磷/硅协同阻燃改性水性聚氨酯的性能研究

以聚醚(N-210)、异佛尔酮二异氰酸酯(IPDI)为基本单体,[(双(2-羟乙基)氨基)甲基]磷酸二乙酯(FRC-6)、一缩二乙二醇(EX)为扩链剂,二羟甲基丙酸(DMPA)为亲水扩链剂,通过改变FRC-6的用量合成了一系列有机磷(P)阻燃改性的水性聚氨酯(WPU)乳液。采用机械分散的方式将纳米硅溶胶(SiO2的水溶液)按计量加入到上述乳液中,得到一系列磷/硅(P/Si)复配改性的WPU乳液。测试了聚氨酯(PU)的阻燃和热稳定性,并通过傅里叶红外光谱表征了协同体系中主要的官能团,研究表明,当复配体系中的P、Si元素达到一定配比时,PU的极限氧指数(LOI)从17%提高到33.5%,垂直燃烧测试最高可达UL-94V-0级,表明P、Si两种元素在PU中具有良好的协同阻燃效应。     

大豆油基聚氨酯阻燃泡沫的制备与表征

本文以甲醇开环环氧大豆油(ESO)得到大豆油多元醇(SBP),再与三羟甲基氧化膦(THPO),甲苯二异氰酸酯(TDI),表面活性剂(AK8805)和水反应得到大豆油基聚氨酯阻燃硬质泡沫。用红外(FT-IR)和核磁(~1H-NMR)对环氧大豆油和大豆油多元醇进行了表征。通过压缩试验、热重分析(TG)、扫描电镜(SEM)、极限氧指数、垂直燃烧仪等手段对泡沫的性能进行了测试。结果表明,随着三羟甲基氧化磷(THPO)含量增加,泡沫的力学性能和阻燃性能都得到了提高。     

纳米SiO_2改性水性聚氨酯乳液的制备及性能研究

以硅烷偶联剂(KH-550)作为纳米二氧化硅(nano-SiO2)的表面处理剂,以甲苯二异氰酸酯(TDI)、聚醚二元醇(N-220)、二羟甲基丙酸(DMPA)和nano-SiO2等为主要原料,制备nano-SiO2改性WPU(水性聚氨酯)乳液。着重探讨了DMPA的加料方式、DMPA和nano-SiO2用量等对WPU乳液稳定性、粒径分布、耐水性和力学性能等影响。结果表明:采用先加入DMPA后扩链的加料方式,可制得外观及稳定性均较好的WPU乳液;当w(DMPA)=5%、w(改性nano-SiO2)=2.0%时,WPU乳液及其胶膜的综合性能较好。     

废旧涤纶织物制备水性聚氨酯及其阻燃改性研究

进行了废旧涤纶织物的乙二醇醇解,探究最优醇解条件后,以醇解产物对苯二甲酸双羟乙酯(BHET)、异佛尔酮二异氰酸酯(IPDI)、含磷阻燃剂四羟甲基硫酸磷(THPS)等为原料,制备了阻燃性能及服用力学性能俱佳的阻燃改性水性聚氨酯及阻燃改性涤纶织物。结果表明,在涤纶与乙二醇质量比为1∶4,反应温度为196℃,反应时间为5 h时,涤纶织物的醇解率最高且成本最低;在再生水性聚氨酯的R=1.4,n(—NCO)/n(—OH)=4,DMPA%=5%,TMP%=3%,中和度100%,阻燃剂THPS与聚氨酯乳液的体积比为1∶2时,得到的阻燃改性聚氨酯乳液外观均匀且贮存稳定。涤纶织物经乳液浸渍、烘干后,可获得优良的服用性能及阻燃功能,平均经向断裂强力可达60 N/5 cm,极限氧指数可达29.7%,垂直燃烧损毁长度可低至11.75 cm,可到达UL94-V0级。     

无卤阻燃硅溶胶改性水性聚氨酯的研究

以聚醚(N -210)、异佛尔酮二异氰酸酯(IPDI)为基本单体,一缩二乙二醇(EX)为扩链剂,二羟甲基丙酸( DMPA)为亲水扩链剂,制备出固含量为30％的水性聚氨酯(WPU)乳液.采用机械分散的方式将纳米硅溶胶按计量加入到WPU乳液中,得到一系列硅溶胶改性的WPU乳液.研究表明,硅溶胶在WPU中分散得比较均匀,硅溶...     

