Preparation and Performance of Waterborne Polyurethane/Nanosilica Hybrid Materials

The polyurethane prepolymer was synthesized, and hydrophilic nano-sized silica (A200) was added to the prepolymer with KH550 as a coupling agent, then a waterborne polyurethane/nanosilica hybrid material (WPUNS) was obtained by a sol-gel process. The structure and performance of the WPUNS films were studied by FTIR, TG, DSC and physical mechanical testing. The particle size and distribution of WPUNS hybrid emulsion was analyzed by a dynamic light scatter (DLS). The morphology of emulsion and films were observed by Transmission Electron Microscope (TEM) and Atomic Force Microscope (AFM), respectively. FTIR analysis indicates the formation of chemical bond between WPU and A200. TEM images display that A200 particles were encapsulated by PU macromolecules and formed a composite particles structure. As the mass fraction of A200 increased from 0 to 2%, the particle size increased from 79.9 nm to 139.9 nm, the tensile strength of the films increased from 6.32 MPa to 20.46 MPa, water absorption decreased from 28.3% to 6.3%, and the hardness was also improved. The TG result indicates that A200 can improve thermal stability of WPUNS. DSC shows that there is no clear effect of nanosilica on the glass transition of soft segments. AFM displays that the smoothness of the films increases with A200 addition.     

环氧大豆油和硅氧烷改性水性聚氨酯胶黏剂

以环氧大豆油(ESO)与3-氨基丙基三乙氧基硅烷(KH550)双重交联改性水性聚氨酯(WPU).通过FTIR、TG、DSC、DMA、AFM、粒径分析仪、拉力试验机等仪器对改性的水性聚氨酯进行了表征.研究了ESO和KH550的含量对水性聚氨酯乳液、胶膜以及胶黏剂性能的影响.分析了KH550对水性聚氨酯结晶性能和微相分离的影响.研究发现,随着ESO与KH550的加入,水性聚氨酯乳液的性能得到改善,胶膜的吸水率先减小后增大,拉伸强度逐渐增大,断裂伸张率逐渐减小.水性聚氨酯胶黏剂对PVC的T-剥离强度先增大后减小.随着KH550含量的增加,热稳定性逐步改善,结晶性降低,软段与硬段相混合程度提高.当ESO为4%、KH550为2%(均为质量分数)时,水性聚氨酯胶黏剂的综合性能最好.     

水性聚氨酯/纳米SiO_2杂化材料的制备及性能研究

首先合成内交联的WPU预聚体,以KH550为偶联剂,加入亲水性的纳米SiO2(A200),通过溶胶-凝胶过程合成了一种水性聚氨酯/纳米SiO2杂化材料(WPUNS)。通过FTIR、TG、DSC、物理机械性能测试对WPUNS的结构和膜性能进行了研究,用动态激光光散射法测试了杂化乳液的粒径和粒径分布,并用TEM对乳液形貌进行了观察。红外分析表明,WPU大分子和A200之间形成了化学键,粒径和乳液形貌观察显示了PU大分子包裹A200粒子形成了复合粒子结构。当w(A200)由0增大到2%时,粒径由79.9 nm增至139.9 nm,膜的拉伸强度由6.32 MPa增加到20.46 MPa,吸水率由28.3%降低到6.3%,硬度亦相应提高。TG分析表明,A200的加入可以提高材料的耐热性。DSC表明,A200的加入使硬段Tg向高温扩展。     

新型磺酸盐水性聚氨酯乳液的合成及其性能研究

以聚己二酸乙二醇酯二元醇、甲苯二异氰酸酯、乙二胺基己磺酸钠(N60)等为主要原料,制备了一系列不同N60用量的磺酸盐型水性聚氨酯(WPU)乳液。研究了N60用量对WPU乳液及其胶膜性能的影响,并通过FT-IR、TEM、TGA等方法进行表征。结果表明,磺酸盐型WPU乳液的贮存、冻融、高温稳定性均较好。随N60用量的增加,磺酸盐型WPU乳液粒径先减小后增大,粒径分布变窄,胶膜的拉伸强度、吸水率呈上升趋势、断裂伸长率下降。TEM图显示微粒分散性好,呈球形;相对于羧酸型WPU,磺酸盐型WPU胶膜的拉伸强度提高,热稳定性更好。     

