线型聚砜-聚硅氧醚氨酯嵌段聚合物的合成和结构性能的探索

<正> 最近,聚硅氧醚与聚氨酯、聚碳酸酯或聚砜等的嵌段聚合物作为高分子结构材料和功能材料发展较快。本文将带有反应基的齐聚物与予聚物,通过对—NCO基的氢加成反应制得了线型聚砜-聚硅氧醚氨酯嵌段聚合物,考察合成反应特点的同时,初步研究了嵌段聚合物的结构和性能。     

MORPHOLOGY OF BISPHENOL A POLYSULFONE-POLYOXYPROPYLENE SEGMENTED COPOLYMERS

Morphology of bisphenol A polysulfone-polyoxypropylene segmented copolymers was inves-tigated by means of differential scanning calorimetry and transmission electron microscopy. Theresults show that the molecular weights of the hard and soft segments have a pronounced effect onthe morphology of these segmented copolymers, which may changr from three-phase to single-phasestructure depending on the size and the relahve size of the segments. Heat treatment will enhancethe process of phase separation, increasing the domain size of the dispersed phase, Results obtainedby study on the dynamic mechanical properties of these copolymers well support the existence ofthree-phase morphological structure.     

Segmented polyurethanes derived from novel siloxane–carbonate soft segments for biomedical applications

A novel macrodiol based on mixed silicone and carbonate chemistries was synthesized and used as a soft segment precursor in the synthesis of two series of segmented polyurethane (PU) copolymers varying in hard segment content and soft segment molecular weight. The hard segments in these copolymers were derived from 4,4‐methylene diphenyl diisocyanate and 1,4‐butane diol. The phase transitions, microphase separation behavior, and mechanical properties of the copolymers were investigated using a variety of experimental methods. When compared with segmented PU copolymers having predominately poly(dimethyl siloxane) soft segments, these siloxane–carbonate soft segment copolymers exhibit enhanced intersegment mixing, and consequently relatively low mechanical modulus. With relatively low modulus and siloxane units in the soft phase, the siloxane–carbonate PUs have potential for use in cardiac and orthopedic biomedical applications. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

含有机硅三元多嵌段共聚物的研究──Ⅲ．不同硬段、半硬段对含有机硅三元多嵌段共聚物性能的影响

以双酚Ａ聚砜或酚酞作为硬段，聚对羟基苯乙烯、酚醛、聚羟基醚或聚羟基醚砜作为半硬段，聚二甲基硅氧烷作为软段合成了七种三元多嵌段共聚物，并对其稳定性、动态力学性能进行了比较详细的研究。结果表明这类共聚物在溶液中的稳定性及热稳定性主要与半硬段有关；它们的形态结构同属于微相分离，并在很宽的温度范围内表现出优良的弹性体性质。三元多嵌段共聚物中硬段与半硬段的相容性直接影响其力学性能，当两者的相容性好时，其强度高于对应的二元多嵌段共聚物。     

Synthesis and characterization of semicrystalline cycloaliphatic polyester/poly(dimethylsiloxane) segmented copolymers

High molecular weight poly(dimethylsiloxane)/semicrystalline cycloaliphatic polyester segmented copolymers based on dimethyl-1,4-cyclohexane dicarboxylate were prepared and characterized. The copolymers were synthesized using a high trans content isomer that afforded semicrystalline morphologies. Aminopropyl-terminated poly(dimethylsiloxane) (PDMS) oligomers of controlled molecular weight were synthesized, end capped with excess diester to form a diester-terminated oligomer, and incorporated via melt transesterification step reaction copolymerization. The molecular weight of the polysiloxane and chemical composition of the copolymer were systematically varied. The polysiloxane segment was efficiently incorporated into the copolymers via an amide link and its structure was unaffected by low concentrations of titanate transesterification catalyst, as shown by control melt experiments. The homopolymer and copolymers were characterized by solution, thermal, mechanical, and surface techniques. The segmented copolymers were microphase separated as determined by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and by transmission electron microscopy (TEM). It was demonstrated that relatively short poly(dimethylsiloxane) segment lengths and compositions were required to maintain single phase melt polymerization conditions. This was, in fact, the key to the successful preparation of these materials. The copolymers derived from short poly(dimethylsiloxane) segments demonstrated good mechanical properties, melt viscosities representative of single phase polymer melts, and were easily compression molded into films. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3495–3506, 1997     

