低亲水基含量丙烯酸酯-聚氨酯复合乳液及其膜性能的研究

采用自乳化的工艺,以异佛尔酮二异氰酸酯(IPDI)、聚已二酸丁二醇酯(PBA)、二羟甲基丙酸(DMPA)、丙烯酸酯为主要原料,制备了一系列稳定的高固含量聚氨酯-丙烯酸酯复合乳液(PUA)。研究了在DMPA用量最低为0.8%(占固含量的百分比),固含量为40%左右的条件下,PBA的分子量、DMPA的用量、PU/PA对PUA乳液性能及其涂膜性能的影响。     

蓖麻油基聚氨酯——聚丙烯酸酯复合乳液研究

以聚酯二元醇(PBA)、蓖麻油(C.O)、异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)为主要原料合成了蓖麻油基水性聚氨酯(WPU)乳液;以此乳液作为种子通过乳液聚合技术制备了性能优异的聚氨酯-聚丙烯酸酯(PUA)复合乳液。讨论了丙烯酸酯(PA)对PUA材料的耐热、耐水性能的影响,同时探讨了丙烯酸酯与聚氨酯比例、丙烯酸单体中软硬段比例不同对材料性能的影响。     

复合薄膜用水性聚氨酯-丙烯酸酯胶粘剂的合成

以聚醚二元醇、甲苯二异氰酸酯(TDI)、二羟甲基丙酸(DMPA)等为原料合成了聚氨酯预聚体,用丙烯酸羟丙酯(HPA)将其部分封端,制得一种水性聚氨酯丙烯酸酯分散体,再加入乙烯基单体进行自由基引发聚合,制备出水性聚氨酯-丙烯酸酯(PUA)复合乳液。用红外光谱仪(FTIR)、差示量热扫描仪(DSC)、热重分析(TG)、马尔文粒度分析等测试手段,对合成产物进行了结构和性能表征。研究了软硬段质量比、亲水基团含量、丙烯酸酯单体的加入对PUA乳液性能的影响。结果表明,m(软段)∶m(硬段)=2∶1,m(PU)∶m(PA)=4∶1,—COOH质量分数为2.8%,以该乳液配制的胶粘剂应用于包装用CPP/CPP薄膜、OPP/VMOPP薄膜的剥离强度分别达31.9N/m和28.1 N/m。     

聚酯二元醇合成聚氨酯丙烯酸酯复合乳液的研究

以异佛尔酮二异氰酸酯(IPDI)、自制聚酯二元醇、二羟甲基丙酸(DMPA)和甲基丙烯酸甲酯(MMA)、苯乙烯(St)、丙烯酸丁酯(BA)为主要原料,合成了聚酯型聚氨酯丙烯酸酯(PUA)复合乳液,研究了不同相对分子质量的聚酯二元醇、聚氨酯制备时不同NCO/OH比值、添加三羟甲基丙烷(TMP)含量、及合成PUA时不同PU/PA的比值对最终制备的聚氨酯丙烯酸酯复合乳液及涂膜性能的影响。结果表明:1500～2000相对分子质量的聚酯二元醇:在TMP添加量为2%、NCO/OH为1.6～1.8,PU/PA以4︰6合成出的PUA,有着较好的制备稳定性和贮存稳定性,其涂膜硬度、耐水性和耐醇性较好。     

蓖麻油和环氧树脂改性水性聚氨酯-丙烯酸酯的合成与表征

以甲苯二异氰酸酯(TD I)、聚醚型多元醇(N210)、2,2-二羟甲基丙酸(DMPA)、甲基丙烯酸甲酯(MMA)等为主要原料,蓖麻油(C.O.)和脂肪族环氧树脂(RE)为交联剂,以原位乳液聚合法制备出聚氨酯-丙烯酸酯(PUA)复合乳液。以无皂乳液聚合法合成了聚丙烯酸酯乳液(PA),再与聚氨酯(PU)乳液机械混合得到PU/PA共混乳液。探讨了蓖麻油C.O.、RE对复合乳液及涂膜性能的影响,烯丙氧基羟丙基磺酸钠(COPS-1)用量对共混乳液和涂膜性能的影响。结果表明,C.O.、RE分别占PU干质量的5.0%～7.0%和2.0%～3.0%,COPS-1占单体总质量的2.0%时,乳液和涂膜综合性能较好。PUA比PU/PA柔韧性好、断裂伸长率高及附着力好,硬度低,成本高。红外光谱分析发现,PUA与PU/PA中—NH—全部形成氢键。TEM观察到,PUA形成核-壳结构的粒子,粒径较小。通过AFM扫描发现,PUA存在硬段与软段的微相分离。     

丙烯酸酯改性水性聚氨酯乳液的制备及性能研究

采用物理共混和核-壳聚合法制备了丙烯酸酯改性水性聚氨酯(PU/PA,PUA)乳液,并对不同改性方法制得的乳液进行了研究。通过红外(FTIR)、透射电镜(TEM)、差示扫描量热(DSC)、热重分析(TGA)、耐水性和力学性能测试等研究了丙烯酸酯改性聚氨酯乳液及涂膜的结构与性能。结果表明具有核-壳结构的PUA乳液涂膜耐水性、耐热性和固含量较水性聚氨酯(PU)有明显的提高,力学性能稍有下降;PUA综合性能优于PU/PA。     

