PLA/PBAu嵌段共聚物合成工艺优化及降解性能

以端羟基聚乳酸（PLA）、聚己二酸-丁二醇-尿素（PBAu）为预聚物,六亚甲基二异氰酸酯（HDI）为扩链剂,制备出一种新型PLA/PBAu嵌段共聚物。研究了扩链剂用量、扩链温度以及催化剂用量对PLA/PBAu嵌段共聚物分子量的影响,确定了合成PLA/PBAu嵌段共聚物的最佳工艺条件。采用核磁共振、凝胶渗透色谱、差示扫描量热仪、扫描电镜等对共聚物薄膜结构及性能进行表征。结果表明：成功合成了PLA/PBAu嵌段共聚物,分子量可达10×10⁴,玻璃化转变温度约为41℃;并且随着PBAu含量的增加,共聚物的结晶度逐渐增加。以NaOH溶液为模拟液进行加速降解实验发现,当PBAu含量为30%时,可以显著提高嵌段共聚物的降解速率,并且通过调节PLA、PBAu预聚物的含量,可以控制嵌段共聚物的降解速率。     

PLA/PBAu嵌段共聚物合成工艺优化及降解性能

以端羟基聚乳酸(PLA)、聚己二酸-丁二醇-尿素(PBAu)为预聚物,六亚甲基二异氰酸酯(HDI)为扩链剂,制备出一种新型PLA/PBAu嵌段共聚物。研究了扩链剂用量、扩链温度以及催化剂用量对PLA/PBAu嵌段共聚物分子量的影响,确定了合成PLA/PBAu嵌段共聚物的最佳工艺条件。采用核磁共振、凝胶渗透色谱、差示扫描量热仪、扫描电镜等对共聚物薄膜结构及性能进行表征。结果表明:成功合成了PLA/PBAu嵌段共聚物,分子量可达10×10~4,玻璃化转变温度约为41℃;并且随着PBAu含量的增加,共聚物的结晶度逐渐增加。以NaOH溶液为模拟液进行加速降解实验发现,当PBAu含量为30%时,可以显著提高嵌段共聚物的降解速率,并且通过调节PLA、PBAu预聚物的含量,可以控制嵌段共聚物的降解速率。     

PLA-b-PMMA嵌段结构对PC/PLA共混形态和性能的影响

制备了具有不同嵌段长度的聚乳酸b聚甲基丙烯酸甲酯（PLA-b-PMMA),并将其作为大分子相容剂用于聚碳酸酯/聚乳酸（PC/PLA）共混体系,研究嵌段结构对PC/PLA共混体系形态与性能的影响。用傅里叶红外光谱仪和核磁共振氢谱表征嵌段共聚物的结构,用差示扫描量热仪、扫描电子显微镜和力学性能测试表征共混体系的结构及性能。结果表明,PLA-b-PMMA的加入改善了PC与PLA之间的相容性,其增容效果取决于PLA-b-PMMA的添加量及两嵌段的长度;当PLA-b-PMMA添加量为6 %时,PC与PLA之间的相容性较好;在PMMA嵌段长度一定时,随着PLA链段长度从3390提高到9780,共混体系中两相的相容性不断改善,共混物的力学性能增强;在PLA嵌段长度一定时,随着PMMA链段长度从20680提高到99680,增容效果逐渐下降。     

高相对分子质量聚乳酸共聚物的制备及性能研究

聚乳酸(PLA)与聚己内酯多元醇(HO—PCL—OH)的聚氯酯预聚体在双螺杆挤出机内进行熔体扩链,制备了聚乳酸共聚物,研究了熔体扩链产物的相对分子质量、形态结构、热性能和力学性能。结果表明,双螺杆反直挤出制备聚乳酸共聚物是可行的,效果比釜式反应好,熔体扩链后产物的相对分子质量随预聚体比例不同而有很大差异,当 PLA 预聚体与 PCL 预聚体的质量比为60/40时达到最大值166800,进一步增大 PCL 预聚体含量,相对分子质量下降;反应速率与反应温度有很大关系,在反应温度为160、170、180℃时,反应完成时间分别为5、4.5、3 min;共聚物呈现典型的球晶形态,表现出很好的黑十字消光现象,共聚物在120℃时所得球晶半径最大;共聚物的结晶度低于PLA 预聚体的结晶度;共聚物具有较好的力学性能,随 PCL 预聚体含量增加共聚物的韧性增加,拉伸强度与拉伸模量下降。     

