Flame retardant polyesters. I. Phosphorous flame retardants

Commercially available two types of phosphorous flame retardants (FRs) for polyester were compared from the viewpoint of chemical reactivity, reaction mechanism, and byproduct formation. 3‐(Hydroxyphenyl phosphinyl) propanoic acid (HPP) and 9,10‐dihydro‐9‐oxa‐10‐2,3‐dicarbonylpropyl)‐10‐phosphophenanthrene‐10‐oxide (DI) were used as a main chain type and a pendant type, respectively. HPP and DI showed different behavior with ethylene glycol (EG). More acidic HPP reacted with EG spontaneously and then produced esterified terminal hydroxy end group reacted with EG to form terminal diethylene glycol (DEG) end group. But the composition in the HPP solution was not varied for a long time below the esterification temperature. Contrast to HPP, DI showed normal esterification procedure. DI esterified with EG to form DI ester of EG, and DEG formation is not distinct. The difference of reactivity and DEG formation is caused by the difference of acidity in EG solution. For production of phosphorous containing polyester, it is desirable that HPP is introduced into the reactor in the mere solution state and DI in the esterified state. In addition, for production of polyester having the same phosphorous content in commercial scale, it is more beneficial to apply HPP than DI because of low input of FR due to low molecular weight. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesize and Characterization of Flame Retardant Copolyesters PET/Phosphorus Compound

The aim of this study was to achieve a fiber‐grade poly(ethylene terephthalate) (PET) with flame retardancy properties. Flame retardant copolyesters based on ethylene glycol, terephthalic acid, and 3‐(hydroxyphenyl phosphinyl) propionic acid (HPP), as a flame retardant comonomer, were synthesized in presence of antimony trioxide catalyst at laboratory and semi‐industrial scales. At first, copolyesters with the lowest amount of flame retardant comonomer were synthesized at laboratory scale in a one‐pot reactor setup. In the second stage, flame retardant PET was synthesized in semi‐industrial pilot with HPP (PET‐HPP). The obtained copolyesters demonstrated almost identical intrinsic viscosities and other characteristics such as PET. Fourier transform infrared spectroscopy (FTIR), 1H‐NMR spectroscopy, and RMS test were performed. Flame retardancies were evaluated by a limiting oxygen index (LOI) test. The results indicated that the presence of FR significantly improved the flame retardancy and thermal stability of PET‐HPP. LOI values increased from 28% (PET) to 33 (PET‐HPP) (at laboratory scale) and 44% (at semi‐industrial scale). Differential scanning calorimetry analysis showed that the HPP polyester chain had a higher flexibility compared to PET, due to lower glass transition temperature. The effect of adding FR with regard to the thermal stability of PET‐HPP was investigated via thermogravimetric analysis. The physical properties of both the polymers are similar and suitable for textile application. J. VINYL ADDIT. TECHNOL., 25:262–270, 2019. © 2018 Society of Plastics Engineers     

Flammability behavior of unsaturated polyesters modified with novel phosphorous containing flame retardants

Two phosphorous containing reactive flame retardants namely Triallyl phosphate (TAP) and diethylene glycol modified tetra‐allyl phosphate (DTAP) are synthesized and incorporated successfully in commercial Unsaturated polyester (UPR) in various amounts (5, 10, and 15 phr) to yield flame retardant unsaturated polyester (FRUPR) composites. The structures of reactive flame retardant monomers are confirmed by FTIR, ¹H‐NMR, and³¹P‐NMR spectroscopy. Further, FRUPR composites are characterized for their mechanical, thermal, and flame retardant properties. It is observed that tensile strength and hardness of composites are enhanced with the addition of flame retardants; however, flexural strength and impact resistance are lowered. Differential Scanning Calorimetry (DSC) study reveals that there is a significant increase in glass transition temperature with the addition of flame retardants suggesting the formation of dense and crosslinked structure in FRUPR composites. Thermal stability and the flame retardant properties are also observed to be improved with the increase in concentration of flame retardant in UPR as evidenced from Thermo‐gravimetric analysis (TGA). Beyond 10 phr concentration of flame retardants, all composites show V‐0 rating on UL‐94 test. Also, increase in phosphorous content in composites leads to gradual improvement in limiting oxygen index values. POLYM. COMPOS., 38:1483–1491, 2017. © 2015 Society of Plastics Engineers     