水性聚氨酯/硅溶胶复合涂层的制备与性能

将水性聚氨酯乳液与硅溶胶共混,制备了水性聚氨酯/硅溶胶复合乳液。采用TEM、激光粒度分析仪、流变仪、ATR-FTIR、TG对复合乳液及其涂膜进行表征,探讨了硅溶胶用量对复合涂膜性能的影响。ATR-FTIR分析表明,聚氨酯分子和硅溶胶之间可以形成氢键,但不存在化学键结合;TEM、激光粒度分析测试表明,硅溶胶质量分数的增加,使复合乳液粒子粒径增大,粒度分布变宽,当硅溶胶质量分数20%后,乳胶粒子间易发生团聚;流变分析发现,加入硅溶胶后,乳液的表观黏度(ηa)增大,假塑性增强。性能测试结果表明,硅溶胶质量分数20%时,复合乳液具有好的储存稳定性,复合涂膜表现出很好的热稳定性,48 h吸水率仅为18.94%,同时表现出很好的耐溶剂性能,拉伸强度达到28.98 MPa,铅笔硬度达2H,附着力0级。     

Synthesis and characterizations of waterborne polyurethane modified with 3-aminopropyltriethoxysilane

Waterborne polyurethane (WPU) was prepared by the reaction of isophorone isocyanate (IPDI), polyether polyol (PTMG1000), dimethylol propionic acid (DMPA), and trimethylol propane (TMP) and 3-aminopropyltriethoxysilane (APTES) as coupling agent. The films of the WPU were prepared by casting emulsions on Teflon surfaces. The structure of the polyurethane (PU) was characterized by Fourier transform infrared spectrometer (FT-IR), thermogravimetry (TG), X-ray diffraction (XRD), and differential scanning calorimeter (DSC). The mechanical properties and solvent absorption of the cast films were also measured quantificationally. FT-IR indicates that –NH₂ of APTES reacted with –NCO of PU prepolymer. TG analysis indicates that APTES can improve thermal stability of PU. XRD and DSC show that crystallinity of PU decreased with the increase of w(APTES). It was found that greater mechanical properties of WPU were obtained when chemical networks were formed between PU and APTES. As the mass fraction of APTES increases from 0% to 10%, water absorption decreased from 17% to 8%, ethanol absorption decreased from 46% to 30%. The particle size increases with increase of w(APTES).     

葡萄糖改性水性聚氨酯的合成与表征

采用预聚体合成法,以二羟甲基丙酸（DMPA）、葡萄糖（PG）为亲水扩连剂和交联剂制备一种水性聚氨酯乳液。利用FTIR对胶膜结构进行表征,证实葡萄糖已引入聚氨酯主链。TG分析得出PG改性后的聚氨酯胶膜热稳定性增强。研究了PG用量对该聚氨酯胶膜力学性能的影响,结果表明：随着PG用量的增加,胶膜力学强度得到改善。当PG的用量由0增加至4.68%时,断裂伸长率从529.9%降至276.4%,拉伸强度从10.9 MPa增加至24.2 MPa。     

水性聚氨酯/聚甲基丙烯酸甲酯杂化乳液的合成

用异佛尔酮二异氰酸酯(IPDI)、聚丙二醇(PPG)和二羟甲丙酸(DMPA)合成了水性聚氨酯分散体(WPU),讨论了PPG摩尔质量,NCO/OH及PPG/DMPA比例对WPU乳液和涂膜性能的影响。以WPU为种子与甲基丙烯酸甲酯进行乳液聚合制备杂化乳液,研究了不同PU/PMMA物质的量比例对杂化乳液及涂膜性能的影响,并采用TEM对WPU及杂化乳液粒子进行了表征。结果表明,在以PPG1000为原料,NCO与OH物质的量比为1.4∶1,PPG与DMPA物质的量比为1∶0.8条件下制备的WPU杂化乳液,随着PMMA比例增加,杂化乳液的稳定性和成膜性变差,聚合物膜断裂伸长率降低,但铅笔硬度、耐水性及耐乙醇性均得到了改善。     

