聚乳酸链端烷基链长度对聚乳酸结晶性及水蒸气透过性的影响

分别以十二醇、十八醇、二十四醇和二十八醇为引发剂引发左旋丙交酯(L-LA)开环聚合,合成了链端键接不同长度烷基链的聚乳酸,利用红外吸收光谱(FTIR)、核磁共振氢谱(~1H-NMR)和凝胶渗透色谱(GPC)分析产物结构并计算产物的相对分子质量,通过示差扫描量热技术(DSC)对产物的结晶性能进行了分析,进一步通过薄膜水蒸气透过性实验分析了薄膜试样对水蒸气的透过性能.~1H-NMR和GPC分析结果表明,已将烷基链键接到聚乳酸链端,且固定L-LA与脂肪醇的摩尔比,不同脂肪醇引发合成的试样的相对分子质量基本一致,与理论值相差不大. DSC分析结果表明,在80℃时,聚乳酸的结晶速率随链端烷基链长度的增加而增加,链端为二十四烷基时,可促进聚乳酸在高温下成核,进而促进聚乳酸结晶.随相对分子质量增加,聚乳酸完全结晶时的结晶度略有降低.水蒸气透过性实验结果表明,非晶聚乳酸薄膜对水蒸气的透过能力强于结晶聚乳酸薄膜,聚乳酸的相对分子质量对薄膜的水气透过性影响不大,因此可通过调控聚乳酸的聚集态结构实现对水蒸气透过性的调节,进而将聚乳酸包装材料更好地应用于市场.     

软硬段对聚氨酯弹性体结构性能的影响

采用本体聚合和溶液聚合两种方法,合成了一系列用聚乙二酸丁二醇酯二醇作为软段的聚氨酯弹性体。研究了硬段含量和聚醚添加量对聚氨酯弹性体综合性能的影响。利用红外光谱、热分析、力学性能测试、记忆回弹性能和耐水解老化实验等测试手段对样品进行了表征与分析。结果表明:硬段质量含量为31%~35%时,材料的力学性能较优,形状回复率可以达到75%~85%;软段中聚醚添加量在4%~5%(占软段的质量分数)时,弹性体具有较好的力学性能和耐水解性能。     

“滑轮环”拓扑结构增韧聚乳酸及其形状记忆性能和机理探究

通过羟丙基化改性聚轮烷(HPPR)引发L-丙交酯(LLA)开环聚合,将具有机械互锁特性的"滑轮环"拓扑结构引入到聚乳酸体系中,制备了高韧度的"滑轮环"聚乳酸基聚氨酯高分子体系(SR-PLAU),并将其与化学交联的聚乳酸基聚氨酯体系(CC-PLAU),以及聚乳酸/HPPR原位化学共混体系(PLA/HPPR)进行对比研究.结果表明"滑轮环"拓扑结构的引入有效地提高了聚乳酸基材料的拉伸性能,杨氏模量大幅度下降,当"滑轮环"拓扑结构含量为1%(摩尔分数)时,材料的断裂伸长率提高了10倍;"滑轮环"拓扑结构的引入赋予材料优异的形状记忆性能,形状固定率和形状回复率都达到了90%以上.提出了可能的形状记忆机理,并利用材料的应力松弛特性对形状记忆机理进行了分析验证.为材料的增韧改性和新性能研究提供新的理论和思路.     

软硬段对聚氨酯弹性体结构性能的影响

采用本体聚合和溶液聚合两种方法,合成了一系列用聚乙二酸丁二醇酯二醇作为软段的聚氨酯弹性体。研究了不同硬段含量和聚醚添加量对聚氨酯弹性体综合性能的影响。利用红外光谱,机械性能测试、热分析、耐水解老化实验和记忆回弹性能等测试对样品进行表征与分析。结果表明:当硬段含量为33%～34%,软段中聚醚添加量为4%～5%(占软段的质量分数)时,弹性体具有较好的力学性能和耐老化性能,弹性回复率可维持在80%～85%。     

