新型反应型阻燃剂对羧苯基苯基次膦酸的合成与热稳定性分析

专利名称：反应型阻燃剂羟基苯膦酰丙酸的合成方法专利类型：发明专利
发明人：李继升
申请号：CN201310450849.4
申请日：20130929
公开号：CN104513269A
公开日：
20150415
专利内容由知识产权出版社提供
摘要：本发明公开了一种反应型阻燃剂羟基苯膦酰丙酸的合成方法，包括以下步骤：先用苯、氯化铝、氯化磷合成苯膦二氯与氯化磷形成的络合物；然后用三氯氧磷破坏络合物，合成苯膦二氯；再将丙烯酸滴加到苯膦二氯中合成中间体3-苯基膦酰氯基丙酰氯；最后将上述中间体滴加到蒸馏水中，反应得产品羟基苯膦酰丙酸。

本发明提供的反应型阻燃剂羟基苯膦酰丙酸的合成方法，工艺简单，反应时间短，收率高。

申请人：青岛市首胜实业有限公司
地址：266317 山东省青岛市胶州市胶东街道办事处纺织染整工业园
国籍：CN
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新型含磷阻燃剂阻燃PET热稳定性研究王忠卫;刘炳艳;田秀娟;李艳【摘要】以2-(二苯基膦酰)-1,4-苯二酚(DPO-HQ)和苯基磷酸二氯酯(MPCP)为原料,合成新型磷系阻燃剂聚苯氧基磷酸(2-(二苯基膦酰)-1,4-苯二酚)酯(PDPMP),FTIR、1H-NMR、31P-NMR表征确定了该化合物的分子结构.然后以PDPMP为阻燃剂制备了阻燃PET(FR-PET),极限氧指数(LOI)法考察其阻燃性能;动态热重分析(TGA)研究PET及FR-PET的热稳定性能,选取Flynn-Wall-Ozawa(FWO)和Starink两种动力学方法研究其热降解动力学.结果发现:含磷阻燃剂的加入提高了PET的阻燃性能;初始降解温度提前,FR-pET的活化能低于纯PET;但后期降解阶段活化能增幅明显高于纯PET样品,阻燃剂先于PET分解,生成耐热性较好的炭层,提高了聚酯的热稳定性.【期刊名称】《山东科技大学学报（自然科学版）》【年(卷),期】2016(035)002【总页数】8页(P86-93)【关键词】聚对苯二甲酸乙二醇酯(PET);磷系阻燃剂;极限氧指数;热稳定性;热降解动力学【作者】王忠卫;刘炳艳;田秀娟;李艳【作者单位】山东科技大学材料科学与工程学院,山东青岛266590;山东科技大学材料科学与工程学院,山东青岛266590;山东科技大学材料科学与工程学院,山东青岛266590;青岛职业技术学院,山东青岛266590【正文语种】中文【中图分类】O631聚对苯二甲酸乙二醇酯(polyethylene terephthalate，PET)具有优良的综合性能，目前已广泛应用于合成纤维、工程塑料、电器绝缘材料、薄膜和胶片等领域[1]，然而PET材料与大多数高分子材料一样，具有致命的弱点——易燃性[2]，其极限氧指数为20～22左右，因此PET的阻燃问题是人们在使用过程中需要解决的首要问题。

