聚硅氧烷改性水性聚氨酯的合成及其表面性能

以聚氧化丙烯二醇(PPG)、双羟基亲水性聚硅氧烷多元醇(UC3667)为软段,异佛尔酮二异氰酸酯(IPDI)、1,4-丁二醇(BDO)、二羟甲基丙酸(DMPA)、乙二胺(EDA)为硬段,制备了一系列聚硅氧烷改性水性聚氨酯(WPUs)。用DLS和FTIR表征了水性聚氨酯乳液粒径和膜结构。通过热重分析、拉伸测试、接触角测试、XPS对水性聚氨酯胶膜的性能进了测定。结果表明:随着聚硅氧烷加入量的增多,水性聚氨酯膜拉伸强度先增大后减小;且聚硅氧烷的加入提高了水性聚氨酯膜的热稳定性、断裂伸长率、接触角,降低了水性聚氨酯膜的表面能。当聚硅氧烷质量分数为5.0%时,胶膜表面的硅迁移量达到饱和,表面能为27.27 mJ/m~2。     

丙烯酸酯用量对溶胀-嵌段型水性聚氨酯性能的影响

以甲基丙烯酸甲酯（MMA）、丙烯酸正丁酯（BA）为单体,通过巯基乙醇链转移自由基无规共聚合成端羟基聚丙烯酸酯（PA-OH）,采用嵌段共聚法将PA-OH与水性聚氨酯（WPU）嵌段,通过预聚体分散法制得聚丙烯酸酯嵌段水性聚氨酯乳液（WPUA）,进而通过乳液聚合法制备了一系列以MMA/BA为单体的聚丙烯酸酯嵌段-溶胀水性聚氨酯复合乳液（WPUA-PA）,结果表明WPUA-PA中丙烯酸酯量最多可达到WPUA的240%,当丙烯酸酯量为WPUA的120%时WPUA-PA的性能最佳,此时乳液平均粒径为68 nm、粒径分布指数为0.174,胶膜拉伸强度为13.88 MPa、断裂伸长率为558.3%、吸水率为4.94%,且具有优异的乳液稳定性。     

Influence of the solids content on the properties of waterborne polyurethane dispersions obtained with polycarbonate of hexanediol

Waterborne polyurethane adhesives are an interesting alternative to the current solvent-borne polyurethane adhesives used in the industry. Different aliphatic waterborne polyurethane dispersions (PUDs) with different solids content were synthesised by reacting isophorone diisocyanate (IPDI) with a polycarbonate derived from hexanediol via the acetone method. The PUDs were characterised by Brookfield viscosity, pH, particle size, transmission electron microscopy (TEM) and solids content measurement. The dry polyurethane films were characterised by ATR-IR spectroscopy, plate–plate rheology, differential scanning calorimetry (DSC) and thermal gravimetry (TGA). Their adhesion was evaluated from T-peel tests of flexible PVC/waterborne polyurethane dispersion/flexible PVC joints and single lap-shear tests of aluminium/waterborne polyurethane dispersion/aluminium joints.The PUDs showed bimodal particle size distribution. The mean particle size of the PUDs decreased by increasing their solids content but the particle size distribution of the PUDs increased by decreasing their solids content. As the solids content increased the Brookfield viscosity of the PUDs increased due to lower mean particle size where particle crowding was favoured, the PUD having 44 wt% solids content was an exception (higher particle size but lower polydispersity). On the other hand, the increase in the solids content increased the hard segments content and the degree of phase separation of the polyurethanes. The greater the solids content of the polyurethanes, the lower their glass transition temperatures values and the lower the elastic moduli. Adhesive strength under peel stresses were not affected by the solids content in the polyurethanes but the single lap-shear strength values decreased by increasing the solid contents in the polyurethanes due to lower hard segments content.     

