丙烯酸树脂改性的水性聚氨酯性能与结构

采用丙烯酸树脂（ＰＡ或ＰＡ’）对水性聚氨酯（ＰＵ）改性,研究了丙烯酸树脂改性的水性聚氨酯的性能与结构。结果表明：设计ＰＵ分子链硬段与ＰＡ分子链形成化学键,材料中ＰＵＡ及ＰＵ／ＰＡ中ＰＵ分子链硬段与ＰＡ分子链具有较高的相容性和共混程度;机械共混物ＰＵ／ＰＡ中ＰＵ分子链、ＰＡ分子链之间的共混主要集中于ＰＵ乳胶粒、ＰＡ乳胶粒表层;ＰＵＡ及ＰＵＡ’材料ＰＵ分子链与ＰＡ分子链之间处于一同相分离状态。ＰＵＡ’     

丙烯酸树脂改性的水性聚氨酯结构设计及表征

设计聚氨酯（ＰＵ） 、丙烯酸树脂（ ＰＡ）２ 种树脂的机械共混、化学共混即核－ 壳型聚合过程，及设计该２ 种树脂分子链之间形成的化学键，研究了用丙烯酸树脂改性的水性聚氨酯。分析乳胶粒大小及分布、胶膜材料红外光谱及ＤＳＣ 特征曲线表明：设计ＰＵ 分子链硬段与ＰＡ 分子链形成化学键，得到的材料中ＰＵＡ 及ＰＵ／ＰＡ 中ＰＵ 分子链硬段与ＰＡ 分子链具有较高的相容性和共混程度；核－ 壳型聚合得到的ＰＵＡ 及ＰＵＡ′材料ＰＵ 分子链与ＰＡ 分子链之间处于一定的微相分离状态；机械共混物ＰＵ／ＰＡ 中ＰＵ 分子链、ＰＡ 分子链之间的共混主要集中于ＰＵ 乳胶粒、ＰＡ 乳胶粒表层。     

丙烯酸树脂改性的水性聚氨酯耐水性研究

本文研究了用丙烯酸树脂改性的水性聚氨酯耐水性特征。研究结果表明：通过聚氨酯与丙烯酸树脂机械共混能一定程度提高其耐水性;而实施化学共混即核－壳型聚合过程,形成的核－壳型聚合物具有二者树脂分子链相互贯穿与缠结的互穿网络结构,可以实现二者树脂的性能优势互补和耐水性能显著提高。     

PU/BA-HEMA互穿网络型聚合物的合成及性能

以异佛尔酮二异氰酸酯（IPDI）、二羟甲基丙酸（DMPA）为硬段,聚醚多元醇（N220）为软段,以丙烯酸丁酯（BA）和甲基丙烯酸羟乙酯（HEMA）改性,制备了水性聚氨酯（PU）分散液,测定了水分散液及其膜的物理性能和力学性能。结果表明,与未改性的PU水分散液相比,改性聚氨酯水分散液的粒径均有所增大,表面张力减小,力学性能和硬度提高。HEMA 的引入,形成了具有化学交联的核-壳互穿网络结构的聚合物,说明改性材料中分子链硬段与PA分子链具有较高的相容性。     

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。     

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。     

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。     

热塑性聚氨酯共混物的增容方法

综述了作为聚氨酯弹性体的一种,热塑性聚氨酯（TPU）与其他聚合物共混改性时,可提高增容性的6种方法（如调整分子链结构、改变共混聚合物的极性、化学改生引入反应性官能团、改变分子极性、加入相容剂、形成互穿网络等）,并提到了对相容性影响很大的共混方法和工艺条件.     

丙烯酸酯-聚氨酯改性乳液的性能研究

用丙烯酸酯对水性聚氨酯 (PU)进行共混和共聚改性 ,并对改性效果进行了研究。结果表明 :同改性前的丙烯酸乳液 (PA)乳液及PU乳液相比 ,改性使乳液的粒径、粒子形态发生改变 ,使耐热性、耐溶剂性及粘接强度提高     

PU/EP共混物中的化学反应及粘接性能的研究

合成聚氨酯（PU）预聚体同环氧树脂（EP）共混,加入扩链剂、交联剂,制得PU／EP复合材料,用红外光谱分析研究了共混体系中的化学反应,考察了两聚合物组成对聚合物网络间互穿程度的影响,研究了共混物的粘接性能。     

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.     

