新型生物降解热熔胶基体树脂CDA-PLLGA共混物的制备及其性质

用辛酸亚锡作催化剂,在二乙酸纤维素存在下,通过L-丙交酯和乙交酯的开环聚合,制备了一种新型生物降解热熔胶基体树脂二乙酸纤维素和聚乙丙交酯化学共混物CDA—PLLGA。通过对共混物中所含的接枝共聚物CDA—g—PLLGA的红外光谱和凝胶渗透色谱分析,估测其具有短刷状支化结构,并在共混过程中起增容剂作用。用差示扫描量热法、热重分析法和拉伸试验法等测定了CDA—PLLGA的玻璃化温度、熔点、热失重性能、拉伸强度和降解性能。结果表明,CDA—PLLGA具有良好的热稳定性和强度,降解速度可以通过改变化学共混物中CDA的比例加以控制,因而是一种理想的生物降解热熔胶基体树脂。     

新型聚乙烯-g-聚乳酸接枝共聚物的合成与表征

报道了一类主链为聚乙烯(PE)共聚物,侧链为生物基聚乳酸(PLA)的新型接枝共聚物及其制备方法,并对接枝共聚物结构与性能进行了深入的表征。采用配位聚合与开环聚合相结合的方法,以羟基功能化的聚乙烯共聚物为主链,通过羟基引发L-丙交酯(L-LA)的开环聚合,从而获得聚乙烯-g-PLA接枝共聚物。通过控制单体比例和反应条件,可同时实现接枝共聚物的主链结构以及侧链结构调控。结果表明,少量PLA接枝链的引入可在不明显降低拉伸强度的情况下,有效地改善接枝共聚物的断裂伸长率。热性能表征发现侧链PLA的引入限制了主链聚乙烯的结晶,造成了接枝共聚物结晶温度以及熔点的下降。该接枝共聚物展现出了可用于PLA等生物基聚酯材料的增韧改性或共混增容剂的应用潜力,也为此类接枝共聚物的合成与性能调控提供了重要的参考。     

含聚己内酯的聚乳酸基立构复合物的制备与性能

将聚(右旋丙交酯-ε-己内酯)二元共聚物(PDLCA)以及聚(左旋丙交酯-ε-己内酯)二元共聚物(PLLCA)分别与聚左旋乳酸(PLLA)进行溶液共混,对PLLA进行改性,并进行对比。探讨了共聚物的添加量以及共聚物中LA/CL(LA/CL为共聚物中丙交酯与ε-己内酯的投料摩尔比)的共聚摩尔比对立构复合物的形成以及PLLA力学性能的影响。研究表明,聚己内酯(PCL)柔性链段对PLLA具有增韧效果,经过对比发现,PDLCA中的PDLA链段与PLLA之间形成的立构复合物对材料的拉伸强度具有一定的保持作用,当LA/CL为90/10,PDLCA添加量为50%时,效果最佳,材料的断裂伸长率达到30%,比PLLA的韧性提高了328%,同时,拉伸强度没有明显降低。     

纤维素醋酸酯与聚乳酸接枝共聚物的结构与性能表征

为改善纤维素醋酸酯的热加工性能,以辛酸亚锡为催化剂,通过丙交酯的开环接枝聚合反应,制备了纤维素醋酸酯和聚乳酸接枝共聚物(CDA-g-PLA),利用FTIR、1H NMR、DSC、XRD和TG对其结构和性能进行表征。结果表明,共聚物中存在聚乳酸支链,产物为纤维素醋酸酯与聚乳酸的接枝共聚物;柔性聚乳酸支链的引入,接枝共聚物的玻璃化温度大幅降低,热加工性能得到显著的改善。     

原位法合成聚乳酸接枝淀粉共聚物的研究与应用

首次采用阴离子开环聚合的方法,在淀粉上一步法原位接枝聚合得到聚乳酸和淀粉的接枝共聚物。采用强极性溶剂二甲基亚砜（DMSO）将淀粉溶解,然后以叔丁醇钾为引发剂,引发L-丙交酯接枝聚合,提纯后的接枝产物通过红外光谱、核磁共振、XRD等测试方法进行表征。结果表明,在聚合温度为75 ℃,时间为4 h,原料摩尔比为淀粉/丙交酯/叔丁醇钾为10/75/3条件下,接枝产物的接枝率可达83 %。将该接枝产物添加到淀粉和聚乳酸共混体系中,与未添加接枝物的共混体系相比,添加接枝物的共混体系中淀粉的分布更加均匀,性能更加均一。     

