聚丁二酸丁二醇酯的酶促降解研究

以聚丁二酸丁二酯（PBS）薄片为降解底物,利用角质酶对其进行降解研究,考察PBS的酶促降解行为。利用扫描电子显微镜、差示扫描量热仪和热重分析仪等方法对降解前后的PBS薄片进行了表征分析,并进一步采用质谱仪对降解产物进行分析。结果表明,在酶浓度2.5 U/mL、反应温度37 ℃以及pH 7.4的条件下,经16 h降解PBS薄片的降解率可达93.88 %,在降解时间为2 h时有最大降解速率32.97 μg/cm2·h;PBS薄片有片层脱落降解的现象,促进了角质酶的降解作用;随降解时间的延长,PBS相对结晶度逐渐降低,热稳性也呈现下降趋势;PBS被降解成单体或寡聚物。     

聚丁二酸丁二酯的酶促降解研究

以聚丁二酸丁二酯(PBS)薄片为降解底物,利用角质酶对其进行降解研究,考察PBS的酶促降解行为。利用扫描电子显微镜、差示扫描量热仪和热重分析仪等方法对降解前后的PBS薄片进行了表征分析,并进一步采用质谱仪对降解产物进行分析。结果表明,在酶浓度2.5 U/mL、反应温度37℃以及pH 7.4的条件下,经16 h降解PBS薄片的降解率可达93.88%,在降解时间为2 h时有最大降解速率32.97μg/cm~2·h;PBS薄片有片层脱落降解的现象,促进了角质酶的降解作用;随降解时间的延长,PBS相对结晶度逐渐降低,热稳性也呈现下降趋势;PBS被降解成单体或寡聚物。     

聚ε-己内酯薄膜的脂肪酶促降解

利用脂肪酶对聚ε己内酯（PCL）薄膜进行降解研究,并利用扫描电子显微镜、差示扫描量热仪和热重分析仪、X射线衍射、核磁共振以及质谱等分析方法对降解后的PCL薄膜进行了表征分析。结果表明,PCL薄膜（3 cm×1 cm×0.05 cm）在45 ℃和30 U/mL脂肪酶的作用下,经20 h后失重率可达86.9 %;随着降解时间的增加,PCL薄膜表面发生降解并形成孔洞,且孔洞随降解时间呈现增大趋势;PCL相对结晶度随降解时间的延长而逐渐降低;随降解时间的延长,PCL薄膜的热稳性呈下降趋势;PCL在酶促降解前后化学组成未发生变化。     

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。     

聚丁二酸丁二醇酯(PBS)在不同pH条件下的降解

对聚丁二酸丁二醇酯(PBS)薄膜在不同pH值水溶液中的降解进行对比研究.用失重率及薄膜表面形貌观察等时降解结果进行表征,结果表明:PBS薄膜在不同pH值水溶液中的降解速度为:碱性溶液>酸性溶液>中性溶液.降解过程中不同降解溶液的pH值均有一定程度的下降.     

聚乙二醇嵌段长碳链二酸共聚物的合成与酶降解研究

采用长碳链癸二酸代替丁二酸与丁二醇以及不同含量的相对分子质量为200的聚乙二醇(PEG)嵌段共聚,得到了聚癸二酸丁二醇酯聚乙二醇嵌段共聚物(PBSe-PEG),并采用核磁共振波谱仪、凝胶渗透色谱仪、差示扫描量分析仪、热重分析仪、广角X射线衍射仪等分析手段表征了嵌段共聚物的结构和性能,并且研究了固定化南极假丝酵母菌脂肪酶(简称脂肪酶N435)对PBSe-PEG的降解性。结果表明,几种PBSe-PEG是预期产物,其数均相对分子质量在5×104左右;PBSe-PEG与纯PBSe相比晶型结构相似;随着PEG含量增加,PBSe-PEG的熔融温度（Tm）和结晶温度（Tc）逐渐下降;相比PBS,脂肪酶N435对PBSe-PEG具有更好的降解性。     

聚乳酸的酶促降解研究

采用蛋白酶K对聚乳酸(PLA)薄膜进行酶促降解,考察了溶液起始pH值、降解温度、蛋白酶K浓度、降解时间等因素对薄膜降解率的影响,并研究了后3种因素对溶液pH值变化趋势的影响。利用扫描电子显微镜(SEM)和X射线衍射(XRD)仪观察和分析了薄膜降解前后的形态和结晶情况。结果表明,随溶液起始pH值、降解温度、蛋白酶K浓度的增加,PLA薄膜降解率先增大后降低,随着降解时间的增加,PLA薄膜的降解率先逐渐增大,在6 h后趋于稳定;获得了最合适的降解工艺参数:溶液起始pH值为9.0、降解温度为160℃、蛋白酶K浓度为0.5 mg/mL、降解时间为6 h,在此条件下蛋白酶K对PLA薄膜的降解率可达(94.3±0.8)%。溶液pH值随后3种因素的变化趋势与降解率大体相反,间接反映了PLA薄膜在降解过程中生产了大量单体乳酸。SEM观察到降解后的薄膜表面形成了孔洞及蚀痕。XRD分析结果表明降解后薄膜的相对结晶度降低,晶体区域发生降解。     