熔融扩链反应制备PLA／PBAT多嵌段共聚物

以六亚甲基二异氰酸酯(HDI)为扩链剂,在催化剂辛酸亚锡作用下,通过熔融扩链反应制备了聚乳酸(PLA)/聚(己二酸丁二酯/对苯二甲酸丁二酯)(PBAT)多嵌段共聚物.研究了反应时间、温度、扩链剂用量等工艺条件对PLA/PBAT共聚物结构、相对分子质量的影响.用红外光谱仪、核磁共振仪、偏光显微镜等分析手段对PLA、PBAT和PLA/PBAT共聚物进行了分析表征.结果表明,通过扩链反应,PLA的分子链中引入了新的嵌段,其相时分子质量及柔韧性大幅度提高.     

聚乳酸/聚己内酯增容体系的结晶性能

以丙交酯/己内酯共聚物(LACL)为聚乳酸(PLA)/聚己内酯(PCL)共混物的增容剂,采用溶液共混法制备了PLA/PCL/LACL三元共混物;通过扫描电子显微镜、差示扫描量热仪研究了共混物的形貌和结晶性能。结果表明,加入5%(质量分数,下同)的LACL,分散相的尺寸明显减小;PCL能显著提高PLA分子链的结晶能力,使其结晶温度(T_p)降低,而LACL对PLA/PCL的增容作用,使PLA/PCL/LACL三元共混物中PLA的Tp进一步降低;通过Kissinger方程计算发现PCL和LACL的加入显著降低了PLA的结晶活化能。     

软段分子链结构对PUF性能的影响

通过将聚乙二醇(PEG)、聚己内酯(PCL)、聚乳酸(PLA)和聚四氢呋喃醚(PTMG)等不同特性的聚合物链段引入聚氨酯(PU)基体,制备了具有不同软段结构的聚氨酯泡沫塑料(PUF)。考察了不同软段分子链结构对PUF力学性能、热性能及在土壤中降解性能的影响。结果表明,随着软段中PEG或PLA含量的增加,PUF的拉伸强度下降;不同软段结构PUF的玻璃化转变温度顺序为:PTMG1000相似文献   

不同拓扑结构PEG-PCL嵌段共聚物的结晶研究

合成了不同拓扑结构的聚乙二醇-聚己内酯(PEG-PCL)嵌段共聚物,共聚物结构分别为AB型线性两嵌段(diblock)、ABA型线性三嵌段(triblock)、AB_2型星形(star shape)嵌段共聚物。通过表征发现嵌段共聚物的分子量与设计的分子量接近,且相对分子量分布窄。通过XRD、DSC、热台偏光显微镜(HSPOM)研究了拓扑结构对共聚物结晶的影响。ABA聚合物中间的PEG亲水链受到两端PCL链段阻碍,其结晶衍射峰最弱。三者的等温结晶速率按AB、AB_2、ABA的速率递减,形成的球晶结构规整度则逐渐增加。     

PLA/PCL纤维及其支架的制备与力学性能研究

将一定质量比聚乳酸(PLA)与聚己内酯(PCL)进行共混,通过熔融纺丝得到PLA/PCL初生纤维,再经过热拉伸后得到PLA/PCL纤维;利用自制模具采用手工编织的方法制备了PLA/PCL管道支架;对PLA/PCL纤维及其支架的结构与性能进行了表征。结果表明:当PLA/PCL质量比为40:60时,PLA/PCL初生纤维的综合力学性能较好;拉伸温度和拉伸倍数对PLA/PCL初生纤维的力学性能影响较大,当拉伸温度为85℃、拉伸倍数为7时,所得的PLA/PCL纤维力学性能最好;在一定温度区间内,PLA/PCL支架的支撑力随着定型温度的升高而升高,合适的定型温度应为其玻璃化转变温度至130℃之间,制备的PLA/PCL支架具有良好的弯曲性、压缩性和支撑性能,能满足支架应用的需求。     

