Preparation of an ionic/nonionic polyurethane-silicone dispersion (PUSD) with a high solid content and low viscosity using complex soft segments

A series of ionic/nonionic polyurethane-silicone dispersions (PUSDs) with a high solid content and low viscosity were prepared using isophorone diisocyanate as the hard segment, polytetrahydrofuran polyether diol (PTMG) and polysiloxane diol (PESI) as the complex soft segments and an ionic/nonionic low molecular weight polyether diol (DPSA) as the hydrophilic, chain-extending agent. The morphologies and rheological properties of the ionic/nonionic PUSD were examined using particle-size, TEM, and viscosity analyses. The hydrophobic and mechanical properties of the dispersions were also tested. It was found that under the conditions of a constant NCO/OH ratio (2/1) and weight percentage of DPDA (6%), the PUSD dispersions with higher PESI contents possessed higher average particle diameters and wider particle-size distributions. Particles in the PUSD dispersions are generally spherical and have a typical core–shell structure due to the use of complex soft segments. However, the solid content of the ionic/nonionic PUSD increased first and then decreased as the weight ratio of PESI to PTMG increased. When the ratio ranged from 4/10 to 6/10, the max solid content of the ionic/nonionic PUSD reached up to 58%, but the viscosity of the PUSD was less than 400 mPa.s^?1. Meanwhile, the water contact angle of the films increased due to the formation of a crosslinking structure on the side of the PUSD macromolecule, and when the weight ratio of PESI to PTMG varied from 3/10 to 7/10, the water contact angle of the films increased from 48.3° to 72.3°. In addition, both the freeze-thaw and thermal stabilities of the PUSD dispersions were enhanced as the weight ratio of PESI to PTMG increased. The PUSD coating had good mechanical properties as well.     

亲水基团对高固含量磺酸盐型水性聚氨酯性能的影响

以异氟尔酮二异氰酸酯、六亚甲基二异氰酸酯、聚己二酸1,4-丁二醇酯为主要原料,以1,4-丁二醇为小分子扩链剂,以乙二胺基乙磺酸钠(AAS)为亲水性扩链剂,合成了高固含量的磺酸盐型水性聚氨酯乳液(SWPU)。采用FTIR、TEM、XRD考察了AAS加料方式及扩链时间对水性聚氨酯性能的影响。结果表明,当一次性加入AAS、且扩链时间为25 min时,可得到固体质量分数高达50%的磺酸盐型水性聚氨酯乳液,乳液呈乳白色,乳胶粒都呈规则的球形结构,乳液的黏度为32 Pa.s,平均粒径为166.9 nm,薄膜的摆杆硬度为0.51,XRD中曲线在2θ=21.3°、22.34°、24.24°处均出现了尖锐的衍射峰,分析表明所得产物的乳胶膜具有明显的结晶特性。     

环保型高固含量低粘度聚氨酯复膜胶的研究

选用低毒溶剂做稀释剂,合成了一种在较宽固含量范围,低粘度、贮存稳定的纸塑复合用双组分聚氨酯胶粘剂。探讨了初粘剂用量、NCO/OH摩尔比、固含量等因素对胶粘剂性能的影响,并用红外光谱仪对双组分聚氨酯胶粘剂的固化过程进行了表征。结果表明,控制NCO/OH摩尔比值在0.97-0.99之间,主剂与固化剂的质量比为10:1—1.5时,复膜效果最佳,剥离强度最高,且在常温下,经24h即可完全固化;羟基原料/初粘剂质量比为1/0.45时,初粘性最好,剥离强度最大;固含量为30%-50%时,涂胶效果、剥离强度均较好,使用时可根据情况选择。最终产品溶剂低毒,固含量高,粘度低,涂膜光亮、无白霜,粘接性能好,适合于纸塑复合。     

高固含量低黏度耐蒸煮复膜胶的合成研究

研究了一种可用于高温蒸煮双组分溶剂型复膜胶的合成方法.对催化剂的选择、真空度、反应温度的控制等进行了探讨.对合成复膜胶所用的高分子质量聚酯二醇的制备工艺进行了详细说明;同时探讨了添加剂对复膜胶粘接性能的影响.实验结果表明,该胶粘剂完全适用于135℃、30min蒸煮的要求,且固含量高、黏度低,是一种性能优良的复膜胶.     

