N-甲基二乙醇胺嵌段聚氨酯材料的结构表征和性能研究

以N-甲基二乙醇胺为扩链剂合成了阳离子化及肝素化聚氨酯、重点对其结构进行了表征，分别使用离子型染料染色法、比色法、红外光谱法、元素分析法等方法系统分析了经过离子化以及肝素化处理后聚合物结构的变化，同时采用拉伸试验对其力学性能进行了测试，结果表明聚氨酯经离子化和肝素化处理后，强度有了相当大的提高；通过全血凝固时间实验证明肝素化聚氨酯具有较好的血液相容性，是一种理想的生物医用材料。     

Thermosensitive surface properties of polyethylene film with poly(N-isopropylacrylamide) chains prepared by corona discharge induced grafting

Polyethylene (PE) film was treated by corona discharge and then grafted with N-isopropylacrylamide (NIPAAm) for modification of the surface. The grafted amount was determined by gravimetry and the surface morphology was observed by using a scanning electron microscope. The surface analysis was carried out with a x-ray photoelectron spectroscopy and electron probe microanalysis. It was clarified that grafting was limited surface and there was no change of the surface morphology after grafting. The water absorption at various temperature under the absolute humidity (11.4 g/cm³) and the leakage of electrostatic charge from PE film were measured. PolyNIPAAm that was introduced onto PE surface has hydrophilic-hydrophobic transition properties at the 32°C in the atmospheric condition. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1773–1779, 1998     

医用聚氨酯表面功能化与血液相容性：水分子的作用

在生物医用材料血液相容性的影响因素中,材料表面与水的相互作用极其关键。以医用聚氨酯材料为聚合物模型,综述了医用聚氨酯表面亲水性功能化的研究进展:探讨水在抗血液蛋白非特异吸附以及抗血栓功能中所起的作用;讨论亲水性乙烯类单体、聚乙二醇及其衍生物、肝素及两性离子化合物等改性聚氨酯界面上的水分子行为及其对血液相容性的影响。理解水和水化层在材料和血液接触过程中所起的关键作用,将为聚合物生物材料的表面设计和应用提供重要的依据。     

Imidazolium-based ionic thermoplastic polyurethane with low surface energy and antibacterial activities

A series of novel thermoplastic polyurethane elastomers with both low surface energy and antibacterial activity were synthesized in this paper. Firstly, four imidazole salt diols with different alkyl chain lengths at the N-position of imidazolium cation ([CnIm⁺][Cl⁻]) were prepared. Then, imidazolium-based ionic thermoplastic polyurethane elastomers (Si-ITPUs) were formulated by incorporating polydimethylsiloxane and polytetramethylene glycol as a mixed soft segment, 1,4-butanediol and [CnIm⁺][Cl⁻] as a chain extender, and 4,4′-dicyclohexylmethane diisocyanate. The structure, thermal stability, mechanical properties, physical crosslinking density, and the anti-graffiti properties of Si-ITPUs were evaluated. The surface energy and water absorption were evaluated through static contact angle and water resistance tests, respectively. Furthermore, the antibacterial activities against both Staphylococcus.aureus and Escherichia coli were characterized by the plate colony counting method. The results demonstrated that Si-ITPUs possessed surface energy of approximately 23 mN/m, which conferred excellent anti-graffiti and self-cleaning performance. Furthermore, the increase of the alkyl chain length of substitutions resulted in a decrease in the tensile strength but an increase in the elongation at break. Si-ITPU-C₄ exhibited optimized antibacterial activities with an antibacterial rate of more than 99.9% against both S. aureus and E. coli. This novel polyurethane is anticipated to find applications in the medical device industry and food processing sector.     

前端聚合法合成聚氨酯的研究

使用甲苯二异氰酸酯（TDI）和聚丙二醇（PPG）通过前端聚合,制备出聚氨酯预聚体。研究了前端聚合反应速率与PPG分子质量以及催化剂DBTDL与TDI比例之间的关系。傅立叶红外光谱（FT—IR）分析表明,前端聚合法合成的聚氨酯与传统聚合法合成的聚氨酯具有相同的特征吸收峰,运用扫描电镜（SEM）可以看出前端聚合法合成的聚氨酯具有良好的分散性。     

Characterization of surface-charge-mosaic-modified ultrafiltration membranes prepared by laser-induced surface graft polymerization

