非离子型聚氨酯-丙烯酸酯复合乳液的研究

以甲基烯丙基聚乙二醇醚(HPEG-2000)、异佛尔酮二异氰酸酯(IPDI)为原料合成端甲基烯丙基聚氨酯(HPU),然后将该亲水性齐聚物中间体与丙烯酸酯单体(AC)按不同质量比进行乳液聚合,得到非离子型聚氨酯-丙烯酸酯(PUA)复合乳液。通过红外分析、力学性能测试和热重分析等对PUA复合乳液及胶膜性能进行研究。结果表明,与纯聚丙烯酸酯(PA)乳液相比,PUA乳液凝胶率降为0且成膜性能明显改善。PUA胶膜与PA胶膜相比,耐热性和耐水性较好,断裂伸长率增大但拉伸强度降低。当HPU/AC质量比为20/80时,PUA胶膜综合性能达到最佳。     

有机硅改性水性聚氨酯丙烯酸酯的制备及性能

以异佛尔酮二异氰酸酯(IPDI)、聚氧化丙烯二醇(PPG)、二羟甲基丙酸(DMPA)、丙烯酸羟乙酯(HEA)等为原料合成了含双键的聚氨酯乳液,再与有机硅偶联剂KH570、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)进行自由基聚合,制备了有机硅改性聚氨酯丙烯酸酯(PUA)复合乳液。讨论了KH570用量对PUA胶膜耐水性、耐热性和力学性能的影响,并通过红外光谱、热重分析、粒度分析等测试对其结构和性能进行表征。结果表明,当固体分中KH570质量分数小于7.65%,乳液稳定性良好;随着KH570添加量增大,乳液粒径逐渐增大,胶膜吸水率下降,水接触角增大,耐水性、热稳定性和力学性能得到较大提高。     

丙烯酸酯改性水性聚氨酯树脂合成工艺的研究

以异氰酸酯、聚醚多元醇及二羟甲基丙酸为主要原料,合成了水性聚氨酯预聚体(PU),并且经过扩链、交联、丙烯酸酯复合改性等反应制备了丙烯酸酯改性水性聚氨酯树脂(PUA)。结果表明:对水性聚氨酯进行扩链、交联及丙烯酸酯复合改性,可以使两者优异的性能有机地结合起来,能显著提高水性聚氨酯的拉伸强度、硬度、耐磨性、耐水耐醇性,从而使水性PUA分散乳液胶膜的性能得到明显改善,以满足水性PUA木器漆用的要求。     

异氰酸酯指数对阴离子型水性聚氨酯性能的影响

以二羟甲基丁酸(DMBA)和聚乙二醇(PEG)为亲水扩链剂,甲苯二异氰酸酯(TDI)为异氰酸酯组分,聚氧化丙烯二醇(PPG)为低聚物多元醇组分,采用预聚体法合成了一系列阴/非离子型水性聚氨酯(WPU)。通过万能材料试验机、粒径测试、接触角测定等表征手段研究了异氰酸酯指数(R值)对水性聚氨酯乳液及胶膜性能的影响。结果表明,随着异氰酸酯指数的增加,乳液粒径逐渐增加,Zeta电位绝对值逐渐减小;胶膜的拉伸强度逐渐增加,断裂伸长率逐渐减小,表面接触角逐渐增大。     

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%。     

多官能有机硅低聚物改性阳离子水性聚氨酯的制备

采用自制功能性有机硅活性单体(PS1)对阳离子水性聚氨酯进行改性。研究了PS1用量对改性后聚氨酯乳液的粒径及分布、胶膜耐水性及表面沾水性的影响。结果表明,对聚酯型阳离子水性聚氨酯而言,经PS1改性后,其乳液粒径变大,胶膜耐水性先变好后变差,当PS1用量为5%时耐水性最佳,当PS1用量为7%时可达到最好的拒水效果;但对聚醚型阳离子水性聚氨酯而言,PS1的引入会导致其乳液粒径减小,胶膜耐水性以及拒水性随PS1用量的增加而持续改善,当PS1用量为16%时胶膜的耐水性及拒水性均达到最佳。     