PET的阻燃方法主要分为添加型阻燃和反应型阻燃两大类，其中添加型阻燃是常用的阻燃方法，特点是制备工艺简单，阻燃剂品种多，阻燃效果好[3]。

新型阻燃剂叔丁基化磷酸三苯酯的制备随着人们对安全性能的要求越来越高，阻燃剂的应用也越来越广泛，特别是在建筑、电子、航空等领域中。

阻燃剂可以降低材料的燃烧性能，从而减少火灾事故的发生。

其中，磷酸酯类阻燃剂因其具有高效、环保等特点而备受关注。

本文介绍一种新型阻燃剂——叔丁基化磷酸三苯酯的制备方法及其性能研究。

一、实验原理磷酸酯类阻燃剂主要是通过在材料表面形成炭化层，隔离氧气和燃料，从而抑制燃烧。

其中，磷酸酯类阻燃剂的阻燃效果与其热稳定性、热解产物和炭化层形成等因素有关。

本实验中采用的叔丁基化磷酸三苯酯，是一种具有高效、低毒、低烟等特点的磷酸酯类阻燃剂。

二、实验步骤1.将苯酚和三苯基膦放入反应瓶中，加入适量的碘化铝作为催化剂，加热至反应温度。

2.将叔丁醇滴加到反应瓶中，控制滴加速度和温度，反应达到平衡。

3.反应结束后，将反应物通过水蒸气蒸馏提纯，得到叔丁基化磷酸三苯酯。

三、实验结果本实验中制备的叔丁基化磷酸三苯酯经过红外光谱和核磁共振等多种表征手段进行了分析，其结构和纯度均符合要求。

同时，对其热稳定性和阻燃性能进行了测试。

实验结果表明，叔丁基化磷酸三苯酯具有较高的热稳定性和阻燃性能。

在热重分析中，其失重率较低，表明其在高温下能够保持稳定。

在垂直燃烧测试中，其燃烧时间较长，炭化层形成完整，有效地阻止了燃烧的扩散。

四、实验结论本实验成功合成了一种新型阻燃剂——叔丁基化磷酸三苯酯，并对其进行了性能测试。

实验结果表明，该阻燃剂具有高效、低毒、低烟等特点，在建筑、电子、航空等领域中有广泛的应用前景。

未来还需进一步探究其性能和应用领域，为防火安全事业做出更大的贡献。

苯基次膦酸铝阻燃剂的合成研究
1 苯基次膦酸铝阻燃剂的研究简介
苯基次膦酸铝（Phosphates of Aluminum，简称PAl）是一种新型的阻燃剂，是一种螯合性的核糖核酸铝配合物，它可以与材料表面形成非活性膜，有效抑制发生火灾的可能性。

目前已经有研究表明，苯基次膦酸铝具有良好的抗燃性，可以被用来改善各种制品的阻燃性。

2 合成苯基次膦酸铝阻燃剂的研究
苯基次膦酸铝在合成过程中，需要由苯基次膦酸钠与氢氧化铝反应制得，中间产物经过分离净化及热处理得到苯基次膦酸铝阻燃剂。

研究表明，反应温度、反应时间以及配比条件对合成苯基次膦酸铝阻燃剂的性能有着重要的影响。

此外，在制备过程中，也可以考虑加入适量的溶剂，以进一步提高产品性能。

3 优化反应条件
优化苯基次膦酸铝阻燃剂的反应条件主要是调节反应温度，反应时间和配比条件，以便提高产品的分子量，提升聚合度，优化物性。

研究发现，反应温度越高，反应速率越快，分子量越高，但太高的反应温度也会导致阻燃剂强度不足，产品性能降低；反应时间过短则不足以获得满足要求的聚合度和强度，而苯基次膦酸钠与氢氧化铝的配比不合适也会影响产品的成质量。

