Synthesis,characterization of a DOPO-based polymeric flame retardant and its application in polyethylene terephthalate

A high molecular weight DOPO-based flame retardant(DP-DE) containing phosphorus linked pendent groups was synthesized by a two-step esterification and polycondensation reaction,and characterized by Fourier transform infrared spectroscopy(FTIR),~(13)C nuclear magnetic resonance(~(13)C NMR) and gel permeation chromatography(GPC).After added into polyethylene terephthalate(PET) via melt-blending method,the flame retardancy of DP-DE were monitored by thermo-gravimetric analysis(TGA),limiting oxygen index(LOI) and underwriter laboratories(UL-94) test.The results showed that DP-DE display good flame retardancy in PET.And the thermal stability,char residue yield and LOI values of the composites increased with the increase of DP-DE content.The flame retarded mechanism of DP-DE was investigated by pyrolysis-gas chromatogram-mass(PY-GCMS),in situ FTIR,scanning electron microscope(SEM) and laser Raman spectroscopy(LRS).DP-DE was evidenced to release phosphorus acid and its derivatives,which catalyze carbonization and produce compact carbonaceous layers.Through protecting the polymeric materials substrate from further degradation and inhibiting the pyrolysis degree,both the amount and thermal stability of carbonaceous layers of DP-DE were improved,and hence enhancing the flame retarded performance of PET/DP-DE composites.     

含磷笼网结构多面体低聚倍半硅氧烷阻燃剂的合成及其阻燃环氧树脂性能

采用9,10-二氢-9-氧杂-10-膦菲-10-氧杂（DOPO）-乙烯基三甲氧基硅烷（VTMS）加成物DOPO-VTMS通过水解缩合反应,制备了新型含DOPO基团的笼网结构倍半硅氧烷（DOPO-PolyPOSS）。将不同比例的DOPO-PolyPOSS添加到环氧树脂（EP）中,制备了一系列阻燃EP。采用热重分析（TGA）、动态热机械分析（DMA）、万能拉力机、极限氧指数（LOI）、UL-94和锥形量热计对阻燃环氧树脂的热性能、力学性能和阻燃性能进行了系统研究,并通过热重-红外联用（TGA-IR）、热重-质谱联用（TGA-MS）和扫描电子显微镜（SEM）研究了其阻燃机理,结果表明：DOPO-PolyPOSS可在EP中均匀分散;向EP中加入DOPO-PolyPOSS显著提高了阻燃EP的残炭率,降低了热释放速率（HRR）,延长了点燃时间（TTI）,达到了良好的阻燃效果;当DOPO-PolyPOSS加入量（质量分数）为3%时,阻燃EP的LOI值可从纯EP的25.5%提高至31.7%,并达到了UL-94的V-0阻燃等级。此外,加入DOPO-PolyPOSS可提高EP的拉伸和弯曲性能。对EP凝聚相和气相裂解产物的分析结果表明,DOPO-PolyPOSS阻燃环氧树脂是基于磷硅协同效应而同时在气相和凝聚相阻燃。     

Renewable isosorbide-derived poly(phosphoester) for simultaneously enhanced flame-retardancy and mechanical property of polylactide

Incorporating flame retardant fillers is the most efficient way to improve the fire resistance of polylactide (PLA). However, most flame retardant fillers result in deterioration of the mechanical property of PLA so far. Therefore, to create high-performance PLA materials combining excellent flame retardancy with superior mechanical properties remains highly attractive and challenging. In this study, a novel isosorbide-derived poly(phosphoester) (PIDI) was synthesized and used as a bio-based flame-retardant for PLA. The addition of PIDI showed a marginal effect on the change of the glass transition temperature of the PLA composites, but the crystallinity degree of the PLA composites was improved by the inclusion of PIDI. Benefitting from the improved crystallinity, the tensile strength, flexural strength, and impact strength of PLA composite containing 15 ​wt% PIDI was enhanced by 19.4%, 14.1%, and 36.9%, respectively, compared to the virgin PLA. With the addition of 20 ​wt% PIDI, the PLA composite showed an LOI value of 25.5% and a UL-94 V-0 rating in the vertical burning test. The flame retardant effect of PIDI was also demonstrated by a notable reduction (−46%) in the peak heat release rate (PHRR) of PLA composite containing 20 ​wt% PIDI. Such a renewable isosorbide-derived poly(phosphoester) is one of the promising candidates for PLA bio-composites with an outstanding balance between flame retardancy and intrinsic physical properties.     