A／U-g-A型核壳聚氨酯-丙烯酸酯复合乳液的合成

通过加入双官能团单体甲基丙烯酸-β-羟乙酯(HEMA),采用溶液聚合法和原位乳液聚合法,把聚氨酯与丙烯酸(AA)、丙烯酸丁酯(BA)和苯乙烯(St)等丙烯酸酯单体接枝共聚,合成了PUA为壳、PA为核的聚氨酯-丙烯酸酯(PUA)复介乳液.研究了壳层PA/Pu、总PA/PU、核壳比、BA/St、壳层HEMA/PA和链转移剂含量对乳液制备过程、乳液及涂膜性能的影响.研究结果表明:PUA中的PA、BA、St、HEMA,链转移剂和DMPA与AA中的-COOH的含量(壳层PUA的质量分数)分别为55.6%、25%、17.8%、9%、1%和7%,核壳质量比为1:4时,复合乳液涂膜结构规整,各项性能较好.PUA胶粒的平均粒径在100 nm左右时,分布更均匀.     

水性聚氨酯-丙烯酸酯复合乳液的性能研究

用丙烯酸酯改性水性聚氨酯制备了具有核壳结构的水性聚氨酯-丙烯酸酯(WPUA)复合乳液,系统地研究了水性聚氨酯(PU)含量、nNCO/nOH(初始物质的量比)、亲水性扩链剂二羟甲基丙酸(DMPA)用量及软硬单体质量比对WPUA乳液及其膜的性能的影响.结果显示,WPUA乳液胶粒呈核壳型结构,聚丙烯酸酯(PA)与PU链段具有...     

丙烯酸酯对水性聚氨酯胶粘剂的改性研究

用自乳化的方法制备水性聚氨酯(PU)乳液,然后用丙烯酸酯进行改性,制备出水性聚氨酯和丙烯酸酯共聚乳液(PUA),并把聚丙烯酸酯(PA)乳液与PU乳液不同比例共混。考查了共聚型和共混型PUA乳液胶膜的吸水性、热行为、黏度、T型剥离强度。结果表明,在复合薄膜应用方面,共聚型PUA乳液的性能优于共混型PUA乳液。     

聚酯二元醇合成聚氯酯丙烯酸酯复合乳液的研究

以异佛尔酮二异氰酸酯（IPDI）、自制聚酯二元醇、二羟甲基丙酸（DMPA）和甲基丙烯酸甲酯（MMA）、苯乙烯（St）、丙烯酸丁酯（BA）为主要原料,合成了聚酯型聚氨酯丙烯酸酯（PUA）复合乳液,研究了不同相对分子质量的聚酯二元醇、聚氨酯制备时不同NCO／OH比值、添加三羟甲基丙烷（TMP）含量、及合成PUA时不同PU／PA的比值对最终制备的聚氨酯丙烯酸酯复合乳液及涂膜性能的影响。结果表明：1500～2000相对分子质量的聚酯二元醇：在TMP添加量为2％、NCO／OH为1．6～1．8,PU／PA以4：6合成出的PUA,有着较好的制备稳定性和贮存稳定性,其涂膜硬度、耐水性和耐醇性较好。     

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。     

Morphology and particle size of nanograde polyurethane/polyacrylate hybrid emulsions

Poly(urethane acrylate) (PUA) composite particles were prepared by seeded surfactant‐free emulsion polymerization. The aqueous polyurethane (PU) dispersions were used as seed particles. The diameters of the seed particles of the aqueous PU dispersions and PUA composite latexes were measured by dynamic light scattering. The microstructures of the PUA composite emulsion particles were observed by transmission electron microscopy. The influences of the amount of the hydrophilic chain extender, the types of initiators, and the PU/polyacrylate (PA) weight ratios on the diameters of the aqueous PU and composite emulsions were also studied. The results showed that the PUA composite emulsions formed a core–shell structure with PU as the shell and with PA as the core. The diameter of the PU seed particles and the particle size of the PUA composite emulsions greatly depended on the amounts of the hydrophilic chain extender used in the preparation of the PU seed; when the hydrophilic chain extender concentration was 7.4%, the average diameter of the PUA composite emulsion particles showed the minimum value. The types of initiators and PU/PA weight ratios did not have a significant influence on the diameter of the PUA composite latex particles. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Aqueous PUA emulsion prepared by dispersing polyurethane prepolymer in polyacrylate emulsion

Waterborne polyurethane/polyacrylate (PUA) emulsions were prepared by dispersing polyurethane (PU) prepolymer in polyacrylate (PA) emulsion; therefore, the PU particles formed in the presence of PA nanoparticles. The particle size and its distribution of the composite PUA emulsion were determined by dynamic light scattering. The result shows that the average particle size increases initially and then decreases with increasing PA content, which is confirmed by transmission electron microscope characterization. The surface properties of PUA films were analyzed by water contact angle and atomic force microscope topography. It indicates that the water contact angle and the average roughness of the composite PUA films are larger than those of the PU film. Meanwhile, mechanical properties test, scanning electron microscopy, and thermogravimetric analyses disclose that the PUA films are characterized by enhanced tensile strength, rough fractured surface, and good thermal stability. The preparation method proposed in this article is an effective and convenient way to manufacture composite PUA emulsion. The composite PUA emulsion can be potentially used in coatings. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43203.     