4 研究结论
苯基次膦酸铝阻燃剂是一种新型的阻燃剂，具有良好的阻燃性能，可以改善材料的阻燃性能。

合成这种阻燃剂需要由盐酸和氢氧化铝反
应而成。

反应条件的优化对获得苯基次膦酸铝阻燃剂的分子量、聚合
度和强度有重要影响，必须恰当调节反应温度、反应时间和配比条件
才能获得质量可靠的产品。

磷系阻燃剂阻燃PET的研究进展闫梦祥;张思源;王总帅;闰明涛【摘要】综述了磷系阻燃剂阻燃聚对苯二甲酸乙二醇酯(PET)的改性方法,其中主要有共聚阻燃改性、共混阻燃改性、后处理法以及一些新技术.重点介绍了共聚阻燃改性中以2-羧乙基苯基次膦酸(CEPPA)为代表的磷系阻燃剂以及共混阻燃改性中所用的各种阻燃剂,并指出了PET阻燃的研究方向.目前,PET的阻燃主要向着低毒、低烟、无卤化方向发展,而且开发新型或复配无卤阻燃剂已经成为PET阻燃的必然趋势.%This paper overviewed flame-retardant modification methods for polyesters,which focused on the copolymerization,blending and post-processing methods for flame-retardant modification,and also introduced some new modification technologies.Furthermore,2-carboxyethyl(phenylphosphinic) acid (CEPPA) as a representative phosphorus-containing flame retardant used for polyesters was introduced in detail,and future development direction of flameretardant polyesters was proposed.It should be pointed out that low toxicity,low smoke and halogen-free flame retardants for polyesters are the current direction in development,but the development of new types of halogen-free flame retardants will be a future trend.【期刊名称】《中国塑料》【年(卷),期】2017(031)010【总页数】5页(P1-5)【关键词】聚对苯二甲酸乙二醇酯;磷系阻燃剂;研究进展;发展趋势【作者】闫梦祥;张思源;王总帅;闰明涛【作者单位】河北大学化学与环境科学学院,河北保定071002;河北大学化学与环境科学学院,河北保定071002;河北大学化学与环境科学学院,河北保定071002;河北大学化学与环境科学学院,河北保定071002【正文语种】中文【中图分类】TQ323.4+1PET是各种合成纤维中发展最快、产量最高、应用面最广的一种合成纤维[1]，是三大合成纤维中工艺最简单的一种，其纤维纺织品大量用于衣料、窗帘、幕布、床上用品、室内装饰及各种特殊材料。

磷系阻燃剂的现状与展望 2009-12-23 11:27:21| 分类：默认分类 | 标签： |字号大中小订阅磷系阻燃剂的现状与展望--------------------------------------------------------------------------------来源:中国化工信息网 2009年3月24日随着高分子材料在各个领域的广泛应用，有机高分子，在给人们的生产和生活带来巨大利益的同时，也会带来了潜在的火灾安全问题。

为了减少火灾的发生，世界各国都在致力于研究和应用阻燃剂及阻燃材料。

所谓阻燃剂就是能够提高可燃物的难燃性或自熄性的一种助剂，是塑料助剂中仅次于增塑剂消耗量的助剂。

在各类阻燃剂中，磷系阻燃剂占有重要地位，它不仅克服了含卤型阻燃剂燃烧烟雾大、放出有毒及腐蚀性气体的缺陷，同时又改善了无机阻燃剂高添加量严重影响材料的物理机械性能的缺点，做到了高阻燃性、低烟、低毒、无腐蚀性气体产生。

1 阻燃机理及分类1.1 磷系阻燃剂的阻燃机理磷系阻燃剂的阻燃机理主要是形成隔离膜来达到阻燃效果，形成隔离膜的方式有2种。

(1)利用阻燃剂的热降解产物促使聚合物表面迅速脱水而炭化，进而形成炭化层。

由于单质碳不进行产生火焰的蒸发燃烧和分解燃烧，因此，具有阻燃保护作用。

磷系阻燃剂对含氧聚合物的阻燃作用就是通过这种方式实现的。

其原因是含磷化合物热分解得到的最终产物是聚偏磷酸，而它是强脱水剂。

(2)磷系阻燃剂在燃烧温度下分解生成不挥发的玻璃状物质，它包覆在聚合物的表面，这种致密的保护层起隔离层的作用。

1.2磷系阻燃剂的分类磷系阻燃剂根据磷系阻燃剂的组成和结构，可以分为无机磷系阻燃剂和有机磷系阻燃剂两大类。

无机磷系阻燃剂包括红磷、磷酸铵盐和聚磷酸铵等。

有机磷系阻燃剂包括磷酸酯、亚磷酸酯、膦酸酯和鳞盐等。

下述阐述一下几种常用磷系阻燃剂的特点。

2 无机磷系阻燃剂无机阻燃剂历史悠久，主要是红磷、聚磷酸铵(APP)、磷酸二氢铵等磷酸盐，受热分解出磷酸、偏磷酸和H2O等，并促进成炭覆于基材的表面起到阻燃的效果。