Flame Retardant Finishing of Poly(ethylene terephthalate) Fabric with a Carbon Source Containing DOPO Derivative

9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide( DOPO)-based flame retardant( DOPO-DOPC) which contains carbon source was used to improve the flame retardancy of poly( ethylene terephthalate)( PET) fabrics. The prepared DOPODOPC dispersion was applied onto PET fabrics via two kinds of processes,thermosol process and exhaustion process,and in the later using it alone or together with disperse dyes. The flame retardancy of PET fabrics was determined by limiting oxygen index( LOI) and vertical burning test. The results showed that DOPODOPC could obviously improve the flame retardancy of PET fabrics.The PET fabric treated by 60 g/L DOPO-DOPC dispersion via exhaustion process achieved an LOI value of 32. 3%,for example.The flame retardancy and dyeing performances showed that DOPODOPC dispersion could be used together with a part of disperse dyes in one bath. The thermal stability of DOPO-DOPC and the treated PET fabrics were investigated by thermogravimetric analysis( TGA). And the flame retardant mechanism of DOPO-DOPC treated PET fabrics was further investigated by pyrolysis-gas chromatography/mass spectrometry( Py-GC/MS), Fourier transform infrared spectroscopy( FTIR) and scanning electron microscopy( SEM).     

氢氧化镁/可膨胀石墨/聚丙烯复合材料的热降解过程与燃烧行为

以可膨胀石墨(EG)和氢氧化镁(MH)为无卤阻燃剂，通过熔融共混法制备了无卤阻燃聚丙烯(PP)复合材料(EG/PP、MH/PP和MH/EG/PP)，采用热重法研究了复合材料的热降解过程，以氧指数(LOI)和垂直燃烧(UL-94)评价研究了复合材料的阻燃性能，采用锥形量热仪研究了复合材料的燃烧行为.结果表明:MH和EG间存在显著的协同阻燃作用，在阻燃剂质量分数为60%时，MH与EG质量比为5 : 1的MH/EG/PP材料其氧指数可以达到29.7，与MH/PP复合材料相比提高了11.2%；EG与MH协同具有良好的降低热释放作用，与PP和MH/PP相比，MH/EG/PP复合材料的热释放速率峰值(peak-HRR)分别降低了73.9%和34.2%；EG和MH的协同作用大幅度降低了MH/EG/PP的质量损失速率；结合残炭的形貌结果，揭示了EG和MH协同阻燃机理的关键在于增强了炭层的隔热和隔氧作用.     

2,2,4,4-四乙氧基-6,6-二羟乙氧基环三磷腈的合成及其阻燃应用

通过两次亲核取代对六氯环三磷腈(HCCP)进行接枝改性,合成了4∶2不对称取代的环三磷腈2,2,4,4-四乙氧基-6,6-二羟乙氧基环三磷腈(TDCP),并采用FT-IR、1H-NMR以及31P-NMR进行表征;讨论了合成工艺条件对产率的影响,得到了最优合成工艺物料比为n(HCCP)∶n(EtONa)∶n(HOCH2CH2ONa)=1∶4∶2,两步反应的工艺条件分别为70℃,8h和70℃,40h;改性产物在聚对苯二甲酸乙二醇酯(PET)的缩聚阶段加入参与共聚反应,并作为主链的一部分,合成了新一代结构阻燃型PET聚酯材料,同时,讨论了阻燃剂的加入量对限氧指数的影响,实验结果表明,当加入2%（质量分数）时,限氧指数为30%,UL-94燃烧等级测试可达到V-0级别。     

