Synthesis,characteristic, and properties of waterborne polyurethane based on natural rubber

A series of new waterborne polyurethanes (WPUs) was successfully prepared by prepolymer process from renewable source, hydroxytelechelic natural rubber (HTNR), with different amounts of DMPA (1.6–8.4 wt %), different molecular weights (1000–4000 g mol^?1), and different levels of epoxide (0%–20%) of HTNR. It was found that the urethane conversions of prepolymer were over 80% as calculated by FTIR technique. The resulting HTNR2000‐based WPUs exhibit a uniform particle size, which decreases from 420‐ to 83‐nm diameters with an increase in the amount of DMPA from 2.9 to 6.6 wt %. The particle size also decreases with an increase of soft segment or with an increase of epoxide content. They are well stable more over 6 months and without a significant difference in particle size compared with starting of them. Chemical structure of WPU films was confirmed by FTIR, ¹H‐NMR, and ¹³C‐NMR. Molecular weight and polydispersity were determined by SEC. In addition, thermal and water uptake properties were investigated. The experimental results reveal that the DMPA content, molecular weight of HTNR, and epoxide content play an important key role in water uptake and thermal properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

不同合成工艺制备的脂肪族水性聚氨酯的性能研究

采用异佛尔酮二异氰酸酯（IPDI）、聚己二酸丁二醇酯二醇（PBA）、二羟甲基丙酸（DM-PA）、乙二胺（EDA）等为主要原料,以4种不同的合成工艺制备了固体质量分数大于40％的高固含量水性聚氨酯（WPU）乳液,考察了4种不同合成方式所制备WPU的稳定性、粘度、粒径、耐水性能及力学性能等。结果表明,以不同合成方式所制备的固体质量分数大于40％的WPU均具有较佳的稳定性,乳液的粒径均小于0．51μm,所制备的WPU胶膜具有较高的力学性能,拉伸强度均高于30MPa,其中以方法4所制备的WPU综合性能最佳,拉伸强度达到44．52MPa,断裂伸长率达到770％,吸水率为22．92％。     

芳香族聚酯聚醚型水性聚氨酯的合成及性能研究

以甲苯二异氰酸酯(TDI)、聚酯二元醇(PBA)、聚醚二元醇(N220)、二羟甲基丙酸(DMPA)、三羟甲基丙烷(TMP)等为主要原料合成了一系列水性聚氨酯乳液(WPU).探讨了聚醚与聚酯的含量、交联度等因素对水性聚氨酯乳液外观、粒径以及膜的红外结构、耐热性能和力学等性能的影响.结果表明:聚酯含量的增加有利于提高水性聚氨酯的结晶和耐水性、耐热性能,交联度的增加破坏了水性聚氨酯分子链的规整性,使得其结晶能力下降,耐热性能变化不明显,但是耐水性得到提高.     

A new method to synthesize high solid content waterborne polyurethanes by strict control of bimodal particle size distribution

A new method named two-step emulsification process was developed to synthesize high solid content waterborne polyurethanes by strict control of the bimodal particle size distribution. In the first step, a series of 40% solid content polyester-based (WPU-1) with low content of hydrophilic group and large particle size were firstly synthesized. In the second step, polyether-based prepolymers (WPU-2 prepolymers) with high content of hydrophilic group were firstly prepared and WPU-1 emulsions were used to emulsify WPU-2 prepolymers to obtain the final emulsions with high solid content (WPU-3). The particle size of WPU-3 present bimodal distribution and the diameter ratio and volume percentage of large particles to small particles in WPU-3 were able to be strictly controlled by this method. The viscosity of WPU-3 with 55% solid content was only 489.1 mPa s⁻¹ when the diameter ratio of large particles to small particles was 9.2 and the volume percentage of large particles was 74%.     

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。     

MDI型水性聚氨酯膏化和黏度影响因素

采用四氢呋喃均聚醚(PTMEG-1800),2,2-羟甲基丙酸(DMPA)和二苯基甲烷二异氰酸酯(MDI-50)等为原料合成聚氨酯预聚体,加入乙二胺(EDA)等后扩链得到水性聚氨酯乳液(WPU).WPU乳液黏度的影响因素主要有搅拌速率、-NCO/-OH的量比值(R值)、乳胶粒子粒径大小等,合理控制黏度可以避免乳液膏化现...     