Synthesis,Characterization and Therm al Properties of a Novel Phos2 phorus2Containing Copolyesters B ased on22carboxyethyl(phenylphos2 phinic)AcidHaiming Liu,1Rui Wang,2Xi Xu,1Xiao Kai Sun,2Xiaohui Zhou2 1Depart ment of Polymer Science and Materials,State Key Laboratory of Polymer Materials Engineering,Sichuan U niversity,Chengdu610064,China;2Depart ment of Materials Science and Engineering,Beijing Instit ute of Clot hing Technology,Beijing100029,ChinaAbstract:A novel reactive p ho sp horus2containing monomer,22carboxyet hyl(p henylp hosp hinic)acid (CEPPA)and corresponding p hosp horus2containing copolyesters were synt hesized and characterized by F TIR,1H NMR spect ra.The copolyester,which contains0.6wt%p hosp horus,can reach a lim2 iting oxygen index(LO I)value of29.4%.The t hermal p roperties of p hosp horus2containing flame re2 tardant copolyesters were investigated by differential scanning calorimeter(DSC),t hermogravimetry (T G)under air and nitrogen.DSC shows t hat t he glass2t ransition temperat ures(T g),t he melting point s(T m)and t he melting crystallizatio n temperat ures(T mc)of copolyesters decrease wit h increas2 ing p ho sp horus content,Meanwhile t he cold crystallization temperat ures(T cc)increase wit h increas2 ing p ho sp horus content.T GA shows t hat t he initial deco mposition temperat ures(T id)decrease and t he maximum2rate decomposition temperat ures(T max)increase at air and nit rogen at mo sp here,while char yields increase,wit h t he increase of p hosp horus content.The residues of copolyesters after T GA testing were st udied by Fourier transform infrared spectro scop y to better understand t he mechanism of flame retardancy,which show t hat t he charred residue is mainly composed of Ar2P group containing species.K ey w ords:flame retardant;synt hesis;p ho sp horus2containing copolyesters;t hermal properties Document code:A Article ID:100124381(2008)Suppl220420207IntroductionPolyester resin materials are widely used in a wide range of applications such as flooring,surface coatings,vehicle body panels and appliance housings due to having good mechanical and optical p roperties, resistance to fatigue,resistance to creep f ract ure and wear aspect s.1-3However,t he poor flame retardancy of polyester resins limit s t heir usage in which specific fire retardant properties are required.PET resins can be imparted flame retardance eit her by adding flame retardant s or by incorporating reactive flame retard2 ant s.Incorporating a chemically reactive p hosp horus2 containing monomer into t he polymer chain is one of t he most efficient met hods of imp roving t he flame re2 tardancy of polyesters,which impart s polyesters good flame retardancy,t hermal stabilities,and sim2 ultaneously can minimize negative impact upon p hysi2 cal and mechanical p roperties of t he polymer.4-7 Recently,t he researches mainly focus on t he re2 active p hosp horus2containing flame retardant.The mo st important met hod of synt hesis of flame retard2 ant polyesters is t he esterification of diols wit h p hos2 p horus2containing diacid such as22carboxyl et hyl (p henyl)p ho sp hinic acid(CEPPA).324,8211CEPPA containing carboxylic and p hosp hinic acid f unctional2 ities is a biof unctional copolymerizable p ho sp horus mo nomer disclosed by U.S.patent12,13,and can be copolymerized wit h et hylene glycol(EG)and terep h2 t halate(TPA)to form flame retardant poly(et hlene terep ht halate)and renders t he resulting copolyesters and fibers good fire resistance p roperties and t hermal stabilities.024 材料工程/2009年增刊2(SAMPE China2009)　In t his work,we have synt hesised a p hosp horus2 containing flame retardant,namely22Carbo xyl et hyl (p henyl)p ho sp hinic acid(CEPPA),which after2 wards was int roduced into esterificatio n and polycon2 densatio n system to obtain polyesters wit h enhanced content of p ho sp horus and of aryl group s in t he st ruct ure.The incorporation of a bulky pendant group containing p ho sp horus into t he polyesters is expected to introduce new interesting properties such as high LOI value,enhanced t hermal stability,flame resistance and flexibility.The performances of t he corresponding copolyesters,such as t hermal p roper2 ties and flame retardancy,were st udied by t he con2 ventional met hods:DSC,T GA and LO I,respective2 ly.1　ExperimentalMaterialsDichlorop henyl p hosp hine(DCPP)and acrylic acids were p urchased f ro m Sinop harm Chemical Rea2 gent Beijing Co.,Lt d.