New polymer syntheses: 59. Homo-and copolyesters of 4-(4′-hydrophenoxy)benzoic acid

The homopolyester of 4-(4′-hydroxyphenoxy)benzoic acid (poly(4-HPBA)), was prepared under two different reaction conditions and compared with a sample provided by another research group. Depending on the synthetic route, different melting points, d.s.c. traces and crystal lattices were found. However, after repeated heating and cooling, one thermodynamically stable modification with a melting point of 370–375°C can be obtained. Copolyesters of 4-hydroxybenzoic acid and 4-(4′-hydroxyphenoxy)benzoic acid were prepared with various molar ratios either in the melt (condensation in bulk) or in solution. These copolyesters were characterized by elemental analyses, ¹H n.m.r. spectroscopy, d.s.c. measurements, wide-angle X-ray scattering measurements at various temperatures, and optical microscopy. Whereas copolyesters prepared in solution do not melt below 500°C, those prepared by polycondensation in bulk show melting points down to approximately 260°C and form a nematic melt.     

Thermal cross-linking and anti-meltdrop properties of copolyester containing phosphorus/magnesium salt composites by in situ polymerization

Polyester is widely used in household products because of its good mechanical properties and wears resistance, but polyester is easy to ignite and inclined to produce droplet, so its application range is limited. The cross-linkable magnesium hydroxide nanoparticles were incorporated into flame-retardant polyester, which enables the phosphorus-containing copolyester with thermal cross-linking and anti-meltdrop properties. The nanoparticles were achieved by in situ polymerization and acted as a nucleating agent for improving the crystalline properties of the copolyester. Furthermore, the nanoparticles also enhanced anti-meltdrop properties and reduced the heat and gas release during the combustion process of the copolyester. The maximum heat release rate and total smoke release reduced by 39.8% and 74.4% compared with pure polyester. Specifically, the combustion products of the nanoparticles and phosphorus flame retardant could act a barrier role by covering the carbon layer to isolate air and heat, thereby resulting in excellent anti-meltdrop properties. The simple modification method reported here realizes the collaborative modification of flame retardant and anti-meltdrop properties of phosphorous flame-retardant copolyesters by thermal cross-linking.     

低熔点快固化聚酯热熔胶的合成与性能研究

在对苯二甲酸二甲酯(DMT)和1,4-丁二醇(BD)合成聚酯体系中引入其它共聚组分,制备了快速结晶的低熔点共聚酯热熔胶,其熔点约为70～120℃。由于熔点越低结晶性能越差,因此在合成聚酯热熔胶的基础上,进一步对其进行改性,且对组成与性能的关系进行了研究。结果表明,聚酯热熔胶的熔点和结晶性能随DMT含量的增加而升高;二元醇体系的配比和含量对熔点和结晶性能有很大影响,当混合二元醇物质的量比为1时具有最低的熔点,BD/HD(1,6-己二醇)体系比EG(乙二醇)/HD体系的结晶速率快,BD/HD体系中结晶速率随HD含量的增加而加快。     

Plane stress fracture toughness of physically aged plasticized PETG as assessed by the essential work of fracture (EWF) method

The plane stress fracture toughness of amorphous copolyester (PETG) sheets plasticized by various amount of neopentylglycol dibenzoate (NPGDB in 0, 5, 10 and 20 wt%) was studied in as-received (AR) and rejuvenated (RJ) states by adopting the essential work of fracture (EWF) method. EWF tests were performed on deeply double-edge notched tensile loaded (DDEN-T) specimens at various deformation rates (2,10 and 100 mm/min) at room temperature. It was established that physical aging strongly affected the EWF terms. The specific yielding-related EWF increased with increasing deformation rate and decreased with increasing plasticizer content. The specific non-essential work and its necking-related constituent, which changed parallel to each other, remained constant up to 10 wt% NPGDB content and decreased afterwards. The plastic zone in the DDEN-T specimens was formed by cold drawing which is governed by the entanglement structure. This was demonstrated by the shape recovery of the plastic zone in the broken DDEN-T specimens after heating them above the T_g of the related PETG compound.     