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。     

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.     

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。     

接枝型PUA乳液合成及聚合动力学研究

甲基丙烯酸羟丙酯与水性聚氨酯预聚体反应,得到双烯封端的水性聚氨酯乳液。在乳化剂、引发剂存在下,将丙烯酸酯单体与水性聚氨酯乳液充分混合,并引发聚合,制备了接枝型PUA乳液。TEM观察了PUA乳液的形貌,PUA乳液的粒径在60～120 nm之间;FTIR和NMR表征了合成的PUA结构,显示丙烯酸酯的加入改变了PU本身的氢键相互作用;转化率测试表明,甲基丙烯酸羟丙酯与PU预聚体的反应具有二级动力学特征,而乳化剂的用量影响丙烯酸酯单体与双烯封端聚氨酯乳液的反应速率,反应速率与乳化剂用量符合Rp∝[SDS]0.28。     

丙烯酸酯改性水性聚氨酯核壳复合乳液工艺探究

为了探究聚合工艺对丙烯酸酯(PA)改性水性聚氨酯(PU)性能的影响,选用不同的聚合工艺,合成了具有核壳结构的PUA复合乳液.通过高分辨透射电镜(TEM)、傅里叶红外光谱(FT-IR)、拉伸力学测试和热重(TG)等测试手段比较了不同工艺和引发剂类型对共聚物乳液形态和胶膜性能的影响.研究结果显示,使用偶氮二异丁腈( AIBN)作为引发剂,采用PA单体前乳化法可以得到具有明显核壳结构的复合乳液,乳胶膜综合性能最好,PU和PA具有更好的相容性.     

低亲水基丙烯酸酯-聚氨酯复合乳液涂膜的热分析研究

以异佛尔酮二异氰酸酯(IPD I)、聚已二酸-1,4丁-二醇酯(PBA)、二羟甲基丙酸(DMPA)、丙烯酸酯(PA)为主要原料,采用自乳化工艺制备了固体质量分数均为40%,亲水基团(DMPA的羧基)占固体质量百分数为1%的一系列稳定的聚氨酯-丙烯酸酯复合乳液(PUA);用热重分析(TG)、示差扫描量热分析(DSC)、动态机械热分析(DMA)方法研究PBA的相对分子质量、聚氨酯与丙烯酸酯的质量分数比(PU/PA)对PUA膜热性能的影响。热分析研究表明,增加PBA相对分子质量和加入适量的丙烯酸酯能提高PUA分子的有序程度,有利于PUA成膜物耐热性能的改善;随着PBA相对分子质量的增加,PU软段的非晶部分和PA的硬段相容性增强,微观相分离减小,乳液的混合能达到分子水平。     

水性聚氨酯／聚（丙烯酸丁酯-丙烯腈）互穿聚合物网络的研究

以甲苯二异氰酸酯（TDI-80）、聚醚二元醇（N220）、丙烯酸丁酯（BA）和丙烯腈（AN）为主要原料,采用无皂种子乳液聚合法制备了具有核壳结构的水性聚氨酯／聚（丙烯酸丁酯-丙烯腈）乳液互穿聚合物网络（LIPN）。通过红外光谱仪、热重分析仪、透射电镜、粒度仪等分析手段研究了产物的结构与性能。结果表明,与未改性的水性聚氨酯分散液相比,改性后的聚氨酯分散液的粒径均有所增大,乳液的黏度变化不大。胶膜的硬度和耐水性以及热稳定性显著提高,拉伸强度先增大后减小,断裂伸长率下降。HDDA的引入,形成了具有化学交联的核一壳互穿网络结构的聚合物,表现出明显的互穿协同效应,使WPU与乙烯基聚合物分子链具有较高的相客性。