聚氨酯及水性聚氨酯纳米复合材料结构和力学性能的研究
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摘要
聚氨酯（polyurethane，简称PU）是指含有重复的氨基甲酸酯键（NHCOO）的一类高分子化合物，主要由多异氰酸酯（主要为二异氰酸酯）与多元醇（包括聚酯多元醇和聚醚多元醇）通过逐步加成聚合而成。通过调节软段和硬段的结构和比例，可获得所需最佳力学性能的聚氨酯材料，具有软硬度调节范围广、耐低温、柔韧性好、附着力强等优点。水性聚氨酯（WPU）是以水为分散介质的二元胶态体系，不仅保留了传统溶剂型聚氨酯的一些优良性能，如良好的耐磨性、柔顺性、耐低温性和耐疲劳性等，而且具有无毒、不易燃、无污染、节能、安全可靠等优点，这使得水性聚氨酯己成功地应用在溶剂型聚氨酯所覆盖的领域。
纳米粒子改性聚氨酯材料完美地结合了纳米粒子的刚性、尺寸稳定性、热稳定性及PU和WPU的韧性、易加工性，同时利用了纳米材料表面效应、量子尺寸效应和宏观量子隧道效应，能使涂膜的光学、热学、电学、磁学和力学性能等得到显著提高。
在本论文中，我们进行纳米复合聚氨酯和水性聚氨酯材料的研究。具体的研究内容如下：
(1)传统的聚氨酯合成工艺中，采用超声分散法引入碳纳米管，制备聚氨酯/多壁碳纳米管复合材料（PU/CNT）。本工作采用了不同含量、尺寸及表面修饰官能基的碳纳米管调节PU/CNT的力学性能。此外，采用衰减全反射傅立叶红外光谱分析、动态力学分析、扫描电子显微镜、透射电子显微镜及拉力测试表征PU/CNT纳米复合材料的结构和力学性能。研究结果表明，填充0.1wt%直径10-15nm的CNT可获得最大的抗张强度和伸长率。值得关注的是，CNT的表面羧基化能进一步提高PU/CNT纳米复合材料的抗张强度和伸长率。
(2)通过一步法，采用原位合成未修饰累托石（REC，一种层状硅酸盐）改性的聚氨酯（PU）材料，制备一系列强度、伸长率增强的纳米复合材料。值得关注的是，纳米复合材料中REC含量为2wt%时，具有最大的伸长率（1449%）和强度（32.66MPa），分别约为纯PU薄膜的2.7和1.4倍，REC以未剥离的团聚体及剥离的纳米片存在于PU基质。尽管PU基质的原始结构和相互作用有部分被破坏，但凭借REC薄层表面较强的界面相互作用，应力可以转移至刚性的RECs，材料强度仍有所提高。同时，PU的聚合物链段与REC的交联及在REC的层间滑动可能提高应力。REC含量较高时，过多的未剥离REC团聚体会抑制材料力学性能的改善，并且已经证实有效提高力学性能的关键在于剥离的REC纳米片。因此，本工作提出了一种简单的制备高力学性能的聚氨酯基纳米复合材料的制备方法，而避免了层状硅酸盐的修饰及对片落和分散性的复杂处理。
(3)淀粉纳米晶（StNs）具有类似于剥离的层状硅酸盐的层状结构，在水性聚氨酯（WPU）基质中具有较高的填充率，可制备水性聚氨酯/淀粉纳米晶（WPU/StN）复合物。据报导，制备过程中淀粉纳米晶的自聚集行为导致其部分沉淀，淀粉纳米晶在材料中的填充率始终低于8wt%。然而本研究发现，淀粉纳米晶含量高达30%时，在复合材料中仍然有较好的分散性。此外，该复合材料的力学模量及杨氏模量有显著提高，并且其伸长率约为300%。淀粉纳米晶含量为10wt%时，复合材料表现出最大的抗张强度，为31.1MPa，约为纯WPU的1.8倍，并且杨氏模量约为纯WPU的35.7倍。淀粉纳米晶的活性表面和刚性促使应力传递界面形成，提高了复合材料的耐压能力。随着淀粉纳米晶填量的增加，粒子的自聚集行为导致材料力学性能的下降。然而，淀粉纳米晶的刚性促使材料的杨氏模量增大，在含量为30wt%时取得最大值。由此可得到性能优异的水性聚氨酯基“绿色”生物纳米复合材料。
(4)采用超分子纳米片（SNs）作为填料，制备了新型的水性聚氨酯基复合材料。超分子纳米片是通过β-环糊精（β-CD）与聚环氧乙烷-聚环氧丙烷-聚环氧乙烷-嵌段共聚物（PEO-b-PPO-b-PEO）上的聚环氧丙烷（PPO）片段自组装形成的。值得注意的是，长度适中的PEO链段组装的SNs会导致复合材料的强度、伸长率和杨氏模量的同时增加，可归结于SNs的刚性和WPU基质与由β-环糊精基聚多轮烷连接PEO伸缩链段而组装的纳米片层间的界面协同作用。若缺乏自由伸缩PEO链，尽管材料的杨氏模量在提高，但强度与伸长率均在降低。但是，过长的PEO链会趋于结晶态，而抑制链段与WPU基质间的交联，导致机械性能的降低。此外，相对较高的SNs的填充量，会引发SNs相的尺寸和数目的增长，抑制材料强度与伸长率的提高。
Polyurethane is a class of polymer containing duplicate carbamate (NHCOO), mainlysynthesised by multi-isocyanate (diisocyanate) and polyol (including polyester polyols andpolyether polyols) via the gradual addition polymerization. By adjust the structure andproportion of dissimilar soft segment and hard segment, we could obtain polyurethane withthe optimal mechanical properties, it has a number of exceptional properties, such as a widerange of hardness adjustment, low temperature resistance, good flexibility, adhesion, and so on.Waterborne polyurethane (WPU) is a binary colloidal system using water as the dispersionmedium. It not only preserved the traditional solvent-based polyurethane in a number of goodproperties, such as good wear resistance, flexibility, low temperature resistance and resistanceto fatigue, etc., but also has the advantages of non-toxic, non-flammable, non-polluting,energy saving, safe and reliable, which makes waterborne polyurethane has been appliedsuccessfully in solvent-based polyurethane applications.