水性聚氨酯阻燃涂料研究进展

介绍了阻燃涂料的作用机理及制备方法,着重讨论了膨胀型水性聚氨酯阻燃涂料,最后阐述水性聚氨酯阻燃涂料近几年的研究进展。     

硬段阻燃改性水性聚氨酯的研究

以聚醚210(N-210)、异佛尔酮二异氰酸酯(IPDI)为基本单体,以FRC-5作为扩链剂,用硬段改性的方式将阻燃元素N、P引入到水性聚氨酯中,合成了一系列不同程度改性的阻燃水性聚氨酯。研究了FRC-5的用量对水性聚氨酯阻燃性能、热性能的影响。结果表明,用FRC-5进行扩链可以提高水性聚氨酯的阻燃性和热稳定性。     

环三磷腈衍生物改性的阻燃水性聚氨酯的合成与表征

以三聚氯化磷腈(HCCP)、2,2′-联苯酚和1,6-己二胺为主要原料，合成了具有端氨基的环三磷腈衍生物(HCCP-6),HCCP-6通过化学反应接入WPU预聚物中，制备出系列HCCP-6改性的阻燃水性聚氨酯(NPWPU)。讨论了HCCP-6用量对NPWPU阻燃性能的影响，并利用核磁、红外、极限氧指数测试(LOI)、垂直燃烧测试(UL-94)及扫描电镜(SEM)测试对HCCP-6及NPWPU进行表征。结果表明，HCCP-6质量分数在8%以上，NPWPU胶膜垂直燃烧级别可达到V-0(UL-94)难燃级别；HCCP-6质量分数10%时，胶膜LOI可提高至27.5%;残炭层SEM测试也证明NPWPU有很好的阻燃和自熄效果；HCCP-6可以明显提升NPWPU的力学性能。     

丙烯酸酯改性水性聚氨酯阻燃涂料的研究

以丙烯酸（甲基丙烯酸甲酯、丙烯酸丁酯）改性水性聚氨酯预聚体,制备改性水性涂料;并以三聚氰胺／季戊四醇为协效阻燃剂,从而制备一种改性阻燃水性聚氨酯涂料。对改性涂料进行了吸水率、耐水性测试;对改性阻燃涂料进行了燃烧试验、热重分析（TG）。结果表明,改性涂料的吸水率降低了48．6％。阻燃涂料的阻燃时间可达8min以上,耐高温、阻燃性能明显提升。     

硅烷偶联剂改性阳离子水性聚氨酯的研究

以硅烷偶联剂γ-氨丙基三乙氧基硅烷(KH550)为封端剂对阳离子型水性聚氨酯进行杂化改性,并以KH550和γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)为原料合成新型偶联剂D,对聚氨酯进行复合改性,分别合成了纳米SiO2/PU杂化材料和纳米SiO2/PU复合材料.通过FT-IR、粒径分析、AFM对样品的结构进行表征,并对样品的力学性能和耐水性、耐溶剂性进行测试.结果表明:两种体系均生成了二氧化硅相,二氧化硅相在杂化体系中的分散性好于其在复合体系中的分散性.对提高产品性能而言,化学封端改性比物理共混改性更有效.     

