Syntheses and characterizations of two-component polyurethane flame retardant coatings using 2,4-dichloro modified polyesters

Polyurethane flame retardant coatings are composed of polyols and polyisocyanates. Flame retardant groups are usually introduced to the polyol structure. In this research intermediates were obtained by esterification of 2,4-dichlorobenzoic acid and trimethylolpropane for the purpose of introducing a flame retardant group to the polyol structure. Then chlorine-containing modified polyesters were synthesized by polycondensation of trimethylolpropane, adipic acid, 1,4-butanediol, and the intermediate. The content of 2,4-dichlorobenzoic acid in the intermediate was varied with 10, 20, and 30 wt%. Two-component polyurethane flame retardant coatings were prepared by blending the products with polyisocyanate. Various physical properties of these new flame retardant coatings were comparable to non-flame retardant coatings. They showed drying times of four to seven hours and pot life times of 14–20 hr, which could belong to the flame retardant coatings with long pot life time. The coating with 30 wt% 2,4-dichlorobenzoic acid showed a self-extinguishing property in the vertical burning test. Dept. of Chemical Engineering, Yongin 449-728, Korea. Ansan 425-110, Korea.     

膨胀型阻燃剂的疏水改性及对水性阻燃涂料性能的影响

为了提高水性阻燃涂层的耐水性,以环氧树脂(EP)作为包覆材料,分别采用单一组分和混合组分改性两种工艺对阻燃剂〔聚磷酸铵(APP)、三聚氰胺(MEL)和季戊四醇(PER)〕进行包覆改性,制备出了改性阻燃剂及水性阻燃涂层。借助FTIR分析阻燃剂表面基团;采用SEM观察其微观结构;测量阻燃剂的接触角,并对其粒度分布进行统计;借助TG对阻燃剂及水性阻燃涂层进行测试;并参考国标GB/T1733—1993对涂层耐水性进行了测试。结果表明:两种工艺制备的阻燃剂其表面均包覆EP,且EP用量为阻燃剂质量的15%时,疏水效果达到最佳;阻燃剂经改性后其溶解度降低,接触角增大,使水性阻燃涂层耐水性显著提高,且阻燃剂采用混合组分改性效率更高;聚磷酸铵与EP发生交联生成不饱和富碳结构,加固残炭碳骨架的稳定性及增加涂层残余物的质量。     

Preparation and characteristics of two-component polyurethane flame retardant coatings using 2,3-dibromo modified polyesters

Two-component polyurethane flame retardant coatings were prepared by blending 2,3-dibromo modified polyesters (2,3-DBPOs) and polyisocyanate. 2,3-DBPOs were synthesized by polycondensation of 2,3-dibromopropanoic acid, a flame retardant aliphatic carboxylic acid, with 1,4-butanediol, trimethylolpropane, and adipic acid. The content of 2,3-dibromopropanoic acid was varied at 10, 20, and 30 wt % for the polycondensation reaction. Various physical properties of these new flame retardant coatings were comparable to non-flame-retardant coatings. They showed desirable properties for a flame retardant coating such as rapid drying and 9–12 h of pot life. Coatings with 30 wt % 2,3-dibromopropanoic acid did not burn using the vertical burning test. © 1996 John Wiley & Sons, Inc.     

Synthesis and properties of flame-retardant reactive hot melt polyurethane adhesive

Abstract

A novel liquid polyphosphonate polyol (DMDP) was synthesized from dimethyl methylphosphonate and 1,6-hexanediol. Reactive hot melt polyurethane adhesives with high flame retardancy (HMPURs) were prepared from poly(tetramethylene ether glycol) (PTMG-2000), two kinds of poly(1,4-butylene adipate) (PBA-2000 and PBA-3000) and DMDP or dimethyl methylphosphonate as well as tetrahydrofuran acrylate. Five specimens of flame-retardant HMPURs with different weight percent of DMDP (0, 2, 4 and 6?wt%) and dimethyl methylphosphonate (4?wt%) were obtained. The mechanical properties, thermal stability, flammability, and bonding strength of the specimens were investigated. The results show that with the increase of DMDP content, the elongation at break and tensile strength decrease slightly, and the flame retardancy of HMPURs is significantly improved with the limiting oxygen index (LOI) value increasing from 17.2 to 28.2. The incorporation of DMDP leads to a higher thermal stability of HMPURs at high temperature and more char yield at 650?°C. With the increase of DMDP content, the final bond strength of HMPURs on the same substrate changes little, but the green strength of HMPUR-6 on the same substrate is observably less than other samples. The performance of HMPUR with the reactive flame retardant is superior to that of HMPUR with the additive flame retardant. In addition, the corresponding flame-retardant mechanism of DMDP-containing HMPURs was investigated by pyrolysis-gas chromatography coupled to mass spectrometry (Py-GC/MS). The results indicate that the pyrolysis of the HMPURs releases phosphorus-containing fragments to play a flame retardant role.     

