PDMS改性蓖麻油基水性聚氨酯的制备及防污性能

本研究以低成本的二甲基二甲氧基硅烷为主要原料，通过水解缩合反应制备合成了聚二甲基硅氧烷（PDMS），进而将其引入蓖麻油基水性聚氨酯（CWPU-SOP）中制备了具有防污性能的蓖麻油基水性聚氨酯(PDMS/CWPU-SOP)。结果表明，当PDMS引入量为8%时，与CWPU-SOP薄膜相比，PDMS/CWPU-SOP薄膜接触角提高了25?，达110?，PDMS/CWPU-SOP薄膜的吸水率下降了7%，为15%；PDMS提高了薄膜疏水性和耐水性。PDMS/CWPU-SOP薄膜在不同酸碱性的液滴在其表面可自由滚落且不留痕迹，具有一定的防污性能。     

UV固化氨基胍盐改性蓖麻油基水性聚氨酯的制备及抗菌性能

以蓖麻油（CO）、异佛尔酮二异氰酸酯(IPDI)、阳离子扩链剂N-甲基二乙醇胺（MDEA）、封端剂甲基丙烯酸羟乙酯（HEMA）为主要原料制备一系列紫外（UV）固化型蓖麻油基水性聚氨酯（UWPU）。为进一步提升其抗菌性能，通过引入胍基的方法，成功制备出抗菌型UV固化蓖麻油基水性聚氨酯(GWPU)。通过耐水性测试、抑菌圈测试、抗菌性能测试对实验制备胶膜性能进行检测。 结果表明：GWPU胶膜相对UWPU吸水率有所上升，但均保持在10%以下；GWPU胶膜抗菌方式为接触性杀菌同时不具有溢出性；当氨基胍盐（AH）质量分数为预聚物1.2%时GWPU对金黄色葡萄球菌(S.aureus)、大肠杆菌(E.coli)的抗菌率可达99.9%，且经过抗菌持久性测试后仍能保持99.9%的抗菌性。     

Structure and properties of casting films blended with starch and waterborne polyurethane

A series of casting films blended from starch and waterborne polyurethane (STPU) in aqueous solution were prepared. The structure and properties of the films were investigated by infrared spectroscopy, ultraviolet spectroscopy, scanning electron micrography, strength test, thermogravimetric analysis, and different scanning calorimetry. The results showed that the tensile strength and modules of air‐dried STPU blend films increased with the increase of starch content, while elongation decreased. When starch content was in the range from 80 to 90 wt %, the blend films showed significantly higher tensile strength, breaking elongation, water resistivity, and light transmittance than that of pure starch film, resulting from the miscibility between starch and waterborne polyurethane. Moreover, the STPU films containing 90 wt % starch have higher thermal stability than pure waterborne polyurethane film, and their light transmittance was close to the polyurethane, due to the existence of a strong intermolecular hydrogen bonding between starch and polyurethane. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2006–2013, 2001     

Structure–properties relationship of starch/waterborne polyurethane composites

The blend materials from waterborne polyurethane (WPU)/starch (ST) with different contents (10–90 wt %) were satisfactorily prepared by using the solution casting method. Their miscibility, structure, and properties were investigated by wide‐angle X‐ray diffraction (WAXD), scanning electron microscope (SEM), different scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and the tensile tests, respectively. The results indicated that tensile strength of composite materials not only depended on the starch content, but also related to the microstructure of WPU. The sample WPU2 (1.75 of NCO/OH molar ratio) exhibited hard‐segment order, but WPU1 (1.25 of NCO/OH molar ratio) had no hard‐segment order. The appropriate starch filled into WPU not only decreased the ordered region of soft‐segment matrix, but also hindered the formation of hard‐segment ordered structure. The blend material from 80 wt % WPU1 and 20 wt % starch exhibited better tensile strength (27 MPa), elongation at break (949%), and toughness than others. With an increase of starch content, the WPU matrix with dispersed starch in the blends transited to dual‐phase continuity and then to starch matrix with dispersed WPU. The results suggested that a certain extent of miscibility existed between WPU and starch in the blend materials on the whole composition ratio. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3325–3332, 2003     

