Alkylpolyglycoside inducing poly (butylene terephthalate) non-woven graft copolymerization of chitosan

In order to improve the wettability and biocompatibility of the poly （butylene terephthalate） non-woven （PBTNW）, the method of surface modification is used to graft copolymerization of chitosan （CS） onto the PBTNW under alkylpolyglycoside （APG） inducing. The product is thoroughly characterized with the Fourier transform infrared spectroscopy （FrIR）, the electron spectroscopy for chemical analysis （ESCA）, the thermogravimetric （TG） and the scanning electron microscopy （SEM）. It is found that chitosan is successfully grafted onto PBTNW. In addition, the water contact angles, hemolysis tests and cytotoxicity evaluation tests show an improvement in wettability and biocompatihility as a result of graft copolymerization of chitosan. So the CS-grafted PBTNW exhibits greater superiority than the original PBTNW. The CS-grafted PBTNW can be a candidate for blood filter materials and other medical applications.

Nanocellulose: Effect on Thermal, Structural, Molecular Mobility and Rheological Characteristics of Poly(Butylenes Adipate-Co-Butylene Terephthalate) Nanocomposites

The concern with environmental preservation is a very current and relevant topic. Regarding polymers, the search for potentially ecofriendly matters has been the subject of scientific research. In this context, this work aimed to study the effect of adding nanocellulose (nCE) with 1, 3, and 5 wt.% on poly(butylene adipate-co-butylene terephthalate) (PBAT). Thermal, structural, relaxometric, and rheological assessments were carried out. Quantitative evaluation of PBAT copolymer by high field NMR revealed 56.4 and 43.6 m.% of the butylene adipate and butylene terephthalate segments, respectively. WAXD measurement on the deconvoluted diffraction patterns identified that nCE was a mixing of Cellulose I and Cellulose II polymorph structures. At any composition, nanocellulose interfered with the PBAT crystallisation process. Also, a series of new PBAT crystallographic planes appeared as a function of nanocellulose content. PBAT hydrogen molecular relaxation varied randomly with nanocellulose content and had a strong effect on the hydrogen relaxation. PBAT cold crystallisation and melting temperatures (Tcc and Tm) were almost unchangeable. Although Tcc did not change during polymer solidification from PBAT molten state, the sample’s degree of crystallinity varied with composition through the transcrystallization phenomenon. Nanocomposite thermal stability decreased possibly owing to the catalytic action of sulfonated amorphous cellulose chains. For the sample with 3 wt.% of nanocellulose, the highest values of complex viscosity and storage modulus were achieved.

TRANSESTERIFICATION OF POLY(BISPHENOL A CARBONATE) WITH AROMATIC AND ALIPHATIC SEGMENTS IN BUTYLENE TEREPHTHALATE-CAPROLACTONE COPOLYESTER

In this article, the transesterification of poly(bisphenol A carbonate) (PC) with butylene terephthalate-caprolactone copolyester at a weight ratio 50/50 (BCL(21)) was thoroughly investigated by proton nuclear magnetic resonance spectroscopy ('H-NMR), in conjunction with a model compound. The 1 H-NMR results of the annealed blend PC/BCL(21) show that the formation of bisphenol A-terephthalate ester units is the same as in the annealed blend of PC with PBT, and the transesterification actually occurs between PC and butylene terephthalate (BT) segments in BCL(21). By comparison with the model compound bisphenol A dibutyrate, the new signal appearing at δ= 2.56 in the 1H-NMR spectrum confirms the existence of bisphenol A caprolactone ester units resulting from the exchange reaction of PC with caprolactone (CL) segments. 1H-NMR analysis of the transesterification rates reveals that the reaction of PC with aromatic and aliphatic segments in BCL(21) proceeds in a random manner. The miscibility of the blend PC/BCL(21) copolyester is favorable for the transesterification of PC with BT segments and CL segments.

Enzymatic Modification of Poly (ethylene terephthalate) Fiber with Lipase from Aspergillus oryzae

Lipase preparation from Aspergillus oryzae could act on ester bonds on the surface of poly （ethylene terephthalate） fibers and a possible hydrolytic product mono （2-hydroxyethyl） terephthalate was released. After the iipase modification, there were more carboxyi groups on the treated poly （ethylene terephthalate） fabric surface that resulted in binding with more cationic dyes. Increased hydrophilicity and antistatic ability of poly （ethylene terephthalate） samples were found based on moisture regain, water contact angle and static half decay time.