扩链剂改性对聚丁二酸丁二醇酯薄膜室温降解老化过程的影响

将扩链剂与聚丁二酸丁二醇酯（PBS）共混，制备改性PBS薄膜。通过万能拉伸试验机、差示扫描量热仪（DSC）、傅里叶变换红外光谱仪（FTIR）和旋转流变仪等，表征PBS薄膜和扩链改性PBS薄膜室温降解老化后结构与性能的变化。结果表明：室温老化降解4周后，PBS薄膜的应变100%拉伸强度较改性PBS薄膜大幅度下降，扩链剂改性PBS可以减缓拉伸性能老化衰减。随着老化时间增加，改性前后PBS薄膜在室温老化过程储能模量、损耗模量、复数黏度明显下降，未改性PBS薄膜变化更明显。PBS薄膜在室温下降解未对晶区造成破坏，主要发生无定形区。而扩链改性使PBS分子链增加，减少PBS膜非晶区分子链断裂，有助于抑制无定型区降解老化。     

吹膜级PBS/PLA复合材料的制备与性能研究

利用熔融共混法制备了综合性能优良的吹膜级聚丁二酸丁二酯/聚乳酸(PBS/PLA)复合材料,并通过万能试验机、差示扫描量热分析仪、热重分析仪、透气透湿分析仪分别测试了PBS/PLA复合材料及其薄膜的力学性能、热性能、阻隔性能。结果表明,制备的PBS/PLA复合材料较纯PBS树脂具有更好的刚性,且所吹塑的薄膜与包装用低密度聚乙烯膜各项性能相当。     

己二醇改性PBS共聚酯的酶催化降解及溶剂效应

采用己二醇对聚丁二酸丁二醇酯(PBS)改性,合成了不同比例、分子质量均在6×105左右的聚丁二酸丁二醇/己二醇酯(PBSH),并以其为底物分别在2种不同的有机溶剂氯仿(CHCl3)和四氢呋喃(THF)中,研究了洋葱假单胞菌(PC)脂肪酶对其催化降解规律和溶剂效应。以GPC测试了共聚物降解前后的分子质量变化;以TG分析了酶降解共聚物前后热性能的变化;以MALDI-TOF-MS对降解产物进行了分析。研究结果表明:PBSH在2种溶剂中都能快速降解;降解60 h后2种共聚物的相对分子质量均减小,分子质量分布均变宽;但在氯仿中酶催化活性更高,PBSH降解速率更快;降解前后热失重5%时热分解温度均降低;MALDI-TOF-MS结果表明:在2种溶剂中降解产物中含SH(丁二酸己二醇酯)片段较多,且氯仿中降解产物种类更多,并易于成环。     

Biodegradable polymers based on renewable resources VIII. Environmental and enzymatic degradability of copolycarbonates containing 1,4 : 3,6‐dianhydrohexitols

Environmental and enzymatic degradations were investigated on a series of copolycarbonates consisting of equimolar amounts of 1,4 : 3,6‐dianhydrohexitols (1,4 : 3,6‐dianhydro‐D ‐glucitol (1a) and 1,4 : 3,6‐dianhydro‐D ‐mannitol (1b)) and alkylene diols (1,4‐butanediol, 1,6‐hexanediol, 1,8‐octanediol, and 1,10‐decanediol) or oligo(ethylene glycol)s (di‐, tri‐, and tetraethylene glycols). Fourteen different copolycarbonates with number average molecular weights in the range of 1.1–4.2 × 10⁴ were prepared by solution polycondensation as described in our previous article. Biodegradability of the copolycarbonates was assessed by soil burial degradation tests in composted soil at 27 °C and by enzymatic degradation tests in a phosphate buffer solution at 37 °C. In general, biodegradability of the copolycarbonates increased with increasing chain lengths of the methylene groups of alkylene diols or of the oxyethylene groups of the oligo(ethylene glycol)s. SEM observations of the film surfaces of polymers recovered from soil burial indicated that the copolycarbonates were degraded by microorganisms in soil. In enzymatic degradation, the copolycarbonates containing alkylene diol components showed high degradability with Pseudomonas sp. lipase, whereas the copolycarbonates containing oligo(ethylene glycol) components were not degraded at all. The enzymatic degradability of the copolycarbonates is discussed with reference to the geometrical structure around the carbonate linkages and the microstructure and hydrophobicity of the polymer chains. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1679–1687, 2005     

