PA6-b-PPG嵌段共聚物的合成与表征

以己内酰胺、己二酸、聚丙二醇(PPG)等为原料,采用高压反应釜进行熔融缩聚,合成了一系列热塑性弹性体尼龙6-b-PPG(PA6-b-PPG)嵌段共聚物。通过傅立叶变换红外分析、核磁共振氢谱对其化学结构进行表征,通过差示扫描量热、热失重分析其热性能,通过差示扫描量热分析、广角X射线衍射及偏光显微镜分析其结晶性能,并测试了材料的力学性能。结果表明,聚合产物为PA6硬段与PPG软段的嵌段共聚物;制备的系列PA6-b-PPG嵌段共聚物熔点在209~225℃之间,起始热分解温度在380~397℃之间。随着PPG含量的增加,PA6-b-PPG嵌段共聚物从γ型结晶向α型结晶转变,密度、硬度、拉伸强度、弯曲强度逐渐降低,而断裂伸长率逐渐增加。可以通过调整软硬段的比例得到不同力学性能的PA6-b-PPG嵌段共聚物,以满足不同条件下的需求。     

PEG含量对PA6/PEG嵌段共聚物结构与性能的影响研究

利用常规的己内酰胺常压水解开环聚合法,通过聚合过程中加入聚乙二醇(PEG)1000制得了PA6/PEG嵌段共聚物,研究了PEG的不同含量对PA6/PEG嵌段共聚物的影响,并通过傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)、X射线衍射仪(XRD)、差示扫描量热(DSC)、热重分析(TG)等测试对产物进行分析。结果表明,PA6与PEG1000发生了嵌段共聚反应,两者之间以酯键相连并交替排列;PEG1000的加入破坏了PA6的分子结构,改变了晶型;随着PEG含量的增加,PA6晶粒尺寸越不均匀,PA6/PEG共聚物的韧性增大,弹性增加,熔点和结晶温度降低,相应的熔融和结晶的温度范围变宽,同时分解温度降低,但其加工的热稳定性良好。     

一步法合成聚醚酰胺嵌段共聚物及其抗静电性能研究

采用一步法合成了由聚乙二醇(PEG)链段和聚酰胺6(PA6)链段组成的聚醚酰胺嵌段共聚物,用红外光谱和核磁共振波谱等手段确证了它的化学结构。随着合成配方中己内酰胺用量的减少,聚醚酰胺嵌段共聚物相对分子质量下降,PA6链段变短。合成的聚醚酰胺嵌段共聚物具有微相分离结构,表面电阻率随着其中PEG链段含量的增加而下降。将合成的聚醚酰胺嵌段共聚物以10%的质量分数添加到ABS塑料中,其表面电阻率由1014Ω量级下降到1011Ω量级,拉伸强度变化不大,断裂伸长率有所下降。     

PET-PA6嵌段共聚物的组成和结构研究

采用差示扫描量热(DSC)法、红外光谱(FTIR)法、元素分析法和核磁共振氢谱(1H-NMR)法对不同配比的PET-PA6嵌段共聚物的结构、组成和性能进行了分析。结果表明:PA6和PET反应后形成了相容性较好的共聚物而非共混物,分子链结构特征是以软段PA6封端的共聚物;共聚反应中加入的PA6质量分数为5%～20%时,随PA6投料比增加,共聚物的熔融温度、冷结晶温度、玻璃化转变温度均呈下降趋势;元素分析法和1H-NMR法测得PET-PA6嵌段共聚物的实际组成与投料比非常接近,实际生产中可通过合理控制投料比来制备所需材料。     

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。     

PA6T/1010共聚物热性能研究

以对苯二甲酸、己二胺和癸二酸、癸二胺为原料合成了新型半芳香PA6T/1010共聚物,通过差示扫描量热仪(DSC)、熔点测定仪和热重分析仪(TG)对不同组成PA6T/1010的熔融行为、结晶行为和热稳定性进行了表征。结果表明:当PA6T含量大于40%时,PA6T/1010共聚物的结晶性能明显下降,熔融峰和结晶峰均消失;当PA6T含量为40%时,共聚物共熔点降至165℃;PA6T/1010共聚物的热降解过程为一步降解,热降解温度超过400℃。     

PET-PEG嵌段共聚物的序列结构研究

用直接酯化法合成了一系列不同 PGE含量的 PET- PEG(聚对苯二甲酸乙二醇酯-聚乙二醇 )嵌段共聚物。用 FTIR、H1- NMR等测试手段对嵌段共聚物的序列结构进行分析。证明 PET- PEG嵌段共聚物的组成与投料比非常接近 ;其分子链结构特征是以硬段 PET封端的多嵌段共聚物 ;PEG含量影响大分子链的序列结构 ,随 PEG含量的增加 ,硬段长度减小 ,软段长度增加。     