聚乙交酯和聚乙丙交酯缝线的研制

本文用DSC、TGA、X射线衍射和毛细管流变仪研究了聚乙交酯(PGA)和聚乙丙交酯(PGLA)的热性能、结晶性和流变性,讨论了纺丝及后加工的工艺条件,制得了PGA和PGLA编织线。PGA和PGLA的体内外降解结果表明,PGA不如PGLA容易水解,PGA和PGLA缝线在家兔体内40～60天后被完全吸收,临床应用效果良好。     

官能化接枝共聚物增容PA6/PS共混物的研究

将苯乙烯(St)和甲基丙烯酸环氧丙酯（GMA）通过乳液聚合接枝到聚丁二烯(PB)上,形成核壳结构接枝共聚物PB-g-PS和官能化接枝共聚物PB-g-(St-GMA),并考察了其对聚酰胺6/聚苯乙烯(PA6/PS)共混物相容性的影响。对共混物的流变性能、动态力学性能和形态结构进行了分析,结果表明,引入1 %官能化单体GMA后,共混物的平衡扭矩增加,PA6与PS两相的玻璃化转变温度差值变小,分散相尺寸明显减小,PB-g-(St-GMA)可以改善PA6/PS共混物的相容性。继续增加PB-g-(St-GMA)中GMA含量时,共混物相容性下降。     

壳聚糖在离子液体中的均相接枝共聚

以离子液体1-丁基-3-甲基咪唑氯盐([BMIM]Cl)为反应介质,壳聚糖(CS)与L-丙交酯(L-LA)发生均相接枝共聚反应,得到了壳聚糖与L-丙交酯的接枝共聚物。考察了单体和催化剂的用量、反应的温度和时间对接枝率的影响规律。并利用红外光谱、核磁共振氢谱、热重分析等对接枝共聚物进行了表征,证实了L-丙交酯在壳聚糖分子链上发生了接枝共聚。实验结果表明,在[BMIM]Cl中进行的L-丙交酯与壳聚糖的均相接枝共聚反应效率高于非均相反应。     

国外有关塑料助剂研究的期刊文摘

正立体络合物对PLA/PMMA共混物光化学老化的独特影响[Polymer Degradation and Stability(2018),150,92-104]本项研究重点关注了紫外光对聚乳酸/聚(甲基丙烯酸甲酯)(PLA/PMMA)共混物熔融挤出产生的影响,特别强调了PLA立体络合物对共混物光化学行为的独特影响。通过将高分子量聚(L-丙交酯)(PLLA),聚(D-丙交酯)(PDLA)     

D,L-丙交酯提纯溶剂的选择

考察了两种绿色无毒溶剂乙酸乙酯和乙醇在D,L-丙交酯提纯过程中的使用情况. 以熔点为指标表征重结晶后D,L-丙交酯的纯度，考察了重结晶温度、时间及D,L-丙交酯/溶剂比例对D,L-丙交酯重结晶收率的影响. 结果表明，在不同重结晶温度、时间及溶剂用量下，两种溶剂提纯3次后D,L-丙交酯的熔点均能达到聚合的要求. 使用两种溶剂提纯的经济性对比表明，乙醇较适宜作为D,L-丙交酯扩大生产中的提纯溶剂，其最佳的提纯条件为温度4℃或更低，重结晶时间在1 h以上，乙醇使用量为2.5 mL/g. 在此条件下，提纯3次后D,L-丙交酯的收率约为63%. 对重结晶所得物质进行了元素分析、FT-IR分析及1H-NMR分析，结果表明所得产物为环状D,L-丙交酯结构.     

Thermorheological and mechanical behavior of polylactide and its enantiomeric diblock copolymers and blends

In this study, different compositions of nearly monodispersed diblock copolymers of dl-lactide or d-lactide and l-lactide were synthesized by living ring-opening polymerization with a dinuclear indium catalyst. The effects of molecular weight and block length ratio on the rheological behavior of dl and l-lactide diblock copolymers in the disordered state were investigated. For comparison, blends of PDLLA and PLLA homopolymers of equivalent molecular weights to the diblock copolymers were prepared. We found that the time–temperature (t–T) superposition principle is applicable to the diblock copolymers PLLA-b-PDLLA and blends in the disordered state. However, the t–T superposition failed at low temperatures close to the temperature of crystallization. In contrast, diblock copolymers PLLA-b-PDLA formed stereocomplex crystallites of high melting point (slightly above 200 °C) that causes a viscosity enhancement. The failure of t–T superposition was found due to existing of micro homo or stereocomplex crystallites. The non-isothermal crystallization behavior was investigated using differential scanning calorimetry (DSC). The DSC thermograms of blends exhibited a single glass transition at 50–60 °C followed by melting point of PLLA at 177 °C. With decreasing of the PLLA content in the blends, the intensity of the melting peak decreased. In addition, different crystallization behavior was observed for diblock copolymers compared to their equivalent blends. Specifically, low temperatures and enthalpies of melting peaks were observed for diblock copolymers. These also show improvement in elongation at break and tensile strength as compared to their counterpart homopolymer blends.     

