STUDY ON THE EPOXY RESIN TOUGHENED BY HYDROXY-TERMINATED BUTADIENE-ACRYLONITRILE COPOLYMER

Toughened epoxy resin with excellent properties was obtained by adding organic acid anhydride curing agent and hydroxy-terminated butadiene-acrylonitrile copolymer (HTBN), which is cheaper than CTBN. The anhydride reacts with both epoxy groups on epoxy resin and hydroxyl groups on HTBN. As a result the soft long chains of HTBN and the rigid chain of epoxy resin form one network, giving the resin toughness. Two-phase structure of the toughened resin was observed by SEM and TEM.     

Monte-Carlo simulation of copolymer mass spectra

A computer program, MACO5, was developed which employs the Monte-Carlo approach to simulate the time-variation of the mass spectral peak intensities of a copolymer sample during the synthesis of an A/B copolyester via reactive blending of a mixture of homopolyesters A and B or when a copolymer undergoes partial degradation. The program was first used to simulate literature data consisting of a series of mass spectra of a butadiene/styrene copolymer subjected to partial ozonolysis. It was also used to investigate the role of terminal groups in reactive blending processes. Two models were developed: the first one describes inner-group ester-ester exchange reactions, the second describes the process in which and active terminal groups attacks an ester group. The predictions of the two models are compared with recent experimental mass spectral data concerning a poly(ethylene adipate-co-ethylene terephalate) copolyester.     

A STUDY ON THE TOUGHENING OF EPOXY RESIN BY HTBN-EPOXY RESIN PRECOPOLYMER

A novet toughened epoxy resin was obtained by using aprecopotymer of epoxy resin and hydroxy-terminated butadiene-acrylonitrilecopolymer(HTBN)and amine curing agent.The cured toughened resin hasexcellent mechanical properties due to the two-phase structure,which has beenobserved from SEM and TEM.     

ENHANCEMENT OF COMPATIBILITY OF POLYPROPYLENE AND NYLON-66 BY MALEATED POLYPROPYLENE

The compatibility of PP/N-66 blending system modified with maleated polypropylene was studied by means of SEM, DMA and other mechanical testing. It was found that when proper amount of modifier was applied, the compatibility was greatly enhanced and the impact toughness was significantly improved. An important direct evidence of the formation of the interfacial copolymer was also found. However, when excessive amount of modifier was used, the modification effect was not conspicuous. The phenomena were interpreted from a view of molecular motion that the interfacial block copolymer forced the two components to 'compatibilize' and many flexible PP molecules were set free from the restraint of the crystallites of plain PP so as to absorb much more impact energy.     

The early stage of the morphology development of immiscible polymer blends during melt blending: Compatibilized vs. uncompatibilized blends

The early stage of the morphology development has been studied for the blending of two immiscible polymers. Controlled experiments were carried out in a batch mixer in such a way that the rate of melting was low enough to follow up the morphology development of dilute and concentrated systems. For a dilute or semidilute polypropylene and polyamide 6 (PP/PA6) blend with 0.5, 5, or 10 wt % PA6, particles formed in the very early stage of melt blending were very small, of the order of 0.25 to 0.3 μm in radius. They immediately began to grow in size when no compatibilizer was added, indicative of coalescence even in the very early stage of melt blending and/or in very dilute systems (0.5 wt % PA6). Further growth of the particles was eliminated with the introduction of a graft copolymer compatibilizer providing evidence of the stabilizing effect of the copolymer from the very beginning of melting blending. However, the behavior of the morphology development of a concentrated PP/PA6 (80/20) system was similar to that reported in the literature. The average radius of the particles of the uncompatibilized blend decreased with increasing mixing time, whereas that of the compatibilized blend remained almost constant during mixing. The most favorable conditions to obtain a fine morphology seems to be the following: rate of melting/plastification of pellets < rate of dispersion (deformation + breakup) of the polymer melt to small particles < rate of stabilization (with an adequate copolymer). © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 601–610, 2001     