丙烯酸酯改性蓖麻油基水性聚氨酯乳液的制备

以改性蓖麻油(MCO)、聚碳酸酯二醇(PCDL)、异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)和二羟甲基丙酸(DMPA)等为原料合成水性聚氨酯种子乳液,通过MCO的双键活性位实现丙烯酸酯(AC)单体的种子乳液聚合,得到聚氨酯–丙烯酸酯(PUA)乳液。通过FT–IR(傅里叶变换红外光谱)分析、激光粒度仪、旋转黏度计研究了AC单体含量及配比、助剂用量对PUA乳液性能的影响。通过电子拉力试验机、耐水试验和动态力学分析仪研究了不同AC含量PUA膜的力学、耐水和动态力学性能。结果表明:通过种子乳液共聚,PUA均显示一个玻璃化温度,说明聚丙烯酸酯与聚氨酯具有较好的相容性;当n(MCO):n(PCDL)=1.2,n(甲基丙烯酸正丁酯):n(甲基丙烯酸甲酯)=0.9,w(乳化剂SDS)为2.0%,w(引发剂AIBN)为0.2%时所合成的PUA稳定性最好,且具有适中的黏度和较好的粒径分布;随AC含量的提高,PUA胶膜耐水性提高,胶膜硬度和弹性模量逐渐提高,拉伸强度和伸长率均在w(AC)为10%时出现最大值。     

有机硅改性水性聚氨酯膜处理温度对性能的影响

采用聚四氢呋喃二醇(PTMG)和异佛尔酮二异氰酸酯(IPDI)为主要原料,端羟基聚二甲基硅氧烷(HTPDMS)为改性剂,通过改变HTPDMS的含量合成一系列改性的水性聚氨酯(WPU)乳液。乳液室温成膜后,在不同温度下进行热处理。采用核磁共振(NMR)测试、粒径测试、X射线光电子能谱(XPS)、耐水性能和力学性能等测试对样品进行了表征,考察了不同HTPDMS含量及不同后处理温度对WPU乳液及涂膜性能的影响。结果表明,Si元素在胶膜表面的显著富集,使胶膜耐水性能提高;随着乳胶膜后处理温度的升高,Si元素迁移能力明显提高,拉伸强度也明显提高。采用扫描电子显微镜观察了WPU膜的断面形貌,当HTPDMS引入到聚氨酯分子链中,聚氨酯基质出现了不同程度的相分离。     

葡萄糖改性水性聚氨酯及其生物降解行为研究

以异佛尔酮二异氰酸酯(IPDI)、聚环氧丙烷二醇(N210)作为主原料,葡萄糖(PG)作为交联剂制备了水性聚氨酯。对样品乳液进行平均粒径和稳定性测试,对胶膜进行了硬度、力学性能、耐水性以及热稳定性表征;采用土埋法对胶膜进行降解试验,并对降解后的样品进行表征。结果表明:葡萄糖的加入可以明显提高水性聚氨酯的力学性能,当PG含量为2.5%时,胶膜的拉伸强度达到40 MPa,邵A硬度达到78;葡萄糖的加入明显提高了聚氨酯胶膜生物降解速率,120 d内胶膜的力学性能几乎完全损失,样品破碎粉化。研究表明:葡萄糖作为交联剂既可以提高水性聚氨酯胶膜的性能,也可以促进聚氨酯在环境中自然降解。     

妥尔油改性水性聚氨酯的合成及性能研究

由妥尔油和二乙醇胺反应,合成了妥尔油二乙醇酰胺。采用异佛尔酮二异氰酸酯(IPDI)、妥尔油二乙醇酰胺、聚1,3-丙二醇、二羟甲基丙酸(DMPA)、三羟甲基丙烷(TMP)和三乙胺(TEA)为原料,合成了妥尔油改性水性聚氨酯。采用热失重分析仪(TGA)和X射线衍射(XRD)仪对胶膜的热分解性及其结晶度进行测定,同时对乳液的粒径和胶膜的耐水性及拉伸强度等性能进行检测。结果表明,经妥尔油二乙醇酰胺改性后,水性聚氨酯乳液的粒径增加,但稳定性良好,而胶膜的耐水性和热稳定性提高。     

Waterborne Polyurethane-Acrylate Containing Different Polyether Polyols: Preparation and Properties

The waterborne polyurethane–acrylate (PUA) was prepared based on isophorone diisocyanate, polyether polyol, dimethylol propionic acid, hydroxyethyl methyl acrylate, butyl acrylate (BA) and styrene (St). Fourier transform infrared spectrometry (FT-IR), Ultraviolet-visible spectrophotometry (UV-Vis) and Differential scanning calorimetry (DSC) were employed to investigate the structures, optical transparency and thermal properties. Some physical properties of the aqueous dispersions such as viscosity, particle size and surface tension were measured. Some mechanical performances and solvent resistance of films were investigated. When the ratio of the BA/St was 30/70, the films had excellent water and alkali resistances. The obtained PUA composites have great potential application such as coatings, leather finishing, adhesives, sealants, plastic coatings and wood finishes.     