Synthesis,characterization and corrosion protective properties of boron-modified polyurethane from natural polyol

A novel attempt has been made to incorporate boron in the backbone of castor oil to develop boron-modified polyester (BCPE) and polyurethane (BPU). The overall reaction strategy involved “single pot multiple reactions” in minimum solvent achieving about 50% reduction in the use of volatile organic compounds (VOCs) during the synthetic procedure. Spectral (I.R., ¹H NMR and ¹³C NMR), physicochemical and thermal (TGA and DSC) analyses of BCPE and BPU were carried out by standard methods. The physico-mechanical and corrosion/chemical resistance performances (in various corrosive media) tests of BPU coatings were also conducted to evaluate their coating properties. These studies revealed that (i) the incorporation of boron has a significant influence on structural and physico-chemical aspects, thermal stability as well as on coating properties of BPUs, (ii) interestingly, BPUs showed very good performance in alkaline media (unaffected in 5 wt% NaOH for 50 h) as compared to their other previously reported oil-based counterparts, (iii) boron, here, acts both as a modifier and crosslinker and (iv) BPUs serve as novel and promising candidates for use as corrosion protective coating material, which can be safely employed up to 220 °C.     

Preparation of polyurethane wood adhesives by polyols formulated with polyester polyols based on castor oil

The aim of this work was the synthesis of polyester polyols from renewable sources as one of the important compounds of polymeric polyurethane (PU) adhesives. The polyester polyols were synthesized by condensation polymerization of different dicarboxylic acids with castor oil and the reaction conditions were in agreement with green chemistry principles. The preparation of PU wood adhesives was carried out by the reaction of each obtained polyester polyol with 4, 4′-diphenylmethane diisocyanate (MDI). The adhesive performance was improved by mixing the obtained polyester polyols with polypropylene glycol (PPG 400) and butanediol (BD). Different NCO/OH ratios were used to obtain adhesives with appropriate properties. The structures of the synthesized polyesters and adhesives were characterized by FTIR, thermogravimetric analysis (TGA) and lap shear strength values were also determined in various conditions such as cold water, hot water, acid and alkali solutions.     

蓖麻油改性聚醚型水性聚氨酯乳液的性能

以聚醚、甲苯二异氰酸酯(TDI)、一缩二乙二醇、蓖麻油为主要原料,二羟甲基丙酸(DMPA)为亲水扩链剂,三乙胺为中和剂制备了稳定的阴离子水性聚氨酯乳液(WPU),研究了NCO/OH摩尔比、DMPA及蓖麻油的加入量对WPU的耐水性、稳定性和力学性能的影响,结果表明:改性后的乳液具有较好的稳定性,适量的蓖麻油可提高胶膜的拉伸强度及耐水性。当聚醚与蓖麻油质量比为7︰3、DMPA为5%、NCO与OH摩尔比为1.3时,WPU综合性能最好。     

聚氨酯嵌缝材料的研制

描述了聚氨酯嵌缝材料的制备方和生产工艺过程。     

纳米SiO_2改性水性聚氨酯胶粘剂的制备及性能

以PBA(聚酯二元醇)、IPDI(异佛尔酮二异氰酸酯)、DMPA(2,2-二羟甲基丙酸)和BDO(1,4-丁二醇)为原料,DBTDL(二月桂酸二丁基锡)为催化剂,TEA(三乙胺)为中和剂,乙二胺为扩链剂,水为介质,采用共混法和原位聚合法合成了纳米SiO_2(纳米二氧化硅)改性WPU(水性聚氨酯)胶粘剂。研究结果表明:纳米SiO_2能有效提高WPU胶膜的热稳定性,并且采用原位聚合法制得的纳米SiO_2改性WPU胶粘剂之性能优于共混法;当w(纳米SiO_2)=2.0%、w(DMPA)=4.7%(均相对于预聚体质量而言)和R=n(—NCO)/n(—OH)=3.0时,采用原位聚合法制得的纳米SiO_2改性WPU胶粘剂的综合性能相对最佳。     

