【作者】 周玉波；

【导师】 唐小真；

【作者基本信息】 上海交通大学 ， 材料学， 2009， 博士

【摘要】 聚膦腈是一类主链上以磷氮原子交替排列,侧链为不同有机取代基的新型无机高分子材料。由于它将有机分子紧密地结合起来,且主链具有区别于有机碳链的特性,从而表现出传统聚合物无法比拟的独特物理化学性能。聚膦腈最大的特点是侧链的易于设计性,改变侧基可以赋予聚合物新的性能。但高分子量聚膦腈制备困难且成本过高,而膦腈齐聚物又由于其力学性能较差,限制了其广泛应用。聚氨酯是一类重要的多用途聚合物材料,拥有优良的耐磨性能、耐疲劳性、耐化学腐蚀性、优异的柔顺性、极好的阻尼性和生物相容性等。但传统原料制备的聚氨酯由于其耐热耐寒性能、阻燃性能和疏水性能不足等缺点限制了其应用领域。本文期望在不过度牺牲聚氨酯的机械性能的前提下,探索利用膦腈齐聚物优越性能来改善聚氨酯的耐热耐寒性能、阻燃性能和疏水性能,制备出一系列新型的聚膦腈/聚氨酯无机/有机共聚材料。本文合成了几种含羟基的功能性膦腈齐聚物,分别将它们作为聚氨酯各种组份:添加剂、扩链剂、交联剂和多元醇,制备了多种新型聚膦腈/聚氨酯无机/有机共聚材料。详细考察了膦腈齐聚物对共聚材料耐热耐寒性能、阻燃性能和表面性能的影响。具体研究内容如下:1.六苯氧基环三膦腈共混改性热塑性聚氨酯—聚膦腈作为添加剂研究了热塑性聚氨酯和六苯氧基环三膦腈(HPCP)共混材料。结果表明,共混材料具有较好的热稳定性,起始热分解温度提高17℃;材料具有较好的阻燃性能,由改性前的易燃材料成为垂直燃烧测试(UL 94)为V-2级的阻燃材料;HPCP有一定的降粘作用,共混材料的熔融指数(MFI)由52.5 g/10min上升到59.4g/10min,可以改善TPU的加工性能;接触角测试(CA)表明共混材料具有更低的表面能,由原来的35.9 mN·m-1下降到28.0 mN·m-1。2.聚环膦腈/聚氨酯共聚物的制备及性能研究—聚膦腈作为扩链剂合成了一种含砜基、且羟基封端的环膦腈齐聚物。通过傅立叶红外光谱(FTIR)、核磁共振(NMR)和凝胶渗透色谱(GPC)测试验证了所得产物化学组成符合预期的设计,并以此为扩链剂制备了新型的热塑性聚环膦腈/聚氨酯共聚物。X-射线衍射(XRD)分析表明该共聚物是无定形聚合物。热失重分析(TGA)表明共聚物的起始热分解温度提高22℃,差示扫描量热分析(DSC)表明共聚物的玻璃化转变温度(Tg)由原来的-20.6℃下降到-32.3℃,具有较好的耐热耐寒性能。CA表明共聚物的水接触角由原来的78.6o上升到104.5o,疏水性能优于传统热塑性聚氨酯。3.聚苯氧基线膦腈交联聚氨酯的制备及性能研究—聚膦腈作为交联剂合成了带羟基的线性苯氧基膦腈齐聚物,FTIR、NMR和GPC验证了其化学组成,并以其为交联剂制备了热固性聚氨酯(PUOs)。XRD分析表明PUOs是无定形聚合物,TGA分析结果表明PUOs的失重5%的热降解温度提高78℃;DSC分析表明PUOs的Tg由原来的-13.6℃下降到-32.4℃。PUOs的拉伸强度保持较好(改性前18.4MPa,改性后17.7MPa),而断裂伸长率稍有提高(改性前328.5%,改性后386.7%)。CA的测试表明PUOs的水接触角由原来的74.8o上升到94.6o,具有比传统聚氨酯更好的疏水性。4.聚含氟线膦腈交联聚氨酯的制备、形态及性能研究—聚膦腈作为交联剂合成了带羟基的线性含氟膦腈齐聚物,FTIR、NMR和GPC证明了其化学组成,以其作为交联剂制备了聚氨酯(PUPFs)。FTIR和元素分析(EA)证明了PUPFs的化学组成与我们设计的一致。XRD分析表明PUPFs是无定形聚合物,原子力显微镜(AFM)分析表明PUPFs的微相分离程度高于传统聚氨酯。DSC表明PUPFs具有较低的玻璃化温度(Tg, PUPF-4= -41℃),这说明PUPFs有极好的耐低温性。PUPFs的拉伸强度保持较好(改性前18.4MPa,改性后16.9MPa),而断裂伸长率稍有提高(改性前328.5%,改性后399.5%)。CA的测试表明PUPFs有较低的表面能,PUPF-4的表面能为22 mN·m-1。5.热固性聚膦腈-氨酯的制备及性能研究—聚膦腈作为多元醇以带羟基的线性苯氧基膦腈齐聚物为多元醇,甲苯二异氰酸酯(TDI)为硬段,1,4-丁二醇(BDO)为扩链剂制备热固性聚膦腈-氨酯。与传统聚氨酯相比,聚膦腈-氨酯表现出更高的热稳定性。根据聚合物在800℃时的残留率可估算得到聚膦腈-氨酯氧指数为32 %,优于传统聚氨酯的18 %,具有理想的阻燃性。聚膦腈-氨酯的水接触角可达到118.7o,远高于传统聚氨酯的75.0o。6.聚膦腈微球交联聚氨酯共聚材料的制备、形态及性能研究—聚膦腈作为纳米交联剂首次探索制备了含羟基的聚膦腈微球,并将其引入到聚氨酯基体中形成交联网络结构。扫描电镜(SEM)表明聚膦腈微球较好地分散在聚氨酯基体中。与纯聚氨酯相比,共聚材料的热稳定性显著提高。具有明显特点的是拉伸测试表明共聚材料的拉伸强度明显增加(由改性前12.5MPa上升到改性后19.2MPa),并且断裂伸长率基本保持不变。此外,共聚材料比纯聚氨酯具有更好的疏水性,水接触角由改性前的70.5o上升到96.3o。更多还原

【Abstract】 Polyphosphazenes are a class of novel inorganic macromolecules containing alternate phosphorus-nitrogen single and double bonds with two organic side groups being attached to each phosphorus atoms. Because the phosphorus-nitrogen bonds are extremely flexible due to the low torsional energy and a large variety of side groups, polyphosphazenes can be made with a wide range of chemical and physical properties. However, polyphosphazenes have far proven to be of limited their wider applications due to polyphosphazenes of high molecular weight are high production costs and difficult to produce. And mechanical properties of phosphazene oligomers are poor. Polyurethanes are an important and versatile class of polymer materials, which are receiving steadily increasing attention and becoming important engineering materials due to their high abrasion resistance, wearability, chemical resistance, high impact strength