Crystallization and Dynamic Mechanical Behavior of Coir Fiber Reinforced Poly(Butylene Succinate)Biocomposites

The crystallization behavior,crystal morphology and form,and viscoelastic behavior of poly(butylene succinate)(PBS)and coir fiber/PBS composites(CPB)were investigated by differential scanning calorimetry(DSC),polarized optical microscopy(POM),X-ray diffraction(XRD)and dynamic mechanical analysis(DMA).The results of DSC measurement show that the crystallization temperature increases with the filling of coir fibers.POM images reveal that the spherulitic size and crystallization behavior of PBS are influenced by the coir fibers in the composites.XRD curves show that the crystal form of pure PBS and CPB are remaining almost identical.In addition,the storage modulus of CPB significantly increases comparing with the pure PBS.This predicted the dimensional stability and improved load-deformation temperature.In conclusion,the addition of coir fibers has a significant effect on the thermal properties of the matrix.

Non-isothermal Crystallization Kinetics of Modified Poly(ethylene terephthalate) with Ultraviolet Protection

The non-isothermal crystallization kinetics of modified poly(ethylene terephthalate) (PET) with the function of ultraviolet (UV) protection was studied by means of differential scanning calorimetry. The kinetics of the modified polymer under non-isothermal crystallization was analyzed by Ozawa equation. The crystallization behavior of the modified polymer obeyed Ozawa theory. The additives in the polymer whose function was UV-resistant acted as crystal nucleus in the processing of crystallization, which resulted in the increase of Avrami index and the crystallization rate of the cooling system.

Alkaline earth metal-based minerals/wastes-catalyzed pyrolysis of poly(ethylene terephthalate)/poly(butylene terephthalate)for benzenes-enriched oil production

The pyrolysis of poly(ethylene terephthalate)(PET)/poly(butylene terephthalate)(PBT)catalyzed by five alkaline earth metal-based minerals/wastes,namely calcined dolomite,calcite,magnesite,calcium carbide slag(CCS),and ophicalcitum,was conducted by a pyrolyzer-gas chromatography-mass spectrometer(Py-GC-MS)with the objective of recovering benzenes-enriched oil.Compared with magnesium-based catalysts and pure CaO,the calcium-based catalysts with calcium hydroxide as the main component performed better catalytic effect,which could simultaneously promote the hydrolysis of ester products and the decarboxylation of aromatic acids after hydrolysis.For PET,the addition of solid base catalysts at 600℃promoted the complete degradation of aromatic acids and aryl esters,which accounted for 32.6%and 30.7%of the pyrolysis oil,respectively.The content of benzene in oil increased from 8.8%to 31.7%–78.8%.For PBT,the addition of solid base catalysts at 600℃completely decomposed the aromatic acids,which accounted for 67.1%of the pyrolysis oil,and the content of benzene in oil increased from 12.3%to 34.5%–81.0%.During the deoxygenation of polyester pyrolysis products,increasing temperature was more effective for the decomposition/conversion of acetone and tetrahydrofuran,while increasing the alkalinity of the reaction environment contributed to the rapid decrease in acetaldehyde and aryl ketone contents.

淀粉的改性及其对淀粉/PBAT/碳酸钙复合材料结构和性能的影响

采用甘油、六偏磷酸钠(SHMP)和聚乙二醇(PEG)改性木薯淀粉并制备改性淀粉/聚己二酸对苯二甲酸丁二醇酯(PBAT)/碳酸钙复合材料,采用傅里叶变换红外光谱仪(FTIR)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)、差示扫描量热仪(DSC)、热失重分析仪(TG)等对改性淀粉和复合材料进行分析,研究改性淀粉对复合材料结构和性能的影响。结果表明,甘油的外增塑作用和PEG、SHMP的内增塑作用使淀粉化学结构改变、无定形成分增加,淀粉颗粒由饱满的圆球状变成了不规则的大颗粒,250℃前稳定性提高,250℃后稳定性降低,有利于使用加工和热分解,不同改性剂改性淀粉结晶熔融行为存在差异;复合不会改变PBAT、碳酸钙和淀粉的原有晶型,但相容性的差异导致复合材料热性能和力学性能的差异,改性淀粉增加了复合材料的韧性,甘油、SHMP和PEG的协同改性使淀粉与PBAT、碳酸钙的相容性最佳,复合材料的综合性能最好。