二醋酸纤维素与聚己内酯单丙烯酸酯接枝共聚物的合成与表征

采用“两步法”合成了二醋酸纤维素与聚己内酯单丙烯酸酯接枝共聚物(CDA-g-PCLA)。首先以聚己内酯单丙烯酸酯(PCLA)与2,4-甲苯二异氰酸酯(TDI)反应,得到端异氰酸酯预聚物(NCOPCLA),然后将该预聚物与二醋酸纤维素(CDA)进行接枝反应得到接枝共聚物(CDA-g-PCLA)。结构分析的结果表明:PCLA是通过化学键连接到CDA上;热分析表明:接枝共聚物的粘流温度(Tf)比纯二醋酸纤维素的粘流温度低,而且随着接枝率的提高,粘流温度降低。     

Synthesis and properties of graft copolymer of cellulose diacetate with poly(caprolactone monoacrylate)

Cellulose diacetate grafting poly(caprolactone monoacrylate) copolymers (CDA‐g‐PCLA) were synthesized by a two‐step reaction of cellulose diacetate (CDA) with poly(caprolactone monoacrylate) (PCLA). The isocyanate‐terminated intermediate (NCOPCLA) was prepared and grafted onto cellulose diacetate chains. The results of the structure analysis indicated that PCLA was connected to CDA by chemical bonding. The flow temperature of graft copolymers was lower than that of the pure CDA and decreased with increasing the grafting percentage. Outdoor soil burial tests and active sludge tests indicated that the graft copolymers have good biodegradability in natural conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 85–90, 2003     

The effect of end groups of PEG on the crystallization behaviors of binary crystalline polymer blends PEG/PLLA

The effect of end groups (2OH, 1OH, 1CH₃ and 2CH₃) of poly(ethylene glycol) (PEG) on the miscibility and crystallization behaviors of binary crystalline blends of PEG/poly(l-lactic acid) (PLLA) were investigated by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). A single glass-transition temperature was observed in the DSC scanning trace of the blend with a weight ratio of 10/90. Besides, the equilibrium melting point of PLLA decreased with the increasing PEG. A negative Flory interaction parameter, χ₁₂, indicated that the PEG/PLLA blends were thermodynamically miscible. The spherulitic growth rate and isothermal crystallization rate of PEG or PLLA were influenced when the other component was added. This could cause by the change of glass transition temperature, T_g and equilibrium melting point, T⁰_m. The end groups of PEG influenced the miscibility and crystallization behaviors of PEG/PLLA blends. PLLA blended with PEG whose two end groups were CH₃ exhibited the greatest melting point depression, the most negative Flory interaction parameter, the least fold surface free energy, the lowest isothermal crystallization rate and spherulitic growth rate, which meant better miscibility. On the other hand, PLLA blended with PEG whose two end groups were OH exhibited the least melting point depression, the least negative Flory interaction parameter, the greatest fold surface free energy, the greatest isothermal crystallization rate and spherulitic growth rate.     

HPAM-g-P(NIPA-co-DMAM)的合成与温敏行为

利用端基转换法合成了不同组成及相对分子质量的端丙烯酰胺基聚（N-异丙基丙烯酰胺-co-N,N-二甲基丙烯酰胺）［poly(NIPA-co-DMAM), PID］大分子单体;与丙烯酰胺聚合后再水解,得到以PID为侧链,浊点在37～63℃的接枝共聚物［HPAM-g-P(NIPA-co-DMAM), HGPID］。利用¹H NMR及端基分析等对大分子单体和接枝物的组成及结构进行了表征;考察了接枝共聚物侧链的组成和链长、共聚物质量浓度和外加盐浓度等因素对其水溶液的热敏特性及温敏增稠性的影响。     