Nanoparticles modified polyurethane combine stiffness, dimensional stability, thermalstability of nanoparticles with toughness, ease of processing of WPU perfectly, while takingadvantage of the nano-surface effect, quantum size effect and macroscopic quantumtunneling effect, enhance significantly the optical, thermal, electrical, magnetic andmechanical properties of coating.
In this paper, polyurethane-based and waterborne polyurethane-based nanocompositewas studied. All the relative studies are outline as follows.
(1) Polyurethanes/multi-walled carbon nanotube (PU/CNT) composites were preparedwith a help of ultrasonically dispersing CNT in the traditional procedure of synthesizingpolyurethane. In this case, the various loading levels, sizes and surface-modified groups wereconsidered to regulate the mechanical performances of the PU/CNT nanocomposites.Moreover, the structure and mechanical properties of all the PU/CNT nanocomposites wereinvestigated by attenuated total reflection-Fourier transform infrared spectroscopy, dynamicmechanical analysis, scanning electron microscope, transmission electron microscope, andtensile testing. The results showed that a moderate loading-level of0.1wt%and a diameter of10-15nm for CNT could produce the maximum tensile strength and elongation while it wasworth noting that the surface carboxylation of CNT could further enhance the tensile strengthand elongation of the PU/CNT nanocomposites.
(2) The unmodified rectorite (REC), a kind of layered silicate, was incorporated intopolyurethane (PU) as matrix by the process of one-pot synthesizing polyurethane in situ, andhence produced a series of nanocomposite materials with enhanced strength and elongation. It is worth noting that the nanocomposite containing2wt%REC had the maximum elongation(1449%) and strength (32.66MPa) as ca.2.7-and1.4-fold over those of neat PU film,respectively.Meanwhile, the unexfoliated agglomerates and exfoliated nanoplatelets of RECco-existed in PU matrix. By virtue of strong interfacial interaction on the surface of REClamella, the stress facilely transferred to the rigid RECs and hence contributed to theenhancement of strength in spite that the original structure and interaction in the PU matrixwere partly cleaved. Moreover, the intertwisting of polymer chains in PU matrix with REC aswell as the gliding among the REC lamellae might produce greater strain. Nevertheless,excess unexfoliated REC agglomerates under high loading level inhibited the enhancement ofmechanical performances, which verified the key role of exfoliated REC nanoplatelet inimproving mechanical performances. As a result, this work submitted a simple method todevelop a polyurethane-based nanocomposite with high mechanical performances withoutany modification of layered silicates and the complicated treatment for exfoliation anddispersion.