含磷多元醇的合成及其阻燃改性PUR硬泡

利用甲基磷酸二甲酯(DMMP)与多元醇经酯交换反应制备了反应型含磷阻燃多元醇,研究了催化剂种类和用量及反应温度、时间等工艺参数对酯化反应转化率的影响,同时优化了工艺条件,合成的多元醇含磷量可达12%~15%。将合成的多元醇替代部分聚醚4110用于制备阻燃聚氨酯硬泡,采用极限氧指数法(LOI)对其阻燃性能进行了表征,并与普通聚氨酯硬泡进行了比较。研究结果表明,在添加少量的混合阻燃剂时,阻燃聚氨酯硬泡的LOI可达30%以上。     

锥形量热仪在饰面型防火涂料防火性能研究中的应用

用锥形量热仪的方法研究了不同阻燃剂含量的饰面型防火涂料点燃时间、热释放速率、有效释放热及总烟气释放量等项目,结果表明:随着阻燃剂含量的增加,热释放速率、有效释放热等参数随之降低;此外,在市面上选取3种饰面型防火涂料,用大板法和锥形量热仪法进行了研究,结果表明:随着耐火极限的延长,有效释放热、热释放速率等参数数值明显减小,同理论分析一致。     

Allyl phosphonium salt–modified clay for photocured coatings: Influence on the properties of polyester acrylate‐based coatings

In this study, bentonite clay was modified with a phosphonium salt and this modified clay was used to prepare polyester acrylate based coatings to improve their flame retardancy and mechanical properties. Photocured composites were prepared with 1, 2, and 3 wt% phosphonium salt modified clay and for comparison 1 wt% nonmodified clay containing composites were also prepared. Modified clay displayed good dispersion properties due to its increased basal spacing. Composites were characterized by FT‐IR and XRD measurements. According to XRD results, it was found that the modified clay was exfoliated in the composites. Furthermore, we investigated the effect of allyl phosphonium salt modified clay on the thermal, mechanical, and flame retardant properties of polyester acrylate based composites coatings. When compared with neat clay containing coatings, modified clay containing photocured coatings exhibited increased modulus and enhanced thermal properties due to increased crosslinking density. Moreover, the presence of the phosphonium salt enhanced the flame retardancy of the polyester based coatings. POLYM. COMPOS., 36:946–954, 2015. © 2014 Society of Plastics Engineers     

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     

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。     

DIDOPO与POSS/EG协同阻燃环氧树脂泡沫及机理研究

以对苯乙基桥链9,10⁃二氢⁃9⁃氧杂⁃10⁃磷杂菲⁃10⁃氧化物（DIDOPO）、聚甲基倍半硅氧烷（POSS）、膨胀石墨 （EG）为复配阻燃剂对环氧树脂（EP）泡沫进行阻燃改性,研究了复配阻燃剂对EP泡沫材料的阻燃效果和阻燃机理。结果表明,当DIDOPO/POSS=3∶1（质量比,下同）、DIDOPO/EG=1∶3时,复配阻燃体系的阻燃效果最佳;添加20 %（质量分数,下同） DIDOPO/POSS复配阻燃剂的加入可以使EP泡沫的UL 94测试达到V⁃0级; 添加20 %的 DIDOPO/EG复配体系可以使EP泡沫的极限氧指数（LOI）提高至30.8 %,UL 94测试达到V⁃0级;阻燃体系具有一定的抑烟效果。     

Preparation and characterization of weather resistant silicone/acrylic resin coatings