Synthesis,characterization and properties of biodegradable poly(butylene succinate)‐block‐poly(propylene glycol) segmented copolyesters

BACKGROUND: To obtain a biodegradable thermoplastic elastomer, a series of poly(ester‐ether)s based on poly(butylene succinate) (PBS) and poly(propylene glycol) (PPG), with various mass fractions and molecular weights of PPG, were synthesized through melt polycondensation. RESULTS: The copolyesters were characterized using ¹H NMR, gel permeation chromatography, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, mechanical testing and enzymatic degradation. The results indicated that poly(ester‐ether)s with high molecular weights were successfully synthesized. The composition of the copolyesters agreed very well with the feed ratio. With increasing content of the soft PPG segment, the glass transition temperature decreased gradually while the melting temperature, the crystallization temperature and the relative degree of crystallinity decreased. Mechanical testing demonstrated that the toughness of PBS was improved significantly. The elongation at break of the copolyesters was 2–5 times that of the original PBS. Most of the poly(ester‐ether) specimens were so flexible that they were not broken in Izod impact experiments. At the same time, the enzymatic degradation rate of PBS was enhanced. Also, the difference in molecular weight of PPG led to properties being changed to some extent among the copolyesters. CONCLUSION: The synthesized poly(ester‐ether)s having excellent flexibility and biodegradability extend the application of PBS into the areas where biodegradable thermoplastic elastomers are needed. Copyright © 2009 Society of Chemical Industry     

脂肪酶N435对PBSA与PBSH的酶催化降解和分子模拟

分别采用2种酸1种醇和2种醇1种酸分别对聚丁酸丁二醇酯（PBS）改性,合成了不同化学结构的共聚酯聚（丁二酸丁二醇酯-co-己二酸丁二醇酯）（PBSA）和聚(丁二酸丁二醇-co-丁二酸己二醇酯)（PBSH）,并在磷酸缓冲液以它们为底物在磷酸缓冲液中,研究了对脂肪酶N435降解反应感受性的异同。采用质量损失率和凝胶渗透色谱评价了降解前后共聚酯相对分子质量的变化;广角X衍射仪和热重分析仪分析了酶降解前后共聚酯结晶度和热性质的变化;偏光显微镜对降解后的材料进行了形貌观测。结果表明,相比于PBS,PBSA和PBSH对脂肪酶的感受性有很大提高,24 h后降解率分别达到90 %和60 %以上,并且PBSA降解速率比PBSH快;降解后两种共聚酯相对分子质量变化不大,但相对分子量分布系数变宽,结晶度增大;降解3 d后PBSA的热稳定性降低,而PBSH的热稳定性提高。     

Improvement of Processability of PCL and PBS Blend by Irradiation and its Biodegradability

Poly(ε‐caprolactone) (PCL) was blended with poly(butylene succinate) (PBS), (PCL/PBS = 30/70) to improve the heat stability of PCL. The processability of the blended samples (PHB02) was improved due to enhancing of melt strength by γ‐rays irradiation in the dose range between 10 and 50 kGy. High speed production of a thin film and production of foam have been achieved by this process. The soil degradation test showed that PHB02 film buried in the soil was almost degraded (97%) after two months and completely degraded after two and a half months. On the contrary, the sample on the surface degraded to only 3.5% after four months. From these findings it was confirmed that microorganisms contribute to degradation in the soil. In the case of PHB02 foam samples, 65% degradation was achieved after four months. The PHB02 sample used as garbage bags was well degraded (almost 50%) after a two months burial test. The enzymatic degradation test showed that after treatment for 24 h, the weight loss of PHB02 irradiated with 30 kGy and unirradiated samples were 80% and 90%, respectively. Enzymatic degradation for PHB02 films led to the suggestion that the biodegradation process proceeds from the surface to the inside of the sample by erosion.     

