聚醚和聚酯型水性聚氨酯胶粘剂的制备及性能比较

摘 要 用二羟甲基丙酸作为亲水单体，分别合成了聚醚型和聚酯型的水性聚氨酯，并进行各种性能比较。用二羟甲基丙酸作为亲水单体制备的乳液，稳定性较好，贮存期在半年以上。当二羟甲基丙酸含量相当时，聚醚型的比聚酯型的耐水性要好，但强度不如后者。     

涂料用水性聚氨酯的研制

合成了稳定的聚醚型阴离子聚氨酯乳液.研究了w(二羟甲基丙酸)、n(异氰酸根)与n(羟基)之比、中和剂的种类对乳液和胶膜性能的影响.实验结果表明:乳液的黏度、稳定性随着w(二羟甲基丙酸)的增大而增大,当w(二羟甲基丙酸)为7.5%时乳液和胶膜性能最好;涂膜的拉伸强度随n(异氰酸根)与n(羟基)之比增大而增大,断裂伸长率随n(异氰酸根)与n(羟基)之比增大而减小,适宜的n(异氰酸根)与n(羟基)之比应在7.5～8.0之间;用三乙胺做中和剂得到的乳液外观和稳定性好于氢氧化钠和氨水.     

指甲油用水性聚氨酯-丙烯酸酯复合乳液的制备与性能

选用异佛尔酮二异氰酸酯、聚醚二元醇、二羟甲基丙酸、1.4-丁二醇、三羟甲基丙烷、甲基丙烯酸甲酯、功能性单体等为原料,采用阴离子自乳化法合成了指甲油用水性聚氨酯-丙烯酸酯复合乳液。该复合乳液完全满足当前对水性指甲油的要求。     

水性聚氨酯耐水性的研究

以聚醚多元醇和甲苯二异氰酸合成了水性聚氨酯乳液。研究了二羟甲基丙酸亲水扩链剂、三羟甲基丙烷交联剂和乙二胺对水性聚氨酯涂膜耐水性的影响，制备了耐水性好的水性聚氨酯树脂。     

自乳化聚氨酯乳液胶粘剂的制备

本文用二羟甲基丙酸作为亲水单体合成了自乳化聚氨酯乳液。该乳液稳定性达到半年以上,胶膜强度大于10MPa,扯断伸长率大于350％。     

一种聚氨酯乳液的研制

以异弗尔酮二异氰酸酯IPDI和饱和聚酯二元醇以及二羟甲基丙酸(DMPA)为主要原料制备聚氨酯乳液,该乳液具有优良的机械强度、耐水性和耐热性。     

聚酯型水性聚氨酯的合成与表征

以2,4-甲苯二异氰酸酯、聚ε-己内酯二元醇、二羟甲基丙酸、三羟甲基丙烷等为原料,采用丙酮法制备了聚酯型水性聚氨酯乳液,并对其性能进行了研究.结果表明,当nNCO/nOH在1.3～1.7、二羟甲基丙酸质量分数在4%～8%时,制得的乳液贮存稳定;三羟甲基丙烷的引入,能明显改善聚氨酯胶膜的耐水性.经透射电镜、激光粒度仪及热重分析表明,所制得的聚氨酯胶粒为较规整的圆球状,粒径呈单峰分布.在260℃内,胶膜有较好的热稳定性.     

聚氨酯乳液的电位及其稳定性

以聚氧化丙烯二醇、甲苯二异氰酸酯、二羟甲基丙酸、2-甲基丙二醇、三乙胺和多元胺为原料合成了一系列不同离子基团含量的聚氨酯乳液，并测定了乳液的ζ电位，以及高温、冻融、机械稳定性和抗电解质能力。     

水性氨酯油木器漆的研制

采用气干性植物油与三羟甲基丙烷(TMP)的醇解产物,代替传统的聚酯聚醚多元醇与甲苯二异氰酸酯(TDI)和二羟甲基丙酸(DMPA)反应,用三乙胺中和,加水稀释得到自乳化的水性氨酯油乳液.由此乳液制备了性能优良的水性氨酯油木器漆,并对影响乳液性能的各种因素进行了探讨.     

