Emulsifyable air drying urethane alkyds

A novel monomer, acrylamido (A) tertiary (T) butane (B) sulfonic (S) acid (ATBS) a commercially available ionic moiety was used as a replacement of dimethylol propionic acid (DMPA) in synthesis of polyurethane dispersion. IR technique was used to confirm the chemical structure and formation of polyurethane dispersions. Polyurethane dispersions were investigated for various coating properties, such as drying times, pencil hardness, adhesion, chemical and solvent resistance. Polyurethane dispersion based on ATBS showed better thermal, chemical and coating properties than those prepared by DMPA anionomer.     

遇水膨胀型聚氨酯的制备与性能研究

以异佛尔酮二异氰酸酯(IPDI)、聚酯二元醇、二羟甲基丙酸(DMPA)、三羟甲基丙(烷TMP)等为原料,合成了遇水膨胀型聚氨酯。用FTIR对该聚氨酯进行了结构表征,并对其遇水体积膨胀率和力学性能进行了研究。结果表明:NCO/OH摩尔比(异氰酸酯指数)为1.3～1.4时试样遇水体积膨胀率较高;随着DMPA用量的增加,试样的遇水体积膨胀率增大,拉伸强度保持率降低;加入TMP后,聚氨酯形成化学交联,拉伸强度保持率得到改善但,是试样的体积膨胀率随着TMP用量的增加而降低。     

基于羧酸-磺酸盐的聚氨酯乳液的制备及性能研究

以二羟甲基丙酸(DMPA)和1,2-二羟基-3-丙磺酸钠(DHPA)为亲水扩连剂制备含有磺酸基团的水性聚氨酯微乳液。利用傅立叶变换红外光谱(FT-IR)对DHPA和水性聚氨酯的结构进行表征,证实了目标产物DHPA的生成,并作为亲水扩链剂引入PU链上。研究表明,随着DHPA含量增大,乳胶粒平均粒径减小,粒径分布宽度变窄。聚氨酯乳液呈假塑性流体特征。所制得的聚氨酯表面活性剂对丙烯酸单体具有良好的乳化性能,可用于乳液聚合中。     

不同相对分子质量PEG制备DDI型水性聚氨酯及其织物整理应用

以二聚脂肪酸二异氰酸酯( DDI)、不同相对分子质量的聚乙二醇(PEG)、二羟甲基丙酸( DMPA)为主要原料,采用丁酮法制备预聚体,然后在乳化剂存在下制成水性聚氨酯(WPU).研究了PEG相对分子质量对WPU的影响以及其应用到织物整理上的效果.结果表明,当PEG相对分子质量为1000和1500时,DDI型水性聚氨酯整...     

水性聚氨酯的合成及其改性的研究

研究了 n NCO/n OH、扩链剂 ( BD)及二羟甲基丙酸 ( DMPA)的含量对水性聚氨酯合成及涂膜性能的影响 ,确定了较佳的配方。并利用甲基丙烯酸酯类单体合成聚氨酯 -丙烯酸酯共聚复合乳液来改善水性聚氨酯的性能     

Synthesis and properties of polyurethane ionomers based on carboxylated polycaprolactone

Polycaprolactone containing carboxyl groups (CPCL, M̄_n = 1200) was prepared from caprolactone (CL) and dimethylol propionic acid (DMPA). Based on the CPCL, 4,4′‐diphenylmethane diisocyanate (MDI) and 1,4‐butanediol (BD), a novel series of polyurethane ionomers could be synthesized with ions in the soft segment. The tensile modulus and ultimate elongation of the ionomer cast films increased, and the glass transition temperature of the CPCL‐rich phase moved to a higher temperature after ionization. Moreover, this kind of ionomers showed small amounts of hard segment crystallinity by DSC. WAXD shows an ionic peak at 2θ = 8.6° for the ionomer with carboxylate in the hard segment, which is not present in the ionomer with carboxylate in the soft segment. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 2049–2056, 2000     