PET-PA/PA6共混纤维的酸性染料染色性能

为开发酸性染料可染改性聚酯(PET)纤维,将不同共聚比例的PET-聚酰胺(PA)共聚物与聚己内酰胺(PA6)以不同共混比例共混纺丝,制备PET-PA/PA6共混纤维,研究了PET-PA/PA6共混物的热性能、可纺性及共混纤维的酸性染料染色性能。结果表明:PET-PA/PA6共混物中,PET-PA与PA6在无定形区是部分相容的;PET-PA/PA6共混物具有良好的可纺性,其中PA嵌段和PA6共混质量分数均为20%(PET-PA-20/PA6-20)的共混纤维的断裂强度2.54 c N/dtex、断裂伸长率31.0%,满足后续加工的要求;PA嵌段和PA6共混质量分数均为10%(PET-PA-10/PA6-10)共混纤维采用酸性染料染色时,染浴p H值应控制在4.5~5.5;升高温度和延长染色时间都能提高PET-PA-10/PA6-10共混纤维的染料上染率;随PET-PA/PA6着共聚物中PA嵌段比例的增加,共混纤维染料上染率迅速增大,PET-PA-20/PA6-20共混纤维在100℃时,酸性染料上染率可达到99.03%。     

三嵌段共聚物PS-b-PEG-b-PS与聚苯乙烯共混薄膜的表面形貌与性能研究

使用原子转移自由基聚合(ATRP)制备三嵌段共聚物PS-b-PEG-b-PS.通过红外光谱、核磁共振氢谱(1H-NMR)和凝胶渗透色谱(GPC)对嵌段共聚物结构及分子量进行表征.将嵌段共聚物与聚苯乙烯溶液共混成膜,使用原子力显微镜(AFM)和接触角测试仪(CA)对不同含量嵌段共聚物共混膜的表面形貌和性能进行了分析表征.PEG链段与PS链段在共混膜中发生了微相分离,由于PEG链段对PS链段的热力学排斥作用以及PS的硬链段特性,PS不能在PEG微区上方形成覆盖,因而在薄膜表面形成大量孔洞,PEG微相区位于孔洞底部.随嵌段共聚物含量增加,孔洞(PEG微区)尺寸增大.当嵌段共聚物含量增加10％以后,孔洞内出现PS微相区,导致形成“胞状”结构.嵌段共聚物含量增加使得共混薄膜的亲水性和表面张力增大.     

酯交换反应对PET／PA6共混体系性能的影响

研究了PET与PA6在熔融共混时的酯-酰胺交换反应。采用DSC、SEM、FTIR等测试手段探讨了酯-酰胺交换反应对组分熔点、结晶度及共混物形态的影响。结果发现：酯-酰胺交换反应产生的嵌段共聚物会使组分熔点降低，且反应程度越深熔点降低越多；组分的结晶度也随酯-酰胺交换反应程度的加深而降低；产生的嵌段共聚物可增加组分间的相容性，提高共混体系的力学性能。     

Synthesis and characterization of poly(siloxane-urethane)s

A series of polyurethane block copolymers based on hydroxy-terminated polydimethylsiloxane and poly(propylene glycol) soft segments of molecular weights 1818 and 2000, respectively, were synthesized. The hard segments consisted of 4,4′-diphenylnethane diisocyanate and 1,4-butanediol as the chain extender. Samples with different molar ratios were prepared. We tried to synthesize polydimethylsiloxane-based polyurethanes (PDMS-PU) containing a hard block as major fraction and a soft block as minor fraction for preparing toughened rigid systems. After a study of the pure polydimethylsiloxane-based polyurethane and poly(propylene glycol)-based polyurethane (PPG-PU), (mixed polyol)-based block copolymers and blends of PDMS-PU and PPG-PU were synthesized, and characterized by means of differential scanning calorimetry, tensile testing and scanning electron microscopy. In (mixed polyol)-based copolymers and lower hard-segment content blends, macro-phase separation occurred, but blends with higher hard-segment contents showed significant reduction in amounts of phase separation.     