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。     

Preparation and characterization of waterborne polyurethane containing PET waste/PPG as soft segment

Soft drinks poly(ethylene terephthalate) (PET) bottles were depolymerized by glycolysis using a 1 : 3 molar ratio of PET repeating unit to glycols like neopentyl glycol (NPG) and dipropylene glycol (DPG). Further, a series of waterborne polyurethanes (WPUs) was synthesized using pure polypropylene glycol (PPG), and glycolyzed oligoesters/PPG blends in different molar ratios as soft segment. Thermal property of WPU was tested by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Moreover, viscosity and particle size of WPU were also investigated. The results show that introduction of a certain amount of glycolyzed oligoester to soft segment makes the degree of hard‐soft domain microphase separation smaller, and can also improve thermal stability of WPU. Furthermore, WPUs synthesised from glycolyzed oligoesters and PPG blends possess larger particle size, better particle size distribution, relative lower and more stable viscosity. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42757.     

Growth kinetics and mechanism of wet granulation in a laboratory-scale high shear mixer: Effect of initial polydispersity of particle size

The effect of initial polydispersity of particle size (unimodal versus bimodal distribution) and binder characteristics on the growth kinetics and mechanism of wet granulation was studied. Wet granulation of pharmaceutical powders with initial bimodal particle size distribution (PSD) presented growth kinetics consisting of two stages: fast growth followed by slow growth. The fast stage is controlled by the amount of binder and high probability of coalescence due to the collisions of small and large particles. The second stage is characterized by slow agglomeration of powder mixtures with water content 13.6% v/w, and slow breakage of powder mixtures with water content of 9.9% and 11.7% v/w. The wet granulation of powders with initial unimodal PSD exhibited slow growth kinetics consisting of one stage, since similar particle sizes do not promote agglomeration. The experimental results were better described by a population balance equation using a coalescence kernel that favors growth rate by collision between small and large particles. In general, the probability of a successful collision increased with higher size difference between particles, smaller particle size, and higher binder content.     

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。     

羟基型水性聚氨酯的合成及其柔性水性木器清漆的制备

采用丙酮法利用聚酯二元醇（PE-1000）、二羟甲基丙酸（DMPA）、1,6-己二醇（HDO）、三羟甲基丙烷（TMP）和异佛尔酮二异氰酸酯（IPDI）反应,经中和、加水分散,合成出羟基型水性聚氨酯.并用制成的树脂和水性多异氰酸酯固化剂（Bayhydrol XP2655）以及消泡剂、流平剂、助溶剂等制备出柔性水性木器清漆.通过傅里叶红外光谱、差示扫描量热仪、热重分析仪、粒度仪、各种涂膜测试仪等仪器进行表征.测试结果表明：当树脂的数均分子量设计为5 000～6 000、DMPA的含量为4.5％～5.0％、HDO的含量为8.0％～10.0％、TMP的含量为5.0％～5.5％、中和度为1.0左右时制备出的树脂粒径、黏度和吸水率较小,贮存期l a以上.且条件范围内合成的水性木器清漆耐磨性好,丰满度高,柔软性佳,手感好,耐水、耐醇性好.     

聚酯-聚醚混合型水性聚氨酯的合成工艺研究

以聚己二酸丁二醇酯二醇（PBAG）和聚乙二醇（PEG）为软链段,以异佛尔酮二异氰酸酯（IPDI）和二羟甲基丙酸（DMPA）为硬链段,采用预聚体法制备了水性聚氨酯（WPU）,研究了R值（NCO／OH摩尔比）、DMPA用量、聚酯与聚醚摩尔比等对乳液的粘度、粒径、稳定性和聚氨酯胶膜力学性能的影响。结果表明,选用尺值为2．0、DMPA质量分数为3．5％、聚酯与聚醚摩尔比为2．5,制备的聚酯-聚醚混合型WPU的粒径可以达到310nm,粘度达到65mPa·s,其离心稳定性和wPU膜力学性能良好。经WPU涂层整理织物的耐静水压达到6．08kPa,透湿量达4550g／（m2×24h）,符合服用性能的要求。     