己内酯/乙交酯嵌段共聚物的合成及水解行为研究

以辛酸亚锡为催化剂,合成了己内酯预聚物(PCL),再与乙交酯(GA)熔融共聚,制备了嵌段型己内酯乙交酯共聚物(PCL/GA)。利用GPC、FT-IR、1H-NMR和13C-NMR等对PCL/GA的结构进行了表征,确认合成的共聚物为嵌段型聚酯共聚物。利用XRD和DSC测试了PCL/GA的结晶状态和热学性能,测试发现合成的共聚物均为结晶型聚合物,且结晶情况与单体组成有关,利用石英微晶天平考察了PCL/GA(80/20)在海水中的水解行为,发现前3 h聚酯降解速率波动较大,推断是由于初期嵌段聚酯吸水与降解作用同时进行所致,随着吸水作用的完成,后期嵌段聚酯的降解速率维持在80 ng/(cm2.h)左右,降解速率稳定。利用POM、SEM观察了水解过程中薄膜结晶及形貌变化。     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

Methyl 2,4,6-decatrienoates Attract Stink Bugs and Tachinid Parasitoids

Halyomorpha halys (Stål) (Pentatomidae), called the brown marmorated stink bug (BMSB), is a newly invasive species in the eastern USA that is rapidly spreading from the original point of establishment in Allentown, PA. In its native range, the BMSB is reportedly attracted to methyl (E,E,Z)-2,4,6-decatrienoate, the male-produced pheromone of another pentatomid common in eastern Asia, Plautia stali Scott. In North America, Thyanta spp. are the only pentatomids known to produce methyl 2,4,6-decatrienoate [the (E,Z,Z)-isomer] as part of their pheromones. Methyl 2,4,6-decatrienoates were field-tested in Maryland to monitor the spread of the BMSB and to explore the possibility that Thyanta spp. are an alternate host for parasitic tachinid flies that use stink bug pheromones as host-finding kairomones. Here we report the first captures of adult and nymph BMSBs in traps baited with methyl (E,E,Z)-2,4,6-decatrienoate in central Maryland and present data verifying that the tachinid, Euclytia flava (Townsend), exploits methyl (E,Z,Z)-2,4,6-decatrienoate as a kairomone. We also report the unexpected finding that various isomers of methyl 2,4,6-decatrienoate attract Acrosternum hilare (Say), although this bug apparently does not produce methyl decatrienoates. Other stink bugs and tachinids native to North America were also attracted to methyl 2,4,6-decatrienoates. These data indicate there are Heteroptera in North America in addition to Thyanta spp. that probably use methyl 2,4,6-decatrienoates as pheromones. The evidence that some pentatomids exploit the pheromones of other true bugs as kairomones to find food or to congregate as a passive defense against tachinid parasitism is discussed.     

2007～2008年世界塑料工业进展

收集了2007年7月～2008年6月世界塑料工业的相关资料,介绍了2007～2008年国外塑料工业的发展情况,提供了世界塑料产量、消费量及全球各类树脂的需求量及产能情况.按通用热塑性树脂(聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂)、工程塑料(尼龙、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚)、特种工程塑料(聚苯·硫醚、液晶聚合物、聚醚醚酮)、通用热固性树脂(酚醛、聚氨酯、不饱和聚酯树脂、环氧树脂)不同品种的顺序,对树脂的产量、消费量、供需状况及合成工艺、产品应用开发、树脂品种的延伸及应用的进一步扩展等技术作了详细介绍.     

2005～2006年国外塑料工业进展

收集了2005年7月～2006年6月国外塑料工业的相关资料,介绍了2005—2006年国外塑料工业的发展情况。提供了世界塑料产量、消费量及全球各类树脂生产量以及各国塑料制品的进出口情况。作为对比,介绍了中国塑料的生产情况。按通用热塑性树脂（聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂）、工程塑料（聚酰胺、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚）、通用热固性树脂（酚醛、聚氨酯、不饱和树脂、环氧树脂）、特种工程塑料（聚苯硫醚、液晶聚合物、聚醚醚酮）的品种顺序,对树脂的产量、消费量、供需状况及合成工艺、产品开发、树脂品种的延伸及应用的扩展作了详细的介绍。