聚醚型多嵌段共聚物软链段结晶特性的研究

本文使用虹外光谱及膨胀计等方法,对聚四亚甲基醚二醇类多嵌段共聚物的软链段结晶性进行了研究。在聚醚-聚酯多嵌段共聚物中(PTMEG>60％),其软链段结晶的熔点和结晶速率均随PTMEG含量减少而下降。而在聚醚-聚脲胺酯多嵌段共聚物中,由于N—H和C—O—C之间氢键的作用,即使在低温下,其软链段也难于结晶。此外,高倍拉伸会提高上述二类多嵌段共聚物中软链段结晶的熔点和结晶速率。     

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.     

SYNTHETIC STUDIES ON BLOOD COMPATIBLE BIOMATERIALS Ⅲ. SYNTHESIS, CHARAC-TERIZATION AND ANTITHROMBOGENICITY OF DIMETHYLDIPHEN YLPOLYSILOXANE/POLY (OXYTETRAM ETHYLENE)-POLYUREA SEGMENTED COPOLYMERS

A novel class of segmented copolymers, dimethyldiphenylpolysiloxane/poly (oxytetramethylene)-polyurea (PSPEU), was synthesized from α, ω-bis (γ-aminopropyl) dimethyldiphenylpolysiloxane (APMPS), which was prepared by means of basic ring-opening copolymerization of octamethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane and 1, 3-bis (γ-aminopropyl) tetramethyl disiloxane. The relationships between the diphenylsiloxy contents and the properties of APMPS, including refractive index, glass transition temperature, solubility parameter as well as thermal stability, were investigated; meanwhile, the thermal stability, dynamic mechanical properties, mechanical properiesas well as the antithrombogenicity in vitro of the PSPEU were also revealed.     

聚四氢呋喃/聚苯乙烯交联嵌段及接枝共聚物的合成与阻尼性能

合成接枝共聚物和嵌段共聚物是研究阻尼材料的重要途径,这是由于可以在较广的范围内,调整共聚物的结构,使之具有良好的阻尼性能。这里我们选择了端羟基聚四氢呋喃与顺丁烯二酸酐反应,制成端乙烯基大分子单体及端乙烯基遥爪低聚物。然后与苯乙烯共聚,制成接枝共聚物和嵌段共聚物。从两者的比较中探讨各种因素对共聚物阻尼性能的影响规律。认为研究结果将有益于阻尼材料的分子设计,在反应体系及合成方法上,都比较简便,适于工业生产,便于推广应用。     

聚四氢呋喃/聚苯乙烯交联嵌段及接枝共聚物的合成与阻尼性能

Carboxyl vinyl terminated polytetrahydrofuran macromers and telechelic oligomers were synthesized from hydroxyl terminated polytetrahydrofuran by end group conversion. From these macromers or telechelic oligomers and styrene polytetrahydrofuran/polystyrene segmented and graft copolymers were synthesized and the effects of molecular structure on the damping properties of those copolymers were also studied.     