聚丙烯酸酯乳液的制备及其改性的研究

以丙烯酸酯及其衍生物作为主单体,丙烯酸为官能单体,采用乳液聚合法合成聚丙烯酸酯乳液,并用水性聚氨酯对聚丙烯酸酯乳液进行了改性。研究了搅拌速度、引发剂、丙烯酸和水性聚氨酯的含量对乳液及漆膜性能的影响。结果表明：在搅拌速度为200r／min,引发剂、丙烯酸和水性聚氨酯的含量分别为0．8％、0．3％和40％的条件下得到的乳液的稳定性、外观较好,黏度为88mPa㈦漆膜柔韧性好,附着力为一级。红外光谱分析表明合成了聚丙烯酸酯乳液,改性后的聚丙烯酸酯乳液具有聚丙烯酸酯和聚氨酯的复合结构。     

氟改性双组分水性丙烯酸聚氨酯涂料性能研究

以甲基丙烯酸十二氟庚酯（DFMA）、丙烯酸（AA）、甲基丙烯酸羟乙酯（HEMA）、甲基丙烯酸甲酯（MMA）和丙烯酸丁酯（BA）为原料,采用溶液聚合法合成了一系列氟含量不同的水性羟基丙烯酸树脂。将含氟水性羟基丙烯酸树脂、亲水性异氰酸酯固化剂和助剂混合制备氟改性双组分水性丙烯酸聚氨酯（2K—WPU）涂料。利用傅里叶变换红外光谱（FT-IR）对其结构进行了表征,并对涂料的接触角、吸水率和清漆性能分别进行了测试。结果表明,该水性树脂粒径在28．2～68．1nm之间,粒径分布均匀。当水性羟基丙烯酸树脂组成中DFMA质量分数从0增加至20％时,所制备氟改性2K-WPu涂料的水接触角从70．3。增大到97．6。,吸水率从11．4％降低至6．31％,涂膜的耐水性显著提高。清漆性能测试表明,所制氟改性2K．WPu的各项性能优异。     

水性聚氨酯及其复合物的合成与表征

采用丙酮回流法低成本的合成了水性聚氨酯,发现双羟甲基丙酸（DMPA）的用量不低于4．4％（Wt％）,合成的水性聚氨酯才具有较好的乳化能力,并以此为种子乳液,制得了复合乳液,用^1H-NMR、TEM等手段对其进行了表征,结果显示该复合乳液具有明显的核壳结构,且复合乳液的粒径分布比种子乳液稍宽,具有双峰结构;复合物中由于聚丙烯酸酯的存在,亲水性有所降低;力学性能显示,复合物的拉伸强度有所提高,而断裂伸长率有所下降。     

聚丙烯酸酯共混改性水性聚氨酯乳液的性能研究

自制了水性聚氨酯乳液,并采用共混方法制备了丙烯酸酯改性水性聚氨酯乳液。研究了共混膜的结构和性能,结果表明共混改性的涂膜性能比水性聚氨酯乳液涂膜性能有明显的提高。     

Synthesis and properties of a novel UV-curable waterborne hyperbranched polyurethane

A series of ultraviolet (UV)-curable waterborne hyperbranched polyurethane dispersions (WHPUDs) have been successfully synthesized by modifying the hyperbranched polyester H10, which was prepared using pentaerythritol as a core molecule and dimethylolpropionic acid as monomers, with succinic anhydride, toluene diisocyanate (TDI), and hydroxypropyl acrylate (HPA). The H10 was characterized by ¹H nuclear magnetic resonance spectroscopy and matrix-assisted laser desorption/ionization time of flight mass spectrometry. The properties of the WHPUDs with different content of succinic anhydride and TDI–HPA have been investigated by measuring the stability, the particle size, and the rheological behavior. The effects of the content of succinic anhydride and TDI–HPA were studied in terms of UV-curing rate, water resistance, and thermogravimetric behaviors of WHPUD coatings. The WHPUDs showed good appearance, particle size, viscosity, and storage stability. The WHPUD films showed superior photosensitivity and the percent conversion of C=C bonds reached about 80% when the radiation time was 50 s. Moreover, the UV-cured films had good water resistance and thermostability, which can benefit a waterborne polyurethane resin for waterborne coatings.     

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%。     

环氧树脂基双组分水性聚氨酯的制备及其在木器涂料中的应用

为提高双组分水性聚氨酯的室温交联速度,将N-苄基乙醇胺引入到环氧树脂制备了环氧树脂基水性多元醇,表征了多元醇的化学结构,并测定了其相对分子质量、粒径分布和玻璃化温度等主要技术参数。将环氧树脂基水性多元醇与多异氰酸酯配合制备了双组分水性聚氨酯,采用红外光谱法研究了室温交联反应过程。研究结果表明:多元醇分子结构中引入苄胺基加快了双组分水性聚氨酯的交联反应速度。将双组分水性聚氨酯制备成水性木器涂料,漆膜具有优异的耐冲击性、附着力、柔韧性、光泽、耐液体介质、硬度、丰满度等性能。     