Surface-charge-mosaic-modified ultrafiltration membranes with charged domains of various sizes (500, 100, or 50 μm) were prepared by two-step laser-induced surface graft polymerization using a striped photomask. First, the surface of an ultrafiltration membrane was treated with 4-vinylpyridine after laser irradiation using a striped photomask. Subsequently, the striped photomask was shifted and the surface that was initially shaded from the laser beam by the photomask was exposed to laser irradiation and treated with acrylic acid. The surface element distribution, surface chemical structure, and ion-exchange capacities of the treated membrane were determined by scanning X-ray photoelectron spectroscopy (XPS) analysis, time-of-flight secondary ion mass spectrometry (TOF-SIMS) with imaging capacities, and acid–base titration, respectively. Oxygen and carbon distribution maps determined by the scanning XPS analysis and the TOF-SIMS maps for ¹⁶O⁻ and ²⁶CN⁻ ions show that the surface of the treated membrane had striped domains composed of poly(4-vinylpyridine) and poly(acrylic acid). The anion- and cation-exchange capacities of the treated membranes were approximately 2.0 mEq/m². The ultrafiltration rate of these membranes was markedly lower than that of a nontreated ultrafiltration membrane, but increased as the charge domain size decreased. The membrane flux of sodium ions also increased with decreasing charge domain size. This tendency was much stronger for sodium ions than for glucose. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1141–1149, 1998     

Comparison of properties of acrylic–polyurethane hybrid emulsions prepared by batch and semibatch processes with monomer emulsion feed

Aqueous acrylic–polyurethane hybrid emulsions were prepared by batch and semibatch polymerization of acrylic monomer mixtures (butyl acrylate, methyl methacrylate and acrylic acid) in the presence of polyurethane dispersion. The acrylic component was introduced in the monomer emulsion feed. The weight ratio between acrylic and polyurethane components was varied to obtain different emulsion properties, microphase structure and mechanical film properties. Scanning electron microscopy, average particle size and molecular weight measurements were performed to characterize the latex systems. Mechanical properties were examined by measuring Koenig hardnesses of dried films. The average particle size increased with the acrylic/polyurethane ratio. Particles of larger than average size and, to some extent, higher than average molecular weights by batch process were formed. Koenig hardnesses decreased with increasing acrylic/polyurethane ratio. Properties of emulsions synthesized by semibatch processes were compared with the results reported for a different polyurethane dispersion. Copyright © 2003 Society of Chemical Industry     

水性聚氨酯胶膜的耐水性能研究

采用预聚体法,以聚酯多元醇、甲苯二异氰酸酯、二羟甲基丙酸(DMPA)制备了聚酯型水性聚氨酯乳液,考察了亲水扩链剂DMPA用量、NCO/OH值、中和剂的种类、中和度、扩链剂乙二胺用量对乳液涂膜耐水性的影响,制备了耐水性较好的水性聚氨酯乳液。     

Characterization of polyurethane foam prepared by using starch as polyol

Polyurethane foams were prepared using starch as a main component of polyols and their structural, mechanical, and absorbing properties for organic solvents were investigated. Fourier transform infrared spectra showed that urethane linkage was formed by the reactions between ? NCO of diisocyanates and ? OH of polyols. When polyurethane foams were prepared at high molar ratio of ? NCO/? OH, the unreacted ? NCO groups were detected. Also, urea linkage was formed by the reaction between diisocyanate and water, which was used as the foaming agent. The micrographs showed that the polyurethane foams had closed‐cell structure, of which the cell size increased with ? NCO/? OH molar ratio. The density of polyurethane foams increased with molecular weight of polyethylene glycol. The compressive moduli of polyurethane foams increased with ? NCO/? OH molar ratio. Polyurethane foams prepared using toluene‐2,4‐diisocyanate as diisocyanate had the highest modulus, while those prepared using hexamethylene diisocyanate had the lowest modulus. In case of the absorbency for the organic solvents, the polyurethane foams prepared at ? NCO/? OH molar ratio of 0.8 had the maximum absorbency. Among several organic solvents, the absorbency for dimethyl sulfoxide was the highest, while the absorbency for tetrahydrofuran was the lowest. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1544–1553, 2007     

Effect of ionic content,solid content,degree of neutralization,and chain extension on aqueous polyurethane dispersions prepared by prepolymer method

There are many variables in the preparation of aqueous polyurethane (PU) dispersions. Carboxylic acid content, solid content, degree of pre/postneutralization of the carboxylic acids, and chain extension all impact dispersion particle size, viscosity, pH, molecular weights, and glass transition temperature. This study evaluated the impact of these variables on a given PU dispersion formulation prepared from isophorone diisocyanate, an aliphatic polyester polyol, dimethylol propionic acid, and hexamethylene diamine with triethyl amine as the neutralizing base and N‐methyl pyrrolidone as the cosolvent. Changes in carboxylic acid content, degree of preneutralization, and chain extension were found to have the expected impacts on dispersions properties. Increased ionic content in the dispersion step led to lower particle size and higher viscosity, increased chain extension with its concurrent increase in molecular improved subsequent film properties. Surprising results were obtained by varying the amount of postneutralization and from increased solids content at the time of dispersion. Unexpectedly, both of these variations led to much higher dispersion viscosities and particle size in solution. To have these changes take place, it is theorized that there is a major change in solution morphology caused by these modifications. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2514–2520, 2005     