and outstanding damping ability. However, conventional polyurethanes have relatively poor thermal, cold, flame resistance and hydrophobicity, which can not meet the special requirements in some application fields. Therefore, phosphazene oligomers are explored to improve thermal, cold and flame resistance properties and hydrophobicity of polyurethane, without dramatic damaging mechanical properties of polyurethanes. In the work, a series of novel polyphosphazene/polyurethane copolymerization materials were prepared.In the paper, a series of phosphazene oligomers with hydroxyl groups had been synthesized and used as different components of polyurethane to synthesize polyphosphazene/polyurethane copolymerization materials, respectively. These components of polyurethane are additives, chain extenders, crosslinkers and polyols. The thermal and cold resistance properties, flame properties and hydrophobicity of polyurethanes were investigated in detail. The main contents were listed below: 1. Thermoplastic polyurethane modified by hexaphenoxytricyclophosphazene- polyphosphazene as additiveThe blending materials were prepared by thermoplastic polyurethane (TPU) blending with different contents of hexaphenoxytricyclophosphazene. The blending materials have better thermal stability. Tonset of the blending material increases 17 oC. The blending materials present flame retardancy, which were observed V-2 rating through the UL 94 test. In addition, hexaphenoxytricyclophosphazene has a good decrease in viscosity to improve TPU processing properties. The MFIs of the blending materials are increased from 52.5 to 59.4 g/10min. The blending materials present lower surface energies than TPU according to contact angle measurements (CA), from 35.9 decreased to 28.0 mN·m-1.2. Synthesis and characterization of poly(oligophosphazene-urethane)s- polyphosphazene as chain extenderHydroxyl terminated phosphazene oligomer containing sulfone groups was synthesized. The results of FTIR, NMR and GPC analysis confirmed the chemical composition. A series of novel thermoplastic poly(oligophosphazene-urethane)s (POUs) were prepared and chain extended by the phosphazene oligomer. X-ray diffraction (XRD) showed that POUs are amorphous. Thermogravimetric analysis (TGA) presented Tonset of POUs increase 22 oC. Differential scanning calorimetry (DSC) showed that present glass transition temperatures (Tg) of POUs decrease from -20.6 to -32.3 oC. The decrease of Tgs showed that POUs could have better low temperature resistance. CA analysis showed water contact angles of POUs increased from 78.6o to 104.5o, which indicated POUs are more hydrophobic than conventional TPU.3. Synthesis and characterization of polyurethanes crosslinked by linear phenoxyphosphazene oligomer-polyphosphazene as crosslinker of polyurethanePhenoxyphosphazene oligomer containing hydroxyl was successfully synthesized. The chemical composition was characterized by FTIR, NMR and GPC. A series of thermosetting polyurethanes (PUOs) were prepared in a two step method, in which polyurethane prepolymer was crosslinked by phenoxyphosphazene oligomer. XRD