聚砜-尼龙6嵌段共聚物结构的研究

<正> 以金属钠作催化剂合成的聚砜-尼龙6嵌段共聚物对尼龙6的吸水性有一定的改善,而且可以作为聚砜与尼龙共混物的相容剂,但共聚物中聚砜组分的含量都不超过25％。这可能与共聚物的结构有关。近年来的工作表明:反相气相色谱法(IGC)是高聚物结构分析的有用的工具之一。我们试图用反相气相色谱法,通过观察嵌段共聚物     

原位复合材料的加工性能

使用ＨＢＩＲｈｅｏｍｉｘ６１０型混合机将四种全芳香族热致液晶聚合物与热塑性树脂熔融共混，研究了混合效果，混合过程的平衡转矩与时间，温度的关系，结果显示，用该混合机可以得到均匀分散的共混体系，这些液晶聚合物具有大大低于纯聚砜的熔体粘度，将其与聚砜熔混，可使其混体系的平衡转矩比纯聚砜减小２－３倍，说明液晶聚合物是一种加工助剂，能用来改善高性能工程塑料的加工性能。     

聚砜-尼龙6嵌段共聚体的溶液性质及其与聚砜、尼龙6均聚物的相容性的研究

<正> 我们曾在前二篇文章中指出非晶型双酚A聚砜(以下用B表示)与结晶形尼龙6(以下用N表示)经共混得到的共混物很脆,而聚砜-尼龙6嵌段共聚物(以下用B-N和N-B-N表示)却具有较B或N更优的耐溶剂性和耐水性,但是嵌段共聚物中B组分含量不能超过25％,这样就限制了材料的使用范围,然而由于B-N(或N-B-N)在同一分     

尼龙1212/尼龙6共混体系的非等温结晶行为

用DSC研究了尼龙 12 12 ,尼龙 6及其共混体系的非等温结晶行为 .结果表明 ,加工历史对尼龙的结晶和熔融行为影响很大 .经双螺杆挤出机挤出的尼龙 12 12和尼龙 6 ,由于应力诱导分子链取向 ,其结晶温度都有不同程度的提高 ,且表现出多重熔融现象 .在共混体系中 ,尼龙 12 12分子在共混物的界面上异相成核结晶 ,提高了其结晶温度 ,但酸酐化SEBS的加入抑制了分子链的运动又使其结晶温度降低 .共混体系降低了尼龙12 12的熔融温度 ,并使得其高熔点的熔融峰逐渐消失 ;而尼龙 6的熔融行为基本上没有变化 .     

毛细管流变仪中尼龙6在聚丙烯中的原位成纤

将聚丙烯与尼龙6的共混物在毛细管流变仪中挤出，通过显微形态观察发现，在研究的共沸比范围和较宽的剪切速度和温度范围内尼龙6均能在聚丙烯基体中成纤，表明这种热塑性树脂的成纤性比热致液晶聚合物的更好。     

三氟乙酸溶液中尼龙6链凝聚缠结的NMR弛豫研究

采用1D和2DNMR技术,归属了三氟乙酸(TFA)溶液中尼龙6链上的主要¹HNMR共振信号.不同温度下测定的自旋-自旋弛豫时间(t2)提供了大分子主链间凝聚缠结及TFA溶液中尼龙6链随温度变化的动力学信息.结果表明,尼龙6主链上亚甲基基团有不同程度的凝聚缠结,距离CO和NH基团越远,凝聚缠结越明显.与CO和NH基团相连的亚甲基基团的缠结不很明显,主要是因为尼龙6链间氢键的存在.升高温度,热运动加快,这些凝聚缠结逐渐减弱.NH质子的t2H值几乎不随温度变化,TFA质子的t2H值随温度升高而快速下降,表明尼龙6链间氢键随温度升高而破坏,TFA质子又与因温度升高而从尼龙6中释放出来的自由NH和CO基团形成新的氢键.     

不同温度下尼龙6性能和结构变化的原位研究

利用拉伸热台对尼龙6在不同温度下的拉伸性能进行了测试和分析.随着拉伸温度的升高,尼龙6样品的屈服强度和杨氏模量逐渐下降.采用了一个阿伦尼乌斯模型来描述尼龙6屈服强度与拉伸温度之间的关系,并描述了尼龙6样品黏度、玻璃化温度对屈服强度的影响.通过原位同步辐射广角衍射分析,我们发现未拉伸的尼龙6样品中的α相与γ相的相对比率随温度升高而下降.在拉伸条件下,随着拉伸温度的升高,样品的结晶部分容易产生滑移或晶区的熔融,有序程度下降,因而样品承载外力的能力下降,体现为屈服强度和杨氏模量的下降.     