Preparation and properties of Waterborne polyurethane/nanosilica composites: A diol as extender with triethoxysilane group

Waterborne polyurethane (WPU) was prepared from toluene diisocyanate, polypropylene glycol, 2,2‐bis(hydroxymethyl)propionic acid and a diol containing triethoxysilane group as the chain extender which was synthesized via Michael addition between 3‐triethoxysilylpropylamine and 2‐hydroxyethylacrylate. Different amounts of nanosilica were incorporated into the WPU to prepare WPU/nanosilica composites. The results showed that the particle size of the emulsions increased and their viscosity decreased first and then increased with increasing the amount of nanosilica. Incorporation of nanosilica into WPU enhanced the water contact angle and thermal stability of the composites films, meanwhile, their tensile strength and hardness increased first and then decreased. However, increasing the amount of nanosilica resulted in reduction in the elongation at break of the films. It suggested that nanosilca was anchored into the side chain of WPU due to the condensation process between the triethoxysilane group in the side chain of WPU molecular and the silanols group on the surface of nanosilica. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40526.     

硅烷偶联剂改性高固含量水性聚氨酯的合成

以聚四氢呋喃二醇、聚己二酸乙二酯和异佛尔酮二异氰酸酯等为主要原料,以硅烷偶联剂KH550为改性剂,2,2-二羟甲基丙酸(DMPA)和(1,3-二氨基)-丁基磺酸钠(HSJ)为亲水扩链剂,采用自乳化和外乳化相结合的方法合成阴离子型高固含量硅烷偶联剂改性水性聚氨酯(WPU)乳液。考察了乳化剂、扩链剂、硅烷偶联剂用量,异氰酸酯基与羟基摩尔比(R值)等对乳液和胶膜性能的影响。通过傅里叶变换红外光谱、热重分析和接触角测试分析了改性前后WPU的结构。结果表明:DMPA,HSJ,乳化剂,硅烷偶联剂的质量分别占总固体质量的1.60%,0.26%,1.60%,1.50%,R值为1.20时,可得到固含量54%、黏度低、稳定性好、耐水、耐热性能优异的WPU乳液。     

有机硅协同改性含氟聚氨酯

采用细乳液法结合超声分散技术制备出水性聚氨酯（WPU）、含氟水性聚氨酯（FPAPU）和KH570、羟基硅油协同改性的氟硅水性聚氨酯乳液（SiFPAPU）。通过红外光谱（FTIR）、粒度分布（PSA）、接触角（CA）、表面能分析、原子力显微镜（AFM）、扫描电镜（SEM）、热失重（TG）、拉伸试验表征了WPU、FPAPU、SiFPAPU复合乳液表面性能、热稳定性和力学性能。结果表明随着有机硅协同组分加入,SiFPAPU乳液粒径降低为44.0nm,但粒径分布变宽;成膜后,水相和油相（CH₂I₂）接触角分别达到122.6°、92.5°,表面能降低为11.82mJ/m²,乳胶膜表面平整均一,断面出现明显分层。同时SiFPAPU热稳定性增强,拉伸强度较未改性聚氨酯提高126.1%。     

赖氨酸扩链的生物基水性聚氨酯的制备与性能研究

以异佛尔酮二异氰酸酯(IPDI)、聚四氢呋喃二醇(PTMG-2000)为主要原料,二羟甲基丙酸(DMPA)、赖氨酸(Lys)等作为小分子扩链剂,制备了含赖氨酸成分的水性聚氨酯(WPU)乳液.讨论了Lys用量对WPU乳液及胶膜性能的影响,并采用FT-IR、TGA等检测方法进行表征.结果表明:随着Lys用量的增大,WPU乳...     

