Preparation and physical properties of polyurethane flame retardant coatings using phosphorus-containing lactone modified polyesters

Two-component polyurethane flame retardant coatings were prepared using phosphorus-containing lactone modified polyesters (PLMPs) and polyisocyanate. PLMPs were synthesized by poly-condensation of dimethyl phenylphosphonate, a flame retardant component with polycaprolactone, adipic acid, and trimethylolpropane. PLMPs were prepared with dimethyl phenylphosphonate content from 10 to 20 wt%. It was found that various physical properties of these new flame retardant coatings were comparable to non-flame retardant coatings. The flammability of coatings depends strongly on the dimethyl phenylphosphonate content in PLMP. Coatings with 20 wt% dimethyl phenylphosphonate content did not burn in the vertical burning test. Dept. of Chem. Eng., Yongin 449-728, Korea. Ansan 425-110, Korea.     

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.     

Preparation and physical properties of two-component polyurethane flame-retardant coatings using trichloro modified polyesters

Trichloro modified polyester polyols were synthesized by two-step condensation reactions. An intermediate compound was synthesized by the esterification of trichloroacetic acid with trimethylolpropane in the first step. In the next step, polycondensation of the intermediate, 1,4-butanediol and trimethylolpropane with adipic acid was carried out. Two-component flame-retardant polyurethane coatings were prepared by blending these modified polyester polyols and polyisocyanate. The physical properties of these new coatings were comparable to non-flame-retardant coatings. They showed a drying time of 3–4 h and a pot life time of 10–13 h, which could belong to the flame-retardant coatings with long pot life times. Coating with 20 wt % trichloroacetic acid showed a self-extinguishing property in the vertical burning test. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 913–920, 1998     

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     

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.     

Flame-retardant thermoplastic polyurethane based on reactive phosphonate polyol

Propylene oxide (PO) was used to block polycarboxyethyl phenyl ethylene phosphinate (PCEPEP) synthesized by 2-carboxyethylphenylphosphinic acid (CEPPA) and ethylene glycol (EG) to obtain a reactive phosphonate polyol. The results of chemical titration analysis and Fourier transform infrared spectrum (FT-IR) showed that the end-capping effect was best when the molar ratio of PO to acidic functional groups in PCEPEP was 6:1. Moreover, the obtained phosphorus-containing polyol was used as a reactive monomer to be introduced into thermoplastic polyurethane (TPU) to prepare flame retardant TPU. Cone calorimetry results demonstrated that TPU containing 20 wt% phosphorus-containing polyol showed a reduction of 3.8%, 72.2%, and 39.3% in the peak heat release rate, total heat release and total smoke release, and an increment of 351.9% in mass retention. The addition of phosphonate polyol enhanced the char-forming performance of TPU, which effectively prevented the transfer of combustible gas and heat, and displayed a good flame retardant effect.     

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。     

Biomaterial Based Polyurethane Adhesive for Bonding Rubber and Wood Joints

An intermediate compound for synthesizing polyester polyol was prepared from glycosylation of potato starch by reacting it with ethylene glycol in presence of sulphuric acid. Glycol glycoside thus prepared was characterized by HPLC and FTIR. This polyhydroxy compound was replaced in varying amounts with trimethylolpropane for polyester polyol synthesis. Sebacic acid was used as dicarboxylic acid along with castor oil for polyester polyol formulation. Polyols were reacted with toluene 2,4-diisocyanate adduct for polyurethane formation. Polyester polyol and polyurethane were characterized by FTIR. Polyurethane was utilized for bonding wood as well as rubber joints. Bond strength was measured by means of lap shear strength and peel strength for wood and rubber joints, respectively. Chemical resistance of polyurethane adhesive was also evaluated. This revised version was published online in July 2006 with corrections to the Cover Date.     

Polyurethane coatings based on linseed oil phosphate ester polyols with intumescent flame retardants

The effect of intumescent flame retardants on the properties of polyurethane (PU) coatings based on 2 kinds of phosphate ester polyol was studied. Synthesizing polyols, phosphorylation of epoxidized linseed oil with phosphoric acid was performed in the presence of isopropyl alcohol (IPA polyol) or diethylene glycol butyl ether (DGBE polyol). The obtained polyols were characterized by Fourier transform infrared (FTIR) and ³¹P nuclear magnetic resonance (NMR) spectroscopy. The properties of neat PU coatings based on 2 polyols and those filled with different content (up to 25 wt%) of melamine (Mel), ammonium polyphosphate (APP), and expandable graphite (EG) were studied using thermal gravimetric analysis (TGA), and tensile and cone calorimeter tests. It was found that IPA polyol contained not only phosphate monoesters and diesters, as DGBE polyol, but also phosphate triester and pyrophosphate monoester. Due to this difference, IPA neat and filled coatings had higher tensile characteristics and char residue in a TGA test. Also, the flame retardancy of IPA coatings, compared with that of DGBE coatings, was higher. In a cone calorimeter test, coatings filled with Mel showed a small increase of flame retardancy, but the total smoke release (TSR) of wood samples with coatings decreased noticeably. The effect of APP on the flame retardancy of coatings was higher, but in contrast, the TSR of samples increased with increasing APP content. Even greater decrease of flammability parameters and a simultaneous significant decrease of TSR were shown by the samples with IPA coatings filled with EG.     

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。     

聚酯丙烯酸杂化多元醇水分散体的制备

以间苯二甲酸-5-磺酸钠(5-SSIPA)与新戊二醇缩聚,制备亲水性中间体.用该中间体与羟基丙烯酸树脂、新戊二醇、三羟甲基丙烷和己二酸进一步缩聚,制得聚酯丙烯酸杂化树脂,加水分散后得其水分散体.研究了反应温度、羟基丙烯酸树脂的玻璃化温度及含量对杂化多元醇水分散体及其相应涂膜性能的影响.结果发现,适宜的杂化反应温度为22...     