低粘度高固含量醋酸乙烯-丙烯酸酯共聚乳液胶粘剂的研制

介绍了一种低粘度、高固体含量的醋酸乙烯-丙烯酸丁酯-丙烯酸异辛酯共聚乳液胶粘剂的合成工艺及性能。该乳液粘度低于2500mPa.s,固体含量≥52%,较低的玻璃化温度和良好的耐水性能,应用于卷烟和防水涂料的生产。     

复合可聚合乳化剂制备高固含量低黏度聚丙烯酸酯乳液

以DNS-86和F-6为复合可聚合乳化剂APS为引发剂,MMA、BA为单体采用半连续法制备20%固含量种子乳液,以种子乳液为介质,选用4种不同类型乳化剂:非离子可聚合乳化剂F-6,阴离子可聚合乳化剂DNS-86、常规非离子乳化剂OP-10、常规阴离子乳化剂SDS进行不同组合,同时滴加预乳化液、引发剂、缓冲剂直接二次成核制备62%固含量二元粒径分布乳液。重点研究了乳化剂复合方式、用量及配比、反应温度等对聚合稳定性、乳液流变性等的影响。,     

高固含量阳离子水性聚氨酯的性能研究

以聚酯二元醇为软段、异佛尔酮二异氰酸酯(IPDI)和N-甲基二乙醇胺(N-MDEA)为主要原料,采用丙酮法合成了高固含量(约50%)的CWPU(阳离子水性聚氨酯),并着重探讨了N-MDEA含量、软段种类对该CWPU的基本性能、结晶性能、力学性能和粘接性能等影响。结果表明:当w(N-MDEA)=5.5%～7.0%(相对于预聚体质量而言)时,可制得稳定的高固含量CWPU;软段的结晶性越好,高固含量CWPU的力学性能和粘接性能越高;当软段为聚己二酸己二醇酯(PHA)时,相应高固含量CWPU的邵A硬度(84)、拉伸强度(55 MPa)和剥离强度(初始剥离强度、24 h剥离强度为68.2、90.4 N/25 mm)相对最大,可作为胶粘剂使用。     

用磺酸型亲水扩链剂制备高固含量聚氨酯乳液

以聚(四氢呋喃-co-氧化丙烯)二醇为软段、异佛尔酮二异氰酸酯为硬段,以1,2-二羟基-3-丙磺酸钠(DHPA)作为亲水扩链剂,用自乳化法合成了一系列稳定的高固含量聚氨酯乳液,分析了DHPA用量对乳液及其胶膜性能的影响。结果表明:所得聚氨酯乳液的粒径呈多元分布,乳胶粒子呈球形;乳液为假塑性流体;随着DHPA用量的增加,乳液平均粒径逐渐减小,粒径分布变窄,固含量不断增大,当DHPA质量分数为7%时,乳液的总固物质量分数可达61%。乳液具有较好的高、低温及贮存稳定性能。随着DHPA用量的增加,聚氨酯乳液胶膜的拉伸强度逐渐增大,扯断伸长率则先增大后减小;当DHPA质量分数为5%时胶膜的综合力学性能最佳;DHPA用量对胶膜的热稳定性没有明显影响。     

IPDI-based polyurethane ionomer dispersions: Effects of ionic,nonionic hydrophilic segments,and extender on particle size and physical properties of emulsion cast film

Isophoron diisocyanate (IPDI) -based polyester polyurethane (PU) dispersion in water was prepared in a prepolymer mixing process. Dimethylol propionic acid (DMPA), triethylamine (TEA), and triethyl tetramine (TETA) were used, respectively, as potential anionic center, neutralizing agent, and chain extender in aqueous phase. The effects of DMPA, butanediol (BD), and nonionic hydrophilic segment, viz. monofunctional ethylene–propylene oxide ether polyol, on the particle size of dispersion and the mechanical and viscoelastic properties of the emulsion cast films were systematically analyzed.     