有机磷阻燃剂改性水性聚氨酯的制备

以聚己二酸-1,4-丁二醇酯二醇(PBA)、2,2-二羟甲基丙酸(DMPA)、异佛尔酮二异氰酸酯(IPDI)和有机磷阻燃剂10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-膦杂菲-10-氧化物(DOPO-HQ)等为原料制备了阻燃型水性聚氨酯(WPU),考察了DOPO-HQ含量对WPU的黏度、硬度、力学性能和氧指数(LOI)等影响。结果表明:当DOPO-HQ含量从0增至12%(相对于PBA质量而言)时,WPU的黏度降低,成膜硬度增大,断裂伸长率下降,而拉伸强度由11.02 MPa提高到23.76 MPa,LOI由21.0%提高到27.2%(达到难燃级别)。     

磷酸酯阻燃改性MDI型水性聚氨酯的研究

以二苯基甲烷二异氰酸酯(MDI)和聚乙二醇(PEG-600)为主要单体、N,N-双(2-羟乙基)氨基乙基膦酸二乙酯(FRC-5)为部分或全部扩链剂,制备了一系列不同FRC-5掺量的阻燃WPU(水性聚氨酯)。研究结果表明:当w(FRC-5)=15%(相对于PEG-600和MDI总质量而言)时,WPU胶膜的LOI(极限氧指数)为27%,同时热稳定性也有所提高;当w(FRC-5)=12%时,可得到性能稳定、阻燃性能较佳且胶膜平整的WPU。     

Synthesis and characterization of waterborne and phosphorus-containing flame retardant polyurethane coatings

Phosphorus-containing flame retardant water-dispersed polyurethane coatings were produced by incorporating different amounts of a phosphorus compound onto the polyurethane main chain. The novel phosphorus containing compound (phosphorus phenyl dihydroxy) was synthesized in three steps using benzaldehyde, pentaerythritol, phenyl phosphonic dichloride, and acetic acid. The addition of phosphorus phenyl dihydroxy to the main chain of polyurethane, in which NCO/OH ratio was kept constant at 1.5 and the amount of dimethylolpropionic acid (DMPA) at 3.5 wt%, increased the hardness and abrasion resistance, but only slightly decreased the gloss values of the polyurethane paints. All the samples showed superior impact resistance and flexibility. Moreover, increasing the phosphorus content increased the char yield, and the maximum fire retardancy was reached at 1.5% P content with a limiting oxygen index (LOI) value of 29. Kimya B?lümü, 06531 Ankara, Turkey.     

Inorganic/organic phosphorus-based flame retardants synergistic flame retardant rigid polyurethane foam

The flame-retardant rigid polyurethane foam (RPUF) composites are fabricated by ammonium polyphosphate (APP) with pentaerythritol phosphate (PEPA), phenoxycycloposphazene (PCP), and aluminum diethylphosphinate (ADP), respectively, which are labeled as RPUF-1, RPUF-2, and RPUF-3. The influence of flame retardants on the apparent density and compressive strength of RPUF is studied. The results reveal that flame retardants not only improve the apparent density, but also improve the compressive strength of RPUF composites. The limiting oxygen index (LOI) results reveal that these inorganic/organic phosphorus-based flame retardants improve the LOI significantly, especially for RPUF-2 and RPUF-3 systems. The cone calorimeter test results suggest that the peak of heat release of RPUF-1, RPUF-2, and RPUF-3 systems decrease by 38%, 41%, and 52% likened to that of pure RPUF. And APP and ADP system performs best in declining the heat release. And APP and PEPA systems perform best in decreasing the smoke release. The flame retardancy mechanism of RPUF composites is analyzed in details.     

Preparation and performance of waterborne polyurethane coatings based on the synergistic flame retardant of ferrocene,phosphorus and nitrogen

A synergistic reactive flame-retardant polyol (AFeDH) containing ferrocene, phosphorus, and nitrogen elements was synthesized from ferro-formaldehyde, 5-amino-1,3, 4-thiadiazole-2-mercaptan, 9,10-dihydro-9-oxa-10-phos-phaphenanthrene-10-oxide and hydroxyl terminated polybutadiene acrylonitrile, and then applied for flame retarding waterborne polyurethane (WPU). The chemical structures of intermediates and final products were well characterized to confirm the successful preparation of ternary P-N-Fe flame retardant. The effects of incorporated AFeDH on thermal stability, flame retardancy and mechanical properties of AFeDH/WPU films were systematically studied. The results indicated that LOI value increased with the increase amount of AFeDH, while the value then decreased as the loading content above 6 wt%. This increase in flame retardancy results from the competition between the catalytic degradation of iron and the catalytic carbonization. Benefiting from the good synergistic effects among each element of AFeDH, the WPU/AFeDH films perform the decreased heat release and smoke production. Moreover, the flame retardant films also show the enhanced tensile strength of 33.8 MPa and elongation at break of 763.3%. Therefore, this novel halogen-free flame retardant shows an excellent synergistic effect among P, N, and Fe elements, which has a great potential in the application of flame retardant WPU.     