生物基异山梨醇改性磺酸盐水性聚氨酯的制备及性能

以异佛尔酮二异氰酸酯(IPDI)、聚碳酸酯二元醇(PCDL)、季戊四醇三丙烯酸酯(PETA)为主要原料,以自制的含磺酸基的低聚物聚酯二元醇(SO3-2OH)为亲水单体,二羟甲基丁酸(DMPA)作为亲水扩链剂,合成了含磺酸基的聚氨酯预聚物,再采用生物基二元醇──异山梨醇(IS)对其进行改性,制备了可紫外光固化的异山梨醇改性磺酸盐水性聚氨酯(UV-SIWPU)乳液.通过傅里叶变换红外光谱仪(FT-IR)、紫外可见近红外分光光度计(UV-VIS-NIR)、凝胶渗透色谱(GPC)、光学接触角测量仪(OCA)等仪器对该乳液及其涂膜的结构、形貌和性能进行了分析.结果表明:当SO3-2OH含量为20％,IS含量为75％时,所制备的UV-SIWPU涂膜的综合性能优异:水接触角为23.2°,吸水率为11.6％,在水中浸泡7 d后不泛白、不脱落,耐水性较好,拉伸强度为6.5 MPa,断裂伸长率为253％,铅笔硬度达到2H,在550 nm处的透光率达到96.0％,热稳定性和防雾性能良好.     

Preparation and properties of waterborne polyurethane adhesives modified by polystyrene

Waterborne polyurethane (WPU) adhesives modified by polystyrene (PS) were prepared through a prepolymer mixing process from diisocyanates, an anionic polyester, internal emulsifiers, a neutralizer, a chain extender, and PS dispersions. The latter was preformed via the in situ polymerization of styrene in poly(1,4‐butanediol adipate) diol. Transmission electron microscopy, Fourier transform infrared spectroscopy, and ¹H‐NMR techniques were used to characterize the PS dispersions and polyurethane (PU)–PS prepolymer. Experimental results with respect to the performance of the PU–PS adhesives indicate that suitable PS/polyester diol weight ratios improved the mechanical properties, thermal stability, water resistance, and initial adhesive strength of the pristine WPU adhesives. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

羟基硅油共聚改性水性聚氨酯的制备、表征与性能

引言 水性聚氨酯是一类重要的皮革涂饰剂,它耐磨、柔韧性好,可增加皮革的美观和耐用性.水性聚氨酯链上含有亲水基团,因此形成的涂膜耐水性差,常需要改性.     

Preparation and properties of polyurethane acrylates modified by saturated alcohols

Polyurethane acrylates (PUAs) modified by saturated alcohols were synthesized by saturated alcohols, isophorone diisocyanate (IPDI), 2-hydroxyethyl acrylate (HEA) and polycaprolactone triol (PCL). The molecular structures were identified by Fourier transform infrared (FTIR) spectroscopy. Real time infrared (RTIR) spectroscopy was used to investigate the conversion vs. irradiation time plots of photopolymerization of synthesized PUAs. The volume shrinkage was measured by using laser displacement sensor (LDS). The adhesion in the glass, polycarbonate (PC) and polyvinyl chloride (PVC) substrates was tested by the laser micrometer and universal testing machine. The glass-transition temperature (Tg) and storage modulus (E′) were measured by dynamic mechanical analysis (DMA). The pendulum hardness, pencil hardness and flexibility were also tested. The results showed that the synthesized PUAs had low volume shrinkage and excellent adhesion in glass, PC and PVC substrates.     