Flame retardant polyesters. III. Fibers

Most of the commercial flame retardant (FR) polyester fibers are produced using copolymerization with phosphorous FRs. We investigated the fiber properties, dyeing properties, and flame retardancy according to the phosphorous FR type. The physical properties of both the fibers are similar and suitable for textile application. But the dye adsorption rate is much faster in the case of main chain type. This is resulted from higher chain mobility analyzed by glass transition temperature. The main chain type FR polyester fiber adsorbed the dyestuff at lower temperature and reached exhaustion more quickly. And the resistance to chemicals such as acidic and alkaline solutions at high temperature have similar tendency with dye absorption. The migration of dyestuffs and chemicals into the polymer chain has good correlation with chain mobility of the polymers. The main chain type polyester fiber shows better flame retardancy than pendant type polyester, which might be brought about from more rapid degradation into polyphosphoric acid. The main chain type polyester fiber shows better flame retardancy than pendant type polyester. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

耐热阻燃聚酯的制备及性能研究

以精对苯二甲酸与乙二醇为主要原料,在聚酯聚合过程中引入可与聚酯熔体发生化学反应的磷系高分子阻燃剂,最终制得新型耐热阻燃聚酯树脂。该聚酯的极限氧指数(LOI)可达44.4%,与普通共聚型阻燃聚酯相比,不仅满足难燃材料的要求,同时具有更高的熔点(≥255℃),更优异的热稳定性、结晶性以及耐酸碱性能,可广泛应用于印花面料、工业丝、单丝及工程塑料等领域。     

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     

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     

Thermal degradation studies of molybdenum containing polyester thermosets

A study has been made of the effect of molybdenum trioxide on the thermal degradation of a series of chlorinated and brominated polyester thermosets. Like antimony oxide, it showed flame retardant activity in all the halogenated polyesters. It was shown to affect the char yield, and the temperature and weight loss of each degradation step. X-Ray diffraction studies of the degraded dibromoneopentyl glycol polyesters showed that in air a near-quantitative yield of molybdenum trioxide was present above 550 °C. Some dioxide was present before the final char oxidation step occurred. In a nitrogen atmoshphere the trioxide was reduced to the dioxide at first, but this finally reacted to give the carbide at around 900 °C. Infrared spectroscopy showed that inclusion of the molybdenum trioxide resulted in structural changes in the high-temperature polyester residues which were more prominent when bromine was present. Elemental analysis of the residues indicated that the presence of the trioxide in the brominated polyesters accelerated the release of bromine at high temperatures and confirmed its char-promoting tendencies.     

有色阻燃异径聚酯FDY热收缩率的探讨

以阻燃聚酯切片与高色牢度色母粒为原料,制备了有色阻燃异径聚酯全拉伸丝(FDY),重点探讨了工艺条件对其热收缩性能的影响。结果表明:在试验范围内,有色阻燃异径聚酯FDY的热收缩率较有色普通异径聚酯FDY的高;拉伸温度对有色阻燃异径聚酯FDY热收缩率的影响很小,而定形温度与纺丝速度对其影响较大,且有色阻燃异径聚酯FDY的热收缩率随定形温度的升高而下降,随纺丝速度的降低而降低。     

磷系阻燃聚酯性能的研究

用红外光谱表征了磷系阻燃聚酯的结构,研究了磷系阻燃聚酯的特性粘数、DSC、氧指数、可纺性等性能.结果表明,磷系阻燃单体分子中的柔性链段亦被引入大分子主链中,使磷系阻燃聚酯的玻璃化温度(Tg)、熔点(Tm)相应降低.磷系阻燃聚酯具有良好的阻燃性,当磷系阻燃单体含量为4.5%时,磷系阻燃聚酯氧指数为32.8%.但由于侧基的空间体积较大,使得磷系阻燃聚酯的结晶性有所降低,导致拉伸强度降低.实验结果表明磷系阻燃聚酯纤维的物性指标能够满足后加工要求.     

Thermal cross-linking and anti-meltdrop properties of copolyester containing phosphorus/magnesium salt composites by in situ polymerization

Polyester is widely used in household products because of its good mechanical properties and wears resistance, but polyester is easy to ignite and inclined to produce droplet, so its application range is limited. The cross-linkable magnesium hydroxide nanoparticles were incorporated into flame-retardant polyester, which enables the phosphorus-containing copolyester with thermal cross-linking and anti-meltdrop properties. The nanoparticles were achieved by in situ polymerization and acted as a nucleating agent for improving the crystalline properties of the copolyester. Furthermore, the nanoparticles also enhanced anti-meltdrop properties and reduced the heat and gas release during the combustion process of the copolyester. The maximum heat release rate and total smoke release reduced by 39.8% and 74.4% compared with pure polyester. Specifically, the combustion products of the nanoparticles and phosphorus flame retardant could act a barrier role by covering the carbon layer to isolate air and heat, thereby resulting in excellent anti-meltdrop properties. The simple modification method reported here realizes the collaborative modification of flame retardant and anti-meltdrop properties of phosphorous flame-retardant copolyesters by thermal cross-linking.     