阴离子型水性聚氨酯和阳离子型水性聚氨酯的合成及分析

以甲苯二异氰酸酯（TDI）和聚酯二醇等为基本原料,在NCO／OH比例及反应物量相同的情况下,分别合成了阴离子型水性聚氨酯和阳离子型水性聚氨酯。对它们进行了红外光谱分析、热重分析、粒径分析、吸水率测定和力学测试。结果表明：合成的阴离子水性聚氨酯无残余的-NCO,粒径、吸水率小于阳离子型水性聚氨酯,拉伸强度、断裂伸长率大于阳离子型水性聚氨酯,耐水性强于阳离子型水性聚氨酯。     

水性聚氨酯/蒙脱土复合乳液的合成及性能表征

本文通过蒙脱土插层聚合法制备了水性聚氨酯/蒙脱土复合乳液。通过单体插层于蒙脱土中,与聚氨酯聚合反应,均匀分散于水性聚氨酯中。用FTIR和TEM测试表征,观察到蒙脱土均已聚合入聚氨酯包裹。研究结果表明:当蒙脱土含量在5%左右时,该乳液涂膜具有较好的耐热性、10%分解温度比普通聚氨酯提高了大约20℃,拉伸强度和断裂强度达到最高值,分别为2.31Mpa和17.94N/mm。随着蒙脱土含量的增大,乳液粒子粒径增大,耐水性增强。蒙脱土含量达到5%时,乳液粒径为108nm,吸水率降至31.9%。     

环氧基四配位硅改性水性聚氨酯及性能分析

通过二步法制备了环氧基四配位硅（ETCS）改性水性聚氨酯，研究了n（-NCO）：n（-OH）、二羟甲基丙酸（DMPA）的含量、ETCS含量对水性聚氨酯乳液及成膜性能的影响，确定了n（-NCO）：n（-0H）在1．5-1．7之间，DMPA质量分数在5％左右，ETCS质量分数小于3％时制得的乳液外观呈蓝光半透明，粒子半径小，稳定性高；涂膜耐热性高、吸水率低。实验证明ETCS作为扩链剂比乙二胺作扩链剂时合成的水性聚氨酯各方面性能均有提高。     

DHPA扩链剂合成磺酸型水性聚氨酯的性能研究

合成了一种新型磺酸型扩链剂1,2-二羟基-3-丙磺酸钠(DHPA),并通过红外光谱法证明了其化学结构。利用这种扩链剂与异佛尔酮二异氰酸酯、聚醚多元醇等反应,制备出固含量高、热稳定性好和力学性能好的磺酸型水性聚氨酯(SWPU)乳液及薄膜。与同时合成的羧酸型水性聚氨酯(CWPU)对比发现,SWPU乳液的固体质量分数可达50%以上,而CWPU乳液固体质量分数不超过40%;SWPU乳液的粒径比CWPU小,粒径分布窄;SWPU薄膜具有更好的热稳定性和弹性模量;SWPU薄膜耐溶剂性比CWPU薄膜好,但耐水性比CWPU薄膜差。     

Synthesis and characterization of multiple cross-linking UV-curable waterborne polyurethane dispersions

A series of multiple cross-linking ultraviolet (UV) curable waterborne polyurethane dispersions (UV-PUDs) were synthesized by modification of diglycidyl ether of bisphenol-A-based epoxy resin (E51) through ring-opening by 3-aminpropyltriethoxysilane (APTES). Initially, APTES-E51 was synthesized using APTES to open the epoxy groups of E51. Then, APTES-E51 was incorporated into the chains of polyurethane, and multiple cross-linking UV-PUDs were produced. The chemical structures were confirmed by the Fourier-transform infrared spectroscopy (FTIR) and the effect of the APTES-E51 content on the UV-PUDs properties was investigated. The average particle size of UV-PUDs was determined by dynamic light scattering (DLS). The result showed that the average particle size increased with increasing APTES-E51 content and the stability of the UV-PUD storage diminished when the content of APTES-E51 was 10.0%. After modification by APTES-E51, the water absorption of the UV-cured films decreased and the water contact angle (CA) increased significantly. Thermogravimetry analysis (TGA) of the UV-cured films illustrated that APTES-E51 modified UV-curable waterborne polyurethane could exhibit good thermal stability. In addition, mechanical property of the cured films showed that the incorporation of APTES-E51 also improved tensile strength of the cured films. We can obtain good storage stability, satisfied water resistance, and high thermal stability and tensile strength when the APTES-E51 content of the UV-PUD was 9.1%.     