主链含酰亚胺环和炔基的聚酰亚胺型聚氨酯弹性体的合成及阻燃性能简

以均苯四甲酸酐、D,L-苯丙氨酸和1,4-丁炔二醇为原料合成了一种含有酰亚胺环和炔基的二醇,并以其为扩链剂,采用预聚体法,与4,4-二苯基甲烷二异氰酸酯(MDI)和聚四氢呋喃醚二醇(PTMG)反应,合成了不同硬段含量的主链含有酰亚胺环和炔基的热塑性聚酰亚胺型聚氨酯弹性体. 用红外光谱(FTIR)、电子拉力机、热失重分析(TG)、广角X射线衍射(XRD)、UL-94垂直燃烧和极限氧指数对聚酰亚胺型聚氨酯弹性体进行了表征. 结果表明,这种聚氨酯呈现出无定形结构;其拉伸强度随着硬段含量的增加而增大;与传统的热塑性聚氨酯相比,酰亚胺环和炔基改性的聚酰亚胺型聚氨酯弹性体的热分解过程非常缓慢,呈现出较好的热稳定性;不同硬段含量的聚酰亚胺型聚氨酯弹性体的UL-94垂直燃烧均达到V-2级别;其极限氧指数随着硬段含量的增加而增大.     

主链含酰亚胺环和炔基的聚酰亚胺型聚氨酯弹性体的合成及阻燃性能

以均苯四甲酸酐、 D,L-苯丙氨酸和1,4-丁炔二醇为原料合成了一种含有酰亚胺环和炔基的二醇, 并以其为扩链剂, 采用预聚体法, 与4,4-二苯基甲烷二异氰酸酯(MDI)和聚四氢呋喃醚二醇(PTMG)反应, 合成了不同硬段含量的主链含有酰亚胺环和炔基的热塑性聚酰亚胺型聚氨酯弹性体. 用红外光谱(FTIR)、 电子拉力机、 热失重分析(TG)、 广角X射线衍射(XRD)、 UL-94垂直燃烧和极限氧指数对聚酰亚胺型聚氨酯弹性体进行了表征. 结果表明, 这种聚氨酯呈现出无定形结构; 其拉伸强度随着硬段含量的增加而增大; 与传统的热塑性聚氨酯相比, 酰亚胺环和炔基改性的聚酰亚胺型聚氨酯弹性体的热分解过程非常缓慢, 呈现出较好的热稳定性; 不同硬段含量的聚酰亚胺型聚氨酯弹性体的UL-94垂直燃烧均达到V-2级别; 其极限氧指数随着硬段含量的增加而增大.     

侧链为光敏感基团的可生物降解聚氨酯的合成及表征

设计合成2-甲基-2-肉桂酰氧甲基-1,3-丙二醇(MCO)作为扩链剂,并以聚乳酸二醇(PLA diol)为软段,异佛尔酮二异氰酸酯(IPDI)和MCO为硬段制备了一系列侧链含有肉桂基团的可生物降解聚氨酯.结果表明MCO具有较高的反应活性,可满足制备高分子量聚氨酯的要求.聚氨酯结构中的肉桂双键可在紫外光和光引发剂的共同作用下,发生快速的交联反应,短时间内形成交联结构.软段结构相同时,凝胶含量随MCO含量的增加而增加.硬段结构相同时,凝胶含量随软段分子量的增加而减少.适度的交联可提高拉伸强度和形变回复率.     

钛酸四丁酯增韧改性聚乳酸/淀粉共混材料

制备了钛酸四丁酯[Ti(OBu)4]增韧改性的聚乳酸(PLA)/淀粉共混材料,测试了材料的加工流变性能、力学性能、共混形态、结晶性能及疏水性能和降解性能。结果表明:当mTi(OBu)4∶mPLA=0.20时,共混材料的冲击强度提高了40.9%,而弯曲强度下降了59.2%;FT-IR和SEM显示钛酸四丁酯的化学架桥作用增加了共混材料中聚乳酸与淀粉的相容,其吸水率随钛酸四丁酯含量的增加而减少,掩埋150 d后质量下降5%~8%。     

聚乳酸扩链及热性能研究

采用L-乳酸熔融缩聚,制备了粘均相对分子质量较低的聚乳酸,并以亚磷酸三苯酯和1,4-丁二醇二缩水甘油醚为扩链剂对其扩链。亚磷酸三苯酯和1,4-丁二醇二缩水甘油醚可以有效提高聚乳酸的粘均相对分子质量,但是,扩链产物PLLA-TPPi和PLLA-BDDE的粘均相对分子质量未随亚磷酸三苯酯和1,4-丁二醇二缩水甘油醚的用量呈线性变化,而是表现为一峰值。PLLA-TPPi和PLLA-BDDE的玻璃化温度均随扩链产物的粘均相对分子质量的增大而提高;与PLLA-BDDE相比,PLLA-TPPi链中的TPPi结构更能有效促进PLLA链的结晶。     