Effect of expandable graphite on the properties of intumescent flame‐retardant polyurethane foam

Water‐blown rigid polyurethane foam (PUF) with two different particle sizes (180 and 300 μm) of expandable graphite (EG) as a flame‐retardant additive were prepared, and the effects on the mechanical, morphological, water absorption, thermal conductivity, thermal, and flame‐retardant properties were studied. In this investigation, EG content was varied from 5 to 50 php by weight. The mechanical properties of PUF decreased with increasing EG loading in both cases. The water absorption of the PUF increased with an increase in the EG loading mainly because of the collapse of foam cells, as evidenced from the scanning electron microscopy pictures. The thermal conductivity of the EG‐filled PUF showed that the insulation properties decreased with EG loading. The flame‐retardant properties (limiting oxygen index and char yield measurement) of the PUF improved with increasing EG loading. PUF filled with the higher particle size EG showed better mechanical properties and fire‐retardant properties than the PUF filled with the lower particle size EG. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and enzymatic degradation of high molecular weight aliphatic polyesters

The aliphatic polyesters with high molecular weight have been prepared according to two methods. First is the synthesis of the polyesters by polycondensation of dimethyl succinate (DMS) with 1,4‐butanediol (BD) using various metal alkoxides as a catalyst. Among the metal alkoxides used, titanium tetraisopropoxide [Ti(OiPr)₄] gave the best results (highest molecular weight and yield). Thus, we have prepared aliphatic polyesters using a variety combinations of diesters [MeOOC—(CH₂)_x—COOMe, x = 2–8] with BD by the catalysis of Ti(OiPr)₄. The polyesters with high number‐average molecular weight (M_n > 35,000), except dimethyl adipate (DMA, x = 4)/BD polyester (M_n = 26,900), were obtained in high yield. The melting temperatures (T_m) of polyesters were relatively low (43.4–66.8°C) except that (115.6°C) of the DMS/BD polyester. Second is the synthesis of high molecular weight polyesters by chain extension reaction of lower molecular weight (M_n = 15,900–26,000) polyesters using hexamethylene diisocyanate (HDI) as a chain extender. The M_n values of chain‐extended polyesters consequently increased more than two times (M_n = 34,700–56,000). The thermal properties of polyesters hardly changed before and after chain extension. Enzymatic degradations of the polyesters were performed using three different enzymes (cholesterol esterase, lipase B, and Rhizopus delemar lipase) before chain extension. The enzymatic degradability varied depending on both thermal properties of polyesters [melting temperature and heat of fusion (crystallinity)] and the substrate specificity of enzymes, but it was the following order: cholesterol esterase > lipase B > R. delemar lipase. The ¹H‐NMR spectrum of water‐soluble degraded products of the polyester indicated that the polyester was degraded into a condensation product of diol with diester in a monomer form. The enzymatic degradation of chain extended polyesters was slightly smaller than that before chain extension, but proceeded steadily. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 340–347, 2001     

石墨烯微胶囊/海藻酸钙对涤纶织物的阻燃处理

为提高涤纶织物的阻燃性能,并解决涤纶织物的熔滴现象,本文采用石墨烯微胶囊与海藻酸钠共混制备出阻燃涂覆液,采用浸轧法制备阻燃涂覆涤纶织物。考察涂覆涤纶织物的阻燃性能,力学性能以及热学性能,结果表明：25g/L的海藻酸钠和1g的石墨烯微胶囊阻燃涂覆处理后的涤纶织物的极限氧指数由19.7%,上升到28.34%,达到难燃织物的标准。整理后的涤纶织物达到了V-0标准,涤纶织物燃烧后产生的熔滴的现象消失。织物的断裂强力由135.21N降低到了106.77N。涂覆处理前后,织物达到最大热分解速率的温度未产生明显变化,残炭率由12.07%上升到了26.98%,最大质量损失速率由1.79%/℃降低到了0.96%/℃。同时整理前后涤纶织物的热焓值由58.4J/g上升至68.4J/g。织物的导热系数由0.587 W/cm.℃×10_-4^提高到0.842W/cm.℃×10_-4^{,热学性能得到了充分的提高。}织物燃烧后所形成的残炭由无到连续且致密。     

Flame retardancy and thermal properties of organoclay and phosphorous compound synergistically modified epoxy resin

Phosphorous flame retardants (PFRs) are common halogen‐free flame retardants. However, the flame retardancy of PFRs has not been fully exploited. Herein, the synergistic flame retardant effect of a typical phosphorous compound, 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO), and organoclay on epoxy is studied. Results show that the peak of heat release rate (pHRR) and smoke production rate of modified epoxy resin (EP) with both 2.0 wt % phosphorus and 4.0 wt % organoclay are only 40% and 46% of that of neat EP resin, respectively, while the sole use of 2.0 wt % phosphorus only decrease the pHRR to 59% of that of neat EP resin. The structure and thermal decomposition behavior of as‐prepared nanocomposites are analyzed, and a synergistic flame retardant mechanism is proposed. This investigation opens a new approach to obtain halogen‐free EPs with higher flame retardancy and better overall properties than the EPs loaded with DOPO only. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43367.     