Preparation and properties of modified graphene oxide incorporated waterborne polyurethane acrylate

In this study, a new modifier (KPG) was prepared by modifying graphene oxide with γ‐glycidoxypropyl trimethoxysilane (KH560) and polydimethylsiloxane (PDMS). KPG was in turn added to aqueous urethane acrylate for the fabrication of waterborne polyurethane polyacrylate emulsion modified with KH560‐PDMS composite (KPG/WPUA). Textural characterizations of the KPG/WPUA coating were achieved via Fourier transform infrared, SEM, TGA and AFM techniques, which revealed that the KPG/WPUA film possessed a smooth surface. The synthesized KPG/WPUA films were tested for mechanical properties, hydrophobicity and acid/water corrosion performance which suggested their highly hydrophobic surface. KPG/WPUA with 0.1% KPG showed a contact angle of 118.35°, 30.35° higher than that of pristine WPUA. The KPG/WPUA film exhibited higher thermal stability, i.e. a 5% weight loss temperature of 305 °C, which was 30 °C higher than that of pristine WPUA film. The Young's modulus and elongation at break of the KPG/WPUA film were 34.1 MPa and 74.88% respectively, which were higher than that of WPUA film. Furthermore, KPG/WPUA films exhibited greater resistance (without obvious blistering and the white spotting phenomenon) to H₂O₂, HCl and water corrosion than pristine WPUA. The superior performance of KPG/WPUA films was attributed to the network chain structure formed upon the introduction of KPG into WPUA. The outstanding performance of KPG/WPUA films in terms of mechanical properties, thermal stability and high resistance to acidic and water corrosion makes them interesting alternative contenders for target applications. © 2019 Society of Chemical Industry     

环氧树脂改性含硅自消光水性聚氨酯树脂的制备及性能

以聚己二酸1，4－丁二醇酯多元醇(PBA)、异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸（DMPA）、1，4-丁二醇（BDO）、端羟丙基聚二甲基硅氧烷(PDMS)和环氧树脂(E-51)为单体合成聚氨酯预聚体，三乙胺（TEA）作为中和剂，乙二胺（EDA）作为后扩链剂，合成了一系列环氧树脂改性含硅自消光水性聚氨酯树脂乳液。采用粒度分析仪测定乳液粒径、FTIR表征胶膜表面结构、SEM观察胶膜表面，并分析了胶膜的光泽度、水接触角、热力学等性能。结果表明：在n(PBA)：n(PDMS)=1:2的条件下，环氧树脂添加量为5 %时，乳液粒径为1152 nm，胶膜60?光泽度为3.4；水接触角为107.3?，疏水性能最优；胶膜拉伸强度可达24.42 MPa，断裂伸长率在362 %，力学性能最优；胶膜热失重50 %时温度较未添加E-51的胶膜提高了18.3 ℃。     

新型紫外线固化环氧树脂/丙烯酸酯改性水性聚氨酯的合成与性能

合成了一种新型的具有高交联密度和优异涂膜性能的环氧树脂和丙烯酸酯同时改性的紫外线（UV）固化水性聚氨酯（UV-EP-AC-WPUD）。通过环氧基团与以异氰酸酯基团（-N=C=O）封端的聚氨酯预聚体之间的反应引入质量分数为4%的环氧树脂E-20。同时,通过聚氨酯链的-N=C=O与二元丙烯酸酯（PEDA）以及季戊四醇三丙烯酸酯（PETA）的羟基之间的反应引入碳碳双键（C=C）,C=C的含量达到4.65 meq·g-1。 质量分数为3%的光引发剂Irgacure 2959被用于引发涂膜中C=C的聚合,涂膜的凝胶含量在12 s UV辐射之后达到91%,意味着C=C的聚合和交联速度快,同时所得到的涂膜的交联度非常高,不溶于溶剂丙酮,测试表明环氧树脂和两种丙烯酸酯单体已经成功嵌入聚氨酯链中,涂膜具有优异的力学性能和化学性能。     

