Enzymatic Degradation of Poly(butylenesuccinate)/Thermoplastic Starch Blend

The degradation of thermoplastic starch blend in the presence of commerciala-amylase and unpurified amylase of microbial origin was investigated.The blends consisting of thermoplastic starch and poly(butylene succinate)have potential use in packaging applications thus,it is essential to establish susceptibility to degradation.Molar mass loss,gravimetric weight loss,and molecular structure were evaluated.The changes in the surface were observed with scanning electron microscopy.It was confirmed that there was a significant difference in gravimetric weight loss between the blends degraded in two different solutions.Unpurified enzymes of microbial origin,produced by Rhizopus oryzae cultures decomposed analyzed materials more efficiently than purified commercial ones.Moreover,it was proved that in applied conditions,the molar mass of PBS fraction did not change significantly.

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.

Thermal Behavior and Crystal Transition of Biodegradable Poly(butylenes adipate)Revealed by Two-Dimensional Correlation Spectroscopy

In the present study,thermal behavior and crystal transition of pure poly(butylene adipate)(PBA)upon heating process were investigated by FTIR spectroscopy.To gain further insight into the thermal behavior alteration and the phase transition of PBA,we performed two-dimensional(2D)correlation analysis.We found thatβ-form PBA crystal undergoes not only the melting process but also crystal transition upon the heating process.

洋葱假单胞菌产脂肪酶条件的优化

采用Rashid N p-nPP比色法,通过单因素试验和正交试验对洋葱假单胞菌(Pseudomonas cepacia)产脂肪酶的培养基主要成分和发酵条件进行优化,以提高聚丁二酸丁二醇酯(PBS)的生物降解速率。结果表明,该菌种产脂肪酶的最适培养基为菜子油5.0 g/L,酵母膏0.5 g/L,乳化剂Tween-60 2.5 g/L,培养基初始pH 8.0;最适培养条件为接种量9%,培养温度35℃,摇床转速130 r/min,培养时间3 d。在此优化培养基条件下,洋葱假单胞菌产脂肪酶活性可达32.935 U/mL。

降解菌株的筛选及其对聚丁二酸丁二醇酯薄膜的降解

从活性污泥中筛选得到1株具有聚丁二酸丁二醇酯(PBS)降解能力的菌株LSU 1601,经菌体形态特征、菌落培养特征、生理生化鉴定和16S rDNA基因序列分析,初步鉴定为德氏食酸菌(Acidovorax de1afiedii)。结果表明,菌株LSU1601在培养温度为30℃、培养基起始pH值为6.8、培养时间为48 h以及振荡转速为120 r/min的条件下,具有较高的产PBS降解酶的能力;同时菌株在培养温度为30℃,培养基起始pH值为6.8的条件下,经84 h的培养,对PBS薄膜的降解率可达到48.2%;经微生物降解作用,PBS薄膜表面出现明显侵蚀痕迹,且随着降解时间的增加,侵蚀作用更加明显;PBS经微生物降解产生了1,4丁二醇单体、1,4-丁二酸单体以及丁二酸-丁二醇二聚体,未发现其他的寡聚体。

聚乳酸与聚丁二酸丁二醇酯共混体系发泡行为的研究

通过熔融共混法制备聚乳酸/聚丁二酸丁二醇酯(PLA/PBS)共混体系和PLA/PBS/反应型增容剂(Cp)共混体系,并通过间歇式釜压发泡成型制得泡沫样品,研究了PLA/PBS共混体系和PLA/PBS/Cp共混体系的结晶行为、相态结构、流变行为和发泡行为。结果表明,PBS的加入对PLA降温结晶的影响不大,其熔体弹性有所提升,且PBS含量的变化对共混体系泡孔形态的影响较小;在PLA/PBS/Cp共混体系中,Cp的加入对共混体系中PLA的结晶性能有明显的提高;另外随着Cp含量的增加,其熔体弹性也显著增加;Cp可以有效地提高PLA与PBS间的相容性,改善泡孔的形态。