MMA含量对PUA复合乳液性能的影响研究

以甲苯二异氰酸酯(TDI-80)，聚醚二元醇(N210)，二羟甲基丙酸(DMPA)和甲基丙烯酸甲酯(MMA)为主要原料，采用原位乳液聚合法，合成聚氨酯-丙烯酸酯(PUA)复合乳液，在保证二羟甲基丙酸(DMPA)含量、中和度等不变的情况下，研究了MMA含量对乳液的性能及外观的影响。结果表明，MMA对乳液外观、贮存稳定性、力学性能、吸水性等均有重要影响。MMA最佳含量为20％～30％。     

二羟甲基丙酸用量对聚氨酯-丙烯酸酯离聚物乳液性能的影响

用甲苯二异氰酸酯、聚己二酸新戊二醇酯多元醇(PDGA)、二羟甲基丙酸(DMPA)和甲基丙烯酸-2-羟乙酯合成了聚氨酯-丙烯酸酯(PUA)离聚物乳液,讨论了DMPA用量对其性能的影响。结果表明,当DMPA与PDGA的摩尔比增大时,PUA离聚物乳液的平均粒径减小,粒径分布变窄,黏度增大,稳定性提高,但DMPA用量过高时,会使具有高表面能的小粒子团聚,从而给PUA离聚物的乳液性能带来负面影响。     

Waterborne polyurethane dispersions obtained by the acetone process: A study of colloidal features

Waterborne polyurethane (PU) dispersions were prepared from isophorone diisocyanate (IPDI), 2‐bis(hydroxymethyl) propionic acid (DMPA), 1,4‐butane diol (BD), poly(propylene glycol) (PPG), and triethylamine (TEA) by means of phase inversion through the acetone process. Changes in DMPA content, initial PU content in acetone, phase‐inversion temperature, evaporation conditions, and solvent nature were found to have a great impact on dispersion properties. Using a DMPA concentration of 0.30 mmol/g_pol, stable PU dispersions could only be obtained when the initial PU content in acetone was at least 60 wt %, and phase‐inversion temperature was lower than 30°C. However, when increasing the PU content to 75 wt %, stable dispersions were obtained using DMPA concentrations three times lower. Finally, viscosity curves during the water addition step as well as a phase diagram were determined to understand the particle formation mechanism. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚醚型阴离子水性聚氨酯乳液的合成及性能研究

采用聚乙二醇、甲苯二异氰酸酯、二羟甲基丙酸为基本原料,用预聚法合成了稳定的聚醚型水性聚氨酯乳液。探讨了NCO/OH(摩尔比)、DMPA用量、中和度等对水性聚氨酯性能的影响。实验表明:当预聚温度为80℃、乳化温度为30℃时,初聚NCO/OH为2.0、总NCO/OH为1.2、DMPA用量为4%、中和度为100%、TMP与DMPA的摩尔比控制在1:4左右时合成的聚醚型阴离子水性聚氨酯具有较好的乳液稳定性,且涂膜的耐水性和机械性能优良。     

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。     

Performance of palm oil‐based dihydroxystearic acid as ionizable molecule in waterborne polyurethane dispersions

Waterborne polyurethane dispersions (WPUDs) containing a renewable palm oil‐based 9,10‐dihydroxystearic acid (DHSA) as an isocyanate‐reactive compound bearing ionizable carboxylic group to incorporate hydrophilic groups into the polymer chain have been successfully prepared. The WPUDs were prepared by using polyether and polyester polyols of 2000 molecular weight, DHSA and its traditional petroleum‐based counterpart 2,2‐bis(hydroxymethyl)‐propionic acid (DMPA), and an aliphatic diisocyanate (isophorone diisocyanate, IPDI). A comparison was made between the properties of WPUDs obtained using blends of DHSA and DMPA at different molar ratios and a reference WPUD based on DMPA. The particle size of polyester type WPUDs containing DHSA was reduced at a 0.5 to 0.5 molar ratio of DMPA to DHSA. A lower initial temperature was used in the preparation of NCO‐prepolymers with DHSA as compared to DMPA and this eased the preparation of WPUDs. The effect of molar ratio of DMPA to DHSA on the properties of films and coatings prepared with WPUDs was evaluated. The best properties were obtained with WPUDs prepared with a 0.5 to 0.5 molar ratio of DMPA to DHSA. The incorporation of renewable palm oil‐based DHSA into WPUDs improved water resistance (lower water uptake) and exhibited good combination of properties including hardness, adhesion strength, tensile strength, and elasticity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43614.     