Synthesis and adhesion properties of waterborne polyurethane dispersions with long‐branched aliphatic chains

In this study, a series of waterborne polyurethanes (WPUs) with different contents of long‐branched aliphatic chains were synthesized through variation of the amount of diol chain extender trimethylol propane monooleate (TMPM). The effects of the TMPM content on the adhesion properties of the WPUs were investigated in terms of their surface tension, interfacial tension, contact angle, and adhesion strength. Fourier transform infrared and ¹H‐NMR spectra demonstrated the successful incorporation of TMPM into the polyurethanes. An increase in the TMPM content produced decreases in the surface tension of the WPUs and the interfacial tension and contact angle between the WPUs and plastic films. This indicated that the wetting properties of the WPUs on the plastic films was improved. The improved wettability enhanced the adhesion strength of the WPUs, and this showed that the long‐branched aliphatic chains could effectively improve the adhesion performance of the WPUs on the plastic films. Moreover, TMPM, with its hydrophobic aliphatic chains, increased the hydrophobicity and thermal stability of the WPU films. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41688.     

Stability and properties of waterborne polyurethane/clay nanocomposite dispersions

Factors that can affect the stability of waterborne polyurethane (WBPU)/clay nanocomposite dispersions are reported. It is suggested that the dispersion stability depends on the carboxyl acid salt content, clay content, sonication (mechanical forces), and clay surface structure. It was observed that the dispersion stability increased with increasing carboxyl acid salt content after applying sonication (mechanical forces) in clay with OH groups (Cloisite 30B) up to 23.58 mol% DMPA. Encapsulated (WBPU20-30B4-M and WBPU23-30B5-M) clay in PU particles was formed using the above combination. The dispersion with clay encapsulated in PU particles had the longest storage time of all of the dispersions. The zeta potential, particle size, particle size distribution, and viscosity of the dispersions also depend on carboxyl acid salt content, clay content, sonication (mechanical forces), and clay surface structure.     

Preparation and characterization of waterborne epoxy latexes and epoxy/(silica sol) composites

A series of waterborne epoxy latexes was synthesized, and epoxy/(silica sol) composite latexes were prepared. The effects of functional monomer methacrylic acid (MAA) and silica sol on the latex particle size, morphology, and stability were investigated. With increasing amounts of MAA, the conversion rate increased, the particle size reduced, and the viscosity of the epoxy latexes increased. The epoxy latexes had storage stability and could be stored at room temperature for more than 6 months with a solid content variation of less than 1%. For the (silica sol)‐modified waterborne epoxy latexes, the effects of preparation techniques and silica sol content on the latexes and latex films were investigated. When the silica sol content increased, the particle size of the composite latexes decreased. The morphology investigation showed that when the silica sol content increased, the uneven surface level of the latex films was increased. The increase of elemental silica on the surface was in accord with the improvement of the water resistance of the composite latex films. The heat resistance of these films was improved as well, and their overall performance was better than that of the epoxy latex films. J. VINYL ADDIT. TECHNOL., 20:57–64, 2014. © 2014 Society of Plastics Engineers     

含PDMS侧链的水性聚氨酯的制备及性能研究

以异佛尔酮二异氰酸酯(IPDI)、聚酯二元醇(PCL)、二羟甲基丙酸(DMPA)、三乙胺(TEA)、乙二胺(EDA)、氨乙基氨丙基聚二甲基硅氧烷(AEAPPDMS)等为原料,采用二次自乳化法,合成系列含PDMS侧链的改性水性聚氨酯(SiPU)。探讨了AEAPPDMS含量对乳液粒径、黏度与涂膜耐水性、机械强度的影响。结果表明:改性后的水性聚氨酯综合性能良好,水性聚氨酯的主链上引入PDMS侧链导致涂膜的吸水率显著下降。     