高收缩共聚酯合成性能与成纤性能研究

通过共聚酯PEIT(间苯二甲酸、对苯二甲酸、乙二醇共聚物)的合成及其全拉伸丝(FDY)纺丝的成功实验,研究了高收缩PEIT共聚物合成工艺中共聚组分间苯二甲酸(IPA)的摩尔百分数对共聚酯PEIT的玻璃化温度、熔点的影响,探讨了该PEIT共聚物的结晶性能及其纺丝工艺条件对高收缩纤维性能的影响。     

含二苯并-14-冠-4冠醚环主链型液晶共聚酯的设计与合成

以4,4-′(α,ω-亚烷基二酰氧)二联苯甲酰氯(M1)、顺(反)式-4,4′-双(4-羟基苯基偶氮)二苯并-14-冠-4(M2、M3)和1,10-癸二醇(M4)为单体,通过溶液共缩聚反应,合成了两个系列新的含冠醚环的主链型液晶共聚酯。共聚酯的分子量不高。单体的化学结构通过IR、UV-Vis1、H-NMR和元素分析等方法确证。共聚酯的性质采用[η]、DSC、TG、WAXD和POM等方法进行了研究。发现所有的共聚酯加热到各自的熔融温度以上都能形成液晶态,在液晶态可以观察到向列相的丝状织构或纹影织构。共聚酯的熔融温度(Tm)和各向同性温度(Ti)随共聚酯分子中柔性间隔基的改变呈规律性变化。     

低熔点共聚酯的流变性研究

由对苯二甲酸(PTA)、间苯二甲酸(IPA)、丁二醇(BDO)共缩聚制备了低熔点共聚酯。采用Rosand RH7型毛细管流变仪对不同摩尔百分比组成的共聚酯的流变性进行了研究。结果显示:低熔点共聚酯是典型的假塑性流体,随着温度升高,剪切黏度下降,非牛顿指数增大;随着剪切速率的增大,低熔点共聚酯黏流活化能降低。比较了两种组成的低熔点共聚酯的流变性,发现随着第三单体IPA的增加,低熔点共聚酯的剪切黏度降低,非牛顿指数减小。分析了第三单体对低熔点共聚酯流变行为的影响。     

多组分共聚酯纤维在碳酸钠/乙二醇中的碱减量处理

研究了多组分共聚酯在碳酸钠(Na2CO3)的有机溶剂乙二醇溶液中的碱处理条件,如温度、碱浓度和碱处理时间与纤维减量率的关系,考察了处理后纤维表面形态和纤维的强度变化,利用红外光谱分析了碱处理残留物的结构。研究结果表明,在乙二醇中,以低浓度弱碱Na2CO3代替强碱NaOH同样可以获得较为理想的碱处理效果。在温度为100～120℃、时间为60～120 min下进行碱处理,碱减率保持在20%左右,纤维强度保持在80%以上;红外光谱表明,共聚酯在乙二醇/Na2CO3中的碱解产物与其在水/NaOH中的一致。     

丙三醇对PBST共聚酯结构和性能的影响

基于生物可降解性聚酯——聚丁二酸-共-对苯二甲酸丁二醇酯(PBST),通过原位添加不同含量的丙三醇作为第四单体,制备出共聚改性的PBST共聚酯。通过核磁共振仪(NMR)、差示扫描量热仪(DSC)、广角X射线衍射仪(WAXD)及接触角测试,分别对PBST共聚酯的结构和性能进行了研究。结果表明:丙三醇的加入并没有改变PBST共聚酯的化学组成和结构;随着丙三醇含量的增加,共聚酯的玻璃化转变温度先上升后下降,而熔点是逐步降低的;改性前后和拉伸前后PBST的晶型均未发生变化,但分子结构的规整性受到破坏,且发生拉伸诱导取向;改性PBST共聚酯的亲水性能较纯PBST有明显提高。     

Effect of chemical compositional distribution on solid-state structures and properties of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

Solid-state structures and crystallization kinetics were compared between poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [PHB-HV] and PHB/PHB-HV blends exhibiting the cocrystallization. As cocrystallizable blends, both the blends showing complete cocrystallization, i.e. the PHB content in the crystalline phase is the same as that of the whole blends, and the blends forming a PHB-rich crystalline phase were used. The PHB and HV content in the cocrystalline phase were determined by high-resolution solid-state ¹³C NMR spectroscopy. In order to determine these contents with a minimum experimental error, site-specific ¹³C-labeled PHB/PHB-HV blends and PHB-HV copolymers were used. The crystallinity, lamellar structures, spherulite growth rate, and melting behavior were analyzed by wide-angle X-ray diffraction, small-angle X-ray scattering, polarized microscope, and differential scanning calorimetry, respectively. In these data, no difference was observed between the complete-cocrystallizable PHB/PHB-HV blends and the PHB-HV copolymers with the same overall HV content. On the other hand, the PHB/PHB-HV blends forming a PHB-rich crystalline phase has the amorphous layers thicker than that of the PHB-HV copolymers with the same overall HV content. Based on the collected data, the similarity and differences in the solid-state structures and properties between PHB-HV copolymers and cocrystallizable PHB/PHB-HV blends were discussed.