19.47 %,极限氧指数达31。所有涂层硬度均为6H,涂层热稳定性随纳米锌质量分数的增加而增加,而透光率逐渐下降。     

The use of nanoclay in preparation of epoxy anticorrosive coatings

Epoxy/clay nanocomposites (NC) have become a very interesting topic among researchers in the past two decades because nanoclays have a positive effect on the mechanical, thermal and especially barrier and anticorrosive performances of the polymers. In this study epoxy NCs and NC-based epoxy coatings were prepared by the solution intercalation method using Cloisite 30B as nanoclay. WAXD and SEM analyses revealed that a mainly exfoliated structure was obtained in epoxy NC with 1 wt% clay content, while higher clay loadings reduced the number of exfoliated clay nanolayers and produced a mainly intercalated structure. EIS, TGA and DMA analyses showed that epoxy NCs with clay content below 5 wt% exhibited increased corrosion stability, thermal stability, glass transition temperature (T_g) and storage modulus (G′), in both glassy and rubbery states due to the nanoscale dispersion of Cloisite 30B and the barrier effect of individual nanolayers. Enhanced mechanical properties were also noticed at higher clay loadings, but the rate of improvement was lower. The highest extent of exfoliation and the most homogeneous macromolecular network was found for NC with 1 wt% of clay, leading to the highest improvement of thermal and anticorrosive properties. The salt spray test results showed that anticorrosive properties of epoxy coatings in the presence of 3 wt% and especially 1 wt% of Cloisite 30B were significantly better, thus indicating that nanoclay efficiently modifies the commercial epoxy coatings.     

Polystyrene-based composites and nanocomposites with reduced brominated-flame retardant

Polystyrene was melt blended with a halogen-based flame retardant (FR), hexabromocyclododecane, and a non-halogenated FR, triphenyl phosphate (TPP), in a twin-screw extruder. An organically modified montmorillonite (Cloisite 15A) was used to prepare FR polystyrene nanocomposites. The flammability properties and thermal stability of FR polystyrene composites and nanocomposites were investigated. X-ray diffraction analysis showed that the exfoliation structure of organically modified montmorillonite in polystyrene nanocomposites may be achieved by melt-compounding in a twin-screw extruder. Furthermore, a good dispersion of FRs and nanoparticles of organically modified montmorillonite was observed by energy dispersive X-ray analysis. Thermogravimetric analysis demonstrated that the thermal stability of FR nanocomposites enhanced in the presence of clay nanoparticles and antioxidant. The aim of this study was to reduce the FR level, especially in the brominated FRs. The good results obtained by the limiting oxygen index test showed high-performance flammability properties in the composites containing hexabromocyclododecane and TPP, resulted from the synergy effects between these two FRs. However, in spite of producing high thermal performance polystyrene nanocomposites and dispersing clay nanoparticles efficiently into the polystyrene matrix, the flame retardancy properties were deteriorated in the presence of clay nanoparticles. Therefore, the organically modified clay (Cloisite 15A) was not a good synergic compound to improve the flame retardancy of polystyrene nanocomposites.     

Preparation of modified polyesters containing triphosphorous and their applications to PU flame-retardant coatings

Three phosphorous functional groups were introduced in one structural unit of polymer backbone to enhance the flame retardancy of PU coatings. In the first step, we synthesized tetramethylene bis(orthophosphate) (TBOP) that contained two phosphorus functional groups in one structural unit. In the next step, we synthesized modified polyesters (ATBTP-10,-20,-30) that contained triphosphorous groups by condensing polymerization of TBOP, 1,4-butanediol, trimethylolpropane, adipic acid, and phenylphosphonic acid (PPA). The amount of PPA in the ATBTPs was 10, 20, and 30 wt%. Then, flame-retardant PU coatings (AHFC−10,−20,−30) were prepared by curing ATBTPs with hexamethylene diisocyanate-biuret (curing agent) at room temperature. From the TGA analysis of diphosphorus-modified polyester (ATBT) and ATBTPs, the residues of ATBT, ATBTP-10, ATBTP-20, and ATBTP-30 were 24.6, 27.5, 29.2, and 31.9%, respectively. From this result, it was found that the residue increased in relation to the amount of PPA. Physical properties of the films of flame-retardant coatings were deteriorated with the addition of PPA (flame retarding component), however, all the films of flame-retardant coatings, except AHFC-30, met the required physical properties standard for coatings. Char lengths of the AHFCs measured by the 45° Meckel burner method were 2.9∼4.8 cm, and LOI values were 28∼31%, which indicates that the prepared AHFCs showed good flame retardancy.     