脂肪族水性聚氨酯的合成

以聚四氢呋喃醚和异佛尔酮二异氰酸酯为原料,在预聚反应中引入二羟甲基丙酸亲水扩链剂,以三乙胺为中和剂合成了阴离子型脂肪族水性聚氨酯,研究NCO/OH摩尔比、DMPA引入量、热处理温度和存放时间对乳液及膜性能的影响。     

无皂乳液聚合制备PUA乳液的稳定性研究

采用无皂乳液聚合法制备丙烯酸酯一聚氨酯复合乳液（PUA）。HEMA作为交联剂引入到聚氨酯主链上,利用核壳交联制得复合乳液。研究了不同的合成工艺、丙烯酸酯单体、DMPA及HEMA含量,引发剂种类等对乳液稳定性的影响。研究发现,将丙烯酸酯单体溶胀于水性聚氨酯乳液中再进行聚合可大大提高乳液的稳定性;采用1．0％～12％的AIBN为引发剂、DMPA质量分数为4．5％、HEMA质量分数为4．0％～4．5％、丙烯酸酯单体质量分数为30％时,可制得外观及稳定性良好的PUA复合乳液。     

Temperature sensitive water vapour permeability and shape memory effect of polyurethane with crystalline reversible phase and hydrophilic segments

Polyurethanes based on poly(caprolactone) (PCL) diol, hexamethylene diisocyanate, 4,4′‐diphenylmethane diisocyanate and hexamethylene diamine were modified by hydrophilic segments, diol‐terminated poly(ethylene oxide) or dimethylol propionic acid (DMPA). Differential scanning calorimetry, dynamic mechanical tests, tensile tests, and measurement of water vapour permeability were carried out to characterize these polyurethanes. Temperature sensitive water vapour permeability, that is, the abrupt increase of water vapour permeability at the melting temperature of the PCL phase, was enhanced by modification with hydrophilic segments. Fatigue in shape memory effects was minimized by introducing some amount of DMPA units into the polyurethane chain. © 2000 Society of Chemical Industry     

金红石型纳米钛白粉在车辆涂料中的应用

介绍了金红石型纳米二氧化钛在丙烯酸金属烘干漆中的应用,通过将有机光稳定剂及不同比例的金红石型纳米二氧化钛加到丙烯酸金属烘干漆中,并检测其相应的性能,观察金红石型纳米二氧化钛对涂膜的耐候性、硬度、附着力、颜料沉淀以及金属闪光漆的随角异色效果的影响。     

丙烯酸改性芳香族聚醚聚氨酯分散体热稳定性的研究

本利用丙烯酸酯与带有活性官能团的聚氨酯预聚体反应，生成了水分散的丙烯酸酯改性聚氨酯分散体。FTIR、SEM及TG／DTG分析测试结果表明：由于分子中各链段之间及分子之间的相互作用，聚合物的热稳定性比单一活性氢化合物(N330、DMPA)与TDI反应时生成物的热稳定性明显提高，     

偶联剂改性水性聚氨脂木器涂料

以甲苯二异氰酸酯（TDI）、聚醚二醇（N210）、二羟甲基丙酸（DMPA）为基本原料,在无溶剂的条件下,利用硅烷偶联剂通过合成和扩链的方法改性水性聚氨酯,制得了一系列不同含量硅烷偶联剂改性的水性聚氨酯乳液.性能测定表明：以此乳液再配以其他助剂制得的水性聚氨酯建筑用木器涂料,具有优异的粘附力、耐水性和力学性能.     

封闭型环氧改性水性聚氨酯的合成研究

以4,4’-二苯基甲烷二异氰酸酯（MDI）、聚醚二元醇N210、交联剂三羟甲基丙烷（TMP）、环氧树脂E44、二羟甲基丙酸（DMPA）、封闭剂己内酰胺（ε-CL）为主要原料,采用自乳化法合成出封闭型环氧改性的水性聚氨酯乳液。对其进行了FT—IR红外表征,研究了DMPA用量、中和度对乳液的外观和稳定性的影响。结果表明,通过环氧改性并交联的水性聚氨酯乳液稳定性及成膜的耐水性和力学性能大大提高。     