showed that PUOs are amorphous. TGA presented Tonset of PUOs increased 78 oC. DSC showed that present Tg of PUOs decreased from -13.6 to -32.4 oC. PUOs maintained good tentile properties (CPU is 18.4 MPa and PUO-1 is 17.7 MPa). Break of elongation is slightly enhanced (CPU is 328.5 % and PUO-1 is 386.7 %). CA analysis showed water contact angles of PUOs increased from 74.8o to 94.6o, which indicated PUOs are more hydrophobic than conventional TPU.4. Synthesis and characterization of polyurethanes crosslinked by fluorine containing oligophosphazene- polyphosphazene as crosslinkerFluorine-containing oligophosphazene (OFHBP) was successfully synthesized. The chemical composition was identified by FTIR, NMR and GPC. The obtained OFHBP was used as crosslinker to prepare polyurethanes (PUPFs). The composition of the PUPFs was confirmed by FTIR and EA. XRD showed that PUPFs are amorphous. Studies on atomic power microscope (AFM) had found that PUPFs are higher microseparation than conventional polyurethane. DSC showed that PUPFs have lower glass transition temperatures (Tg)s than CPU, such as Tg of PUPF-4 is -41 oC. It could conclude that PUPFs display in super resistance in low temperature. PUPFs maintained good tentile properties (CPU is 18.4 MPa and PUPF-1 is 16.9 MPa). Break of elongation is slightly enhanced (CPU is 328.5 % and PUPF-1 is 399.5 %). CA analysis showed PUPFs are low surface energies. The surface energy of PUPF-4 is 22 mN·m-1.5. Synthesis and characterization of thermosetting polyphosphazene-urethanes- polyphosphazene as polyolA series of thermosetting polyphosphazene-urethanes (PPUs) were prepared by a two step process using the polyphenoxyphosphazene as polyol, toluene diisocyanate as hard segments and 1, 4-butanediol as chain-extender. The FTIR spectra demonstrated that the composition of PPUs conformed to our expectation. PPUs presented higher thermal stability. LOI of PPUs was estimated from the residues at 800 oC about 32 indicated that flame resistance of PPUs were superior to that of CPU (LOICPU≈18). CA analysis showed water contact angles of PPUs increased from 75.0o to 118.7o, which indicated PPUs are more hydrophobic than CPU.6. Synthesis and characterization of novel polyurethane crosslinked by poly (cyclotriphosphazene-co-4,4′- sulfonyldiphenol) microspheres copolymerization materials -polyphosphazene as nano-crosslinkerThe organic inorganic polyurethane hybrid copolymerization materials based on PZSMs were successfully fabricated with netlike structure for the first time. The results on the microstructure of the copolymerization materials indicated that the PZSMs could be dispersed in the polyurethane matrix well. The copolymerization materials displayed the excellent thermal stability. In addition, copolymerization materials showed evident characteristics as improvement in tensile strength (PU is 12.5 MPa and PU-4 is 19.2 MPa) and almost invariability in elongation at break by adding PZSMs into the polyurethane matrix. The copolymerization materials are more hydrophobic than pure polyurethane, water contact angles increasing from 70.5o to 96.3o.更多还原