木质素在合成可降解高分子材料中的应用研究进展

简述了木质素的结构、特性和分类情况,并综述了近年来国内外使用木质素来增强和改善聚对苯二甲酸-己二酸丁二酯、聚乳酸、聚己内酯和聚丁二酸丁二酯等合成可降解高分子材料性能的研究进展。指出木质素与合成可降解高分子材料复合可以赋予复合材料多种功能特性,如紫外屏蔽、抗菌、阻隔等,并能改善材料的生物降解性能,同时实现降本增效的目标。最后提出当前木质素与合成可降解高分子材料复合材料工业化生产应用存在的问题,并对木质素基全生物降解复合材料的未来研究趋势进行展望。

Synthesis and Characterization of Poly（butylene adipate-co-terephthalate） Catalyzed by Rare Earth Stearates

Rare earth （Nd, Y, La, Dy） stearates have been synthesized and used as single component catalysts for the polycondensation of dimethyl terephthalate, adipic acid and 1,4-butanediol for the first time preparing biodegradable poly（butylene adipate-co-terephthalate） （PBAT） with high molecular weight, The microstructures of PBAT were characterized by ^1H NMR spectra. The PBAT exhibits good mechanical properties such as high tensile strength （ca. 20 MPa） and long break elongation （〉700%）.

Effects of Zinc Oxide Nanoparticles on the Morphology and Viscoelastic Properties of Polyamide 6/Poly(butylene terephthalate) Blends

The morphology of polyamide 6/poly(butylene terephthalate)(PA6/PBT, 70/30, W/W) blends filled with pristine Zinc oxide(ZnO) nanoparticles and ZnO surface-modified by γ-glycidoxypropyltrimethoxysilane(K-ZnO) was investigated. The incorporation of ZnO and K-ZnO by one-step compounding both resulted in a smaller size and narrower distribution of PBT domains and the effect of ZnO was greater than K-ZnO. To reveal the underlying mechanism, two-step compounding in which ZnO or K-ZnO was premixed with PA6 or PBT was conducted and the finest morphology was achieved when mixing PA6 with premixed PBT/ZnO. Transmission electron microscopy(TEM) demonstrated that ZnO was distributed in PBT in all cases and K-ZnO was enriched at the interface except when K-ZnO was premixed with PBT. ZnO and K-ZnO caused a deterioration in the melt rheological properties of PBT, which played a dominating role in the morphological changes. In addition, the interfacial localization of K-ZnO enhanced the dynamic rheological properties of PA6/PBT blends substantially.

Preparation of Core-Shell Structured Polyacrylic Modifiers and Effects of the Core-Shell Weight Ratio on Toughening of Poly(butylene terephthalate)

Core-shell structured polyacrylic（named CSSP） impact modifiers consisting of a rubbery poly（n-butyl acrylate） core and a rigid poly（methyl methacrylate） shell with a size of about 353 nm were prepared by seed emulsion polymerization. The CSSP modifiers with different core-shell weight ratios（90/10, 85/15, 80/20, 75/25, 70/30, 65/35 and 60/40） were used to modify the toughness of poly（butylene terephthalate）（PBT） by melt blending. It was found that the polymerization had a very high instantaneous conversion（ 95.7%） and overall conversion（99.7%）. The morphology of the core-shell structure was confirmed by means of transmission electron microscopy. Scanning electron microscopy was used to observe the morphology of the fractured surfaces. Differential scanning calorimeter was used to study the crystallization behaviors of PBT/CSSP blends. The dynamic mechanical analyses of PBT/CSSP blends showed two merged transition peaks of PBT matrix, with the presence of CSSP core-shell structured modifier, that were responsible for the improvement of PBT toughness. The results indicated that the notch impact strength of PBT/CSSP blends with a core-shell weight ratio of 75/25 was almost 8.64 times greater than that of pure PBT, and the mechanical properties agreed well with the SEM observation.