Synthesis and properties of block and graft waterborne polyurethane modified with α,ω‐bis(3‐(1‐methoxy‐2‐hydroxypropoxy)propyl)polydimethylsiloxane and α‐N,N‐dihydroxyethylaminopropyl‐ω‐butylpolydimethylsiloxane

In this study, α,ω‐bis(3‐(1‐methoxy‐2‐hydroxypropoxy)propyl)polydimethylsiloxane and α‐N,N‐dihydroxyethylaminopropyl‐ω‐butylpolydimethylsiloxane were used to prepare block and graft waterborne polyureathane–polysiloxane copolymer dispersions. α,ω‐bis(3‐(1‐methoxy‐2‐hydroxypropoxy)propyl)polydimethylsiloxane was synthesized by hydrosilylation, methoxylation and equilibrium reactions; α‐N,N‐dihydroxyethylaminopropyl‐ω‐butylpolydimethylsiloxane was synthesized via hydroxyl protection, alkylation, anionic ring‐opening polymerization, hydrosilylation, and deprotection. Block and graft waterborne polyurethane–polysiloxane copolymer dispersions were prepared by the reaction of poly(propylene glycol) (PPG), toluene diisocyanate (TDI), 2,2‐dimethylol propionic acid (DMPA), 1,4‐butanediol (BDO), α,ω‐bis(3‐(1‐methoxy‐2‐hydroxypropoxy)propyl)polydimethylsiloxane, and α‐N,N‐dihydroxy‐ethylaminopropyl‐ω‐butylpolydimethylsiloxane. The water absorption of block and graft waterborne polyurethane–polysiloxane copolymer films decreased from 163.9 to 40.2% and 17.3%, respectively, when percent of polysiloxane (w/w) increased from 0 to 5%, and the tensile strength of the block waterborne polyurethane–polysiloxane copolymer films decreased while the tensile strength of graft waterborne polyurethane–polysiloxane copolymer films increased with increase of percent of polysiloxane. For graft waterborne polyurethane–polysiloxane films, the tensile strength would decrease when percent of polysiloxane was more than 3%. POLYM. ENG. SCI., 54:805–811, 2014. © 2013 Society of Plastics Engineers     

多羟基化合物改性聚氨酯胶黏剂的制备与应用

采用预聚体合成法,以二羟甲基丙酸(DMPA)、葡萄糖(PG)为亲水扩链剂和交联剂制备一种水性聚氨酯预聚体,再将羧基丁苯胶乳(CSBL)水乳液与去离子水混合均匀进行乳化,制得固含量高达50%的水性聚氨酯(WPU)胶黏剂。利用傅里叶变换红外光谱仪(FTIR)对胶膜结构进行表征,证实葡萄糖已引入聚氨酯主链。热失重分析表明,PG改性后的聚氨酯胶膜热稳定性增强。研究了PG用量对胶黏剂的T-剥离强度和固化时间的影响。随着PG用量的增加,T-剥离强度逐渐增强,当PG质量分数从0%增加到4.68%时,T-剥离强度由57.3 N/(2.5 cm)上升至116.1 N/(2.5 cm),相同处理温度下聚氨酯胶液的固化时间缩短。     

复合薄膜用水性聚氨酯胶粘剂的研究

以聚已二酸1,4-丁二醇酯(PBA)、甲苯二异氰酸酯(TDI)、二羟甲基丙酸(DMPA)等为主要原料合成了水性聚氨酯复膜胶,讨论了亲水性扩链剂DMPA用量对水性聚氨酯复膜胶的稳定性、耐水性、粘接强度等的影响;使用差示扫描量热仪(DSC)和原子力显微镜(AFM)观察了分子结构中的软、硬段微相结构分布。结果表明,当DMPA质量分数占预聚体总质量的2.67%～5.34%时能够制得稳定乳液;水性复膜胶乳液的粘度以及胶膜的吸水率随着亲水性扩链剂DMPA用量的增加而增加,而乳液的粒径随着亲水性扩链剂DMPA用量的增加而减小;硬段含量的增加会降低软段结晶,增加水性聚氨酯复膜胶高分子链的极性和粘接强度,当硬段质量分数为22.79%时,胶膜具有较好的T型剥离强度;提高复合压力能够显著提高T型剥离强度;该复膜胶对聚对苯二甲酸乙二醇酯(PET)膜有着比聚丙烯(OPP)膜更好的粘接效果。     