PBS/黄连素抗菌高分子材料性能

将可降解高分子材料聚丁二酸丁二醇酯(PBS)和黄连素(Berberine)共混,制备了PBS/黄连素复合抗菌材料,并对其力学性能、结晶性能、亲水性能、热性能、抗菌性能及生物降解性能进行了分析。结果表明,当黄连素的添加比例为5%时,与纯PBS相比,复合材料的拉伸强度基本不变,结晶能力增大,疏水性增强,热稳定性增加。抗菌性能测试结果表明,随着黄连素含量不断增加,复合材料的抗菌能力逐渐提升。含有5%黄连素的复合材料对大肠杆菌和金黄色葡萄球菌的抑制作用均能达到91%以上。使用角质酶降解12 h后,含有5%黄连素的复合材料具有较高的降解率,接近95%,与纯PBS的降解率相差较小。因此,黄连素在提高材料抗菌性能的同时,不影响其降解性能。     

Morphology,thermal, and crystallization properties of poly(butylene succinate)‐grafted Nanocrystalline Cellulose by polymerization in situ

The compounds 1,4‐butanediol, succinic anhydride, and nanocellulose (NCC) were used to synthesize poly(butylene succinate)‐grafted Nanocrystalline Cellulose (PBS‐g‐NCC) nanocomposites via polymerization in situ. The resulting structures were examined by transmission electron microscopic (TEM), scanning electron microscope (SEM), ¹H and ¹³C‐nuclear magnetic resonance spectroscopic (NMR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and X‐ray diffraction (XRD) analyses. TEM showed the cellulose to be nanoscale and SEM analysis indicated that 3 wt% NCC dispersed well in PBS matrix. ¹H and ¹³C‐NMR analyses indicated the product to possess peaks characteristic of PBS. DSC analysis clearly showed that the NCC increased the PBS crystallinity when 3 wt% NCC was introduced into PBS matrixes by polymerization in situ, compared to pure PBS. TGA illustrated that the thermal stability of PBS‐g‐NCC was better than that of pure PBS, when 3 wt% NCC was added. XRD analysis suggested that 3 wt% NCC improved PBS crystallinity, which was in good agreement with the present DSC results. POLYM. ENG. SCI., 59:928–934, 2019. © 2018 Society of Plastics Engineers     

Biodegradable polymers based on renewable resources: Polyesters composed of 1,4 : 3,6-dianhydrohexitol and aliphatic dicarboxylic acid units

A series of polyesters was synthesized by the bulk polycondensations of the respective combinations of three stereoisomeric 1,4 : 3,6-dianhydrohexitols [1,4 : 3,6-dianhydro-D-glucitol ( 1 ), 1,4 : 3,6-dianhydro-D-mannitol ( 2 ), and 1,4 : 3,6-dianhydro-L-iditol ( 3 )] with succinyl dichloride ( 4a ), glutaryl dichloride ( 4b ), adipoyl dichloride ( 4c ), and sebacoyl dichloride ( 4d ). Biodegradability of these polyesters was investigated by three different methods, i.e., degradation in an activated sludge, soil burial degradation, and enzymatic degradation. Although polyesters ( 7b–7d ) based on 3 and polyester 6a derived from 2 and 4a were crystalline and scarcely biodegraded, all the other amorphous polyesters were more or less biodegradable. Biodegradability of the polyesters was found to vary significantly depending on their molecular structures. Soil burial degradation of polyesters in the soil that was treated with antibiotics, together with electron scanning microscopic observation, showed that polyesters 5b and 5c prepared from 1 and 4b or 4c were degraded by both bacteria and filamentous fungi, whereas polyester 5d from 1 and 4d was degraded primarily by filamentous fungi. © 1996 John Wiley & Sons, Inc.     

Reactivity of the raw materials and their effects on the structure and properties of rigid polyurethane foams

Formulations for rigid polyurethane foams (RPUFs) based on crude 4,4′‐diphenylmethane diisocyanate, polyether polyol, triethylenediamine, 1,4‐butane diol, poly(siloxane ether), methylene chloride, and water were studied. The stoichiometric ratios of various foam ingredients and their effects on physical properties such as the cream time, gel time, tack‐free time, and density of the RPUF samples were studied. The results indicated that the rate of RPUF formation increased with the catalyst (triethylenediamine and tin) and water content. The density of the RPUF samples blown with water, methylene chloride, and a mixture of water and methylene chloride decreased from 240.1 to 33.4 kg/m³ with an increase in the blowing agent contents. However, the RPUF density increased with increasing contents of 1,4‐butane diol. The cell morphology and thermal properties of the RPUF samples were investigated with scanning electron microscopy, thermogravimetric analysis, derivative thermogravimetry, and differential thermal analysis. Scanning electron microscopy results revealed an average increase in the cell size of the RPUF samples from 162 to 278 μm with increased water content. A thermal behavior study indicated that the RPUF samples decomposed in nitrogen and degraded in air through two and three weight‐loss stages, respectively. Foam pyrolysis in nitrogen and combustion in air led to 15 and 0% char residue, respectively. The results indicated that the thermal stability of the RPUFs was better in nitrogen than in an air atmosphere. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007