界面强化增容反应程度对PLA/PBAT共混物结构和性能的影响

通过熔融共混法将具有不同环氧含量的界面增容剂(Joncryl ADR-4400和Joncryl ADR-4468)引入聚乳酸(PLA)/聚对苯二甲酸-己二酸丁二醇酯(PBAT)共混物中,并采用转矩流变仪、傅里叶红外光谱仪、差示扫描量热仪、动态热机械分析仪、流变仪、电子万能试验机和扫描电子显微镜等仪器研究界面增容反应程度对PLA/PBAT共混物微观分子链行为及宏观性能的影响。结果表明,界面增容剂结构中的环氧基团通过与PLA和PBAT的羟基或羧基反应,在两相界面处形成微交联结构,增强两相界面的相互作用,最终提高共混物的力学性能。材料的宏观性能测试表明,与环氧当量较高的ADR-4400相比,ADR-4468的引入形成了更加完善的微交联结构,界面相互作用更强,使PLA/PBAT/ADR-4468共混物中PLA的玻璃化转变温度提高至54.7℃。当ADR-4468添加量为0.75%时,PLA/PBAT/ADR-4468共混物拉伸强度达36.4 MPa,断裂伸长率达302%,缺口冲击强度可达9.6 kJ/m^(2),较未改性PLA/PBAT分别提高18%、560%和69%,材料刚韧平衡性优良。

静电纺丝HNTs/PBST复合纳米纤维膜的制备及其空气过滤性能研究

采用静电纺丝工艺,以可生物降解的聚丁二酸丁二醇-共-对苯二甲酸丁二醇酯(PBST)为原料,改性埃洛石纳米管(HNTs)为驻极体,制备了HNTs/PBST复合纳米纤维膜,探讨了HNTs对PBST纳米纤维膜的形貌、结构及空气过滤性能的影响。实验结果表明,改性HNTs添加量为10%(w)即可使PBST纳米纤维直径细化,协同增强了纳米纤维膜的物理筛分效应及静电吸引能力,显著提升了材料的综合过滤性能,HNTs/PBST复合纳米纤维膜对PM0.3的过滤效率高达96.67%,且过滤阻力仅为90.5 Pa。

硅油/PBAT复合材料的制备及耐热性能研究

聚己二酸-对苯二甲酸丁二醇酯(PBAT)作为生物可降解材料在包装领域应用广泛,但存在耐热稳定性差、易受环境影响发生老化等问题。本文采用熔融共混的方法,制备了不同添加比的端羟基硅油(SO)/PBAT复合材料,探讨耐热添加助剂对PBAT热稳定性和可降解性能的影响。结果表明,复合材料具有更好的耐热性,当SO质量分数达0.6%时,最终分解温度提高到411.02℃,热分解速率较纯PBAT降低了10.34%。SO的添加显著延缓了PBAT的热氧老化,SO/PBAT降解稳定性得到提升,热氧降解30 d后0.6%SO/PBAT的拉伸强度保持率较纯PBAT提高了27.48%,质量损失率较纯PBAT降低了20.78%。此外,复合材料的分子量下降幅度减缓,低场核磁反演曲线说明SO的添加并未改变PBAT的热氧老化机理。

Dual Effects of Interfacial Interaction and Geometric Constraints on Structural Formation of Poly(butylene terephthalate)Nanorods

When the size of the material is smaller than the size of the molecular chain,new nanostructures can be formed by crystallizing polymers in nanoporous alumina.However,the effect of pore wall and geometric constraints on polymer nanostructures remains unclear.In this study,we demonstrate three new restricted nanostructures{upright-,flat-and tilting-ring}in polybutylene terephthalate(PBT)nanorods prepared from nanoporous alumina.The dual effects of geometrical constraints and interfacial interactions on the formation of PBT nanostructures were investigated for the first time by using X-ray diffraction and Cerius^(2) modeling packages.Under weak constraints,the interaction between pore wall and the PBT rings is dominant and the ring plane tends to be parallel to the pore wall and radiate outward to grow the upright-ring crystals.Surprisingly,in strong 2D confinement,a structural formation reversal occurs and geometrical constraints overpower the effect of pore wall.Rings tend to pile up vertically or obliquely along the long axis of the rod,so the flat-and tilting-ring crystals are predominate in the constrained system.In principle,our study of the nanostructure formation based on the geometrical constraints and the pore wall interfacial effects could provide a new route to manipulate the chain assembly at the nanoscale,further improving the performance of polymer nanomaterial.