Preparation and characterization of weather resistant silicone/acrylic resin coatings were conducted. In order to prepare these coatings, a silicone/acrylic resin (KLD) was first prepared by an addition polymerization reaction of monomers, including n-butyl acrylate, methyl methacrylate, n-butyl methacrylate, and 3-methacryloxypropyltrimethoxysilane (MPTS). In the preparation of the silicone/acrylic resin, T_g of the acrylic copolymer was fixed at 40°C and the contents of MPTS were varied to be 10, 20, and 30 wt%. The weather resistant silicone/acrylic resin coatings were then prepared by blending the synthesized silicone/acrylic resin and TiO₂. The viscosity of the synthesized resin decreased with the content of MPTS, whereas the thermal stability at high temperature increased. The prepared coatings exhibited excellent adhesion to various substrates, and various physical properties of the coatings were satisfactory. The weatherability of the coatings was tested three ways: outdoor exposure test, Weather-Ometer (WOM), and QUV accelerated weatherability tester (QUV). The gloss retention, yellowness index difference, color difference, and lightness index difference were improved at high MPTS concentration. The coatings containing 30 wt% MPTS have especially good weather properties. Dept. of Chem. Eng., Yongin 449-728, Korea. Ansan 425-110, Korea.     

热塑性聚氨酯/微胶囊化聚磷酸铵/氢氧化铝复合材料的制备及性能研究

通过溶胶?凝胶法制备了硅凝胶微胶囊化聚磷酸铵（MAPP）,并通过红外光谱仪（FTIR）、热重分析仪（TG）对MAPP进行了表征;采用熔融共混技术将氢氧化铝（ATH）和MAPP加入到热塑性聚氨酯弹性体（TPU）中,制备出系列阻燃热塑性聚氨酯弹性体（TPU/FR）复合材料,并通过TG、微型量热计（MCC）研究了TPU/FR的热稳定性和燃烧行为。结果表明,在ATH与MAPP总含量为20 %（质量分数,下同）的情况下,相对于TPU/FR1（20 % ATH）复合材料,ATH与MAPP含量分别为5 %、15 %,10 %、10 %和15 %、5 %的TPU/FR复合材料在700 oC下的残炭量分别由16.7 %提高到29.7 %、25.1 %和20.9 %;热释放容量（HRC）分别从327.1 J/（g·K）降低到154.2、164.2和170.1 J/（g·K）;对比TPU/FR2（20 % MAPP）复合材料,TPU/FR4（15 % ATH,5 % MAPP）炭渣的致密性和石墨化程度显著提高,表明ATH与MAPP复合具有显著的阻燃协同作用。     

茶皂素基膨胀型阻燃剂的制备及其在涂料中的应用

采用多羟基、多羧基的活性天然产物茶皂素为原料,与聚磷酸铵和季戊四醇在一定条件下反应,制备一种聚磷酸酯类茶皂素基三位一体新型环保膨胀型阻燃剂。采用傅里叶红外分析技术对阻燃剂进行了结构表征,采用综合热分析仪对阻燃剂的热降解性能进行了研究。结果表明,茶皂素与聚磷酸铵、季戊四醇发生反应,生成聚磷酸酯类茶皂素基膨胀型阻燃剂,且该阻燃剂具有良好的热稳定性,降解热释放较小,高温残留率高,最终的质量残留率高达30.77%。将制备阻燃剂用于阻燃涂料中,并采用氧指数测试仪和锥形量热仪研究了阻燃涂料的阻燃性能和热解性能。研究表明,茶皂素基三位一体膨胀型阻燃剂能显著提高涂料的阻燃性能,阻燃涂料的氧指数值高达34.2%,耐火时间为11.1 min,且锥形量热实验中,该阻燃涂料试样的平均热释放速率（m-HRR）为36.18 kW/m2,总热释放量（THR）为5.25 kJ/m2,平均有效燃烧热（m-EHC）为5.11 kJ/kg,与含复合型阻燃剂的阻燃涂料试样相比,阻燃性能得到极大提高。该制备阻燃剂不含卤素,集三源一体,具有阻燃性能优越,相容性能良好,高效环保等优点。     

A macromolecular halogen‐free flame retardant and its effect on the properties of thermoplastic polyesters