新型含有机硅二元多嵌段共聚物的研究

报道了聚羟基醚（ＰＨＥ）、聚羟基醚砜（ＰＨＥＳ）、酚酞聚羟基醚（ＰＰＨＥ）和聚对羟基苯乙烯（ＰＨＳ）与端胺基聚二甲基硅氧烷（ＰＤＭＳ）通过羟胺缩合生成ＡＢｍｎ新型结构的可溶性含有机硅二元多嵌段共聚物，ｍ值在１～６之间，详细讨论了反应物浓度对共缩聚反应的影响，并通过分子量测定、红外光谱分析和动态力学分析（ＤＭＡ）技术初步确定了其反应机理、结构和动态力学性能．     

多嵌段共聚物分子的组成不均一性

从不同结构层次角度说明了多嵌段共聚物的分子组成不均一性。提出了一种新的看法,即在讨论多嵌段共聚物的形态和性能时,除了链段间的微相分离外,还必须首先考虑不同平均链段长度的多嵌段大分子间的宏观相分离作用。如何表征与控制其组成不均一性是十分重要的课题。     

线型聚芳醚砜-聚醚氨酯嵌段共聚物的合成及其结构性能的初步探讨

<正> 具有抗凝血性和其它一些特殊性能的聚醚氨酯嵌段聚合物,最近颇受注视。本文以异氰酸酯的氢转移加成聚合反应为主的合成方法,在聚合物的主链中引入具有一定结构的其它链段组份,合成了一类新的线型聚芳醚砜-聚醚氨酯嵌段共聚物。并就其结构与性能的关系进行了初步探讨。     

聚酯聚氨酯嵌段共聚物及其离聚体的研究

以烃基封端的聚酯与4,4'-二苯基甲烷二异氰酸酯及N-甲基二乙醇胺合成了3种不同硬段含量的聚酯聚氨酯嵌段共聚物。然后,与γ-丙磺酸内酯反应,制得不同离子化程度的离聚物。通过对这些聚合物进行红外光谱、应力-应变试验、差示扫描量热(DSC)、动态力学性能和介电温度谱的分析,得出硬段含量和离子化程度对材料微相分离和物理性能的影响规律,并探讨了引起材料微观形态变化的原因。     

COMPOSITIONAL HETEROGENEITY OF ETHYLENE OXIDE-BUTYLENE TEREPHTHALATE SEGMENTED COPOLYMER*

A series of ethylene oxide-butylene terephthalate (EOBT) segmented copolymers with differentsoft segment length and hard segment content were synthesized. The compositional heterogeneity was studiedby solvent extraction. The results show that the compositional heterogeneity increases when soft segmentlength and hard segment content increase. The compositional heterogeneity is also reflected in thecrystallization behavior and morphology of soft and hard segment in EOBT segmented copolymer. The morecompositional heterogeneous the EOBT segmented copolymer is, the more different the morphology and thecrystallization behavior between separated fractions. Compared with ethylene oxide-ethylene terephthalate(EOET) segmented copolymer, compositional heterogeneity in EOBT segmented copolymer is weaker. Butthe compositional heterogeneity in EOBT segmented copolymer with long soft segment and high hardsegment content is still obvious.     

共聚聚醚酯酰胺的多重转变及其相态结构

Segmented polyesteramides have been synthesized from N,N'-bis（p-carbomethoxybenzoy）butanediamine（T4T）as crystalline segments and mixture of poly（tetramethylene oxide）with the average molecular weight 1000（PTMO1000）and 1,5-pentanediol（PDO）as soft segments. The polymerization was carried out in the melt at 250℃ for 1-2 h while vacuum was applied. The chemical composition of the copolymer was measured by H1-NMR. The melting behavior of the copolymers was studied by the differential scanning calorimeter. The dynamic mechanical properties were investigated on injection moulded bars by means of dynamic mechanical analysis. It was found that the copolymers with more than 40% molar ratio PDO showed two glass transition temperatures and two melting temperatures. The glass transition temperatures are independent of composition,and thus two fully phaseseparated amorphous phases are present. The melting temperatures change with PDO content. The amount of PDO has an effect on both TmA and TmB . TmA is attributed to the lamella consisting of extended T4T segments,while TmB results from the much thicker lamella consisting of both extended T4T and PDO segments. It is also possible that some PDO is present in the interphase as adjacent re-entry groups. So the resultant copolymer shows that a complex system,two crystalline phases,two amorphous phases and an interphase are involved in the copolymer. The undercooling for these copolymers is small,which means that these segmented copolymers crystallize fast.     