不同粒径的甲基环己基次膦酸盐/环氧树脂阻燃材料的性能比较

采用4种不同粒径的Al(MHP)作为环氧树脂(EP)的阻燃剂,着重讨论了Al(MHP)的粒径对EP复合材料的阻燃性能、热性能以及EP胶粘剂的粘接强度的影响。结果表明,减小Al(MHP)的粒径能显著提高EP复合材料的热性能、分解过程中的残炭率以及EP胶粘剂的粘结强度。当Al(MHP)的粒径从36.50μm减小到4.11μm,Al(MHP)含量为17 wt%的EP复合材料的氧指数(LOI)从34%增加到39%,聚合物空气中热分解到700℃时残炭率由23%增加到31%,剪切强度由4.77 MPa增加到8.44 MPa。     

硼酸盐对阻燃PP复合材料性能的影响

采用熔融共混挤出法,制备了掺杂少量硬硼钙石(CB)或硼酸锌(ZB)的阻燃聚丙烯(PP)复合材料,研究了CB和ZB对填充蜜胺包覆聚磷酸铵(APP-102)、三聚氰胺氰尿酸盐(MCA)阻燃PP复合材料的燃烧性能、热稳定性、机械性能、熔融结晶性能的影响.结果表明:少量CB或ZB(质量分数为2.0％)能有效提高阻燃PP复合材料...     

基于聚磷酸铵的乙烯基酯树脂的阻燃机理研究

乙烯基酯树脂(VER)因其具有良好耐腐蚀性能和优异的物理性能被广泛应用于诸多领域，然而由于VER极易燃，限制了其使用范围.为了提高VER的阻燃性，本文将聚磷酸铵(APP)作为阻燃剂引入VER中，制备得到阻燃乙烯基酯树脂固化物；采用热重分析仪(TGA)表征了VER的热稳定性；扫描电子显微镜(SEM、SEM-EDX)研究了VER燃烧后残炭的微观形貌，表面元素组成及分布；利用极限氧指数(LOI)、垂直燃烧测试(UL-94)、锥形量热(CCT)对其阻燃性能进行测试；采用热重红外光谱联用仪(TG-FTIR)等手段分析APP在VER中的阻燃机理.研究结果表明，当APP的引入量为30 wt%时，乙烯基酯树脂的极限氧指数达到30.3%,通过UL-94 V-0级别. APP在凝聚相和气相中共同发挥阻燃作用.     

一种无卤阻燃乙烯-醋酸乙烯酯共聚物的热分解动力学研究

通过极限氧指数法(LOI)和垂直燃烧(UL-94)测试考察了一种无卤阻燃乙烯-醋酸乙烯酯共聚物(EVA)的阻燃性能;利用热重分析法(TG)研究了纯EVA及阻燃EVA在不同升温速率下的热稳定性及热分解动力学,并采用Kissinger及Flynn-Wall-Ozawa方法计算了纯EVA和阻燃EVA的热分解表观活化能。结果表明,添加40%复合膨胀阻燃剂的EVA复合材料,极限氧指数达到28.6%,UL-94测试达到V-0级,残炭量相对纯EVA明显提高;随着升温速率增大,EVA和阻燃EVA的起始失重温度和各阶段的失重峰温均向高温方向移动;二者在第一阶段的热分解活化能均低于第二阶段,阻燃剂的添加使EVA的最大失重速率明显降低,热分解表观活化能提高,增强了材料的热稳定性和阻燃性。     

Characterizations of Phosphorus - containing Flame - retardant Poly (Ethylene Terephthalate) Copolyester

Copolyesters of phosphorus - containing flame - retardant poly(Ethylene Terephthalate) (PET) have been prepared and characterized with the objection of producing an effective, environmentally friendly, nonfugitive alternatives to halogen flame retardant system for practical application. With means of NMR, DSC, DTA/TGA, SEM and LOI, structure, thermal property and flam-mability are investigated which reveal that the flame -retardant PET when copolymerized with 2 - carboxyethyl (phenylphosphinic) acid (CEPP) confers excellent fire retardancy with LOI > 28, broader thermal degradation temperature and increased char formation.     