丁腈羟增韧环氧树脂形态与力学性能

研究了丁腈羟增韧环氧树脂的力学性能和形态结构，丁腈羟的用量、丁腈羟中丙烯腈的含量、固化条件对所形成的微区尺寸都有较大影响，并进一步影响固化物的力学性能。     

Catalytic hydroxylation of polypropylenes

The regioselective functionalization of both model and commercial polypropylenes of varying tacticity has been conducted by a rhodium-catalyzed functionalization of the methyl C-H bonds of the polymer with diboron reagents. Rhodium-catalyzed borylation of the polypropylenes, followed by oxidation of the boron-containing material, produced polymers containing 0.2-1.5% hydroxymethyl side chains. Both the number-average molecular weights and molecular weight distributions of the polypropylenes were essentially unchanged after the catalytic and oxidative functionalization process. The efficiency of the borylation process was affected by the molecular weight of the polymer, the steric hindrance around the methyl groups, and the ratio of the diboron reagent to the monomer repeat unit. The hydroxylated derivative of the commercial isotactic polypropylene was used as macroinitiator for the aluminum-mediated ring-opening polymerization of epsilon-caprolactone to prepare polypropylene-graft-polycaprolactone. This graft copolymer was an effective compatibilizer for melt blends of polypropylene and polycaprolactone.     

丁腈羟增韧环氧树脂研究——Ⅰ.端异氰酸酯基预聚物法

丁腈羟液体聚合物和甲苯二异氰酸酯反应生成端异氰酸酯基预聚物,加入到环氧树脂中,得到性能良好的增韧树脂。用扭辫仪测定了它的动态力学性能,表明有两个损耗峰。透射电镜照片显示有两相结构,预聚物用量为30Phr时,发生明显的相倒转,从固化机理解释了这种现象。     

苯乙烯-苯乙烯磺酸钠共聚物的制备及其流变性能

采用乳液聚合合成了一种可作为聚丙烯(PP)纤维可染改性添加剂的苯乙烯-苯乙烯磺酸钠共聚物P(St-co-NaSS)。通过傅里叶转换红外光谱仪(FT-IR)和核磁共振氢谱仪(~1 H-NMR)对共聚物的苯乙烯磺酸钠结构单元进行了表征,研究了反应条件对共聚物磺化度的影响;通过差示扫描量热仪(DSC)和热重分析仪(TG)研究了磺酸基团的引入对共聚物的玻璃化转变温度和起始分解温度的影响;通过旋转流变仪研究了磺化度对共聚物剪切黏度的影响;初步探讨了PP/P(St-co-NaSS)共混体系的染色性能。结果表明:当反应时间为2h,反应温度为70℃,引发剂质量分数为0.6%,苯乙烯磺酸钠的摩尔分数为0.01时,共聚物的磺化度f=6.68%(零切黏度η0=19 620Pa·s,属牛顿流体);在10~(-2)~10~(-1) s~(-1)的剪切速率范围内,P(St-co-NaSS)表现出假塑性流体的特征,具有较好的加工流动性。对于PP/P(St-co-NaSS)共混体系,使用阳离子染料染色时,染色深度(K/S值)为2.603 2,使用分散染料染色时,K/S值为10.168 8。P(St-co-NaSS)适合作为聚丙烯纤维的可染改性添加剂。     

Peroxide-containing compatibilizer for polypropylene blends with other polymers

An approach to synthesize interfacial active peroxide graft copolymers, so called precompatibilizers, which are suitable for the universal compatibilization of one special polymer with a number of other polymers, has been presented. As example, this approach is illustrated by the reactive fusion of a random peroxide copolymer (VO) with polypropylene (PP) resulting in a VOgPP precompatibilizer. A mathematical model of the process of the VOgPP synthesis and the conduction of a full-factorial experiment have allowed both the optimization of the synthesis conditions and the prediction of its proceeding. During blending PP with other polymers VOgPP localizes across the blend interphases and initiates radical processes leading to the in situ formation of final compatibilizer macromolecules, which are efficient just for the blends where they are formed. The universality of the precompatibilizer concept is demonstrated in PP blends of the thermoplastic/thermoplastic type (with polystyrene and polyethylene) and of the thermoplastic/thermoset type (with unsaturated polyester resin).     