A halogen‐free flame retardant with a macromolecular structure is presented. Its synthesis proceeds via polymerization of phosphorus‐containing acrylate monomers. The flame retardant was incorporated into poly(ethylene terephthalate) by extrusion. Samples with different concentrations (0.5, 2.5, and 5.0 wt%) as well as a 25 wt% masterbatch were prepared. All samples were transparent and colorless without any visible irregularities. Thermal investigations reveal an unchanged glass transition temperature. Tensile tests show the typical mechanical behavior of poly(ethylene terephthalate), but with an elevated Young's modulus. The burning behavior was investigated by several small‐flame tests in vertical and horizontal orientation, as well as by cone calorimetry. It is shown that samples with 2.5 wt% flame retardant pass the vertical UL94 test (V‐2, 20‐mm flame). The sample cannot be ignited in the horizontal fire test according to FMVSS 302. The oxygen index was measured to 28 vol%. Cone calorimetric measurements show that the effective heat of combustion as well as the total heat evolved is reduced.     

涂料用本体阻燃树脂单体研究进展

本体阻燃树脂是让阻燃单体参与聚合反应,使之成为合成树脂的结构单元而赋予其较好的阻燃性能。该方法具有阻燃剂使用量少,所得树脂阻燃性能持久,基本不影响材料其他性能等优点。文章综述了近年来国内外研究人员对4类含有不同元素的涂料用本体阻燃树脂单体的研究进展,重点介绍了各类阻燃单体的合成方法,在不同合成树脂中的应用,以及所得树脂的成炭率、极限氧指数、UL-94测试等燃烧性能。最后,对涂料用本体阻燃树脂单体的发展前景作了展望。     

高含量玻璃纤维增强阻燃聚酰胺材料的制备与性能

采用双螺杆挤出机制备了聚酰胺6(PA6)/50%（质量分数,下同）玻璃纤维（GF）、PA66/50%GF、PA56/50%GF 3种高含量GF增强阻燃PA复合材料,对比研究了红磷、溴系、磷氮3种阻燃体系下复合材料的力学性能、阻燃性能和激光打标性能。结果表明,不同阻燃体系对复合材料的力学性能有明显影响,吸水平衡后,PA66复合材料的力学性能保持率最高;PA56复合材料在3种阻燃体系中均表现出比PA6、PA66复合材料更好的阻燃性能;红外激光和紫外激光的打标效果存在明显不同,而在阻燃体系和激光光源相同的条件下,PA6、PA66和PA56 3种PA复合材料的激光打标效果没有明显差异。     

阻燃薄膜用聚酯的研制

采用DMT(对苯二甲酸二甲酯)酯交换法，加入一定比例的反应型阻燃剂作为第三单体，合成了阻燃PET(聚对苯二甲酸乙二醇酯)，并进行了双向拉伸薄膜试验。结果表明，制备的阻燃PET切片适台于拉膜，限氧指数有显著提高。     

磷-氮协效阻燃水性聚氨酯的性能

引言目前,市场上基本上采用添加型阻燃剂与水性聚氨酯复配的方式对织物进行阻燃整理,这种方式具有涂层不透明、阻燃剂添加量大、耐水洗性差等缺点。而反应型阻燃水性聚氨酯可以克服这些缺     

水性聚氨酯膨胀型阻燃涂料的研究进展

水性聚氨酯涂料若未经阻燃处理,存在引发火灾的隐患,因此水性聚氨酯的阻燃研究是水性聚氨酯功能化的重要方向之一。介绍了水性聚氨酯阻燃涂料的分类,按不同分类标准可分为共混复配型和反应型,膨胀型和非膨胀型。对水性聚氨酯阻燃涂料阻燃效应和阻燃机理进行了探讨,并重点介绍水性聚氨酯膨胀型阻燃涂料的研究现状。最后提出了现在水性聚氨酯膨胀型阻燃涂料存在的问题,并对水性聚氨酯膨胀型阻燃涂料的发展趋势进行了展望。     

加成型阻燃导热有机硅电子灌封胶的研制

以乙烯基硅油、舍氢硅油为基料,铂络舍物为催化剂制得双纽分加成型有机硅灌封胶。通过添加导热和阻燃填料提高灌封胶的导热性和阻燃性,加入增粘剂改善有机硅的粘接性能。结果表明,100份乙烯基硅油（乙烯基质量分数1％）中含氢硅油（活性氢质量分数0.18％）15份、铂含量10×10^-6、导热填料40份、阻燃剂含量50×10^-6、增粘剂1份,所得灌封忮具有较好的综合性能,能够满足大功率电子元器件的灌封要求。