一种非离子型含氟聚氨酯表面活性剂的合成及性能

以甲苯-2,4-二异氰酸酯(2,4-TDI)、2-甲氧基-3-全氟壬烯氧基丙醇和聚乙二醇(PEG)等为主要原料,通过分布缩合得到一种非离子型含氟聚氨酯表面活性剂,并利用红外光谱对其进行了表征。讨论了加料方式、亲水单体相对分子质量、聚乙二醇用量等因素对产品性能的影响。实验结果表明,当n(2,4-TDI):n(氟醇):n(PEG)=1:1:1.1时,采用先加入TDI和氟醇,反应一段时间后滴加PEG的加料方式,能够合成得到综合性能较好的非离子型含氟聚氨酯表面活性剂。对该表面活性剂在水相中的表面活性进行了测试,所制得的非离子型含氟聚氨酯表面活性剂(FPU-1)的相对分子质量为1310,其临界胶束浓度约为9.54×10-5mol/L,水溶液的最低表面张力为20.88mN/m。     

聚对苯二甲酸丙二醇酯的无卤阻燃化改性

聚对苯二甲酸丙二醇酯作为新型聚酯材料,具有非常优良的性能,但其易燃性很大的限制了它的应用范围。为了提高对苯二甲酸乙二醇酯的阻燃性能,本文以无卤膨胀型EPFR-300A为阻燃改性剂,马来酸酐接枝聚烯烃(POE-g-MAH)弹性体为增韧剂,对聚对苯二甲酸丙二醇酯树脂(PTT)进行阻燃改性。通过热重分析仪(TGA)、示差扫描量热仪(DSC)、扫描电子显微镜(SEM)、力学性能等技术手段研究了阻燃剂和增韧剂对PTT树脂力学、热学和阻燃性能的影响。结果表明,增韧剂POE和POE-g-MAH的添加提高了PTT树脂的综合力学性能。当质量分数相同时,POE-g-MAH对PTT树脂的增韧效果要优于POE,且当POE-g-MAH质量分数为7%时,综合力学性能最佳。当添加相同质量分数增韧剂,EPFR-300A质量分数达到20%时,阻燃PTT材料阻燃性能最佳,极限氧指数(LOI)达到28.0%,垂直燃烧阻燃等级达到UL94 V-0级。EPFR-300A阻燃剂与PTT树脂间相容性良好,可以有效地促进PTT树脂成炭并提高材料的阻燃性能。     

Crystallization and Properties of Novel Polyurethanes Based on the Chain Extender Ethylene Glycol and Aromatic Diisocyanates of Variable Flexibility

Summary: Novel polyurethane elastomers (PUs) were synthesized with ethylene glycol (EG) as a chain extender. The macrodiol was poly(ethylene adipate) (PEA), MW = 2000 ± 50. Two isocyanates were employed: 4,4′-methylene bis(phenyl isocyanate) (MDI) and 4,4′-dibenzyl diisocyanate (DBDI). The conformational mobility of DBDI causes an unusually wide range of mechanical, physical and chemical properties, associated with the possibility of pronounced phase separation into a domain – matrix morphology, and with a higher tendency to crystallization and self-association by hydrogen bonding. Materials were characterized by wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), dynamic mechanical analyses (DMA), and mechanical measurements. Results were discussed in terms of the effect of PUs crystallinity. In the case where the chain extender–diisocyanate couple was EG-DBDI, the hard segments were observed to crystallize. The DBDI based PUs displayed higher flow stress in the hard phase caused by stronger phase segregation.     

Construction of crosslinking network structures by adding ZnO and ADR in intumescent flame retardant PLA composites

Different proportion of nano zinc oxide (nano ZnO) and chain extender (ADR) were combined with the intumescent flame retardant and then added into the PLA matrix. The thermal stability, flame retardant performance, and mechanical properties were studied. The gel content results showed that crosslinking structures were obtained after the addition of nano ZnO and ADR, which were generated by the catalytic chain scission effect of nano ZnO and chain extension effect of ADR. With addition of 1% nano ZnO and 1.6% ADR, the gel content of flame retardant PLA composite reached the highest value (14.2%). Meanwhile, the corresponding flame retardant PLA composite with 1% nano ZnO and 1.6% ADR, named FRPLA/ZnO/ADR-1, exhibited an overall improved properties including the flame retardant properties and mechanical performance, which passed the UL94 V-0 level with a limiting oxygen index value of 40.1%. Compared to FRPLA (flame retardant PLA without ZnO and ADR), the peak heat release rate and the total smoke production of FRPLA/ZnO/ADR-1were reduced by 60% and 67% respectively, and the final mass improved from 12% to 38%. In addition, the tensile strength and elongation at break of FRPLA/ZnO/ADR-1 increased by 25%, 14% compared with that of FRPLA. The impact strength was 15.1 kJ/m², which is similar to the pure PLA (15.6 kJ/m²). It indicated that the addition of nano ZnO and ADR could balance the flame retardant performance and the mechanical properties of the flame retardant PLA.     