有机硅改性无溶剂阳离子型聚氨酯/丙烯酸酯复合乳液的制备

以异佛尔酮二异氰酸酯(IPD I)、聚四氢呋喃二醇(PTMG 1000)、N-甲基二乙醇胺(MDEA)、三羟甲基丙烷(TMP)等为主要原料,通过硅烷偶联剂γ-氨丙基三乙氧基硅烷(KH550)封端改性,制备了无溶剂阳离子型聚氨酯/丙烯酸酯核壳乳液表面施胶剂(PAU)。通过红外光谱(FTIR)、热重分析(TG)、X射线衍射分析(XRD)、透射电镜(TEM)、力学性能等对其结构与性能进行了表征及测试。结果表明,当n(—NCO)∶n(—OH)=1.07∶1,m(St)∶m(BA)=1∶2,w(MDEA)=5.50%(占所有单体质量的总和,下同),w(TMP)=0.55%,w(KH550)=0.69%时,合成的聚氨酯有良好的力学性能与施胶性能,而且有机硅的加入增强了膜的柔韧性。     

3D打印炭黑/水性聚氨酯导电复合材料的制备及性能

采用硅烷偶联剂KH550对炭黑（CB）进行共价键功能化改性,并通过FTIR、DLS和SEM对改性前后的炭黑进行考察。结果表明经过KH550改性得到的炭黑,粒径约为620nm,且分散均匀。通过溶液共混法和流延浇铸法制备了CB/WPU与KH550/CB/WPU导电复合材料。研究对比发现,由于KH550/CB在WPU基体中分散性更好,使导电粒子之间接触更加紧密。当添加量为3%时,其电导率为1.79×10-3 S/m,较CB/WPU复合材料增加了10倍;力学测试显示含量为2%时,其拉伸强度较CB/WPU复合材料增加了175%。并在此基础上利用直写式3D打印,探讨不同的填充图案和填充率对KH550/CB/WPU复合材料导电性能的影响。结果显示选择线型填充、填充率为80%时,导电性能较好,其电导率达到2.66×10-3 S/m。     

改性纳米SiO2/聚氨酯-含氟丙烯酸酯无皂乳液合成及其胶膜性能表征

引言水性聚氨酯相对溶剂型聚氨酯具有不燃、气味小、不污染环境等优点[1-2],从而广泛用于涂料[3]、胶黏剂[4]、油墨[5]等领域。目前,常用于软包装领域的薄膜主要是表面能很低的非极性膜,而水性聚氨酯胶黏剂具有较高的表面自由能,对非极性膜的润湿性差,因此需要降低水性聚氨酯的表面张力,达到润湿非极性膜的目的。     

有机硅/丙烯酸酯改性水性聚氨酯的合成及性能

以异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)、聚酯二元醇(XH-111)、丙烯酸羟乙酯(HEA)和3-氨丙基三乙氧基硅烷(KH-550)等为主要原料,分别制得HEA封端和HEA、KH-550共同封端的水性聚氨酯乳液,再加入丙烯酸酯单体进行自由基引发聚合,分别制备出丙烯酸酯改性和丙烯酸酯、KH-550共同改性的水性聚氨酯复合乳液。通过傅立叶变换红外光谱(FTIR)、热失重分析(TGA)、X射线衍射分析(XRD)和力学性能测试,对改性水性聚氨酯乳液的结构和胶膜的热稳定性、结晶性和力学性能进行了考察。结果表明,改性水性聚氨酯的结晶性降低,热稳定性提高。当w(丙烯酸酯)增大到20%,w(KH-550)增大到15%时,胶膜的拉伸强度由5.6 MPa增加到23.9 MPa,断裂伸长率由491%降到247%。     

Preparation and characterization of waterborne polyurethane/silica hybrid dispersions from castor oil polyols obtained by glycolysis poly(ethylene terephthalate) waste