(Beijing,China)wit h a p uri2 ty of97%and used wit hout f urt her p urification.Te2 rep ht halic acid(TPA),et hylene glycol(EG),and Sb2O3were supplied by Sinopec Tianjin Pet rochemi2 cal Co.,Lt d.(Tianjin,China).All ot her materials were commercially available.Synthesis of22carboxyethyl(phenylphosphinic)acid (CEPPA)22carboxyet hyl(p henylp ho sp hinic)acid(CEP2 PA)was synt hesized according to t he reported litera2 t ures.12,13Dichlorop henylp hosp hine,200.0g(1.12mol) was placed in a reactor under a nit rogen p urge, stirred and warmed to70℃.At temperat ure,drop2 wise addition of acrylic acid92.6g(1.29mol),was started and t he temperat ure was maintained at802 85℃.When t he addition was complete,t he mixt ure was maintained briefly at80285℃.and t hen heated f urt her to1252130℃.The mixt ure was maintained at 1252130°C for one hour and t hen cooled to ambient temperat ure.The desired22carbo xyet hyl(p henyl) p hosp hinic acid can be obtained after hydrolysis of t he above mixt ure which are composed of t he cyclic anhydride of CEPPA acid and t he mixed anhydride of acrylic acid wit h32chlorocarboxyet hyl(p henylp hos2 p hinic)acid.The synt hetic route is shown in Figure1.Fig11　The synt hetic route of CEPPASynthesis of phosphorus2containing copolyesters TPA,EG,CEPPA,and Sb2O3were int roduced in a15002ml four2necked round2bottomed flask e2 quipped wit h a t hermometer and a mechanical stirrer. The mixt ure was heated in nitrogen at mosp here to 235℃under a p ressure of0.3M Pa until t he conver2 sion of t his esterification is at96%.Then t he esteri2 fication product s were t ransferred to a1.0L reactor equipped wit h a nit rogen inlet,a condenser,and a mechanical stirrer.The reactor was fitted to a vacu2 um system and evacuated to remove all oxygen.The reactor was t hen heated to2802285℃under a p res2 sure of less t han50Pa and maintained for223h to give t he p ho sp horus2containing copolyesters.Finally t he heat and vacuum were removed and t he resulting polymer melt s were ext ruded at t he N2pressure and cooled wit h water.Thus copolyesters containing dif2 ferent amount of CEPPA were synt hesized.CharacterizationThe st ruct ure of CEPPA was determined by F T2 IR,1H NMR spect ra,which were performed on a Nicolet F TIR670inf rared spect rop hotometer(Nico2 let,U SA)and a Bruker500(5002M Hz)NMR spec2 t rometer(Fallanden,Switzerland)wit h DMSO2d as a solvent,respectively.The struct ure of p ho sp horus2 containing copolyesters was recorded by using a Nicolet F TIR670inf rared spectrop hotometer.The t hermal behavior of t he copolyesters sam2 ples was recorded using a DSC6200(Seiko Instru2 ment s Inc.,J apan).Indium was used as a standard for temperat ure calibration and t he analysis was made under a co nstant st ream of nit rogen(50ml/min). The weight s of DSC specimens are about5mg.They were heated to300℃,kept at t his temperat ure for10 min to eliminate any previous t hermal history,and124　Synthesis,Characterization and Thermal Properties of a Novel Phosphorus2containing Copolyesters Based on…t hen immediately cooled to room temperat ure.After t he t hermal t reat ment ,t hey were heated at 20℃/min to obtain t he melting endot herm and t he crystal 2lization exot herm f rom 25℃to 300℃and t hen were cooled at -20℃/min f rom 300℃to 50℃to obtain t he cooling crystallization exot herm.The t hermogravimet ric analysis (T GA )was per 2formed wit h a WC T 22D Thermal Analyzer (Beijing ,China )at a heating rate of 20°C /min under air at 2mo sp here and a nit rogen at a flow rate of 50ml/min ,and t he temperat ure ranged f rom room temperat ure to 800℃.Continuous