Effect of ionic content,solid content,degree of neutralization,and chain extension on aqueous polyurethane dispersions prepared by prepolymer method

There are many variables in the preparation of aqueous polyurethane (PU) dispersions. Carboxylic acid content, solid content, degree of pre/postneutralization of the carboxylic acids, and chain extension all impact dispersion particle size, viscosity, pH, molecular weights, and glass transition temperature. This study evaluated the impact of these variables on a given PU dispersion formulation prepared from isophorone diisocyanate, an aliphatic polyester polyol, dimethylol propionic acid, and hexamethylene diamine with triethyl amine as the neutralizing base and N‐methyl pyrrolidone as the cosolvent. Changes in carboxylic acid content, degree of preneutralization, and chain extension were found to have the expected impacts on dispersions properties. Increased ionic content in the dispersion step led to lower particle size and higher viscosity, increased chain extension with its concurrent increase in molecular improved subsequent film properties. Surprising results were obtained by varying the amount of postneutralization and from increased solids content at the time of dispersion. Unexpectedly, both of these variations led to much higher dispersion viscosities and particle size in solution. To have these changes take place, it is theorized that there is a major change in solution morphology caused by these modifications. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2514–2520, 2005     

一种高固含量阴非离子水性聚氨酯的制备与性能研究

在聚氨酯(PU)链段中同时引入阴离子亲水单体和侧链为非离子的双羟基亲水单体(A-100),可以合成出一种稳定的高固含量阴非离子型水性聚氨酯(WPU)。讨论了软段种类、A-100用量等对WPU乳液的固含量及WPU胶膜性能的影响。结果表明:以聚碳酸酯二元醇(PCD)为软段,并引入适量的A-100,可以明显提高WPU乳液的固含量;当w(A-100)=4.2%时,WPU胶膜的综合性能最好;与聚环氧丙烷二元醇(PE220)相比,由PCD和A-100制备而成的WPU,其固含量较高(为57%)、综合性能较好。     

高固体分低粘度羟基丙烯酸树脂的合成

报道了高固体分低粘度羟基丙烯酸树脂的合成方法，讨论了羟基单体、溶剂、引发剂、分子量调节剂、工艺条件等因素对产品的影响，介绍了该树脂的特性和应用效果。     

高固含量聚氨酯的合成及应用研究进展

综述了国内外高固含量PU(聚氨酯)的合成进展及应用,重点介绍了溶剂型PU和WPU(水性聚氨酯)及其影响因素[如原料、扩链剂、溶剂、R值或R=n(-NCO)/n(-OH)等],并展望了未来PU材料的发展方向。     

高固含、低粘度丙烯酸乳液压敏胶工业化生产中粘度控制讨论

对高固含、低粘度丙烯酸乳液压敏胶工业化生产过程中粘度控制及成品贮存稳定性进行了讨论与观察。     

高固含量鞋用水性聚氨酯胶粘剂的合成

以HDII、PDI和聚己二酸-1,4-丁二醇酯为基本原料,二氨基苯磺酸钠(SDBS)和二羟甲基丙酸为内乳化剂,通过丙酮法制备出高固含量(50%以上)、不含有机溶剂和储存稳定的鞋用水性聚氨酯胶粘剂。经红外光谱分析,证实其含有磺酸基团。研究了SDBS和丙酮用量对胶粘剂性能的影响,实验结果表明,其性能达到或超过市售U-54产品。     

高固体份水稀释型聚氨酯丙烯酸酯黏度的影响因素

为了进一步提高水性UV光固化树脂的固含量,以甲苯二异氰酸酯为硬段,聚醚二元醇及聚乙二醇为软段,二羟甲基丙酸(DMPA)为亲水性物质,丙烯酸羟丙酯和季戊四醇三丙烯酸酯为封端剂,三乙胺为中和剂等,合成了固含量约为80%的水稀释型聚氨酯丙烯酸酯预聚物,探讨了软段类型及软段的相对分子质量、-NCO/-OH物质的量比、DMPA的加料顺序及加入量、内交联剂含量、COOH含量等因素对聚氨酯丙烯酸酯的黏度、涂膜性能的影响,同时对制备的产品进行光固化、拉伸强度、红外光谱(FTIR)和凝胶渗透色谱(GPC)分析。结果表明,COOH含量并不是决定预聚物黏度的唯一因素,小分子量的二醇、n(-NCO):n(-OH)在1.7~1.8、DMPA集中在硬段或软段、15%三羟甲基丙烷更有利于降低黏度,而制备的漆膜性能良好,硬度可达H,柔韧性2 mm,最快固化时间2 s,最大拉伸强度11.88 MPa,最大断裂伸长率达21.4%。制得的水性UV光固化涂料的水分减少了目前市面上同类产品的60%以上,降低了涂装时对湿度和干燥时间的要求。     