水性聚氨酯聚丙烯酸酯细乳液的制备及在调湿涂料中的应用

首先以聚氧化丙烯二醇(PPG)、异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)为主要单体,甲基丙烯酸羟乙酯(HEMA)为接枝试剂,合成了接枝聚氨酯预聚体(PU-HEMA),进一步与丙烯酸酯进行共聚反应,制备了水性聚氨酯/聚丙烯酸酯(PU-PA)细乳液。考察了单体用量及PA/PU质量比对乳液性能的影响,发现DMPA、HEMA最佳用量分别为3%和6%。采用FTIR、TG、SEM对PU-PA进行了表征。然后以PU-PA为成膜物,硅藻土、膨润土等为颜填料,所制备的PU-PA调湿涂料(PU-PA-C)性能达到国家内墙涂料和建筑涂料标准,其耐洗刷性大于900次,最大吸水率达到206%。该涂料吸/放湿(水)性能强,可用于室内调湿涂料的涂刷。     

水性紫外光固化合成革用聚氨酯丙烯酸酯树脂的合成及性能研究

采用聚丁二醇(PBG)、2,4-甲苯二异氰酸酯、二羟甲基丙酸(DMPA)和丙烯酸羟乙酯合成了紫外光固化水性聚氨酯丙烯酸酯树脂,利用FT-IR对树脂进行了表征,探讨了树脂亲水基团含量和中和度对乳液性能的影响,分析表征了固化膜的基本性能。结果表明:乳液的粒径随着—COOH含量的提高而下降,乳液的分散性、稳定性及黏度随—COOH含量增加而增大;乳液黏度在中和度为90%时达到最高6.222 mPa.s,粒径达到最小59.8 nm。固化膜的吸水率随—COOH含量的增加而上升,固化膜对PVC板具有很好的附着力,其铅笔硬度随着DMPA/PBG比例的增加而上升。     

聚氨酯水分散体结构与性能的关系研究

以聚四氢呋喃、甲苯二异氰酸酯、二羟甲基丙酸为主要原料合成了WPUD.并采用红外光谱对WPUD分子结构作了表征,同时对分散体的性能进行了测试和分析.结果表明,DMPA用量是影响水分散体性能的主要因素.DMPA影响分散体的形态、稳定性、吸水率、平均粒径.随着DMPA含量的增加,水分散体稳定性提高、吸水率增加.当DMPA的质量分数由0.014％增加到13.57％时,透光率从0.003％提高到88.88％.并研究了聚氨酯硬段和软段的含量对涂膜基本性能的影响,随着硬段含量增加,铅笔硬度有所提高,软段含量增加,柔韧性提高.另外,残留溶剂是影响水分散体稳定性的另一个重要因素,当分散体中残留溶剂含量增加时,稳定性降低.     

Preparation and Properties of Water-borne Polyurethanes

Following a prepolymer mixing process, polyurethane (PU) anionomer dispersions were prepared from polyethylene adipate glycol (PEA), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) and dimethylol propionic acid (DMPA) as a potential ionic centre. Effects of prepolymer molecular weight, PEA molecular weight, hard segment content, DMPA content, degree of neutralization and mixed diisocyanates have been studied in terms of particle size and viscosity of emulsion, and surface, mechanical and dynamic mechanical properties of the emulsion-cast films. Particle size decreased and emulsion viscosity increased with increase in prepolymer molecular weight and PEA molecular weight, DMPA content, the degree of neutralization and IPDI content in mixed isocyanate systems. The decrease in particle size was due to increased chain flexibility and/or hydrophilicity of the PU. The mechanical and dynamic mechanical properties of the PU ionomer dispersions were interpreted in terms of soft segment–hard segment phase separations, hard segment content, chain flexibility and coulombic forces. © of SCI.