Synthesis and properties of segmented block copolymers based on mixtures of poly(ethylene oxide) and poly(tetramethylene oxide) segments

The synthesis and characterisation of segmented block copolymers based on mixtures of hydrophilic poly(ethylene oxide) and hydrophobic poly(tetramethylene oxide) polyether segments and monodisperse crystallisable bisester tetra-amide segments are reported. The PEO length was varied from 600 to 8000 g/mol and the PTMO length was varied from 650 to 2900 g/mol. The influence of the polyether phase composition on the thermal mechanical and the elastic properties of the resulting copolymers was studied.The use of high melting monodisperse tetra-amide segments resulted in a fast and almost complete crystallisation of the rigid segment. The copolymers had only one polyether glass transition temperature, which suggests that the amorphous polyether segments were homogenously mixed. Thermal analysis of the copolymers showed one polyether melting temperature that was lower than in the case of ideal co-crystallisation between the two polyether segments. However, at PEO or PTMO lengths larger than 2000 g/mol two polyether melting temperatures were observed. The copolymer with the best low temperature properties was based on a mixture of PEO and PTMO segments, both having a molecular weight of 1000 g/mol, at a weight ratio of 30/70.     

Characterization of impact polypropylene copolymers by solvent fractionation

The compositional heterogeneity of two impact polypropylene copolymers(IPCs) was studied by a combinatory investigation of temperature rising elution fractionation(TREF) and solvent fractionation.The chain structures and composition of fractions obtained from solvent fractionation were examined in detail.The TREF results shows that there are much more E-P segmented copolymer and more uniform distribution of ethylene sequence in IPC-1,which is responsible for its better comprehensive mechanical performance.The fractions from hexane and heptane are ethylene-propylene rubber phase and E-P block copolymers respectively.The result of solvent fractionation method also shows that custom hexane or heptane extractions can not extract the E-P copolymer completely.     

Perfectly alternating segmented polyimide-polydimethyl siloxane copolymers via transimidization

New strategies for the synthesis of perfectly alternating segmented polyimide-polydimethyl siloxane copolymers were developed by utilizing a transimidization method. Imide oligomers endcapped with 2-aminopyrimidine were reacted with aminopropyl terminated (dimethyl siloxane) oligomers to afford perfectly alternating segmented imide siloxane copolymers. The polymerization was conducted in solvents such as chlorobenzene and chlorofrom. High molecular weight, fully imidized perfectly alternating segmented imide siloxane copolymers were obtained within 2 h at temperatures of 60-110°C. The mechanism of the reaction was further elucidated via model compounds and NMR characterization. The block copolymers exhibited two T_gs due to the microphase separation of the polyimide and polysiloxane phases. The T_g of the polyimide phase was a function of the length of the polyimide block. However, partial phase mixing was also evident from the DSC results on the imide siloxane copolymers prepared with low molecular weight polyimide segments. Thermooxidative stability and tensile properties of the perfectly alternating segmented imide siloxane copolymers were found to be principally dependent on the amount of poly (dimethyl siloxane) incorporated in the copolymer and did not correlate with the poly (dimethyl siloxane) or polyimide block lengths. The stress-strain behavior of both solvent cast films or molded films is also reported. © 1994 John Wiley & Sons, Inc.     

New multiblock poly(ether-ester)s based on poly(trimethylene terephthalate) as rigid segments

A series of novel poly(trimethylene terephthalate)-block-poly(tetramethylene oxide) (PTT--PTMO) segmented block copolymers were synthesised by transesterification in the melt of dimethyl terephthalate, 1,3-propanediol and poly(tetramethylene oxide) glycol (PTMO, 1000 g/mol). A range of multiblock copolymers were synthesized, with flexible PTMO segments contents varying from 20 to 80 wt%. The novel poly(ether-block-ester)s were characterized by using viscometry, hardness measurements, differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and tensile properties.