丙烯酸酯含量对水性聚氨酯性能的影响

采用无皂种子乳液聚合法,以甲苯二异氰酸酯(TDI)、聚酯多元醇、二羟甲基丙酸(DMPA)和甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)等为主要原料合成丙烯酸酯-水性聚氨酯复合乳液,考察了丙烯酸酯含量对水性聚氨酯乳液粒径、运动黏度、胶膜的耐水性和力学性能的影响。试验结果表明,随着丙烯酸酯含量的增加,复合乳液的粒径增大,运动黏度减小,胶膜的耐水性和拉伸强度提高,但胶膜的断裂伸长率有所降低,适宜的丙烯酸酯用量为40%～50%。     

Rheology of highly filled natural CaCO3 composites. I. Effects of solid loading and particle size distribution on capillary rheometry

The rheology of poly(di‐methyl siloxane) suspensions containing various loadings of natural CaCO₃ particles, of several particle size distributions, was studied using capillary rheometry. Highly loaded suspensions were investigated, emphasizing the unique behavior of high filler loaded compositions. Mild shear thinning was observed for most suspensions, whereas shear thickening was observed for suspensions containing nearly maximal possible solid loadings. The dominancy of particle size distribution was demonstrated by studying the relative suspensions viscosity as function of shear rate. It was further illustrated by the influence of the filler specific surface area on the flow properties. A seemingly slight changes in the particles‐specific surface area caused significant changes in the viscosity of maximal solid loaded unimodal suspensions. Fair agreement with the Chong and Krieger and Dougherty models was found for unimodal suspensions, while the combined Farris–Chong model showed an improved fit for the bimodal suspensions. Evidence for wall slip was demonstrated, using scanning electron microscopy and energy dispersive spectrometry, as a clear difference in the extrudate outer and bulk compositions; although no influence on the flow data was observed. POLYM. COMPOS., 28:512–523, 2007. © 2007 Society of Plastics Engineers     

Preparation and characterization of thermoplastic water‐borne polycarbonate‐based polyurethane dispersions and cast films

Stable water‐borne polyurethane dispersions (PUDs) were prepared from bifunctional aliphatic polycarbonate‐based macrodiol, 2,2‐bis(hydroxymethyl)propionic acid (DMPA), 1,6‐diisocyanatohexane, 1,4‐butanediol (BD), and triethylamine. Water‐borne dispersion particles are thus solely formed from self‐assembled linear PU chains. Both PUDs and PUD‐based films were characterized with regards to the concentration of DMPA (ionic species content) and BD (hard‐segment content). Average particle size of PUDs decreased and their long‐term stability increased with increasing DMPA and decreasing BD concentration. Functional properties of cast films made from PUDs are substantially influenced by the character of the original colloidal particle dispersions. The swelling behavior of the films, their surface morphology, and mechanical properties are more influenced by DMPA than BD contents. At DMPA concentrations higher than 0.2 mmol g^?1 of the solid mass of polyurethane, distinct self‐organization of individual nanoparticles into fibril‐like structures was detected by atomic force microscopy and scanning electron microscopy. PU films made from PUD containing high BD as well as high DMPA concentrations have the best utility properties namely sufficient tensile properties and a very low swelling ability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42672.     

二氧化硅溶胶的制备及性能影响研究

以正硅酸乙酯、水、乙醇和酸性催化剂为原料,制备了SiO2溶胶。研究了催化剂的种类、反应温度、反应时间、添加剂等因素对SiO2溶胶性能的影响。实验结果表明：在[H^＋]相同的条件下,酸催化剂对溶胶粘度的影响为：HF〉HCI〉HN03〉H2S04〉HAC,对凝胶时间的影响为：HAC〉H2S04〉HC1〉HN03〉HF,几种溶胶固含量的大小为：H2S04〉HN03〉HCl〉HAC,制备二氧化硅膜用硅溶胶较适合采用盐酸或硝酸作为催化剂;随着反应温度的升高,溶胶的粘度、固含量和粒径均逐步增大,凝胶时间则缩短;随着反应时间的延长,溶胶的粘度、固含量以及粒径逐步增大,凝胶时间则变短;向在溶胶中加入DMF后,溶胶粘度、固含量变小,凝胶时间延长,SiO2粒子的粒径增大。