The effects of clay dispersion on the mechanical,physical, and flame‐retarding properties of wood fiber/polyethylene/clay nanocomposites

In this study, nanosized clay particles were introduced into wood fiber/plastic composites (WPCs) to improve their mechanical properties and flame retardancy, which are especially important in various automotive and construction applications. A high degree of exfoliation for nanoclay in the wood fiber/high density polyethylene (HDPE) composites was successfully achieved with the aid of maleated HDPE (PE‐g‐MAn), through a melt blending masterbatch process. The structures and morphologies of the composites were determined using X‐ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. This article presents the effects of clay content and degree of clay dispersion on the mechanical and physical properties and flame retardancy of wood fiber/HDPE composites that contained a small amount of clay, in the range of 3–5 wt %. We concluded that achieving a higher degree of dispersion for the nanosized clay particles is critical to enhance the mechanical properties and the flame retardancy of WPCs when small amounts of clay are used. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of crosslinker and nanoclay on jute fabric reinforced soy flour green composite

Bio‐based composites were prepared by using soy flour, jute, glutaraldehyde (GA), nanoclay, and glycerol. An optimum concentration of glycerol was used as a plasticizer. The synthesized composites were characterized by various techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The exfoliation of clay layers was detected both by XRD and TEM study. FTIR study showed an interaction between clay, jute, and soy flour. The percentage content of GA and nanoclay was found to have profound influence on various physical properties of the composites. The increase in the concentration of GA and nanoclay improved the thermal stability, flame retardancy, dimensional stability, and most importantly the mechanical properties of the prepared composite. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of photo curable highly hydrophobic coatings using a modified castor oil derivative as a sol-gel component

Modification and use of natural products have gained a lot of interest in recent years due to their environmental friendliness and their availability from different sources. In this study castor oil based photo curable highly hydrophobic coatings were prepared and characterized. Castor oil (CO) was first modified with 3-isocyanato propyl triethoxy silane and then it was hydrolyzed prior to the coating preparation. The resulting precursor was mixed with norbornyl acrylate, hexane diol diacrylate and hydrophobic coatings were prepared with the aid of fluorinated and nonfluorinated alkoxy silane coupling agents. The addition of fluorine showed a significant impact on the properties of the coatings. As the fluorine content was increased in the formulations, flame retardancy and the contact angle values of the coatings increased. The highest amount of fluorine containing coating showed a contact angle of 119°. Then with the addition of nonfluorinated alkoxysilane compounds, a contact angle of 130° was reached. Also the effect of post-cure temperature on contact angle values was investigated.     

Boron-containing UV-curable oligomer-based linseed oil as flame-retardant coatings: synthesis and characterization

A boron-containing UV-curable oligomer was derived from linseed oil, phenylboronic acid and glycidyl methacrylate to use in flame-retardant coating applications. The synthesized UV-curable oligomer was characterized for its structural and physicochemical properties by means of Fourier transform infrared (FTIR), ¹H and ¹¹B-nuclear magnetic resonance (NMR) spectroscopy techniques. The boron-containing UV-curable oligomer (BELO) was added to a conventional polyurethane acrylate (PUA) at varying concentrations ranging from 10 to 40 wt% in the presence of a photoinitiator and a reactive diluent. LOI and UL-94 tests were performed to understand the flame-retardancy behavior of the synthesized BELO oligomer, and the results revealed that the flame retardancy of UV-curable coatings enhanced as the percentage of BELO oligomer in the coating formulations increased. The glass transition temperature (T_g) and thermal stability of cured coatings were analyzed by differential scanning calorimetry and thermogravimetric analysis, respectively. The TGA analysis showed that char yield at 600 °C increased by increasing the BELO oligomer content. The mechanical properties, and stain, solvent, and chemical resistance and thermal behavior of the coatings were investigated. Incorporation of BELO into the PUA coating formulations and the comparison of the properties of BELO-incorporated PUA coatings with those of the conventional PUA coating exhibited interesting results.     

Effect of both silane‐grafted and ion‐exchanged organophilic clay in structural,thermal, and mechanical properties of unsaturated polyester nanocomposites

Unsaturated polyester (UPE) resin including styrene monomer was mixed with organophilic montmorillonite (MMT) clay and its crosslinking polymerization reaction was done in the presence of free‐radical initiator. MMT clay was modified with cetyl trimethly ammonium bromide and trimethoxy vinyl silane. The nanocomposites were characterized by X‐ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), thermogravimetric and dynamic mechanical analyses (TGA and DMA). The exfoliated nanocomposite structure was obtained when the MMT clay was modified in the presence of both modifiers, whereas individual modifications all resulted in intercalated structures. The exfoliated UPE nanocomposite exhibited better thermal and dynamic mechanical properties when compared with pure UPE and other composites, even with 3 wt% clay loading. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

环氧树脂/二烷基次膦酸铝阻燃体系的制备和性能

着重研究了环氧树脂/二乙基次膦酸铝（EP/OP930）阻燃材料的阻燃性能、热分解性能和力学性能。结果表明,OP930的含量仅需15 %（质量分数,下同）就可以使EP/OP930体系的极限氧指数达到29.8 %,垂直燃烧实验达到UL 94 V-0级标准;此外,EP/OP930体系的综合性能良好,不同OP930含量的阻燃材料的力学性能、热稳定性能与原材料相比变化不大。     

Properties of nanocomposites based on maleate‐vinyl ether donor—acceptor UV‐curable systems

UV‐curable nanocomposites based on donor–acceptor crosslinking chemistry were prepared containing organically modified montmorillonites. The coatings were characterized for thermal, mechanical, and morphological properties. X‐ray diffraction and transmission electron microscopy showed that nanocomposites were formed in all samples. Results showed that an increase in the percentage of clay caused an increased modulus and glass‐transition temperature. It was also seen that tensile modulus showed dramatic improvement when compared with the unmodified polyester sample. Real time IR kinetic data showed that higher conversions were obtained at higher clay loadings. Pendulum hardness values and tensile modulus values showed different trends in properties depending on the combination of polymer matrix and organomodification. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007