Migration of Stabilizers from Polypropylene into Simulated Food

This study has investigated the migration of stabilizers from three polypropylene materials: a polypropylene homopolymer, a polypropylene block copolymer, and a polypropylene random copolymer in 10% ethanol, 3% acetic acid, 20% ethanol, 50% ethanol, and isooctane according to Regulation (EU) No. 10/2011. Measurements were performed at 20, 40, and 70°C and migration was evaluated from 10?min to 10 days. Measurements were performed by high-performance liquid chromatography (HPLC) with external calibration. The HPLC method provided high correlation coefficients, good precision, good accuracy, and suitable reproducibility. Diffusion coefficients for stabilizers were obtained using a rigorous model based on Fick’s second law and the values were between 6.1?×?10^?13 and 3.8?×?10^?9?cm²?s^?1. By applying an Arrhenius-type equation to the diffusion coefficients, an estimation of activation energy of the diffusion was obtained. The activation energies were from 39.97 to 98.75?kJ?mol^?1 for the stabilizers. The results indicate that the polypropylene material structure influenced the migration rate, which decreased in the order of the increasing crystallinity in the materials. The diffusion coefficients for stabilizers in the polypropylene random copolymer were higher than in the polypropylene block copolymer and polypropylene homopolymer. The random polypropylene copolymer had the lowest activation energy. These results show that a higher diffusion coefficient indicates a higher migration rate, and a system with a lower activation energy allows more migration.     

Dynamic mechanical and solid-state NMR determination of molecular-scale heterogeneity in a raw elastomer,a microcrystalline polymer,and their blend

Dynamic mechanical and solid-state ¹³C nuclear magnetic resonance (NMR) analyses have been used to assess a molecular-scale heterogeneity in a raw elastomer (butadiene-acrylonitrile copolymer elastomer, NBR), a microcrystalline polymer (poly(vinyl chloride), PVC), and their 50/50 blend. The presence of the microcrystalline heterogeneity in PVC and in the blend was characterized by the temperature dependence of the frequency-swept dynamic mechanical behavior. The NMR T_1ρ relaxation experiments with cross-polarization (CP) and magic-angle spinning (MAS) revealed that (1) NBR contained a substantial fraction (ca. 27%) of a molecular-scale heterogeneity identified as butadiene blocks, (2) the fraction of microcrystallites in PVC was ca. 14%, (3) pure phases of both component polymers were present in the blend, dispersed in the mixed matrix, (4) the upper limit of the heterogeneous domains was estimated to be ca. 2.4 nm, and (5) fractions of heterogeneity tend to increase upon blending, indicating that the solubility of the butadiene block and syndiotactic PVC block decreases in the blend. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 709–716, 1997     

低乙烯含量共聚聚丙烯链结构和相结构与应力应变行为的关系

研究了两种典型的低温抗冲共聚聚丙烯(ICPP)的应力应变行为及温度依赖性,其低温应力应变行为揭示ICPP具有优异的低温抗冲性能和综合力学性能的结构本质.从初始弹性模量、屈服应力及断裂伸长随温度变化所显示的变化规律进一步确认了两种ICPP的序列结构特征和相结构特征.断裂伸长变化显示了乙丙橡胶相的增韧作用,屈服应力变化显示了分散相对基质结合紧密程度的影响,弹性模量则与基质的结晶状况和结晶形态有着比较密切的关系,同时也与乙丙橡胶相和聚丙烯基质的玻璃化转变温度密切相关.     