聚氨醋乳液及其与苯乙烯接枝聚合改性的机理

采用予聚物混合法合成了聚氨酯乳液,考察了合成条件包括予聚物分散温度、－NCO／－OH基团比例、亲水剂的选用等。另外,以苯乙烯作为提高耐水性的改性单体以BHPO－TEPA界面氧化还原体系为引发剂,通过原位聚合法制备了聚氨酯──苯乙烯接枝胶乳并对其进行了结构分析。接枝胶乳可同时提高粘接性能和耐水性能。     

热塑性聚氨酯共混物的增容方法

综述了作为聚氨酯弹性体的一种,热塑性聚氨酯（TPU）与其他聚合物共混改性时,可提高增容性的6种方法（如调整分子链结构、改变共混聚合物的极性、化学改生引入反应性官能团、改变分子极性、加入相容剂、形成互穿网络等）,并提到了对相容性影响很大的共混方法和工艺条件.     

Effect of solvent on the properties of thermoplastic polyurethane/clay nanocomposites prepared by solution mixing

Effect of different solvents on the clay dispersion and the final properties of the thermoplastic polyurethanes (TPUs)/clay nanocomposites prepared via solution mixing was studied. The polyether‐ and polyester‐based TPUs were used along with organically modified clays (C30B, C25A, and C15A) and the pristine montmorillonite (PM). Dimethylacetamide (DMAc) and tetrahydrofuran (THF) were used as solvents for solution mixing. Nanocomposites containing C30B prepared from DMAc solution showed the better clay dispersion than the ones from THF solution, while THF gave the better dispersion of clays for nanocomposites containing C15A. Morphologies of the nanocomposites were observed to be determined not only by the state of clay dispersion in different solvents but also by the interaction between the polymer and the specific clay. Affinity between solvents and clays becomes important when there is no specific interaction between the clay and the polymer of interest, or when the interaction between the two is rather weak. The compatibility between clays and polymers becomes dominating if there exists a specific interaction between the two. FTIR analysis was conducted to study the interactions involved in the nanocomposites. Dynamic mechanical properties measurement was also carried out to see the effect of solvents. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Rigid interpenetrating polymer network foams prepared from a rosin-based polyurethane and an epoxy resin

A series of rigid interpenetrating polymer network (IPN) foams, based on a rosin-based polyurethane and an epoxy resin, were prepared by a simultaneous polymerization technique. The changes in the chemical structure, dynamic mechanical properties, and morphology of the rigid IPN foams were investigated by Fourier transform infrared (FTIR) spectroscopy, dynamic mechanical thermal analysis, and scanning electron microscopy. The FTIR analysis showed clearly that the cure rate of the rosin-based rigid polyurethane foam and the epoxy resin were different and, as a result, these two networks formed sequentially in the final rigid IPN foams. All of the rigid IPN foams exhibited a single, broad glass transition that shifted to lower temperature as the epoxy resin content increased. The experimental composition dependence of T_g's of the rigid IPN foams showed slight positive deviation from the Fox equation for homogeneous polymer systems. No phase separation was observed from the scanning electron microscopy investigation. It could be concluded that these two component networks were compatible in the final rigid IPN foams. This compatibility could be attributed to a graft structure in the polyurethane and the epoxy resin networks arising from the reaction of the hydroxyl groups of the epoxy resin with the isocyanate groups of MDI, and from the reaction of the hydroxyl groups of the polyols with the epoxide groups of the epoxy resin, as suggested by FTIR analysis. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 271–281, 1998     

Microstructure and properties of polyester-based polyurethane/titania hybrid films prepared by sol-gel process

Polyester polyol/titania hybrid resins and their corresponding polyurethane/titania hybrid films were prepared by in situ method via sol-gel process of titanium n-butoxide under acidic condition. The effects of the contents and types of titania sol on the microstructure and some mechanical and optical properties of the hybrids were investigated. It was found that introducing titania into the resin could increase some physical properties such as the viscosity of the resin, modulus, T_g, mechanical strength, abrasion resistance, hardness and UV absorbance, but different titania sols obtained from various molar ratios of water to titanium n-butoxide had an obvious influence on the microstructure and properties of the hybrid films.     