不同端基结构聚丁二酸丁二醇酯的合成和生物降解研究

以丁二酸、丁二醇为原料,通过对不同端基的聚丁二酸丁二醇酯(PBS)进行合成和降解,研究了羟基封端、羧基封端和等摩尔比的PBS在堆肥土土壤悬浮液中的降解情况。通过检测降解过程中失重率的变化及降解前后薄膜表面形貌的变化,得出不同端基结构PBS的降解性能。

THERMAL PROPERTY, MISCIBILITY AND CRYSTALLIZATION BEHAVIOR OF POLY(3-HYDROXYBUTYRATE-co-3-YDROXYHEXANOATE) AND POLY(BUTYLENE SUCCINATE-ADIPATE) (PHBHHX/PBSA) BLENDS

Blends of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) and poly(butylene succinate-adipate) (PBSA), both biodegradable semicrystalline polyesters, were prepared with the ratio of PHBHHx/PBSA ranging from 80/20 to 20/80 by melt mixing method. Differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), dynamic mechanical thermal analysis (DMA), polarizing optical microscopy (POM) and wide angle X-ray diffractometer (WAXD) were used to study the miscibility and crystallization behavior of PHBHHx/PBSA blends. Experimental results indicate that PHBHHx is immiscible with PBSA as shown by the almost unchanged glass transition temperature and the biphasic melt.

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.

MISCIBILITY,CRYSTALLIZATION AND MECHANICAL PROPERTIES OF PPC/PBS BLENDS

In this paper, melt blends of poly（propylene carbonate） （PPC） with poly（butylene succinate） （PBS） were characterized by dynamic mechanical analysis （DMA）, differential scanning calorimetry （DSC）, tensile testing, wide-angle X-ray diffraction （WAXD）, polarized optical microscopy and thermogravimetric analysis （TGA）. The results indicated that the glass transition temperature of PPC in the 90/10 PPC/PBS blend was decreased by about 11 K comparing with that of pure PPC. The presence of 10% PBS was partially miscible with PPC. The 90/10 PPC/PBS blend had better impact and tensile strength than those of the other PPC/PBS blends. The glass transition temperature of PPC in the 80/20, 70/30, and 60/40 PPC/PBS blends was improved by about 4.9 K, 4.2 K, and 13 K comparing with that of pure PPC, respectively; which indicated the immiscibility between PPC and PBS. The DSC results indicated that the crystallization of PBS became more difficult when the PPC content increased. The matrix of PPC hindered the crystallization process of PBS. While the content of PBS was above 20%, significant crystallization-induced phase separation was observed by polarized optical microscopy. It was found from the WAXD analysis that the crystal structure of PBS did not change, and the degree of crystallinity increased with increasing PBS content in the PPC/PBS blends.

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。

Composition Dependence of the Thermal Behavior,Morphology and Properties of Biodegradable PBS/PTMO Segment Block Copolymer

A series of aliphatic biodegradable poly（ether-ester）s based on poly（butylene succinate）（PBS）as hard segment and poly（tetramethylene oxide）（PTMO,M_n=1 000 g/mol） as soft segment were synthesized.The composition dependence of thermal behavior,morphology and mechanical properties was investigated by differential scanning calorimetry（DSC）,atomic force microscopy（AFM）,and tensile testing.The crystallization temperature（T_c） and melting temperature（T_m） of the PBS block within poly（ether-ester）s decrease steadily at first,but decrease sharply with PTMO content above 50 wt%.Two crystallization peaks were detected for PTMO in PBSPTMO60 sample,suggesting the occurrence of fractionated crystallization.The crystallization enthalpies（△H_c） and melting enthalpies（△H_m） of PBS block decrease at first,then increase as PTMO content increases further.AFM has demonstrated that phase-separated morphology transforms from a phase of continuous hard matrix to one of continuous soft matrix containing isolated hard domain as PTMO content is increased.Finally,the results of tensile testing show that the poly（ether-ester）s present the behavior of plastics when PTMO content is below 40 wt%,and of thermoplastic elastomers with PTMO content above 50 wt%.By varying the composition of copolymer,the aliphatic poly（ether-ester）s plastics,or especially biodegradable aliphatic poly（ether-ester）s thermoplastic elastomers can be obtained.