甲酰胺插层改性高岭土对乙烯-醋酸乙烯共聚物(EVA)阻燃性能的改善

将甲酰胺（FA）通过插层改性引入高岭土（Kaol）分子层间,制备得到FA-Kaol改性高岭土材料,产物的插层率达到92.1%;通过红外光谱（FT-IR）、X射线衍射（XRD）和热重分析（TGA）对FA-Kaol结构进行表征。然后通过熔融共混将FA-Kaol添加到乙烯-醋酸乙烯共聚物（EVA）/膨胀阻燃剂（IFR）中,利用极限氧指数（LOI）、垂直水平燃烧（UL-94）、锥形量热（Cone）和万能试验机测试材料的阻燃性能和力学性能。结果表明当FA-Kaol的添加量（质量分数）达到1.5%时,EVA复合材料的阻燃性能、热稳定性能和力学性能得到有效改善。     

新型阻燃三元乙丙橡胶的制备及其阻燃性能研究

采用微胶囊化聚磷酸铵与季戊四醇复配(APP∶PER=3∶1)填充三元乙丙橡胶(EPDM),制备新型阻燃EPDM材料,考察膨胀型阻燃剂(IFR)的填充量对EPDM材料的燃烧性能和热学性能的影响。结果表明,APP和PER复配使用,可协同提高EPDM的阻燃性能。当IFR填充量为40%时,材料的极限氧指数(LOI)可达到31%,UL94垂直燃烧等级达到V0级;最大热释放速率下降81.2%,总释放热降低30.4%;同时EPDM材料高温区热稳定性明显提高,且材料燃烧后可形成膨胀炭层,700℃下残渣量从0.9%提高至17.0%。     

一种新型膨胀阻燃剂的合成及其无卤阻燃乙丙橡胶

采用三氯氧磷、季戊四醇、邻苯二胺为原料合成一种新型磷氮类膨胀阻燃剂四邻苯二胺磷酸酯磷酰氯缩季戊四醇(PDP),通过热重分析(TGA)发现其在700℃氮气氛中具有高达40.8%的残炭率.即使添加20份的炭黑、60份的PDP也能使乙丙橡胶复合材料达到UL-94 V-0级.原位红外光谱揭示残炭中含有丰富的PN键.这归因于PNHC弱碱中氢原子与磷酸酯的相互作用.扫描电镜(SEM)表明燃烧时形成了膨胀炭层.而对乙丙橡胶复合材料的力学性能的研究结果显示增加PDP含量提高了其阻燃性但损害了其力学性能.     

阻燃剂DDPA的合成及在环氧树脂中的应用研究

一锅法合成了一种磷杂菲类阻燃剂2-((9,10-二氢-9-氧杂-10-磷杂菲-10-基)(苯基)甲基)氨基-9',10'-蒽醌(DDPA),采用红外光谱和核磁共振确定了阻燃剂DDPA的分子结构,并将其用于阻燃改性环氧树脂.通过悬臂梁冲击试验机、电子万能力学试验机、热重分析仪(TGA)、差示扫描量热仪(DSC)、氧指数仪...     

Enhanced flame-retardant performance of poly (lactic acid) (PLA) composite by using intrinsically phosphorus-containing PLA