2,2—二羟甲基丙酸（DMPA）性能,用途及合成工艺

2,2-二羟甲基丙酸(DMPA)是染料及农药的中间体,还可以制成一系列的DMPA的酯类和金属盐类,也可用来合成受阻酚类抗氧剂,DMPA作为一种二元醇可以参加缩聚反应。可见DMPA用途极为广泛。本文详尽叙述了DMPA的应用领域,并探讨了其合成工艺。     

亲水单体对聚氨酯丙烯酸复合乳液性能的影响

采用种子乳液聚合法,以甲苯二异氰酸酯(TDI)、聚醚二元醇(N210)、二羟甲基丙酸(DMPA)和甲基丙烯酸甲酯(MMA)为主要原料合成了聚氨酯丙烯酸(PUA)复合乳液。考察了DMPA对PUA乳液的制备和性能的影响;确定了DMPA的添加工艺及中和度。发现随DMPA添加量增加,PUA乳液的外观变好,乳液粒径变小,乳液黏度增大,乳液凝胶量降低,稳定性变好。随DMPA添加量增大,PUA乳液涂膜的吸水率增大,涂膜的耐水性越差。综合得到w(DMPA)=7 5%,采用后添加DMPA的工艺,且DMPA的中和度90%～100%,可得到性能优异的PUA复合乳液。     

Synthesis and characterization of waterborne polyurethane adhesives containing different amount of ionic groups (I)

A series of waterborne polyurethanes (WBPU) containing different amount of 2,2‐bis(hydroxymethyl) propionic acid (DMPA) were synthesized using prepolymer mixing process. Relationships between the DMPA content and physical, mechanical, and thermal properties as well as adhesive behavior at different condition were investigated. Stable aqueous dispersions of WBPU were obtained when the DMPA content was more than 10 mol %. At higher DMPA content, the particle size of the WBPU dispersion was lower but the viscosity of the dispersion was higher. Water swelling and tensile strength of the films increased with increasing of DMPA content. The optimum adhesive strength of WBPU adhesives was found to be depended on the DMPA content, pressing temperature, and pressure on adhesion process. The adhesive strength of WBPU adhesives increased with increasing DMPA content. The optimum pressing temperature decreased with increasing DMPA content. The adhesive strength of WBPU adhesives increased with increasing pressure up to 15 kg f/cm² and then leveled off. The optimum pressing temperature of WBPU adhesives samples containing 24.02, 22.05, and 17.05 mol % DMPA was about 100, 120, and 140°C, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5684–5691, 2006     

Synthesis and characterization of waterborne polyurethane emulsions based on poly(butylene itaconate) ester

Waterborne polyurethane (WPU) prepolymer was synthesised by the reaction of poly(butylene itaconate) ester (PBI, Mn = 1109 g/mol), 1,6-hexanediol, dimethylol propionic acid (DMPA), 2,4-toluene diisocynate (TDI), hydroxyethyl acrylate (HEA), and absolute ethanol as blocking agent, triethylamine as neutralizer. Cross-linked WPU was synthesized by trimethylolpropane (TMP) as crosslinker. The influences of PBI, DMPA, and TMP content on WPU emulsions and films were investigated. The structure of WPU was determined by Fourier transform infrared (FTIR) spectra, thermal properties and glass transition temperature of WPU films were determined by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively, and morphology of the emulsion particles was observed by transmission electron microscopy (TEM). Through TGA, the heat resistance of the cross-linked WPU film was better than WPU film. By DSC analysis, glass transition temperature of cross-linked WPU film (21 °C) was higher than WPU film (10 °C).     

耐水性的水乳性聚酯型聚氨酯胶黏剂的研究

自行合成多种聚酯及其聚氨酯胶黏剂 ,并对其性能进行了比较。研究结果表明 P(H/N) AU耐水性优良 ,当 DMPA含量达 7.6%时其吸水率为 1 5 .3 % ,同 N-2 2 0水性聚氨酯 DMPA含量为 8.3 %时 ,吸水率为 1 6.7%相当。而粘结纸板的剪切强度优于后者。