Toughening modification of PLLA/PBS blends via in situ compatibilization

Biodegradable polymer blends consisting of poly(L ‐lactic acid) (PLLA) and poly(butylene succinate) (PBS) were prepared in the presence of dicumyl peroxide (DCP). The effects of DCP content on the mechanical properties, thermal and rheological behavior, phase morphology as well as the toughening mechanism of the blends were investigated. The notched Izod impact strength of PLLA/PBS (80/20) blend significantly increased after the addition of 0.05–0.2 phr DCP, but the strength and modulus monotonically decreased with increasing DCP content. PBS acted as a nucleating agent at the environmental temperature below its melting temperature and accelerated the crystallization rate of PLLA but had little effect on its final degree of crystallinity. The degree of crystallinity of PBS and the cold crystallization ability of PLLA gradually reduced with increasing DCP content. The addition of DCP induced an increase in viscosity of the blends at low frequencies as well as finer dispersion of PBS particles and better interfacial adhesion between PLLA and PBS, indicating the in situ compatibilization occurred between the two components. The optical clarity of PLLA/PBS blends was significantly improved after the addition of DCP, which was in accordance with the crystallization behavior and phase structure of the blends. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

PP／PE-LLD／SBS共混交联体系的结构与性能研究

采用两步交联法制备PP/PE-LLD/SBS交联共混物。DSC和WAXR测试结果表明,交联作用对共混物组分的结晶度无明显影响;从维卡软化点和TG、DTG曲线可以看出,交联提高了共混物的耐热温度,热稳定性增强;通过DMA测试发现,交联后共混物组分的玻璃化转变温度Tg无明显变化,交联作用对分子链段的运动影响不大;但交联共混物的内耗角tanδ、存储模量Ε′和损耗模量Ε″都有很大提高,刚、韧性增强。交联使共混物的熔体流动速率减小,流动性下降,但仍保持假塑性流体行为,随剪切速率增大出现剪切变稀;交联作用增大了共混物的活化能,分子链间作用力加强,刚性增大,黏度对温度变化更为敏感。     

A comparative study of poly(l‐lactide)‐block‐poly(ϵ‐caprolactone) six‐armed star diblock copolymers and polylactide/poly(ϵ‐caprolactone) blends

This paper deals with the synthesis of a series of six‐armed star diblock copolymers based on poly(l ‐lactide) (PLLA) and poly(?‐caprolactone) (PCL) by ring‐opening polymerization using stannous octoate as catalyst and the preparation of polylactide (PLA)/PCL linear blends using a solution blending technique, while keeping the PLA‐to‐PCL ratio comparable in both systems. The thermal, rheological and mechanical properties of the copolymers and the blends were comparatively studied. The melting point and the degree of crystallinity were found to be lower for the copolymers than the blends due to poor folding property of star copolymers. Dynamic rheology revealed that the star polymers have lower elastic modulus, storage modulus and viscosity as compared to the corresponding blends with similar composition. The blends show two‐phase dispersed morphology whereas the copolymers exhibited microphase separated morphology with elongated (worm‐like) microdomains. The crystalline structures of the copolymers were characterized by larger crystallites than their blend counterparts, as estimated using Sherrer's equation based on wide‐angle X‐ray diffraction data. © 2016 Society of Chemical Industry     

聚乳酸/聚乙二醇共混物的结晶与降解行为

针对聚乳酸（PLLA）亲水性差、降解周期长的问题,利用与亲水性高分子聚乙二醇（PEG）共混的方法对其进行改性。采用转矩流变仪制备了不同组成的PLLA/PEG共混物颗粒,系统研究了PLLA/PEG共混物的结晶和熔融、亲水性和在酸碱介质中的降解行为。结果表明,PEG的加入增强了共混物中PLLA的结晶能力,提高了PLLA在降温过程中的熔融结晶温度。PLLA/PEG共混物在等温结晶中表现出比纯PLLA更快的结晶速度。通过改变PLLA/PEG共混物的组成,可调控材料的表面亲水性和降解速率。随着PEG含量的增多,PLLA/PEG共混物的表面接触角降低。PLLA与PLLA/PEG共混物均可在水溶液中降解,共混物的降解速率高于纯PLLA,随着PEG含量的升高和降解液中酸碱浓度的提高,PLLA/PEG共混物的降解速率加快。     

Phase behavior studies of polyarylate/copolyester blends by thermal and dynamic mechanical analysis

The phase behavior of polyarylate blends with a copolyester based on poly(1,4-cyclohexanedimethylene/ethylene terephthalate) was studied by differential scanning calorimetry and dynamic mechanical analysis. A single glass-transition temperature was observed over the entire composition range. Up to 30% weight polyarylate, the copolyester crystallized readily and its melting point did not change with blend composition. This indicates that transesterification, if it occurred, was negligible. The thermal and dynamic results also suggest a weak polymer-polymer interaction in this system.