(3) Starch nanocrystals (StNs), which possesses a distinct platelet-like structure similar toexfoliated layered silicate, was incorporated into waterborne polyurethane (WPU) matrix athigh loading levels to prepare WPU/StN nanocomposites. As reported, the StN loading levelwas restricted to lower than8wt%because self-aggregation of StN resulted in itssedimentation during preparation. However, in this work, good dispersion of the StNnanophase in the nanocomposites was observed even when the StN loading level reached30wt%. Furthermore, the resultant composites exhibited prominent enhancement in bothstrength and Young’s modulus, and maintained an elongation of greater than ca.300%. A StNloading level of10wt%showed the maximum tensile strength (31.1MPa) and an enhancedYoung’s modulus, respectively ca.1.8-and35.7-fold over those of neatWPU.The activesurface and rigidity of StN facilitated formation of an interface for stress transfer andcontributed to higher stress-endurance. As the StN loading level increased, self-aggregation ofStNs resulted in a decrease in strength; however, the rigidity of StN supported an increase inYoung’s modulus, which was highest in nanocomposites containing30wt%StNs. Highperformance waterborne polyurethane-based “green” bionanocomposites were therebyestablished.
(4) New composites of waterborne polyurethane (WPU) as a matrix were prepared byincorporating rigid supramolecular nanoplatelets (SN) as a filler, which were self-assembledby the selective inclusion of β-cyclodextrin (β-CD) onto poly(propylene oxide)(PPO)segment in the poly(ethylene oxide)-block-PPO-block-poly(ethylene oxide)(PEO-b-PPO-b-PEO). It is worth noting that the SN with moderate PEO length resulted in thesimultaneous increase in strength, elongation and Young’s modulus. It was attributed to therigidity of SN, and the essential association between the WPU matrix and rigid crystalline aggregates of β-CD-based polyrotaxane mediated with stretching free PEO chains. If therewas no stretching free PEO chain, both strength and elongation decreased in spite of anincrease in Young’s modulus. However, too long PEO chains tended to crystalline, and henceinhibited the interfacial entanglement with the WPU matrix, resulting in the decrease ofmechanical performances. Furthermore, the relatively higher loading-level of SN induced theincrease in the size and number of the SN phase, and hence inhibited the enhancement ofstrength and elongation.
纳米粒子改性聚氨酯材料完美地结合了纳米粒子的刚性、尺寸稳定性、热稳定性及PU和WPU的韧性、易加工性，同时利用了纳米材料表面效应、量子尺寸效应和宏观量子隧道效应，能使涂膜的光学、热学、电学、磁学和力学性能等得到显著提高。
在本论文中，我们进行纳米复合聚氨酯和水性聚氨酯材料的研究。具体的研究内容如下：
(1)传统的聚氨酯合成工艺中，采用超声分散法引入碳纳米管，制备聚氨酯/多壁碳纳米管复合材料（PU/CNT）。本工作采用了不同含量、尺寸及表面修饰官能基的碳纳米管调节PU/CNT的力学性能。此外，采用衰减全反射傅立叶红外光谱分析、动态力学分析、扫描电子显微镜、透射电子显微镜及拉力测试表征PU/CNT纳米复合材料的结构和力学性能。研究结果表明，填充0.1wt%直径10-15nm的CNT可获得最大的抗张强度和伸长率。值得关注的是，CNT的表面羧基化能进一步提高PU/CNT纳米复合材料的抗张强度和伸长率。