二聚醇嵌段型聚氨酯与单萜相容性的分子动力学模拟

含有六元环结构的二聚醇嵌段型聚氨酯具有聚氨酯胶粘剂的优异性能,加入增粘树脂可以进一步提高其粘接性能。其中,2者的相容性是胶粘剂体系获得优异性能的关键问题。本文采用分子动力学模拟法研究了二聚醇嵌段型聚氨酯与单萜的相容性,结果表明,二聚醇嵌段型聚氨酯结构中软段与硬段存在着较为明显的相分离行为,在330K附近最易混合。设计了四种软硬段相对含量不同的二聚醇嵌段型聚氨酯的结构,模拟并分析了4种结构的二聚醇嵌段型聚氨酯与单萜的相容性。结果表明,随软段含量增加,二聚醇嵌段型聚氨酯与单萜相容性增加。根据模拟结果讨论了二聚醇嵌段型聚氨酯与单萜共混体系的Huggins-Flory相互作用参数与温度之间的关系,确定了在最优结构和温度下,体系能够良好互容。单萜的加入,提高了胶粘剂体系综合相容性。     

原位聚合法制备聚酯聚氨脂SiO2纳米复合涂料及性能测试

论述用原位聚合法制备了聚酯聚氨酯/SiO_2纳米复合涂料,并利用动态力学分析仪(DMA)、傅立叶变换红外光谱(FT-IR)、紫外可见光谱(UV-VIS)、透射电子显微镜(TEM)、原子力显微镜(AFM)、电子拉力机(Instron Tester)测试了涂膜的性能。结果表明,纳米SiO_2粒子均匀分布在涂膜中,并与聚酯通过化学键结合。纳米SiO_2粒子的加入提高了涂膜的摆杆硬度、玻璃化转变温度及附着力,并极大地改变了界面形貌,但本文研究的纳米SiO_2对聚酯聚氨酯紫外线吸收性和耐磨性没有明显影响。     

Development of a novel microorganism immobilization method using anionic polyurethane

A new microorganism immobilization method involving gelation of anionic polyurethane has been developed. Nontoxic synthetic anionic polyurethane was used, which provides greater mechanical strength than do natural polymers. Similar to the formation of Ca‐alginate gel beads, this method has the advantage of easy preparation. Gel beads are formed only by dropping the anionic polyurethane emulsion into a calcium chloride solution. The feasibility of the proposed immobilization method was tested by an ethanol production process with baker's yeast (Saccharomyces cerevisiae). The result verified that the anionic polyurethane entrapped–cell method developed in this study has great potential for a variety of applications such as biological processes and biological wastewater treatment. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 738–743, 2006     

UV固化工艺制备新型聚氨酯丙烯酸酯人造大理石

以PUA(聚氨酯丙烯酸酯)为基体、炭黑和白炭黑为颜填料,采用UV(紫外光)固化工艺制备出一种新型PUA类人造大理石。研究结果表明:新型人造大理石将传统的成型过程及表面处理环节整合为一步法,极大简化了传统人造大理石的生产工艺;PUA本身具有良好的耐擦伤性、柔韧性、撕裂强度、光学性能和耐候性能,引入炭黑和白炭黑后可进一步增加涂层的硬度和抗冲击强度;以炭黑和白炭黑作为基本色,通过调节两者比例可配制出不同灰度的涂层,并且涂层的基本性能不受影响;该人造大理石具有良好的耐干热性能、耐化学腐蚀性能和耐污染性能,其光泽度为89%～92%,并且表面平整、光滑、饱满且装饰效果极好。     

Preparation and characterization of one-component polyurethane powder adhesives by the solution polymerization technology

A new technology integrating the synthesis and granulation was adopted to prepare the one-component polyurethane powder adhesives (PPAs) by the solution polymerization. The influence of R_total, neutralization, and types of dispersion solution on the properties of PPAs was investigated. It was found that the initial melting temperature increased and storage stability decreased with increasing R_total. The neutralization reaction between the carboxylic group and amino group made the reduction of the sizing temperature and the increase of the T-peel adhesion strength. The granulation behaviors of the polyurethane (PU) prepolymer under different dispersion solutions showed that the PU prepolymer can be effectively blocked by the 20–30 wt % NaHSO₃ or n-butyl alcohol. Furthermore, the blocked polymers formed small particles with the ideal sizing temperature and peel strength. The excellent adhesive property and thermal stability of PPAs could meet the requirements of the industrial gluing in the fields of packaging, lining, and footwear. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47898.