拉伸温度和退火对尼龙6力学性能的影响

尼龙6(P6)制品在使用过程中受环境温度和应力作用后结构可能发生变化从而影响性能.把注射成型的P6哑铃型样品进行退火,利用拉伸热台在不同温度下拉伸得到退火前后样品的应力-应变曲线.通过对应力-应变曲线分析得到了退火前后尼龙6的力学性能.包括杨氏模量、屈服强度、屈服应变随拉伸温度的变化规律,并对实验结果进行了分析讨论.结果表明,退火后尼龙6的力学性能有了明显地提高.     

原位聚合玻纤-尼龙6热塑性复合材料的研究

研究了己内酰胺开环聚合反应,确定了适用于RTM方法原位制备玻纤织物增强热塑性复合材料的工艺。结果表明:表面处理可抑制玻纤对单体的阻聚作用,使单体转化率达97%,尼龙6的分子量大于3.0×105;制备的玻纤方格布增强尼龙6复合材料的力学性能比纯尼龙6有显著提高。SEM分析表明复合材料有着良好的界面连接。     

热塑性甲壳素衍生物N,O-苄基壳聚糖的合成及表征

天然高分子的热塑化一直引起人们的极大关注．由于存在大量的分子内和分子间氢键,一般天然高分子都不能加热塑化,从而限制了其应用．纤维素和淀粉的热塑化改性已有了许多研究．典型的热塑性纤维素衍生物有乙基纤维素、醋酸纤维素和经丙基纤维素等[1,2],有些纤维素衍生物还具有热致液晶性．淀粉的某些衍生物也已有热塑性[3]．在分子结构上,甲壳素／壳聚糖比纤维素或淀粉多了乙酰氨基和氨基,更易形成氢键,分子间作用力更强．迄今,国内外已报道了大量甲壳素／壳聚糖衍生物,但均无热塑性．我们曾合成具有热塑性的氰乙基经丙基壳聚糖,但熔点与分解温度之间只有27℃E4J．热塑性甲壳素的研究不仅为甲壳素的加工利用开辟了新途径,而且也将为热致性甲壳素液晶的研究奠定基础,从而进一步丰富和深化目前以纤维素衍生物为主的热致胆舀液晶研究[5,6]．为此,本文研究了一种新的热塑性甲壳素衍生物,并从结构上讨论了其具有热塑性的原因．     

Bulk and surface properties of blends with semifluorinated polymers and block copolymers

The goal of the investigation presented here is the development of extremely hydrophobic materials based on polysulfone that can be applied, for instance, as fouling-resistant membrane materials. The concept used is the addition of semifluorinated polymers to polysulfone in suitable blend compositions. The influence of molecular parameters like chain structure of the semifluorinated polymer (segmented block copolymers, random copolymers) and segment molecular weight on the state of phase separation in the bulk and its influence on the surface properties have been systematically examined. It could be shown that segmented block copolymers with semifluorinated polyester segments with intermediate segment molecular weight are more suitable in blends with polysulfone than random polysulfone copolymers having semifluorinated side chains with respect to form homogeneous thin films (coatings) with highly non-wetting properties.     

聚砜-聚羟基醚嵌段共聚体的合成与表征

在碱性条件下由羟端基聚砜与双酚A环氧氯丙烷相互作用下制取了聚砜-聚羟基醚嵌段共聚物。溶解度试验、红外光谱、动态和静态力学试验等证明产物确是嵌段共聚物。     

新型高分子材料聚砜类共聚物

本文介绍了聚砜类共聚物的合成方法和表征手段。报道了这类材料的结构和性能。指出了由硬的无定型热塑性链段和结晶链段共聚得到的新材料的优异功能，结晶链段的存在提高了材料的耐溶剂性能和耐应力开裂性。嵌段共聚物(AB或A-B-A)可作为下相容聚合物之间或溶剂之间的相容剂。     

Tailoring of polymer properties in segmented block copolymers

Linking segments of two different polymers in block copolymers offers the opportunity to combine their macroscopic properties and to design tailor‐made materials. This is shown for segmented block copolymers (A‐B)_n in which the basic segment is polysulfone. Incorporation of either hydrophilic and or hydrophobic segments results in a dramatic change of surface properties which is also correlated to the bulk structure of the block copolymers.     