协效阻燃聚丙烯的阻燃性能

本文研究了以聚磷酸铵(APP)为主阻燃剂,次磷酸铝(AHP)和三聚氰胺氰尿酸盐(MCA)为辅阻燃剂的协效阻燃体系对聚丙烯(PP)阻燃性能的影响。 采用垂直燃烧测试、极限氧指数(LOI)测试、热重分析、锥形量热仪测试、扫描电子显微镜分析等技术手段对所制备的阻燃样品进行了阻燃性能分析。 结果表明:单独添加任一质量分数30%阻燃剂,均不能使PP获得良好的阻燃性能;当阻燃剂总质量分数保持在30%,m(APP)：m(AHP)：m(MCA)=4：1：1时获得理想阻燃效果,此时阻燃PP的LOI为33%,垂直燃烧测试达到V-0级,热释放速率峰值(PHRR)从765.7 kW/m²降为122.7 kW/m²。     

Diffusion of polyphosphates into (poly(allylamine)-montmorillonite) multilayer films: flame retardant-intumescent films with improved oxygen barrier

The present paper relies on the original idea to design multifunctional coatings, and in particular highly efficient intumescent flame retardant coatings, based on the diffusion of polyphosphates (PSPs) in exponentially growing "layer-by-layer" films made from montmorillonite (MMT) and poly(allylamine) (PAH). Here, we used polyphosphates as an acid source, polyallylamine as both a carbon source and a swelling agent, and finally clays to reinforce the intumescent char strength and also for their oxygen barrier property. The coatings made from the alternated deposition of n = 60 layer pairs of PAH and MMT reach a considerable thickness of ～18 μm with well-defined ordering of the MMT in the direction parallel to the substrate. Structural, morphological, mechanical, gas barrier, and fire resistance properties of these films have been studied. Excellent oxygen barrier properties and extraordinary fire resistance properties are demonstrated based on the basis of a strong increase of the time to ignition and on a decrease of the heat release rate of polylactide substrates during mass loss calorimeter tests. This new and innovative intumescent flame retardant system based on (PAH-MMT)(n)-PSP coatings is a promising universal treatment for current polymeric materials.     

Thermal stability of food additives of glutamate and benzoate type

Summary An unsaturated polyester/sisal flame retardant composite was formulated using decabromine diphenyl oxide associated with antimony trioxide as additives. The development and use of natural or vegetable fiber reinforced composites is increasing worldwide, since natural fibers come from renewable sources and their use contributes to the so-called 'green technology'. In the present study, the synergic effect of a bromine/antimony (3:1 molar ratio) based flame retardant system with 7.5% Br (mass/mass) added to composites investigated by TG, UL-94V and pyrolysis on a coupled Pyr-GC/MS device. The efficiency of the flame retardant system is confirmed by TG and UL-94V test where the composite containig flame retardant system obtained the highest classification (V-0).     

Polyisobutylene‐based polyurethanes. VI. Unprecedented combination of mechanical properties and oxidative/hydrolytic stability by H‐bond acceptor chain extenders

We describe the design, synthesis, characterization, and testing of novel polyurethanes (PUs) exhibiting unprecedented combinations of outstanding mechanical properties and oxidative/hydrolytic stabilities. This achievement is due to the use of polyisobutylene (PIB) soft segments plus flexible H‐bond acceptor chain extenders (HACEs): the PIB imparts superior oxidative/hydrolytic stability and the HACE produces reinforcing H‐bonds, which lead to outstanding mechanicals. Oxidative/hydrolytic stability was quantitated by retention of tensile strength and elongation after exposure to nitric acid. PUs containing 60–70% PIB retain their mechanical properties, whereas Carbothane®, Bionate®, and Elast‐Eon?, PUs marketed for chemical stability, degrade severely under the same conditions. Various HACEs were identified (e.g., hexaethylene glycol, tripropylene glycol, tributylene glycol, 3,3′‐diamino‐N‐methyl‐dipropylamine, etc.) and their effect on mechanical properties was investigated. A PIB‐ and HACE‐containing PU exhibited 29.2 MPa tensile strength, 620% elongation, and 80 Shore A hardness. Properties were analyzed in terms of stress–strain profiles, differential scanning calorimetry traces, dynamic mechanical thermal analysis plots, and oxidative/hydrolytic stability. The properties of various PIB‐based rubbers, that is, thermoplastic PUs, SIBSTAR®, and thermoset butyl rubber are compared. The novel PUs are promising candidates for biomaterials and industrial applications where a combination of mechanical properties and oxidative/hydrolytic stability is of the essence. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2361–2371, 2010     