改性六方氮化硼/水性聚氨酯涂料的制备与性能

以聚甘油-10(PG)作为稳定剂,超声下对六方氮化硼(h-BN)进行剥离和改性制得PG功能化的少层h-BN纳米粒子(GB).利用GB与水性聚氨酯(WPU)共混得到WPU/GB.通过FTIR、TG、AFM和TEM对GB进行了表征,证实了少层GB的成功制备.动电位极化和电化学阻抗谱测试表明,WPU/GB涂层比纯WPU涂层具有更高的耐腐蚀性能.GB含量为1.0％(以WPU的质量为基准,下同)的WPU/GB1.0复合涂层的耐腐蚀性能最好,极化电阻为1.33×107?·cm2,阻抗|Z|可达到5.37×107?·cm2.此外,与纯WPU相比,WPU/GB1.0腐蚀电流密度从2.64×10–8 A/cm2减小至3.32×10–9 A/cm2,腐蚀电压从–0.309 V增大到–0.037 V,保护效率高达98.74％.     

微波合成含氮掺杂碳量子点改性水性聚氨酯的制备与性能

以柠檬酸和尿素分别为碳源和氮源,微波法合成含氮掺杂碳点N-CDs。以异氟尔酮二异氰酸酯（IPDI）、聚氧化丙烯（PPG-2000）为主要原料,加入不同量的N-CDs制备一系列碳点水性聚氨酯复合材料 （N-CDs/WPU）。通过FTIR、TEM、XPS、UV-vis、荧光光谱和力学性能测试等对复合材料结构和性能进行表征。测试结果表明N-CDs主要由碳氮氧元素组成,表面具有胺基、羟基等活性基团,N-CDs的加入,提高了复合胶膜的力学性能,赋予了胶膜荧光性能。当N-CDs质量分数为0.6%时胶膜拉伸强度达到最大35.00MPa,加入量质量分数为0.8%时荧光强度最佳。     

Studies on the properties of Montmorillonite-reinforced thermoplastic starch composites

Montmorillonite (MMT), a kind of reinforced additive and glycerol-plasticized thermoplastic starch (GTPS) were used in the preparation of Montmorillonite-reinforced themorplastic starch composites (MTPSC) with the method of melt extrusion. Scanning electron microscope (SEM) revealed that MMT were uniformly dispersed in GTPS. Fourier Transform infrared (FT-IR) patterns showed that in the MTPSC the C-O groups of starch molecules shifted to the higher wavenumber, while the reactive hydroxyl groups of MMT shifted to the lower wavenumber. That was caused by the cooperation of the strong absorption that existed between MMT and starch molecules and hydrogen bonds that formed between the reactive hydroxyl groups of MMT and the hydroxyl groups of starch molecules. MMT was on the submicron filling transition state and acted as an obstructor. When MTPSC was stored for 14 days at RH (relative humidity)=39%, the tensile strength, Young's modulus and breaking energy of MTPSC were 27.34, 206.74 MPa and 1.723 N m, respectively. It was obvious that the mechanical properties of MTPSC were greatly improved. At the same time, the effect of water content on the mechanical properties was studied. X-ray diffraction revealed that MMT restrained the crystallization of GTPS effectively. Differential thermal analysis (DTA) and water absorption testing showed that the thermal stability and water-resistant properties of MTPSC were better than those of GTPS.     

Preparation and characterization of the waterborne polyurethane modified with nanosilica

The nano-SiO₂ is used to modify the waterborne polyurethane, and the morphology and performance of the waterborne polyurethane (are studied in) prepared by the in-suit polymerization method and the blending method. The properties and structure have been characterized by fourier transform infrared spectra (IR), differential scanning calorimetry (DSC), Thermal gravimetric (TG), transmittance electron microscopy (TEM) and Dynamical Mechanical Analysis(DMA). The experiment results show that, compared with the blending method, the in-suit polymerization has more advantages in that the nano-SiO₂ is evenly dispersed in the waterborne polyurethane, obviously in microphase separation and better in resistance to high temperature and water.