(2)通过一步法，采用原位合成未修饰累托石（REC，一种层状硅酸盐）改性的聚氨酯（PU）材料，制备一系列强度、伸长率增强的纳米复合材料。值得关注的是，纳米复合材料中REC含量为2wt%时，具有最大的伸长率（1449%）和强度（32.66MPa），分别约为纯PU薄膜的2.7和1.4倍，REC以未剥离的团聚体及剥离的纳米片存在于PU基质。尽管PU基质的原始结构和相互作用有部分被破坏，但凭借REC薄层表面较强的界面相互作用，应力可以转移至刚性的RECs，材料强度仍有所提高。同时，PU的聚合物链段与REC的交联及在REC的层间滑动可能提高应力。REC含量较高时，过多的未剥离REC团聚体会抑制材料力学性能的改善，并且已经证实有效提高力学性能的关键在于剥离的REC纳米片。因此，本工作提出了一种简单的制备高力学性能的聚氨酯基纳米复合材料的制备方法，而避免了层状硅酸盐的修饰及对片落和分散性的复杂处理。
(3)淀粉纳米晶（StNs）具有类似于剥离的层状硅酸盐的层状结构，在水性聚氨酯（WPU）基质中具有较高的填充率，可制备水性聚氨酯/淀粉纳米晶（WPU/StN）复合物。据报导，制备过程中淀粉纳米晶的自聚集行为导致其部分沉淀，淀粉纳米晶在材料中的填充率始终低于8wt%。然而本研究发现，淀粉纳米晶含量高达30%时，在复合材料中仍然有较好的分散性。此外，该复合材料的力学模量及杨氏模量有显著提高，并且其伸长率约为300%。淀粉纳米晶含量为10wt%时，复合材料表现出最大的抗张强度，为31.1MPa，约为纯WPU的1.8倍，并且杨氏模量约为纯WPU的35.7倍。淀粉纳米晶的活性表面和刚性促使应力传递界面形成，提高了复合材料的耐压能力。随着淀粉纳米晶填量的增加，粒子的自聚集行为导致材料力学性能的下降。然而，淀粉纳米晶的刚性促使材料的杨氏模量增大，在含量为30wt%时取得最大值。由此可得到性能优异的水性聚氨酯基“绿色”生物纳米复合材料。
(4)采用超分子纳米片（SNs）作为填料，制备了新型的水性聚氨酯基复合材料。超分子纳米片是通过β-环糊精（β-CD）与聚环氧乙烷-聚环氧丙烷-聚环氧乙烷-嵌段共聚物（PEO-b-PPO-b-PEO）上的聚环氧丙烷（PPO）片段自组装形成的。值得注意的是，长度适中的PEO链段组装的SNs会导致复合材料的强度、伸长率和杨氏模量的同时增加，可归结于SNs的刚性和WPU基质与由β-环糊精基聚多轮烷连接PEO伸缩链段而组装的纳米片层间的界面协同作用。若缺乏自由伸缩PEO链，尽管材料的杨氏模量在提高，但强度与伸长率均在降低。但是，过长的PEO链会趋于结晶态，而抑制链段与WPU基质间的交联，导致机械性能的降低。此外，相对较高的SNs的填充量，会引发SNs相的尺寸和数目的增长，抑制材料强度与伸长率的提高。
Polyurethane is a class of polymer containing duplicate carbamate (NHCOO), mainlysynthesised by multi-isocyanate (diisocyanate) and polyol (including polyester polyols andpolyether polyols) via the gradual addition polymerization. By adjust the structure andproportion of dissimilar soft segment and hard segment, we could obtain polyurethane withthe optimal mechanical properties, it has a number of exceptional properties, such as a widerange of hardness adjustment, low temperature resistance, good flexibility, adhesion, and so on.Waterborne polyurethane (WPU) is a binary colloidal system using water as the dispersionmedium. It not only preserved the traditional solvent-based polyurethane in a number of goodproperties, such as good wear resistance, flexibility, low temperature resistance and resistanceto fatigue, etc., but also has the advantages of non-toxic, non-flammable, non-polluting,energy saving, safe and reliable, which makes waterborne polyurethane has been appliedsuccessfully in solvent-based polyurethane applications.
Nanoparticles modified polyurethane combine stiffness, dimensional stability, thermalstability of nanoparticles with toughness, ease of processing of WPU perfectly, while takingadvantage of the nano-surface effect, quantum size effect and macroscopic quantumtunneling effect, enhance significantly the optical, thermal, electrical, magnetic andmechanical properties of coating.
In this paper, polyurethane-based and waterborne polyurethane-based nanocompositewas studied. All the relative studies are outline as follows.