records of sample temperat ure ,sample weight ,and it s first derivative were taken.The limiting oxygen index (LOI )values were measured on a J F 23oxygen index meter (Jiangning ,China )according to ASTM D2863,wit h sheet di 2mensions of 100mm ×6.5mm ×3mm.To investigate t he mechanism of flame retardan 2cy ,t he st ruct ure of chars of t he p hosp horus 2co ntai 2ning copolyesters after T GA test at air at mosp here was recorded by using a Nicolet F TIR 670infrared spect rop hotometer.2　R esults and discussionSynthesis and characterization of CEPPACEPPA was synt hesized t hrough t he reaction of DCPP and acrylic acid ,and sequent hydrolysis ac 2cording to Figure 1.The st ruct ure of CEPPA was determined by F TIR ,1H NMR spect ra.Figure 2shows t he F TIR spect rum of CEPPA.The st rong band in t he 330022500cm -1range is as 2signed to p ho sp horus acid and carboxylic acids O —H st retching ,which indicates t he formation of P —O H and C —O H.The stretching band observed near1731.13cm -1is att ributed to t he carboxylic acid C =O stretching.In addition ,t he peaks at 1225.90,1419.59and 943cm -1are assigned to carboxylic acid characteristic C —O st retching and in 2plane and out 2of 2plane O —H bending bands ,respectively.Simultaneously ,t he peak observed at about 2907.52cm -1belongs to t he absorption of —CH 2.The peaks at 1143.6and 1122.36cm -1are att ributed to P =O absorption.The peaks at 1050and 968cm -1can be assigned to p ho sp horus acid in 2plane and out 2of 2plane P —O H st retching.14However ,no charac 2teristic absorption peak for P —Cl is observed at a 2round 3002600cm -1,which demonst rates t hat ,t he reactio n of CEPPA proceeded completely.Figure 3shows t he 1H NMR spect rum of CEP 2PA.The peak at about 11.56pp m should be assignedto t he active 2O H (e )of CEPPA (carboxylic acids ).And t he multiplet between 7.48and 7.73pp m corre 2sponds to t he p henyl ring p rotons (a ).The peak at about 2.49pp m is assigned to t he solvent DMSO 2d6(f ).The multiplet between 2.26and 2.30,between 1.96and 2.02pp m can be assigned to t he C H 2p ro 2tons (c ,d )respectively.3,4Above characterizations confirm t hat t he target p roduct CEPPA was synt hesized successfully.Synthesis and characterization of phosphorus 2contai 2ning copolyestersFigure 4shows t he F TIR spect rum of t he p hos 2p horus 2containing copolyester.The absorption of —CH 2is observed at about 2977160cm -1.Thepeaksat1716136and1249.22cm -1are assigned to C =O and C —O ab 2sorption ,respectively.The peaks at 116148and1100.49cm -1are att ributed to t he vibration f rom P224 材料工程/2009年增刊2(SAMPE China 2009)　=O gro up and t he peak at 1020.52cm -1can be as 2signed to P —O —C absorption.Meanwhile ,t he st rong band in t he 330022500cm -1range assigned to p hosp horus acid and carbox 2ylic acids O —H st retching disappears.In addition ,t he absorption of p ho sp horus acid in 2plane and out 2of 2plane P —O H st retching observed at 1050and 968cm 21,respectively disappears ,which indicates t he re 2action of CEPPA and EG ,t he formation of p ho s 2p horus acid ester and Carboxylic acidester.Figure 4　F TIR spectrum of PET 2co 2CEPPATable 1　Phosphorus Content ,Phosphorus Comonomer Molar Fraction ,and Thermal Propertiesof Various Phosphorus 2Containing PolyestersSample code P /wt %CEPPA/mol %T g /℃T cc /℃T m /℃T mc /℃PET00079.07134.33255.24200.49PET030.311.1877.75135.77249.72184.36PET060.622.3775.84151.93245.00181.18PET090.923.1875.18160.80241.65169.78PET12 1.226.7772.20163.17236.94160.38PET15 1.529.5171.51164.38230.12152.95PET181.831.6870.68165.85228.43149.90Differential scanning calorimetry (DSC)analysisDifferential Scanning Calorimet ry (DSC )is use 2f ul in t he determination of relationship s between p roperties and molecular st ruct ures.Samples were heated f rom 25to 300℃in nit rogen at mosp here at a flow rate of 50ml/min and a heating rate of 20℃/min ,and t hen were cooled f rom 300to 25℃at a flow rate of 50ml/min and a heating rate of 220℃/min.As shown in Figure 5,6and Table I ,t he glass 2t ran 2sition temperat