Castor oil polyols (COLs) have been synthesized from glycolyzed oligoester polyol in order to produce waterborne polyurethane (WPU)/silica hybrid dispersions. Soft drinks poly(ethylene terephthalate) (PET) bottles were depolymerized by glycolysis with different molar ratio of poly(ethylene glycol) ( PEG 400), in the presence of zinc acetate as catalyst. The obtained glycolyzed products were reacted with castor oil (CO) to attain castor oil polyols by the process of transesterification. Five castor oil polyols were used with hydroxyl values of 255, 275, 326, 366 and 426 mg KOH g⁻¹. Several castor oil-based, polyurethane/silica hybrid dispersions having soft segment content of 39.6% to 28.2% and two concentrations of SiO₂ nanoparticles (0.5 and 1.0) have been prepared.The incorporation effect of SiO₂ nanoparticles into the PU matrix and the hydroxyl functionality of the COLs on the thermal and mechanical properties of resulting polyurethane films has been examined by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TG) and measurement of the mechanical properties. The degree of phase separation (DPS) between oxide nanoparticles and hard segment, and particle size in the polyurethane, depends to some extent on nanosilica content and the hydroxyl functionality of the polyols employed in the polyurethane preparation process.Thermal stability of obtained hybrid materials depends on the hydroxyl functionality of the COLs and nanosilica content. The T_10% and T_50% (the temperature where 10 and 50% weight loss occurred) of WPU films decreased with the rise of OH functionality of castor oil polyols, caused by the increase of hard segment content. Glass transition temperature increased with increasing OH functionality and SiO₂ content. The hardness, adhesion and gloss quality of the polyurethane films were also determined with a view to assessing the effect of mole ratios of PET to glycol in glycolyzed products, the hydroxyl functionality and the SiO₂ content.     

纳米SiO_2改性水性聚氨酯乳液的制备及性能研究

以硅烷偶联剂(KH-550)作为纳米二氧化硅(nano-SiO2)的表面处理剂,以甲苯二异氰酸酯(TDI)、聚醚二元醇(N-220)、二羟甲基丙酸(DMPA)和nano-SiO2等为主要原料,制备nano-SiO2改性WPU(水性聚氨酯)乳液。着重探讨了DMPA的加料方式、DMPA和nano-SiO2用量等对WPU乳液稳定性、粒径分布、耐水性和力学性能等影响。结果表明:采用先加入DMPA后扩链的加料方式,可制得外观及稳定性均较好的WPU乳液;当w(DMPA)=5%、w(改性nano-SiO2)=2.0%时,WPU乳液及其胶膜的综合性能较好。     

Synthesis and characterization of nanosilica/waterborne polyurethane end‐capped by alkoxysilane via a sol‐gel process

A novel method was used to synthesis nanosilica/waterborne polyurethane (WPU) hybrids by in situ hydrolysis and condensation of tetraethyl orthosilicate (TEOS) and/or 3‐aminopropyltriethoxylsilane bonding at the end of the WPU molecular chain. The hybrid was characterized by scanning electron microscopy, energy dispersive spectroscopy (EDS), transmission electron microscopy, Fourier transform infrared spectroscopy (FTIR), and X‐ray photoelectron spectroscopy (XPS). The results showed that the nanosilica/WPU hybrids with well‐dispersed nanosilica particles were synthesized, in which the particles had typical diameters of about 50 nm. In addition, XPS and FTIR analyses demonstrated that chemical interaction occurred between WPU and silica. The effects of TEOS on surface wettability, water resistance, mechanical strength, and thermal properties of the hybrid were also evaluated by contact angle measurements, water absorption tests, mechanical tests, and differential scanning calorimetry, respectively. An increase in advancing contact angles, water resistance, and tensile strength, as well as decrease in elongation at break and glass transition temperature, were obtained with the addition of TEOS. Water absorption decreased from 17.3 to 5.5%. The tensile strength increased to a maximum of 29.7 MPa, an increase of about 34%. Elongations at break of the hybrids decreased 191%. These results were attributed to the effects of the nanosilica and the chemical interaction between WPU and silica. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

基于羧酸-磺酸盐的聚氨酯乳液的制备及性能研究

以二羟甲基丙酸(DMPA)和1,2-二羟基-3-丙磺酸钠(DHPA)为亲水扩连剂制备含有磺酸基团的水性聚氨酯微乳液。利用傅立叶变换红外光谱(FT-IR)对DHPA和水性聚氨酯的结构进行表征,证实了目标产物DHPA的生成,并作为亲水扩链剂引入PU链上。研究表明,随着DHPA含量增大,乳胶粒平均粒径减小,粒径分布宽度变窄。聚氨酯乳液呈假塑性流体特征。所制得的聚氨酯表面活性剂对丙烯酸单体具有良好的乳化性能,可用于乳液聚合中。