Improving Polylactide Toughness by Plasticizing with Low Molecular Weight Polylactide-Poly(Butylene Succinate)Copolymer

A low-molecular-weight polylactide-poly(butylene succinate)(PLA-PBS)copolymer was synthesized and incorporated into polylactide(PLA)as a novel toughening agent by solvent casting.The copolymer had the same chemical structure and function as PLA and it was used as a plasticizer to PLA.The copolymer was blended with PLA at a weight ratio from 2 to 10 wt%.Phase separation between PLA and PLA-PBS was not observed from their scanning electron microscopy(SEM)images and the crystal structure of PLA almost remained unchanged based on the X-ray diffraction(XRD)measurement.The melt flow index(MFI)of the blends was higher as the amount of PLA-PBS increased,indicating that the block copolymer did improve the mobility of the PLA chains.Moreover,tensile tests revealed that PLA with greater PLA-PBS copolymer exhibited higher elongation at break and it reached the maximum at 8 wt%of PLA-PBS in PLA,which was around 6 times higher than that of pure PLA.Furthermore,the glass transition temperature,measured by differential scanning calorimetry(DSC),markedly decreased with an increasing amount of the copolymer as it decreased from 61.2℃ for pure PLA to 41.3℃when it was blended with 10 wt%PLA-PBS copolymer.Therefore,the PLA-PBS copolymer was shown to be a promising plasticizer for fully biobased and toughened PLA.

DSC Study of Thermal Properties of Biodegradable Poly(Butylene Succinate-co-terephthalate)

Poly （ butylene succinate ） （ PBS ）, poly （ butylene terephthalate） （PBT） and poly （butylene succirmte-coterephthalate） （PBST）s were synthesized from dimethyl succinate and/or dimethyl terephthalate reacting with 1,4- butanediol through a process of transesterification/ polycondmsation in the presence of a high effective catalyst and characterized by means of GPC and DSC. The investigation was mainly focused on the influence of content of terephthalate units on the molecular weight and thermal properties of resulting polymers. It is revealed that the melting temperature and crystallinity of synthesized polymers decrease first with the increase of terephthalate units, then shift to rise gradually by DSC measurements. The results of Flory equation suggest sequence structure of PBSTs is random.

Construction and evaluation of co-electrospun poly (butylene succinate)/gelatin materials as potential vascular grafts

In this study,a series of poly(butylene succinate)(PBSU)/gelatin composites were prepared by electrospinning.The morphology,physicochemical analysis,biomechanical properties,biocompatibility,and biodegradability of the materials were evaluated.The results showed that the ultimate tensile stress of the vascular PBSU/gelatin grafts at(95/5),(90/10),(85/15),and(80/20)was(4.17±0.54)MPa,(3.81±0.44)MPa,2.94±0.69 MPa and 2.11±0.72 MPa respectively,and the burst pressure was(282.7±22.3)kPa,(295.3±3.9)kPa,(306.8±13.9)kPa and(307.6±9.0)kPa respectively,which met the requirements of tissue-engineered blood vessels.Furthermore,the addition of gelatin improved the hydrophilicity and degradation properties of PBSU,thus enhancing cell adhesion and promoting the inward growth of vascular smooth muscle cells.In summary,the research in this paper provides a useful reference for the preparation and optimization of vascular scaffolds.

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.