基于废弃PET的环氧超支化聚酯扩链剂应用性能

以废弃聚对苯二甲酸乙二酯(PET)的降解产物为核心,制备了环氧超支化聚酯扩链剂(EHBP),探究了该扩链剂对聚对苯二甲酸-己二酸丁二酯/聚乳酸/碳酸钙(PBAT/PLA/CaCO_(3))三元复合材料微观结构、热性能、力学性能的影响。结果表明,以PET降解产物制备的EHBP对复合材料有明显的增容作用。扩链剂中的高活性环氧基团能够与PBAT和PLA上的端羧基、端羟基发生开环加成反应,形成扩链大分子以增强PBAT和PLA之间的界面相互作用。当EHBP添加量达到0.6份时,可以明显观察到两相间变得模糊、孔洞减少。缺口冲击强度由6.48 kJ/m^(2)增加到43.02 kJ/m^(2),拉伸强度由10.15 MPa增加到24.59 MPa,断裂伸长率由11.8%增加到56.72%。

二步共混法制备PBAT/PGA材料及其性能

采用二步共混法制备改性聚己二酸/对苯二甲酸丁二酯/聚乙醇酸(PBAT/PGA)共混物,其中,添加多元环氧化合物(ADR)为扩链剂和反应增容剂。首先通过第一步高温熔融共混(235℃),制备得到PBAT/PGA二元预混物;随后添加ADR进行低温共混(170℃),最终得到(PBAT/PGA)/ADR二步法共混物。并采用常见的一步共混法来制备同样配比的PBAT/PGA/ADR共混物作为比照。研究不同加工方式和ADR添加量对共混物流变行为、微观形貌和拉伸性能等方面的影响。结果表明,采用二步共混法,可在保持较大PGA分散相尺寸的同时,又能兼顾改善PBAT/PGA两相界面相容性。相对于PBAT/PGA(65/35)二元共混物和一步法共混物,二步法共混物在拉伸屈服强度、拉伸弹性模量和断裂伸长率方面具有更为均衡的性能。如当ADR添加量为0.8份时,(PBAT/PGA)/ADR(65/35/0.8)二步法共混物的拉伸屈服强度、拉伸弹性模量和断裂伸长率可分别达到11.57 MPa,160.88 MPa和309.5%。此外,测试结果表明,相对于二步法共混物,ADR的扩链/支化反应对一步法共混物流变行为的影响更为显著。

高性能PET珠粒泡沫的制备及机理

聚对苯二甲酸乙二醇酯(PET)高温熔体强度低,难以通过超临界二氧化碳(scCO_(2))发泡技术制备高强度、高膨胀率的珠粒泡沫材料。本文建立了一种基于原位熔体增强的发泡新技术,利用聚对苯二甲酸丁二醇酯(PBT)有效负载扩链剂均苯四甲酸二酐(PMDA)得到扩链剂负载母粒(PMDA-MB)。通过PMDA-MB与PET的共混挤出制备了改性PET,有效地延长并支化PET分子链,大幅度地提升了熔体黏度,有效地改善了PET的发泡性能。进一步通过scCO_(2)珠粒发泡技术制备了具有优异的泡孔结构和高膨胀率的PET泡沫材料。结果表明,当PMDA-MB的质量分数为3%、发泡温度为244℃、发泡压力为25 MPa时,所得PET泡沫平均泡孔尺寸为100.8μm,泡孔密度1.91×10^(6)个/cm^(3),膨胀率达15.2,而且该PET珠粒泡沫材料的力学性能优良,拉伸强度达2.54 MPa,压缩强度达4.08 MPa。

PBAT/纤维素复合材料发泡行为研究

利用熔融共混法制备了己二酸丁二醇酯和对苯二甲酸丁二醇酯的共聚物(PBAT)/纤维素复合材料,将其压板后,以超临界CO_(2)为物理发泡剂,利用间歇式釜压升降温发泡方法,制备了PBAT/纤维素发泡材料。对复合材料的结晶性能,流变性能,发泡材料的发泡性能,压缩回弹性能进行研究。结果表明,纤维素的加入可以促进PBAT样品结晶,随着纤维素含量的增大,PBAT样品冷结晶峰先右移后左移,同时提升了复合材料的储能模量和复数黏度;发泡后,随着纤维素含量的增大,发泡样品的发泡倍率先增大后减小,而泡孔密度先减小后增大再减小;以PBAT-G-GMA为相容剂改善PBAT与纤维素的相容性,发泡样品泡孔形态稳定,纤维素的增加可以增加发泡样品的韧性;发泡样品在130℃浸泡2 h降温泄压后,随着泄压温度的升高,发泡样品的泡孔密度减小,泡孔尺寸及发泡倍率增大;当泄压温度为80℃,纤维素粉含量为10份时,发泡倍率达到13.06倍,泡孔密度为0.37×10^(10)个/cm^(3)。