The intrinsically phosphorous-containing flame-retardant poly(lactic acid)(P-PLA) was synthesized through the chain extension of L-lactide and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) derivative, then P-PLA was melt blended with neat PLA to produce flame-retardant PLA composite(FR-PLA). The flame-retardant properties of FR-PLAs were investigated by Limiting Oxygen Index(LOI), UL-94, and Cone Calorimeter Tests, the results indicated that the flame-retardant properties of PLA composites were significantly improved with the addition of P-PLA due to its excellent ability to carbonize and dilute combustible gases. The LOI value of FRPLA10 composite(consisting of 90 wt% neat PLA and 10 wt% P-PLA) increased from 20.5 to 27.8 and UL-94 rating reached up to V-1, the peak heat release rate and total heat release of FR-PLA composite were lower than those of neat PLA. The flame-retardant mechanism of FR-PLA depended on both condensed and gaseous phases,which was confirmed by the FTIR, Raman and TG-FTIR. Besides, the tensile strength of FR-PLA10 slightly decreased from 72.4 to 61.8 MPa, which met the requirements of most practical applications. Therefore, the modification method used in this work presented a feasible approach to prepare FR-PLA composite with satisfactory mechanical property.     

不同粒径的Sb2O3对PBT阻燃性能的影响

为了改善聚对苯二甲酸丁二醇酯(PBT)的阻燃性能,采用先机械球磨共混、后熔融注塑的方法制备了Sb₂O₃/BPS-PBT复合材料.研究了Sb₂O₃粒径对复合材料阻燃性能的影响,并分析了复合材料的阻燃机理.结果表明:Sb₂O₃使PBT初始分解温度提前,热分解速率减慢;添加相同质量分数的Sb₂O₃,纳米Sb₂O₃在气相阻燃中的效率和促进残炭形成的催化作用均优于微米Sb₂O₃;当溴化聚苯乙烯(BPS)和纳米Sb₂O₃的质量分数分别为10%和5%时,复合材料的LOI为28.3%,UL94达到V-0级.     

含磷环氧树脂的合成及阻燃研究

采用阻燃剂9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)与双酚A型环氧化物(E-51)反应,合成了含磷反应型阻燃环氧化物(E-P),在间苯二胺固化剂作用下,利用E-P制备了含磷反应型阻燃环氧树脂(EP-P). 采用傅里叶红外光谱(FTIR)和热失重分析(TGA)分别对E-P的结构及EP-P的热分解行为进行了表征;通过浸水实验,采用极限氧指数(LOI)和UL-94垂直燃烧等方法对比研究了EP-P与添加聚磷酸铵(APP 422)的添加型阻燃环氧树脂EP-AP的阻燃剂抗迁出性. 结果表明,含磷反应型阻燃环氧树脂EP-P比添加型阻燃环氧树脂EP-AP的阻燃效率高、阻燃耐久性更强.     

稀土氧化物溶胶对羊毛纤维的阻燃改性及其热降解

用稀土氧化物(La2O3,CeO2,Y2O3)溶胶对羊毛纤维进行阻燃处理,并采用氧指数、剩炭率、热分析等方法对处理前后的羊毛纤维的阻燃性能及热降解行为进行研究.实验证明:经处理后的羊毛纤维,剩炭率、氧指数升高,热降解温度提前,活化能改变,放热峰温度升高,阻燃性得到明显改善.依据阻燃羊毛的热降解行为的变化,对该体系处理羊毛的阻燃机理做了初步的探讨.     

碱性钙基膨润土协同卤锑阻燃HDPE的研究

【目的】解决卤锑阻燃高密度聚乙烯(HDPE)复合材料燃烧时发烟量大、熔融滴落严重等问题。【方法】采用自制的碱性钙基膨润土(Ca-MMT)与卤锑阻燃剂复配阻燃HDPE,通过极限氧指数(LOI)、水平燃烧等级、力学性能和热稳定性等测试,研究Ca-MMT和卤锑阻燃剂对HDPE的协同阻燃效应。【结果】HDPE/DBDPE/Sb2O3/Ca-MMT复合材料的LOI由纯HDPE的19.60%提高至32.77%,水平燃烧等级由HB75级提高至HB级,且燃烧时不产生熔滴,具有良好的成炭效应;拉伸强度由13.35MPa提高至23.33MPa,力学性能良好;失重率由纯HDPE的96.17%降至86.50%,热稳定性明显提高。碱性钙基膨润土的最佳添加量为4%。【结论】自制的Ca-MMT与卤锑阻燃剂有较好的协同阻燃作用。