Transformation of “living” carbocationic and other polymerizations to controlled/“living” radical polymerization

Transformation of “living” carbocationic polymerization of styrene and isobutene to controlled atom transfer radical polymerization (ATRP) is described and formation of the corresponding AB and ABA block copolymers with styrene (St), methyl methacrylate (MMA, methyl acrylate (MA) and isobornyl acrylate (IBA) was demonstrated. A similar approach was applied to the cationic ring opening polymerization of tetrahydrofuran leading to the AB and ABA block copolymers with St, MMA and MA using ATRP. Site transformation approach was also used for the ring opening metathesis polymerization of norbornene and polycondensation systems using polysulfone as an example. In both cases, AB and ABA block copolymers were efficiently formed with styrene and acrylates.     

Synthesis and characterization of ABA triblock copolymers containing poly(2,6-dimethyl-1,4-phenylene oxide) as A blocks and tetramethyl bisphenol-A polysulfone as B blocks

α, β-Bis(hydroxyphenol) tetramethyl bisphenol-A polysulfone (PSUT) was synthesized by two different methods, one using a strong base, the other using a weak base. The bifunctional polysulfone containing tetramethyl bisphenol-A chain ends was exploited as a model telechelic that can be used for the preparation of ABA triblock copolymers containing poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) as A segments and PSUT as B segments. PSUT and PPO were incorporated into triblock copolymers by an oxidative coupling copolymerization of PSUT with 2,6-dimethylphenol or by the redistribution of PPO in the presence of PSUT. The mechanism of block copolymerization is discussed. DSC studies indicate that short immiscible PPO and PSUT segments incorporated into a triblock copolymer do not exhibit phase separation. Polymer blends of the PPO–PSUT–PPO triblock copolymers with PPO homopolymer were analyzed by DSC. Both miscible and phase-separated blends can be prepared depending on the molecular weight of both PPO homopolymer and of the PPO segment present in the triblock copolymer. Polymer blends of the PPO–PSUT–PPO triblock copolymer with PSUT were miscible at all compositions.     

The influence of segmented block copolymers in immiscible polymer blends

One mechanism for compatibilization of immiscible polymer blends is adding block copolymers (BCP) that consist of segments chemically comparable to the parent homopolymers in the blend. BCP do both, emulsify the disperse phase to give smaller particles as well as increase the interfacial adhesion between the phases. The influence of segmented BCP in blends of immiscible high‐performance polymers was investigated systematically by variation of the flexibility of the BCP segments. It was shown that the stiffness of the second segment in polysulfone (PSU) block copolymers as well as the PSU segment molecular weight determine the intermixing between the BCP and the PSU matrix.     

PSF-g-PAA和PSF-g-PNIPAAm的合成及其共混膜的环境响应性研究

以氯甲基化双酚A型聚砜(PSF-CH2Cl)为大分子引发剂,通过原子转移自由基聚合法(ATRP)合成了以聚砜(PSF)为疏水主链、分别以聚丙烯酸(PAA)和聚(N-异丙基丙烯酰胺)(PNIPAAm)为亲水侧链的两种梳状两亲性共聚物PSF-g-PAA和PSF-g-PNIPAAm.利用1H-NMR和GPC对合成产物进行表征.然后,分别将PSF-g-PAA和PSF-g-PNIPAAm与PSF进行共混,通过浸没沉淀相转化法制备了共混膜.研究发现,引入20 wt%的两亲性共聚物后,PSF-g-PAA/PSF共混膜的水通量在pH=2~6区间发生明显的变化,即膜的水通量显示出典型的pH响应性;而PSF-g-PNIPAAm/PSF共混膜的纯水通量在20~60℃温度区间显示出典型的温度响应性.     

Synthesis and characterization of semifluorinated polymers and block copolymers

The goal of the investigation presented here was to evaluate the influence of semifluorinated side chains on the bulk structure and the surface properties of polysulfones with different chain structure. Thus, segmented block copolymers consisting of polysulfone and semifluorinated aromatic polyester segments as well as polysulfones having semifluorinated side chains randomly distributed over the polymer backbone were synthesized and characterized. Oxydecylperfluorodecyl side chains were used because of their strong tendency for self-organization. The influence of the chain architecture on the self-organization as well as on the surface properties, particularly the wetting behavior, was examined. It could be shown that despite of the higher self-organizing tendency of block copolymers the surface properties of both polymer types are comparable and depend only on the concentration of side chains.