Study on the thermal degradation behavior and flame‐retardant property of polylactide/PEDPP blends

A phosphorus‐containing polyester, poly (ethylene diglycol phenylphosphinate) (PEDPP) was synthesized from phenylphosphonic dichloride and ethylene diglycol. The structure of PEDPP has been determined by Fourier transform infrared (FTIR) spectroscopy, ¹H nuclear magnetic resonance and matrix assisted laser desorption ionization‐time of flight‐mass spectrometer. A series of polylactide (PLA) blends with various content of PEDPP as flame retardant was prepared by direct melt compounding; the PLA/PEDPP blend is partially miscible. PEDPP is an effective flame retardant for PLA. The limiting oxygen index values increased from 19.7% for pure PLA to 29.0% for the blend containing 10wt% PEDPP. Thermogravimetric analysis‐FTIR analysis indicated that the PEDPP affected the pyrolytic decomposition process of PLA, which is established by the change of the pyrolytic decomposition rate and the gross mass of gaseous fuel formation. The pyrolytic decomposition activation energies of PLA and PLA/10%PEDPP were estimated via Flynn–Wall–Ozawa method. Copyright © 2013 John Wiley & Sons, Ltd.     

无卤阻燃丙烯腈共聚物的制备及性能

以K₂S₂O₈-NaHSO₃ 氧化还原体系为引发剂, 采用水相沉淀自由基聚合法合成丙烯腈(AN)-醋酸乙烯酯(VAc)无规共聚物[P(AN-co-VAc)], 然后在KOH水溶液中进行P(AN-co-VAc)中VAc单元的选择性水解, 再与磷酸和尿素进行磷酰化反应, 制备无卤阻燃丙烯腈共聚物. 用核磁共振氢谱(¹H NMR)、傅里叶变换红外光谱(FTIR)、差示扫描量热(DSC)和热重分析(TGA)对聚合物结构及热性能进行表征, 用凝胶渗透色谱(GPC)测定了P(AN-co-VAc)的分子量及其分布, 并利用FTIR和扫描电子显微镜(SEM)对无卤阻燃丙烯腈共聚物的炭残渣进行分析. 结果表明, VAc与AN发生共聚反应, 制得了P(AN-co-VAc), 随着KOH水溶液pH值的增大, P(AN-co-VAc)中VAc单元迅速水解; DSC分析结果表明, 随着共聚物中VAc单元含量的增大, 共聚物的环化放热分解峰值温度(T_p)增大, 当VAc单元的质量分数为25%时, T_p最大值高达328 ℃, 而阻燃丙烯腈共聚物的T_p高达340 ℃; TGA分析结果表明, 阻燃共聚物在800 ℃时的炭残渣量高达55%以上, 远高于P(AN-co-VAc)的41%, 具有良好的成炭性; 炭残渣的FTIR及SEM结果表明, 阻燃丙烯腈共聚物的阻燃属于凝聚相阻燃.     

Synergistic Efficiency of Tricresyl Phosphate and Montmorillonite on the Mechanical Characteristics and Flame Retardant Properties of Polylactide and Poly(butylene succinate) Blends

The main aim of this research was to investigate the synergistic influence of additives and poly(butylene succinate) (PBS) in improving both the mechanical and flame retardant properties of polylactide (PLA) blends.Tricresyl phosphate (TCP) and montmorillonite (MMT) were the additives used to improve the mechanical characteristics and fire resistance of PLA.Differential scanning calorimetry (DSC) thermograms revealed that the addition of TCP and MMT significantly affected their thermal behaviors.The results of the mechanical and morphological characterizations were in agreement with the changes in thermal behavior.The impact strength and limiting oxygen index (LOI) value of PLA significantly increased with the presence of PBS.The failure mode of the blends as evidenced by scanning electron microscopy (SEM) changed from brittle to ductile.The addition of TCP and MMT produced excellent anti-dripping and self-extinguishing behaviors of the blends,achieving V-0 rating.For the PLA/PBS blends,the synergistic combination of PBS and additives led to an acceleration of cold crystallization,a significant increment of flexibility and impact toughness,and an improvement of flame retardancy.