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.     

低模量聚酯型PU弹性体力学性能的研究

以聚楷酯二醇、甲苯二异氰酸酯（TDI）和扩链剂为原料,制备浇注型PU弹性体,研究了预聚法和一步法、聚酯与聚醚、80/20-TDI和2,4-TDI、聚酯二醇的种类及其相对分子质量、弹性体交联点相对分子质量和硬段质量分数对弹性体力学性能的影响。结果表明,采用预聚法,以聚酯和80/20-TDI为原料合成的PU弹性体的综合性能较好。3种聚酯型PU弹性体中,聚丁二醇己二酸酯二醇的PU弹性体的综合力学性能最好。交联点相对分子质量为4500时,PU弹性体的强度为最大值。     

高固含量丙烯酸酯改性聚氨酯胶粘剂的研制

以聚醚多元醇、聚酯多元醇和蓖麻油为混合多元醇,以改性MDI(4,4′-二苯基甲烷二异氰酸酯)及PAPI(多亚甲基多苯基多异氰酸酯)为混合异氰酸酯,合成了聚氨酯(PU)胶粘剂预聚体;然后以PA(羟基丙烯酸酯树脂)作为PU预聚体的改性剂,制得高固含量的PUA(聚丙烯酸酯改性聚氨酯)胶粘剂。结果表明:当m(改性MDI)∶m(PAPI)=1∶1、n(-NCO)∶n(-OH)=2.2∶1、w(PA)=8%(相对于PU质量而言)和w(丙烯酸羟乙酯)=3%(相对于PU质量而言)时,PUA胶粘剂的综合性能较好。     

Synthesis and characterization of sequential interpenetrating polymer networks of polyurethane acrylate and polybenzoxazine

High‐performance ultraviolet (UV) curable polyurethane acrylate (PUA) coating alloyed with thermally curable polybenzoxazine (PBA) is developed. The hybrid polymer networks of PUA and PBA‐a were prepared by sequential cure methods, i.e., UV cure of the PUA followed by thermal cure of the PBA fraction. The effects of sequential cure were investigated in terms of mechanical, thermal, and physical properties of the resulting polymer alloys. The fully cured PUA/PBA‐a alloy films showed only single glass transition temperature (T_g) suggesting high compatibility between the two polymer networks, possibly of an interpenetrating polymer network type. The storage modulus in a glassy state and T_g of PUA/PBA‐a alloys were found to substantially increase with increasing PBA‐a content. Furthermore, degradation temperature at 10% weight loss of the PUA/PBA‐a alloy films was relatively high whereas the char yield at 800°C was found to increase with a PBA‐a component. Hardness was enhanced, whereas water absorption and water vapor permeation rate of the alloy were suppressed by the incorporation of the PBA‐a into the polymer alloys. As a consequence, the properties of UV curable PUA networks can be positively tailored and enhanced by forming hybrid network with PBA‐a. POLYM. ENG. SCI., 54:1151–1161, 2014. © 2013 Society of Plastics Engineers     

单体含量对核壳结构聚氨酯-聚丙烯酸酯乳液性能影响

以水性聚氨酯（PU）为种子乳液,以丙烯酸酯（PA）为聚合性单体,采用种子乳液聚合法合成核壳结构聚氨酯-聚丙烯酸酯乳液（PUA）。研究了单体含量对乳液及胶膜性能的影响。实验结果表明：随着乙烯基单体含量的增加,乳液颜色加深,稳定性下降,胶膜的断裂伸长率降低,硬度和耐水性增加。当乙烯基单体和PU百分比（M／P）为25％时,乳液的稳定性大于12个月,胶膜的断裂伸长率为498％,硬度为0．64,吸水性为22．8％。红外光谱分析表明合成了PUA。     

粒料法合成不同相对分子质量和软段的聚氨酯分散体研究

以异佛尔酮二异氰酸酯(IPDI)为硬段、二羟甲基丙酸(DMPA)为亲水单体,采用粒料法合成了不同Mη(黏均相对分子质量)和不同软段的PU(聚氨酯)离聚物粒料,并制备了固含量约为40%的PUD(PU分散体)。结果表明:PU的Mη随R值[R=n(-NCO)/n(-OH)]增加呈先升后降态势;PU的Mη越高,PUD的平均粒径越小,粒径分布越窄,黏度越大;PUD粒子呈大小不一的球形结构,并且PU的Mη越高,PUD胶膜的拉伸强度越大;聚酯型PUD胶膜的拉伸强度大于聚醚型PUD,并且前者的软段和硬段之间相容性较好,而后者的软段和硬段之间因出现相分离现象而相容性较差;PUD胶膜的吸水率均不超过5.93%,说明其耐水性能优异。