In-situ polyurethane/polyacrylate microemulsion formation: the effects of acrylic content in wood coating application

In-situ surfactant-free emulsion polymerization was utilized to prepare polyacrylate/polyurethane (PUA) microemulsions in the absence of surfactant and organic solvent. For this purpose, PUA with higher acrylate content was successfully prepared, with the aim to reduce the coating cost. The dynamic light scattering results showed that the particle size of PUA microemulsion displayed a unimodal distribution and the particle size was ranged from 33 to 61 nm. In comparison with PUA prepared with conventional miniemulsion polymerization, the particle size distribution coefficient dropped by one order. Atomic force microscopy, together with thermogravimetric analyzer, demonstrated good compatibility and interaction between PU and acrylic components, and no phase separation was detected even at 58 wt% acrylic content. With the incorporation of acrylic component, the thermal stability and maximum stress were improved. The maximum stress greatly increased from 4.6 to 30.9 MPa, and the maximum stress of in-situ PUA was nearly three times larger than that of PUA prepared by miniemulsion polymerization. The effects of acrylic content on water resistance, pencil hardness, adhesion, and impact strength of wood coating were evaluated. With increasing the acrylic content, the water resistance and pencil hardness increased, though the impact strength of in-situ PUA films was slightly reduced.     

Preparation,mechanical properties of waterborne polyurethane and crosslinked polyurethane‐acrylate composite

The waterborne polyurethane (PU) prepolymer was first prepared based on isophorone diisocyanate, polyether polyol (NJ‐210), dimethylol propionic acid (DMPA), and hydroxyethyl methyl acrylate via in situ method. The crosslinked waterborne polyurethane‐acrylate (PUA) dispersions were prepared with the different functional crosslinkers. The chemical structures, optical transparency, and thermal properties of PU and PUA were confirmed by Fourier transform infrared spectrometry, ultraviolet–visible spectrophotometry, and differential scanning calorimetry. Some physical properties of the aqueous dispersions such as viscosity, particle size, and surface tension were measured. Some mechanical performances and solvent resistance of PUA films were systemically investigated. The experimental results showed that the particle sizes of the crosslinked PUA aqueous dispersions were larger than the PU and increased from 57.3 to 254.4 nm. When the ratios of BA/St, BA/TPGDA, and BA/TMPTA were 70/30, PUA films exhibited excellent comprehensive mechanical properties. The tensile strength and elongation at break of the film were 2.17 MPa and 197.19%. When the ratio of BA/St was 30/70, the film had excellent water resistance and was only 6.47%. The obtained PUA composites have great potential application such as coatings, leather finishing, adhesives, sealants, plastic coatings, and wood finishes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Waterborne polyurethane and modified polyurethane acrylate composites

Abstract

Waterborne polyurethane (PU) and a series of PU acrylate (PUA) composite dispersions were synthesised from isophorone diisocyanate, polyester polyols, dimethylol propionic acid, hydroxyethyl methyl acrylate, butyl acrylate and methyl acrylate. Fourier transform infrared, ultraviolet visible and differential scanning calorimetry were used to demonstrate structures, optical transparency and thermal stabilities of PU and PUA. The PUA sample had lower glass transition temperature of hard segment and higher decomposition temperature than the PU sample. Performances of the dispersion and film were studied by means of apparent viscidity, particle size and particle size distribution index, surface tension and mechanical property. The results indicated that the solvent resistance and mechanical property of PUA film were improved compared with the pure PU film. The obtained stable PUA composite samples have excellent integrated properties and have a great potential application in meeting the highly diversified demands in modern technologies, such as coatings, leather finishing, adhesives, sealants, rubbers, plastic coatings and wood finishes.     

Influence of an oligomer polyol and monomers on the structure and properties of core–shell polyurethane–poly(n‐butyl acrylate‐co‐styrene) hybrid emulsions

The free‐radical polymerization of alkenyl‐terminated polyurethane dispersions with styrene and n‐butyl acrylate was performed to obtain a series of stable polyurethane–poly(n‐butyl acrylate‐co‐styrene) (PUA) hybrid emulsions. The core–shell structure of the emulsions was observed by transmission electron microscopy, and the microstructure was studied by ¹H‐NMR and Fourier transform infrared spectroscopy. The effects of the poly(propylene glycol)s (number‐average molecular weights = 1000, 1500, and 2000 Da) and the mass ratios of polyurethane to poly(n‐butyl acrylate‐co‐styrene) (PBS; 50/50, 40/60, 30/70, 20/80, and 10/90) on the structure, morphology, and properties of the PUAs were investigated. The average particle size and water absorption values of the PUAs increased with increasing of PBS content. However, the surface tension decreased from 34.61 to 30.29 mN/m. PUA‐2, with a bimodal distribution, showed Newtonian liquid behaviors, and PUA‐3 showed a great thermal stability, fast drying characteristics, and excellent adhesion to packaging films. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43763.     