ures (T g )and t he melting point s (T m )of copolyesters decrease wit h increasing p ho sp horus content.This is because incorporation of CEPPA dis 2rupt s t he original struct ure and makes t he resulting copolymer chain more flexible.Meanwhile t he cold crystallization temperat ures (T cc )increase and t he melting crystallization temperat ures (T mc )decrease wit h increasing p hosp horus content ,respectively ,in 2dicating difficulty in crystallization wit h increased CEPPA concent ration.3,16In addition ,t he addition of CEPPA in PET greatly affect s t he crystallization and st ruct ure.Fig 2ure 5,6shows t hat t he T m and T mc of t he copolyes 2ters decrease wit h t he increasing content of CEPPA.And t he T cc value increases wit h t he increasing con 2324　Synthesis ,Characterization and Thermal Properties of a Novel Phosphorus 2containing Copolyesters Based on …tent of CEPPA.While t he content of p hosp horus va 2ries f rom 0wt %to 1.8wt %,t he T mc and T m value of copolyesters varies from 200.49℃to 149.90℃and f rom 255.24℃to 228.43℃,respectively.And t hecontent of p ho sp horus varies from 0wt %to 1.8wt %,t he T cc value of copolyesters varied from 134.33℃to 165.85℃.Table 2　Decomposition Temperature ,Residual Char ,and LOI Values of Phosphorus 2Containing CopolyestersSample code Air at mosphereT id /℃T max /℃Char yield at 700℃/wt %N 2at mosphereT id /℃T max /℃Char yield at 700℃/wt %LOI PET0418.2445.38/575.21 1.37415.79453.279.2023.3PET03412.2448.80/570.39 1.40415.55454.0411.426.9PET06411.8449.11/575.52 1.44414.72454.2014.729.4PET09411.8450.97/576.30 1.90414.50455.2915.130.4PET12410.4451.13/581.43 2.10414.07459.5315.531.5PET15409.3451.60/583.76 2.82413.86461.2316.733.7PET18402.3453.15/574.603.41412.16461.3917.735.9Therm al decomposition behaviors of phosphorus 2con 2taining copolyestersThe effect of CEPPA on t he t hermal stability of t he copolyesters was st udied by means of t hermo 2gravimet ric experiment s carried out at a heating rate of 20℃/min under air and nit rogen at mosp here.Figure 7,8show t he mass lo ss and mass lo ss rate curves obtained from T GA experiment s in air and nit rogen ,Table II gives t he initial decompo sitiontemperat ures (T id ),t he maximum decompo sition rate temperat ures (T max )and t he residues of samples at 700℃.As can be seen in Figure 7,8and table II ,t he p ure PET and t heir copolyesters have similar t hermal stabilities.And t he initial decompo sition temperat ures (T id )of t he copolyesters decrease wit h increasing p ho sp horus content under nit rogen and air at mo sp heres ,which is att ributed to t he poorer stabil 2ity of O =P —O t han —C —C —bond.17,18424 材料工程/2009年增刊2(SAMPE China 2009)　Furt hermore,Figure7shows two stage decom2 position patterns.The first is similar to t heir t hermal degradatio n in nit rogen(Figure8),located f rom a2 bout3002520℃.The second is not found in t heir degradatio n in nit rogen at mo sp here,which is owing to a f urt her oxidative degradation of carbonaceous residue located from5202650℃.The maximum2rate degradation temperat ures of t he first stage increase wit h increasing p hosp horus content under nit rogen and air at mo sp heres.Howev2 er,t he maximum2rate degradation temperat ures of second stage under air at mosp here slightly changes wit h increasing p ho sp horus content.This behaviour may be att ributed to p ho sp horus2containing group s t hat decompo se at earlier stages and forms a p ho s2 p horous2rich char layer.The t hick layer prevent s f urt her decompo sition of t he copolyesters by raising t he maximum2rate degradation temperat ure of second stage and leads to a high char yield.On t he ot her hand,t he char yield of copolyesters increase wit h increasing p hosp horus content under ni2 t rogen and air at mosp here.Simultaneously,t he a2 mount of char formed f ro m t he samples depends on t he amount of CEPPA,and correlates well wit h t he LOI values of t he copolyesters.This is because p ho s2 p horus2containing copolyesters are easy to form p ho s2 p horic acid