Segmented block copolymers based on liquid natural rubber

Segmented block copolymers were prepared from hydroxyl-terminated liquid natural rubber (HTNR) and poly(ethylene oxide) (PEO). Toluene 2,4 diisocyanate (TDI) was used as the coupling agent for combining both types of segments. Keeping the molecular weight of HTNR constant, a series of materials were prepared using PEO with varying molecular weights. Their thermal and mechanical properties were evaluated. With increasing the PEO content, the properties vary from soft to rigid elastomers and rubber-toughened plastics. This variation in properties is caused by the changes in the sample morphology, which depends on the relative fractions of the hard and soft segments. Water absorption capability of these block copolymers was determined. Hydrogels with water content approximately up to 80% were obtained.     

Microstructural organization of polydimethylsiloxane soft segment polyurethanes derived from a single macrodiol

Segmented polyurethane (PU) block copolymers were synthesized using 4,4′-methylenediphenyl diisocyanate and 1,4-butanediol as hard segments and oligomeric ethoxypropyl polydimethylsiloxane (PDMS) as the soft segments, with hard segment contents ranging from 26 to 52 wt%. The microphase separated morphology, phase transitions, and degrees of phase separation of these novel copolymers were investigated using a variety of experimental methods. Like similar copolymers with mixed ethoxypropyl PDMS/poly(hexamethylene oxide) soft segments, PU copolymers containing only ethoxypropyl PDMS soft segments were found to consist of three microphases: a PDMS matrix phase, hard domains, and a mixed phase containing ethoxypropyl end group segments and dissolved short hard segments. Analysis of unlike segment demixing using small-angle X-ray scattering demonstrates that degrees of phase separation increase significantly as copolymer hard segment content increases, in keeping with findings from Fourier transform infrared spectroscopy measurements.     

PEG-PET嵌段共聚物序列结构的研究

本文应用GPC、FTIR、TLC、NMR等方法分析、鉴定、研究了实验室自制的PEG-PET嵌段共聚物的嵌段比例、分子量及序列结构,并证实共聚物是一种以PET硬段封端的多嵌段共聚物。     

Effect of soft segment molecular weight on tensile properties of poly(propylene oxide) based polyurethaneureas

Influence of soft segment molecular weight and hard segment content on the morphology, thermomechanical and tensile properties of homologous polyurethaneurea copolymers based on narrow molecular weight poly(propylene oxide)glycol (PPG) oligomers were investigated. A series of polyurethaneureas with hard segment contents of 12–45% by weight and PPG number average molecular weights <M_n> of 2000 to 11,800 g/mol were synthesized and characterized structurally by SAXS and mechanically by DMA and stress strain analysis. Bis(4-isocyanatocyclohexyl)methane and 2-methyl-1,5-diaminopentane were used as the diisocyanate and the chain extender respectively. All copolymers displayed microphase separation by SAXS and DMA. The critical entanglement molecular weight (M_e) of PPG is reported to be around 7700 g/mol. Our mechanical results suggest that when copolymers possess similar hard segment contents and are compared to those based on soft segments with number average molecular weights (M_n) greater than M_e, they generally displayed higher tensile strengths and particularly lower hysteresis and creep than those having soft segment molecular weights below M_e. These results imply that soft segment entanglements in thermoplastic polyurethaneureas may provide a critical contribution to the tensile properties of these copolymers – particularly in the range where the soft segment content is dominant.     

Influence of soft segment composition on phase-separated microstructure of polydimethylsiloxane-based segmented polyurethane copolymers

Segmented polyurethane block copolymers were synthesized using 4,4′-methylenediphenyl diisocyanate (MDI) and 1,4-butanediol (BDO) as hard segments and various soft segments derived from poly(hexamethylene oxide) (PHMO) and poly(dimethylsiloxane) (PDMS)-based macrodiols and mixtures thereof. The microstructure and degrees of phase separation were characterized using a variety of experimental methods. Copolymers synthesized with the PDMS macrodiol and from PDMS/PHMO macrodiol mixtures were found to consist of three phases: a PDMS phase; hard domains; and a mixed phase of PHMO, PDMS ether end group segments and some dissolved hard segments. Two models were used to characterize the small-angle X-ray scattering from these copolymers: pseudo two-phase and core-shell models. Analysis using both methods demonstrates that as the PDMS content in the soft segment mixture increases, the greater the fraction of hard segments involved in hard domains than are dissolved in the mixed phase. Findings from analysis of the carbonyl region of FTIR spectra are also in agreement with greater hard/soft segment demixing in copolymers containing higher PDMS contents.     