Thermal behaviors and flame‐retardancy of styrene–ethylene–butadiene–styrene–block copolymer containing various additives

The thermal behaviors and the flame‐retardancy of styrene–ethylene–butadiene–styrene–block copolymer containing various additives were studied. The combustion was measured by the Underwriter laboratory (UL) test and cone calorimeter test and thermogravimetric analysis and program‐mass spectroscopy were applied to analyze the thermal behaviors. The blend with halogen additives showed the best result in the UL test. However, the blend with red‐phosphorous was the best in the cone calorimeter test. As the styrene sequence in the copolymer tended to degradate at a lower temperature, the major scission products spouted out from the polymer surface originated from polystyrene. The shorter the ignition times of the blends with red‐phosphorous were, the lower the peak heat release rates were. It was an interesting phenomenon because it suggested that the chemical structure of the residue changed to more stable polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 156–161, 2007     

Biodegradable polymers based on renewable resources. IV. Enzymatic degradation of polyesters composed of 1,4:3.6‐dianhydro‐D‐glucitol and aliphatic dicarboxylic acid moieties

Enzymatic degradation of a series of polyesters prepared from 1,4:3.6‐dianhydro‐D ‐glucitol (1) and aliphatic dicarboxylic acids of the methylene chain length ranging from 2 to 10 were examined using seven different enzymes. Enzymatic degradability of these polyesters as estimated by water‐soluble total organic carbon (TOC) measurement is dependent on the methylene chain length (m) of the dicarboxylic acid component for most of the enzymes examined. The most remarkable substrate specificity was observed for Rhizopus delemar lipase, which degraded polyester derived from 1 and suberic acid (m = 6) most readily. In contrast, degradation by Porcine liver esterase was nearly independent of the structure of the polyesters. Enzymatic degradability of the polyesters based on three isomeric 1,4:3.6‐dianhydrohexitols and sebacic acid was found to decrease in the order of 1, 1,4:3.6‐dianhydro‐D ‐mannitol (2), and 1,4:3.6‐dianhydro‐L ‐iditol (3). Structural analysis of water‐soluble degradation products formed during the enzymatic hydrolysis of polyester 5g derived from 1 and sebacic acid has shown that the preferential ester cleavage occurs at the O(5) position of 1,4:3.6‐dianhydro‐D ‐glucitol moiety in the polymer chain by enzymes including Porcine pancreas lipase, Rhizopus delemar lipase, and Pseudomonas sp. lipase. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 338–346, 2000     

涤纶阻燃技术研究进展

综述了聚酯纤维阻燃化处理方法,分析了卤系和磷系阻燃剂及其对聚酯的阻燃改性作用,以及聚酯/无机纳米复合材料的热稳定性与阻燃性。指出:磷系共聚阻燃改性技术辅以其它反应性单体、纳米添加剂等有利于改善涤纶的抗熔滴性和炭化阻燃作用。     

Preparation,characterization and properties of a halogen‐free phosphorous flame‐retarded poly(butylene terephthalate) composite based on a DOPO derivative

A phosphorous flame retardant (DOPO‐MAH) was synthesized through the reaction between of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) and maleic anhydride (MAH) and confirmed by FT‐IR, ¹H NMR, and ³¹P NMR techniques. The obtained flame retardant was then melt blended with poly(butylene terephthalate) (PBT) to prepare flame retardant PBT/DOPO‐MAH composites. The composites were characterized by LOI, UL‐94, and mechanical tests as well as scanning electron microscopy, thermogravimetric analysis, and differential scanning calorimetry analysis. On adding 20 wt % DOPO‐MAH, LOI increased from 20.9 to 25.7 and the UL‐94 V‐0 rating was achieved, whereas the tensile and flexural properties were notably improved. Torque‐time profile during the melt blending and intrinsic viscosity of the composite indicated that DOPO‐MAH acted as both flame retardant and chain extender for the PBT matrix. The results showed that PBT/DOPO‐MAH composite is a promising material for its good comprehensive properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1301‐1307, 2013     

磷－溴双元素阻燃涤纶切片的研制

分析了磷－溴（Ｐ－Ｂｒ）阻燃剂的特性及阻燃机理。应用Ｐ－Ｂｒ阻燃剂进行了阻燃涤纶切片的开发研制试验，结果表明：Ｐ－Ｂｒ阻燃剂阻燃效果好、能高度分散并有良好的热稳定性，其所制阻燃涤纶切片有良好的可纺性。