Halogen‐free flame‐retardant waterborne polyurethane with a novel cyclic structure of phosphorus−nitrogen synergistic flame retardant

A novel phosphorus?nitrogen flame retardant, octahydro‐2,7‐di(N,N‐dimethylamino)‐1,6,3,8,2,7‐dioxadiazadiphosphecine (ODDP), with bi‐phosphonyl in a cyclic compound, was synthesized by the reaction of POCl₃, NH(CH₃)₂·HCl with OHCH₂CH₂NH₂ in CH₂Cl₂ solution, and characterized by Fourier transform infrared spectrometer, nuclear magnetic resonance, and mass spectrum. ODDP has been successfully reacted with polyurethane (PU) as a chain extender to prepare phosphorus–nitrogen synergistic halogen‐free flame‐retardant waterborne PU (DPWPU). Limiting oxygen index (LOI), UL‐94, thermogravimetric analysis and scanning electron microscopy suggest the excellent flame retardancy of the DPWPU polymer. When the content of ODDP was 15 wt %, the LOI of DPWPU was 30.6% and UL‐94 achieved a V‐0 classification. Compared with the unmodified WPU, the thermodecomposition temperature of the DPWPU was reduced and the amount of carbon residue was increased to 18.18%. The surface of carbon residue was shown to be compact and smooth without holes, which would be favorable for resisting oxygen and heat. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41288.     

改性赤泥协同膨胀型阻燃剂阻燃聚乙烯

以聚磷酸铵（APP）、季戊四醇（PER）和三聚氰胺（MEL）复配的膨胀型阻燃体系（IFR）为主要阻燃剂,表面改性后的赤泥（Ti-MRM）作为协效剂阻燃聚乙烯（PE）,采用熔融共混法制备PE基阻燃复合材料（PE/IFR-Ti-MRM）。通过热重分析仪（TGA）、垂直燃烧仪（UL-94）、极限氧指数测定仪（LOI）及扫描电镜（SEM）等对其热氧稳定性、燃烧等级、阻燃性能和残炭形貌进行了表征与分析。结果表明：加入改性赤泥的PE/IFR-Ti-MRM复合材料形成的炭层更加致密和连续,当最优配比时,复合材料的极限氧指数达到32.2,燃烧等级达到V-0级;而PE/IFR阻燃复合材料的极限氧指数只能达到27.5,燃烧等级为V-2级。     

有机硅改性水性聚氨酯研究进展

介绍了有机硅改性水性聚氨酯(WPU)的特点,综述了近年来有机硅封端、嵌段共聚及其与丙烯酸酯复合改性制备有机硅改性WPU的研究进展;最后对有机硅改性WPU的研究方向进行了展望。     

有机硅偶联剂改性水性聚氨酯的合成

采用预聚体——封端混合法,用2,4-甲苯二异氰酸酯（TDI）与聚醚多元醇（PEG-1000）进行预聚反应,同时用有机硅偶联剂（A-110）对聚氨酯改性。探讨改性工艺条件对水性聚氨酯性能的影响。     

有机硅改性封端型水性聚氨酯的合成

通过在封端型水性聚氨酯中引入有机硅单体（A-110）,合成了有机硅水性聚氨酯（WBPSU）;讨论了羟基聚醚类型、有机硅含量、改性温度和时间等因素对分散体耐水性和成膜性的影响,并将其应用于棉织物的防皱整理,评定了整理效果。