Small angle x-ray studies of siloxane-urea segmented copolymers

Novel segmented copolymers were synthesized using aminopropyl terminated linear poly(dimethylsiloxane) oligomers as the soft component and various diisocyanates as the hard segments. As a result of the large differences in the cohesive energy density (solubility parameter) between the two components, phase separation occurs to form a microdomain structure at relatively low oligomer molecular weights. Since chain extenders were not employed during the synthesis, the “hard” segments are strictly related to the length of the diisocyanate moiety utilized in the reaction, In this paper we utilize these copolymers as reasonable models for investigating the various methods available for determining the interfacial layer thickness between the hard and soft phase. Specifically, in these systems there is no hard segment length distribution as is the usual case for segmented urethanes. Utilizing Porod's law, and appropriate analysis, both positive and negative deviations were found in the systematic series of copolymers. The degree of positive and negative character was found to be dependent upon copolymer composition. Negative deviations were accounted for in terms of a finite interfacial thickness, which turned out to be relatively small as anticipated, while the positive deviations were assigned to isolated hard segments that reside within the soft segment matrix, i.e., concentration fluctuations. In calculating the interfacial thickness, several methods were applied and in general, close agreement was obtained. Finally, correlation function analysis in conjunction with determination of the coherent Porod lengths, etc. were determined and discussed accordingly. Cautionary comments are also provided for researchers who apply less complete small angle x-ray scattering (SAXS) analysis to related block or segmented copolymers with regard to phase separation behavior.     

Polyurethane tri‐block copolymers—Synthesis,mechanical, elastic,and rheological properties

A series of polyurethane tri‐block copolymers were synthesized by reacting a 4,4′‐methylenebis(phenyl isocyanate) (MDI)‐endcapped poly(tetramethylene oxide) (PTMO, M_n = 2,000 g/mol) with a monoamine‐diamide (6T6m) hard segment (HS). The concentration of the HS in the copolymer was varied between 9 and 33 wt % by changing the length of the soft mid‐block segment. The structure of the copolymers was analyzed by nuclear magnetic resonance, the amide crystallinity was investigated by Fourier transform infra‐red and the thermal properties were studied by differential scanning calorimetry. The mechanical and elastic properties of the tri‐block copolymer were subsequently explored by dynamic mechanical analysis, compression set and tensile experiments, and the melt rheological behavior was studied by a parallel plate method. The amide end groups displayed a high crystallinity and the modulus of the tri‐block copolymers was relatively high. The fracture strain increased strongly with the molecular weight and the copolymers demonstrated a ductile fracture behavior for molecular weights above 6000 g/mol. Good compression set values were obtained for the tri‐block copolymers despite their low molecular weight. In the molten state, the tri‐block polymers displayed a gelling effect at low frequencies, which was believed to be a result of a clustering of the end‐segments. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Multiscale Modeling of the Morphology and Properties of Segmented Silicone-Urea Copolymers

Abstract  

Molecular dynamics and mesoscale dynamics simulation techniques were used to investigate the effect of hydrogen bonding on the microphase separation, morphology and various physicochemical properties of segmented silicone-urea copolymers. Model silicone-urea copolymers investigated were based on the stoichiometric combinations of α,ω-aminopropyl terminated polydimethylsiloxane (PDMS) oligomers with number average molecular weights ranging from 700 to 15,000 g/mole and bis(4-isocyanatocyclohexyl)methane (HMDI). Urea hard segment contents of the copolymers, which were determined by the PDMS molecular weight, were in 1.7–34% by weight range. Since no chain extenders were used, urea hard segments in all copolymers were of uniform length. Simulation results clearly demonstrated the presence of very good microphase separation in all silicone-urea copolymers, even for the copolymer with 1.7% by weight hard segment content. Experimentally reported enhanced properties of these materials were shown to stem from strong hydrogen bond interactions which leads to the aggregation of urea hard segments and reinforcement of the PDMS.     

Block copolymers of polycarbonates with several hydroxy-terminated elastomers to yield thermoplastic elastomers for higher service temperature

The synthesis of block copolymers and the study of their morphology were undertaken to find improved thermoplastic rubbers for service at elevated temperatures. The basis was the extraordinary properties possessed by ABA-type block copolymers in which the terminal blocks are polystyrene and the central block is either polyisoprene or polybutadiene. In these systems it has been well established that the unusual properties are a result of domain formation in which the hard and the soft blocks aggregate separately into distinct phases. The hard segment is thought to act both as a crosslink and as a filler. Block copolymers were synthesized with different soft and hard segments. The effects of these segments and of their properties on the morphology and the stress-strain properties of the block copolymers were measured and evaluated. Electron microscopy and birefringence were used to determine the morphology. It was found that the glass transition temperatures of the segments, the bulk of the monomer unit in the glassy segment, and the morphology determined the strength of the material. Some of the materials prepared have tensile strengths of 0.1 kg/cm² or more at temperatures in excess of 180°C and therefore appear promising as elastomers for service at elevated temperatures.