or anhydrides which can cause acid2catal2 ysed char accumulation and tend to inhibit complete oxidation of t he carbon to carbon dioxide,and conse2 quently contributed to increase t he amount of char and t he LO I values of copolyesters.Thus,t he char formation can cause increase in t he amount of residue and a retardation of t he release of volatile f uel,lower t he t hermal co nductivity of t he burning materials, and consequently,reduce t he mass loss of t he poly2 mers.19-21Limited oxygen index(LOI)testTo investigate flame retardancy of p hosp horus2 containing copolyesters,t he limited oxygen index (LO I)values of t he copolyesters wit h different CEP2 PA content s,and t he compositions of p hosp horus2 containing copolyesters and correspo nding LO I values are listed in Table II.The LOI values of copolyesters increase wit h t he increasing content of CEPPA. While t he content of p hosp horus reaches1.8wt%,t he LO I value of copolyester is reached35.8demon2 st rating t hat CEPPA has good flame retardant effect on t he copolyesters.The structure of the residues of copolyesters after TG AtestFigure9　F TIR spectra of residues of PET18after T GAtest at different temperat ures at air at mosphereTo f urt her understand t he oxidative t hermal de2 compo sition of p hosp horus2containing copolyesters, Changes in t he F TIR spectra wit h temperat ure for t he copolyester(PET18)at air at mosp here are inves2 tigated.Figure9displays t he F TIR spectra of resi2 dues after T GA test f rom room temperat ure to 525℃.As shown in F TIR spect ra,at450℃,t he ab2 sorption bands between2500and3700cm-1assigned to O—H group become broadened.The intensities of absorption bands at170021720cm-1and124021250 cm-1which are att ributed to C=O and C—O st retc2 hing,respectively decrease f rom room temperat ure to 450℃.At450℃,The peak at1122.39cm-1(P=O absorption)disappears and t he intensity of t he peak at1099.24cm-1(P=O absorption)decreases,indi2 cating t he gradual degradation of t he group s in t he rage f rom room temperat ure to450℃.22,23Simultaneously,at400℃,new peak assigned to C=C st retch of benzene ring and Ar2P st retch was observed at1600-1550cm-1and about1415cm-1, respectively indicating t he existence of species contai2 ning Ar2P group.The copolyester after t hermal deg2 radation at575℃at air at mosp here shows a typical spect rum of highly carbonized materials.As shown in Figures8,at temperat ure up to575℃,changes in t he peak absorption became evident.The vibration band of C—H group appearing at2980-2960cm-1524　Synthesis,Characterization and Thermal Properties of a Novel Phosphorus2containing Copolyesters Based on…disappear and t he absorption bands between2500and 3700cm-1assigned to O—H group become more broadened.24At525℃,The peaks at1700-1720cm-1and 124021250cm-1att ributed to C=O and C-O st retc2 hing,respectively and t he peaks at1122.39and 1099.24cm-1assigned to P=O absorption respec2 tively,decrease nearly entirely.The intensity of t he broadened peaks at160021610cm-1and1415cm-1 greatly increase,which show t he residue is mainly composed of Ar2P group and p hosp hate.A similar suggestion was reported by Wei Liu.253　ConclusionsCEPPA can be copolymerized wit h TPA and EG in t he conventio nal melt polymerizatio n p rocess used for PET.The copoyester,which contains0.6% p hosp horus,can reach a limiting oxygen index(LO I) value of29.4%.Incorporation of CEPPA into PET increases t he cold crystallization temperat ure and re2 duces t he glass2transition temperat ures,t he melting point s,t he heating crystallization temperat ures of t he resulting copolymers.Meanwhile,t he t hermal stabilities of p hosp2containing copolyesters de2 crease,while char yields increase wit h increasing p hosp horus content.F TIR spectra of residues of t he copolyester show t hat t he charred residue is mainly composed of Ar2P group containing species.References[1]　Tachita Vlad2Bubulac;Corneliu Hamciuc;Oana Petreus.HighPerform.Polym.2006,18,255.[2]　P. 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