Effect of Mixing Strategy on the Structure-Properties of the PLA/PBAT Blends Incorporated with CNC

Polylactide(PLA)/poly(butylene adipate-co-terephthalate)(PBAT)blend nanocomposites including 3 wt%of cel-lulose nanocrystals(CNCs)were prepared by melt compounding method in a twin-screw extruder and an inter-nal mixer.Blend nanocomposites were formulated by diluting three different masterbatches prepared by solution casting method that contained 7 wt%of CNC.These masterbatches were:(m1)PLA/PBAT/CNC masterbatch;(m2)PLA/CNC masterbatch;and(m3)PBAT/CNC masterbatch.These were to explore how different prepara-tion methods affect the dispersion and localization of CNC and hence the properties of PLA/PBAT/CNC blend nanocomposites.Scanning electron microscopy(SEM)was used to study the structural changes of the blends.Rheological properties of PLA/PBAT blends and PLA/PBAT/CNC blend nanocomposites were also investigated.In the samples prepared by internal mixer,the rheological behavior of blend nanocomposite prepared through premixing of CNC particles with PLA showed a transition from liquid-like to a gel-like behavior.According to the rheological results and differential scanning calorimetry(DSC)analysis,it was found that the CNC overall enhanced the viscoelastic properties of blends and improved the PLA crystallization,respectively.Dynamic mechanical analysis(DMA)illustrated that the incorporation of CNC also enhanced the elastic modulus of PLA/PBAT blends specifically above the glass transition temperature of PLA.The expected improvements in mechanical properties did not occur due to the possible existence of residual solvent in the blends.

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.

Influencing Factors and Process on <i>in Situ</i>Degradation of Poly(<i>Butylene Succinate</i>) Film by Strain <i>Bionectria ochroleuca</i>BFM-X1 in Soil

This is the first report on the PBS film degraded by any Bionectria ochroleuca fungal strain. The fungal strain BFM-X1 was isolated from an air environment on a vegetable field and was capable of degrading poly(butylene succinate) (PBS). The taxonomic identity of the strain BFM-X1 was confirmed to be Bionectria ochroleuca (showing a 99% similarity to B. ochroleuca in a BLAST search) through an ITS rRNA analysis. The bio-degradation of the PBS film by strain BFM-X1 was studied. Approximately 97.9% of the PBS film was degraded after strain BFM-X1 was inoculated at 28?C for 14 days. The degradation efficiency of BFM-X1 against PBS film under different soil environmental conditions was characterized. The results indicated that 62.78% of the PBS film loss was recorded in a 30-d experimental run in a sterile soil environment indoors. On adding strain BFM-X1 to a soil sample, the PBS degradation rate accelerated approximately fivefold. Furthermore, both temperature and humidity influenced the in situ degradation of the PBS by strain BFM-X1, and temperature may be the major regulating factor. The degradation was particularly effective in the warm season, with 90% of weight loss occurring in July and August. Scanning electron microscope observations showed surface changes to the film during the degradation process, which suggested that strain BFM-X1preferentially degraded an amorphous part of the film from the surface. These results suggested that the strain B. ochroleuca BFM-X1 was a new resource for degrading PBS film and has high potential in the bioremediation of PBS-plastic-contaminated soil

Upcycling of Poly(butylene adipate-co-terephthalate)into Dual Covalent Adaptable Networks through Chain Breaking-Crosslinking Strategy

Poly(butylene adipate-co-terephthalate)(PBAT),a widely studied biodegradable material,has not effectively addressed the problem of plastic waste.Taking into consideration the cost-effectiveness,upcycling PBAT should take precedence over direct composting degradation.The present work adopts a chain breaking-crosslinking strategy,upcycling PBAT into dual covalent adaptable networks(CANs).During the chainbreaking stage,the ammonolysis between PBAT and polyethyleneimine(PEI)established the primary crosslinked network.Subsequently,styrene maleic anhydride copolymer(SMA)reacted with the hydroxyl group,culminating in the formation of dual covalent adaptable networks.In contrast to PBAT,the PBAT-dual-CANs exhibited a notable Young's modulus of 239 MPa,alongside an inherent resistance to creep and solvents.Owing to catalysis from neighboring carboxyl group and excess hydroxyl groups,the PBAT-dual-CANs exhibited fast stress relaxation.Additionally,they could be recycled through extrusion and hot-press reprocessing,while retaining their biodegradability.This straightforward strategy offers a solution for dealing with plastic waste.