(1) Polyurethanes/multi-walled carbon nanotube (PU/CNT) composites were preparedwith a help of ultrasonically dispersing CNT in the traditional procedure of synthesizingpolyurethane. In this case, the various loading levels, sizes and surface-modified groups wereconsidered to regulate the mechanical performances of the PU/CNT nanocomposites.Moreover, the structure and mechanical properties of all the PU/CNT nanocomposites wereinvestigated by attenuated total reflection-Fourier transform infrared spectroscopy, dynamicmechanical analysis, scanning electron microscope, transmission electron microscope, andtensile testing. The results showed that a moderate loading-level of0.1wt%and a diameter of10-15nm for CNT could produce the maximum tensile strength and elongation while it wasworth noting that the surface carboxylation of CNT could further enhance the tensile strengthand elongation of the PU/CNT nanocomposites.
(2) The unmodified rectorite (REC), a kind of layered silicate, was incorporated intopolyurethane (PU) as matrix by the process of one-pot synthesizing polyurethane in situ, andhence produced a series of nanocomposite materials with enhanced strength and elongation. It is worth noting that the nanocomposite containing2wt%REC had the maximum elongation(1449%) and strength (32.66MPa) as ca.2.7-and1.4-fold over those of neat PU film,respectively.Meanwhile, the unexfoliated agglomerates and exfoliated nanoplatelets of RECco-existed in PU matrix. By virtue of strong interfacial interaction on the surface of REClamella, the stress facilely transferred to the rigid RECs and hence contributed to theenhancement of strength in spite that the original structure and interaction in the PU matrixwere partly cleaved. Moreover, the intertwisting of polymer chains in PU matrix with REC aswell as the gliding among the REC lamellae might produce greater strain. Nevertheless,excess unexfoliated REC agglomerates under high loading level inhibited the enhancement ofmechanical performances, which verified the key role of exfoliated REC nanoplatelet inimproving mechanical performances. As a result, this work submitted a simple method todevelop a polyurethane-based nanocomposite with high mechanical performances withoutany modification of layered silicates and the complicated treatment for exfoliation anddispersion.
(3) Starch nanocrystals (StNs), which possesses a distinct platelet-like structure similar toexfoliated layered silicate, was incorporated into waterborne polyurethane (WPU) matrix athigh loading levels to prepare WPU/StN nanocomposites. As reported, the StN loading levelwas restricted to lower than8wt%because self-aggregation of StN resulted in itssedimentation during preparation. However, in this work, good dispersion of the StNnanophase in the nanocomposites was observed even when the StN loading level reached30wt%. Furthermore, the resultant composites exhibited prominent enhancement in bothstrength and Young’s modulus, and maintained an elongation of greater than ca.300%. A StNloading level of10wt%showed the maximum tensile strength (31.1MPa) and an enhancedYoung’s modulus, respectively ca.1.8-and35.7-fold over those of neatWPU.The activesurface and rigidity of StN facilitated formation of an interface for stress transfer andcontributed to higher stress-endurance. As the StN loading level increased, self-aggregation ofStNs resulted in a decrease in strength; however, the rigidity of StN supported an increase inYoung’s modulus, which was highest in nanocomposites containing30wt%StNs. Highperformance waterborne polyurethane-based “green” bionanocomposites were therebyestablished.
(4) New composites of waterborne polyurethane (WPU) as a matrix were prepared byincorporating rigid supramolecular nanoplatelets (SN) as a filler, which were self-assembledby the selective inclusion of β-cyclodextrin (β-CD) onto poly(propylene oxide)(PPO)segment in the poly(ethylene oxide)-block-PPO-block-poly(ethylene oxide)(PEO-b-PPO-b-PEO). It is worth noting that the SN with moderate PEO length resulted in thesimultaneous increase in strength, elongation and Young’s modulus. It was attributed to therigidity of SN, and the essential association between the WPU matrix and rigid crystalline aggregates of β-CD-based polyrotaxane mediated with stretching free PEO chains. If therewas no stretching free PEO chain, both strength and elongation decreased in spite of anincrease in Young’s modulus. However, too long PEO chains tended to crystalline, and henceinhibited the interfacial entanglement with the WPU matrix, resulting in the decrease ofmechanical performances. Furthermore, the relatively higher loading-level of SN induced theincrease in the size and number of the SN phase, and hence inhibited the enhancement ofstrength and elongation.
引文
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