交联型PUA复合乳液的合成、表征与性能探究

采用半连续法以异佛尔酮二异氰酸酯（IPDI）、聚醚210、二羟甲基丙酸（DMPA）等为聚氨酯原料,甲基丙烯酸甲酯（MMA）和丙烯酸丁酯（BA）为丙烯酸酯类单体,甲基丙烯酸羟丙酯（HPMA）为偶联剂,过硫酸钾（K₂S₂O₈）为引发剂,三羟甲基丙烷（TMP）为交联剂,合成了具有明显核壳结构的丙烯酸酯改性水性聚氨酯（PUA）乳液。通过傅里叶红外光谱和透射电镜对聚合物结构和乳胶粒形态进行表征,并通过接触角（CA）、力学性能测试,差示量热扫描（DSC）和热重分析（TG）等手段研究了乳胶膜的性能。结果显示,当TMP用量为0.8%时,乳胶粒呈核壳结构,乳液稳定性能好,乳胶膜的拉伸强度达到12.5MPa,对水的静态接触角为96°,耐水性和耐热性也有显著提高。     

不同官能度水性聚氨酯丙烯酸酯的合成及性能

以丙烯酸羟乙酯与季戊四醇三丙烯酸酯作为封端剂,分别合成了二官能度水性聚氨酯丙烯酸酯(WPUA2)和六官能度的水性聚氨酯丙烯酸酯(WPUA6),并用红外光谱、粒径仪、热重分析对合成产物结构和性能进行表征。研究表明,相比于使用低官能度WPUA2紫外光固化所得聚氨酯丙烯酸酯(PUA)涂膜,加入单体或使用多官能度WPUA6,都可使PUA固化膜凝胶率提高20%以上,吸水率降低30%;质量损失10%,分解温度增大82℃。提高预聚物官能度可有效提高涂膜交联密度和耐热性能,并具有与加入活性单体相似的应用效果。     

光聚合型聚硅氧烷改性聚醚聚氨酯丙烯酸酯低聚物的合成、表征与性能

以羟烷基聚硅氧烷(Q4-3667)、聚丙二醇(PPG-2000)、异佛尔酮二异氰酸酯(IPDI)、二乙醇胺和丙烯酸β-羟乙酯(HEA)为原料合成了一种光聚合型有机硅改性聚醚聚氨酯丙烯酸酯低聚物(Si~5E~5PUA),并用傅里叶红外光谱(FTIR)、核磁共振氢谱(1HNMR)、核磁共振硅谱(29SiNMR)和凝胶渗透色谱(GPC)对其结构进行了表征。详细研究了Si~5E~5PUA与不同单体配比体系的黏度、光聚合性能、聚合过程的体积收缩及其固化膜的玻璃化转变温度。结果表明,Si~5E~5PUA与丙烯酸酯单体具有良好的相容性;其体系具有优异的光聚合性能,最终双键转化率达90%以上,单体官能度的增加可以提高固化膜的玻璃化转变温度,Si~5E~5PUA体系的体积收缩在3.3%~5.6%。     

丙烯酸树脂改性水性聚氨酯的结构与性能研究

采用丙烯酸树脂对水性聚氨酯进行改性，得到了共混改性（PU／PA）、共聚改性（PUA’）、接枝改性（PUA）3种丙烯酸改性水性聚氨酯聚合物。通过对改性聚氨酯乳液的激光粒度分析，乳胶膜的红外光谱、热分析、透明性、耐化学性及扫描电镜进行分析，结果表明：改性后的水性聚氨酯，各项性能均有不同程度的提高。在机械共混聚合物PU／PA体系中，聚氨酯分子链和丙烯酸树脂分子链间具有一定的相容性及共混性；在共聚反应聚合物PUA’、PUA体系中，聚氨酯分子链和丙烯酸树脂分子链形成核壳结构，且在PUA中，聚氨酯分子链和丙烯酸树脂分子链之间形成的化学键，可以有效的提高二者的相容性及共混程度。     

阴离子改性PUA紫外光固化胶粘剂的制备及性能

以异佛尔酮二异氰酸酯(IPDI)、二羟甲基丁酸(DMBA)和聚四氢呋喃醚二醇(PTMG)等为主要原料,制得聚氨酯(PU)预聚体;然后将其与丙烯酸羟乙酯(HEA)反应,制得HEA封端的聚氨酯丙烯酸酯(PUA)预聚体;最后在PUA预聚体中加入中和剂等助剂,制备出阴离子改性PUA紫外光(UV)固化胶粘剂。研究结果表明:当w(DMBA中-COOH)=1.2%(相对于PU预聚体质量而言)、中和度=n(中和剂)∶n(DMBA)=80%、以PTMG为多元醇且偶联剂采用预处理法加入时,相应的阴离子改性PUA型UV固化胶粘剂的耐水性、粘接强度和耐久性俱佳。