HDI/IPDI对水性聚氨酯及胶膜性能的影响

采用预聚体分散法制备了一系列固含量为50%的水性聚氨酯(WPU),并通过傅里叶红外光谱(FT-IR)、粒径分析仪、X射线衍射(XRD)、差示扫描量热分析(DSC)、拉力试验机等仪器进行表征,研究了HDI/IPDI摩尔比对WPU的乳液性能和胶膜结晶性能、力学性能、耐水性能,以及基材EVA/PVC粘接性能的影响,分析了不同摩尔比的HDI/IPDI和粘接时间与WPU胶黏剂对EVA/PVC粘接性能的关系。研究发现,随着HDI/IPDI摩尔比增加,水性聚氨酯的乳液性能、软硬段的结晶性都得到提高,而胶膜拉伸强度呈先增大后减小的趋势,断裂伸长率则先减小后增大。所有WPU胶膜都有很好耐水性,胶膜吸水率都在5.0%（质量）以下。粘接实验结果表明,WPU胶黏剂对EVA/PVC具有优异的粘接性能,24 h后可对基材产生界面破坏,随着HDI/IPDI摩尔比增加,胶黏剂的粘接强度增大。当HDI/IPDI=7∶1时,水性聚氨酯的综合性能最好。     

聚丙烯酸酯乳液复合改性水性聚氨酯胶粘剂的研究

研究了一种聚丙烯酸酯乳液复合改性水性聚氨酯胶粘剂的方法,以及聚丙烯酸酯的玻璃化温度Tg、功能单体等改变对改性后的PUA复合乳液的粘接性能的影响。结果表明：聚丙烯酸酯乳液的分子结构不同对复合乳液的粘接性能影响很大,通过改变聚丙烯酸酯乳液的用量、Tg、羟基含量、羧基含量等可以得到综合性能更优的复合乳液。     

Micromorphology and adhesive properties of sulfonated polyurethane/polyacrylate emulsions prepared by surfactant-free polymerization

Novel eco-friendly sulfonated polyurethane/polyacrylate (SPUA) emulsions were synthesized by surfactant-free emulsion polymerization method using PU as seeds. The sodium sulfonate modified polyester polyol (SDNP) was used as internal emulsifier to make the PU emulsion disperse in deionized water. Effects of the SDNP content on the properties of the emulsions and membranes were studied. Dynamic light scattering (DLS) result showed that the average particle sizes of SPUA emulsions decreased first from 124.1 nm to 102 nm when the SDNP content was lower than 40 wt% and then increased to 138 nm. Transmission electron microscopy (TEM) morphology showed that the particle sizes were all spherical and an apparent core-shell structure was observed. Fourier transform infrared spectroscopy (FT-IR) result ascertains that SPUA was successfully prepared. X-ray photoelectron spectroscopy (XPS) analysis demonstrates that the carbon, oxygen, nitrogen, sulfur, and sodium peaks were all revealed and the polyurethane component was rich in the upper surface. Thermo gravimetric analysis (TGA) of the membranes showed that the thermal stability of the SPUA membranes was enhanced by increasing the SDNP content. Scanning electron micrograph (SEM) results demonstrates that the coexistence of a dual phase. The SPUA could be used as adhesives in footwear industry, and the T-peel strength of the SPUA membranes increased from 5.98 N/mm to 12.06 N/mm when the SDNP content was up to 40 wt%. The wettability of SPUA emulsions on the rubber surface results showed that the emulsions could wet the rubber surface well.     

环氧树脂改性水性聚氨酯的制备及其性能研究

以异佛尔酮二异氰酸酯(IPDI)、聚酯多元醇(PEDA)为主要原料,二羟甲基丙酸(DMPA)为亲水性扩链剂,通过添加不同种类和不同含量的环氧树脂(E-12、E-51)进行改性,合成了环氧树脂改性水性聚氨酯(EWPU)乳液,讨论了DMPA含量、环氧树脂种类和含量对EWPU乳液粒径、粘度、贮存稳定性以及胶膜吸水率和力学性能的影响。结果表明,环氧树脂中的环氧基团在整个反应过程中没有参与反应,保留在EWPU乳液中;DMPA质量分数为4%、环氧树脂E-12质量分数为8%时,制备的EWPU乳液和胶膜的性能较好。     

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