Synthesis and characterization of high solid content aqueous polyurethane dispersion

Aqueous polyurethane (APU) dispersions having a solid content of 50% were synthesized using dimethyol propionic acid (DMPA) as the stabilizing moiety. The principal diols used were poly‐1,4‐butylene adipate glycol (PBA). The diisocyanates used in this study were a 30:70 blend of hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI). All these samples were neutralized using triethylamine (TEA) and chain‐extended using ethylene diamine (EDA). The effects of the COOH content, NCO/OH molar ratio, and molecular weight (M_n) of PBA on the properties of APU dispersion and its cast film were studied. Dynamic light scattering results revealed that these high solid content dispersions shown broad particle size distributions as well as bimodal. Differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMA) results showed that as the hard segment content increased, the melting point (T_m) of the APU cast film increased, but the glass transition temperature (T_g) did not show significant alteration, when a PBA lower than 1000 M_n was used, the APU exhibited faint soft‐segment crystallization and tended to form amorphous polymer. Tensile and T‐peel strength tests attained excellent mechanical properties, such as a maximum Young's modulus of 166 MPa and the elongation at break reached to 2000%. T‐peel strength test (PVC/PVC) yielded a maximum peel strength value of 8.8 N/mm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

低黏度环氧树脂／反应性聚氨酯固化体系的研究

使用聚乙二醇与聚丙二醇的共聚物（PEG-PPG）和二苯基甲烷二异氰酸酯（MDI）为原料,在催化剂的存在下合成末端有异氰酸酯基的反应性聚氨酯。该反应性聚氨酯在催化剂XCT．cat57及固化促进剂XCT—cat37的存在下,再与一种低黏度双酚A型环氧树脂按不同的比例混合,由此组成了低黏度环氧树脂／反应性聚氨酯固化体系。研究了低黏度共混物的黏结效果,评价了其固化物的黏结强度。研究结果显示,当m（环氧树脂6002）：m（反应性聚氨酯）等于50：50时,共混树脂固化物具有最佳的力学性能。     

高固含量水性聚氨酯鞋用胶的制备与性能

以异佛尔酮二异氰酸酯(IPDI)、聚己内酯二醇(PCL)和二羟甲基丙酸(DMPA)为原料,三乙胺(TEA)为中和剂,乙二胺(EDA)为扩链剂,采用以水为基的混合介质合成了油包水(W/O)型的高固含量(为60%)WPU(水性聚氨酯)鞋用胶。研究结果表明:当w(DMPA)=5%(相对于预聚体质量而言)、中和度为90%和R=n(—NCO)∶n(—OH)=1.6∶1时,所得WPU鞋用胶的综合性能相对较好,其稳定性优、黏度适中、初粘力≥0.85 k N/m、终粘力为5.94 k N/m或被粘基材的剥离破坏,完全满足制鞋工艺对初粘力的基本要求以及鞋类产品对终粘力的基本要求。     

Preparation and characterization of high solid content cationic waterborne polyurethane with core-shell structures

In this study, core-shell structured cationic waterborne polyurethane (WPU) dispersions with high solid content were prepared. To this end, prepolymer A was synthesized from polytetramethylene ether glycol (PTMG), isophorone diisocyanate (IPDI), castor oil (CO) and 1,4-butanediol (BDO) without integration of the hydrophilic groups. Prepolymer B with hydrophilic groups was prepared from PTMG, IPDI, CO, BDO and N-methyldiethanol amine (MDEA). WPU dispersion with a core-shell structure could be generated by mixing, neutralizing, and emulsifying of the prepolymer A and the prepolymer B. The results indicated that the generation of WPU dispersions through this technique exhibited a milky appearance while the pH values range from 5.30 to 5.60. The optimal combination of prepolymer A and prepolymer B (at a ratio of 5:5) resulted in a dispersion with the highest solid content (50.4%), lowest viscosity (69 mPa·s), and narrowest particle size distribution. As the proportion of prepolymer A to prepolymer B decreases, the tensile strength of WPU film reduces while the elongation at break and glass transition temperature increases. Moreover, initially the contact angle with water was decreased instead of increase. However, modifications in a ratio of prepolymer A and B was not showed any significant impact on the thermal stability performance of the WPU films.