聚脲多元醇对聚氨酯泡沫阻燃性的影响

使用含氮结构型阻燃聚脲多元醇和阻燃剂对聚氨酯高回弹泡沫的阻燃性进行研究,考察了配方中聚脲多元醇用量及阻燃剂品种对泡沫烟密度及氧指数的影响。研究结果表明,聚脲多元醇具有显著的抑烟作用,与三聚氰胺、阻燃剂R一起使用时,协同阻燃效应明显,不仅能有效降低泡沫燃烧时的发烟量,还能显著提高泡沫的氧指数。     

Automated determination of pot life of two-component reactive coatings

The process of pot life screening of two-component coatings is significantly accelerated by using an automated coating formulation system with viscosity measurement capability. High-throughput methods are revolutionizing the processes used in polymer and coatings development. A high-throughput approach to characterize the effect of formulation variables on pot life of two-component solventborne coatings is presented. Using an automated formulation system with viscosity measurement capability, the viscosity of the coatings formulations is measured periodically to determine the viscosity–time profile. As examples, variables such as catalyst type, catalyst level, polyol composition, polyol to isocyanate ratio, and pot life extender were selected as formulation variables and their role in pot life were explored. Compared to traditional pot life determination methods using efflux viscosity cups, the high-throughput approach greatly improves the speed and efficiency of the process and allows many more compositions to be explored.     

苯酐聚酯多元醇聚氨酯硬泡的阻燃性研究

以国产苯酐聚酯多元醇为主要原料制备了组合聚醚,再与多异氰酸酯反应,制备了阻燃型聚氨酯硬质泡沫。讨论了苯酐聚酯多元醇、硅油及发泡剂等因素对泡沫阻燃性的影响。结果表明,该组合聚醚与多异氰酸酯反应,制得的阻燃型聚氨酯硬质泡沫,其氧指数在28以上,压缩强度为300kPa,达到了国家标准GB／T8624-1997中B2级氧指数的要求。     

The flame‐retardant effect of calcium hypophosphite in various thermoplastic polymers

The flame‐retardant behavior of calcium hypophosphite (CaHP) was investigated in different thermoplastic polymers including polyamide 6 (PA), poly (lactic acid) (PLA), thermoplastic polyurethane (TPU), and poly methyl metacrylate (PMMA). CaHP was used at three different amounts of 10, 20, and 30 wt%. The characterization of the composites was performed using limiting oxygen index (LOI), vertical burning test (UL 94), thermogravimetric analysis (TGA), and mass loss calorimeter test. According to the test results, CaHP enhances the fire‐retardant properties in different levels depending on the polymer type. The CaHP exhibits its flame‐retardant effect via the formation of foamed char structure in the condensed phase and via the dilution and radical scavenging effect in the gas phase.     

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.     

阻燃聚合物聚醚多元醇的合成及其阻燃性能的研究

采用高活性聚醚多元醇作为基础聚醚,将几种含氮化合物分散或接枝到高活性聚醚多元醇结构中,生成含有聚合物微粒分散体的接枝型阻燃聚合物聚醚多元醇.重点对阻燃聚合物聚醚多元醇合成的条件、原料最佳配比以及在聚氨酯泡沫中的阻燃性能进行了研究.结果表明,此种方法合成的阻燃聚合物聚醚多元醇具有颗粒分布均匀、粘度低、物料流动性好等优点,...     

新型含磷阻燃剂的制备及性能

以双三羟甲基丙烷为原料合成一种新型含磷阻燃剂,该阻燃剂分子量较大,具有稳定的环状结构,热稳定性高于常用阻燃剂,阻燃效果好。探讨了原料配比、反应温度、反应时间对产率的影响,考察了目标产物的热稳定性能及其对不同织物的阻燃效果,用傅里叶变换红外光谱仪表征了中间体及目标产物的结构。结果表明,当原料配比为1∶3时,磷化温度为50℃,磷化时间5h,胺化温度为75℃时,反应效果较好,收率可达90%以上。目标产物对于锦纶的阻燃效果比较明显,对涤纶、棉有一定的阻燃效果,对于混纺、腈纶阻燃效果不明显。     

多功能阻燃剂聚醚多元醇亚磷(膦)酸酯的合成

以三溴苯基缩水甘油醚为阻燃单体，与环氧丙烷／环氧氯丙烷共聚制备具有阻燃特性聚醚多元醇，后者与亚磷酸三甲酯的酯交换反应和Arbuzov重排反应，合成了新型聚醚多元醇亚磷(膦)酸酯(PEPP)高分子阻燃剂。通过元素分析和IR及^1H NMR等分析方法对其化学结构进行了表征。研究了反应物料配比、催化剂、反应时间等因素对PEPP物理性质及收率的影响。应用试验结果表明，PEPP是一种热稳定性高、阻燃效果好，同时兼有增塑剂和抗氧剂功能的新型阻燃剂。     

低密度及阻燃低密度高回弹聚氨酯泡沫研制

采用聚醚多元醇和阻燃聚合物多元醇为主要原料,制备了低密度及阻燃低密度高回弹聚氨酯泡沫,讨论了低密度高回弹聚氨酯泡沫性能及阻燃聚合物多元醇TM-300用量对聚氨酯泡沫性能的影响。结果表明,低密度高回弹泡沫密度可低至35kg/m3,性能与一般密度聚氨酯泡沫相当。随着TM-300用量增加,阻燃低密度高回弹聚氨酯泡沫的硬度和拉伸强度增加,撕裂强度和伸长率下降;TM-300可有效提高聚氨酯泡沫的阻燃性能,氧指数可达到32,各项性能均较优异。