多单体接枝聚丙烯对PBT/PP共混体系的形态结构及力学性能影响研究

研究了甲基丙烯酸缩水甘油酯 (GMA)和苯乙烯 (St)多单体熔融接枝聚丙烯 (PP g (GMA co St) )对聚对苯二甲酸丁二酯 (PBT) 聚丙烯 (PP)共混物的形态结构和力学性能的影响 .利用双螺杆挤出机对PBT PP合金进行共混挤出 ,使用DSC、FT IR和SEM、TEM等手段对共混物进行了分析和相形态观察 ,并测试了力学性能 .实验证明 ,熔融共混过程中PP g (GMA co St)的环氧基团可以与PBT的端羧基发生化学反应 ,就地生成了PBT g PP共聚物 ,该共聚物可对PBT PP合金起到良好的增容剂作用 ,使共混物的相区尺寸显著减小 ,共混物的拉伸强度和冲击强度等力学性能同时得到明显改善 ,达到了弹性体系或小分子增容所难以达到的力学性能平衡的效果 .此外 ,TEM的研究还在PBT PP g (GMA co St)共混物中发现了特殊的微相分离结构     

丙烯腈-苯乙烯共聚物对聚甲醛的热稳定化作用

研究了丙烯腈-苯乙烯(AS)共聚物对聚甲醛(POM)的热稳定化作用. 结果表明, 在动态混炼条件下, 添加少量的AS共聚物可使POM的熔体稳定性和熔融滞留时间明显增大, AS最优添加质量分数为3%; 在静态加热条件下, AS的加入可使POM在升温过程中的分解温度显著提高, 在恒温过程中的失重率明显降低. 在动态或静态条件下, AS共聚物对POM热稳定性的贡献效果一致, 并且同时加入AS和三聚氰胺对POM的热稳定性改善更为显著. 红外分析结果表明, AS对POM的热稳定化作用源于分子链上的氰基对甲醛的有效吸收.     

Synthesis of Propylene Diblock Copolymers via Metallocene and Borane Chemistry

An isotactic chain end unsaturated polypropylene was prepared by the homogeneous metallocene catalyst Et(Ind)₂ZrCl₂ with MAO. Herein, the chain end unsaturated polypropylene proceeded the hydroboration reaction to prepare borane‐containing polypropylene. The borane‐containing polypropylene could be transformed to hydroxyl‐terminated polypropylene, PPOH. And then the polypropylene‐nylon 6 diblock copolymer, PP‐b‐NY6, was synthesized from telechelic PPOH by converting this prepolymer with toluene diisocyanate and using the resulting materials as macroactivators for anionic caprolactam polymerization. Meanwhile, this investigation used borane‐containing polypropylene and oxygen to produce free radicals at the chain end on the polypropylene. Experimental results indicate that the free radical is an effective initiator for the polymerization of methyl methacrylate to produce diblock PP‐b‐PMMA. The block copolymers are characterized by IR, NMR, and DSC analyses. The diblock copolymer is a good compatibilizer for polymer blends.     

相形态对聚合物反应共混过程的影响

通过采用典型的热力学不相容共混体系聚烯烃弹性体/聚苯乙烯(POE/PS),利用流变学和形态研究的方法,考察了不同相形态(海岛结构和双连续结构)对聚合物反应共混过程的影响.研究发现相形态对聚合物原位增容共混反应有显著的影响,界面反应的进程与界面形态的变化能力直接相关.对于双连续结构的共混物,其形态稳定性最差,因而最有利于界面反应的发生;而在海岛结构的共混体系中,界面反应的进程则取决于界面变形的难易程度,黏度比小的体系更容易发生界面反应。     

苯乙烯-甲基丙烯酸四甲基哌啶醇酯共聚物光防护行为的研究

本文用力学性能、分子量、ESR、IR等测定方法,研究比较了大分子受阻胺PDS和小分子受阻胺Tinuvin-770对聚丙烯的光防护作用。结果表明,二者的光防护作用都是通过形成>NO·稳定自由基机理;并能有效地接枝在聚丙烯上,而PDS还具有“微交联“作用。光氧化监测表明,PDS较耐光分解,其光氧化防护中所产生的>NO·稳定自由基在整个老化过程中保持一定的浓度,加之大分子化改善了PDS的热稳定性,耐抽提性,相容性,因而使PDS具有较高的光防护效率。