Effect of dimethyldichlorosilane on the oxygen permeated through a siloxane-based polyurethane ionomer

The oxygen permeated through the film made by a polyurethane (PU) ionomer is demonstrated to be a siloxane-based polyurethane ionomer by infrared spectra. For siloxane-based polyurethane ionomer molecules in an aqueous solution, the surface tension was found to decrease slightly with an increase in the concentration of dimethyldichlorosilane (DMDCS) but to increase slightly with an increase in the ratio of NCO to OH. Owing to the increased phase volume of siloxane-based polyurethane ionomer molecules resulting from the hydrogen bonding effect and/or intermolecular interaction in the aqueous solution, the number-average particle sizes of these ionomer molecules increase considerably with an increase in the DMDCS concentration and the NCO/OH ratio, respectively. More importantly, the volume of the oxygen permeated through the film was found to be larger for the film made by the PU ionomer molecule with 0.02% (by weight) DMDCS than for the film made by the PU ionomer molecule without DMDCS. Our experimental results also suggest that the use of DMDCS in preparing siloxane-based polyurethane ionomers does substantially raise the amount of oxygen diffusing into the film made by these ionomer molecules. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 981–988, 1997     

Water vapor‐permeable polyurethane ionomer

The reaction of toluene diisocyanate with 2,2,3,3‐tetrafluoro‐1‐propanol (fluoro compound) or 3‐glycidoxypropyl trimethoxysilane(siloxane compound) and other additives to form the structure of the fluoro‐based or siloxane‐based polyurethane (PU) ionomer has been proven by infrared spectra. Experimental results indicated that the amount of water vapor permeability of the film made by fluoro‐based or siloxane‐based PU ionomer appeared to gradually increase with increasing concentration of the siloxane compound or fluoro compound, as a result of the formation of more porosities. Our experimental results also showed that the water vapor absorption was seen to be larger for the film made by siloxane‐based PU ionomer film than for the film made by fluoro‐based PU ionomer film, as a result of increased hydrophilic groups attached to the backbone of the PU ionomer molecule. For the film prepared by siloxane‐based PU ionomer, both tensile strength and elongation appeared to increase with an increase in the concentration of siloxane compound. This may be the result of the intermolecular interaction between siloxane‐based PU ionomer molecules themselves, thus enhancing the crosslinking capability of the ionomer molecules. On the other hand, both tensile strength and elongation for the film prepared by fluoro‐based PU ionomer decreased with increasing concentration of the fluoro compound, as a result of intramolecular interaction greatly reducing the crosslinking capability of the ionomer molecules. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3767–3773, 2006     

Study of fluorescence from fluorescent dye‐based polyurethane ionomer

6‐Amino‐2‐(3‐chloro‐2‐hydroxy‐propyl)‐ benzo[de]isoquinoline‐1,3‐dione (DYE‐A) and 2‐benzyl‐6‐hydroxy‐benzo[de]isoquinoline‐1,3‐dione (DYE‐B) have been successfully synthesized in our lab, and their structures have been proven by IR, NMR, and mass spectra. The fluorescence performance appears to be better for DYE‐A than for DYE‐B as a result of DYE‐A having more electron donating substituents that are strongly excited when absorbing UV light. These fluorescent dyes have further reacted with toluene diisocyanate and other additives to form the fluorescent dye‐based polyurethane (PU) ionomer molecules, and the structures of these molecules have been demonstrated by IR spectra. In aqueous solution, our experimental results indicate that the fluorescence performance is seen to be better for DYE‐A than for DYE‐B. Increased concentration of DYE‐A molecule attached to the backbone of the PU ionomer molecule may reduce the fluorescence performance of this PU ionomer molecule, resulting from the intramolecular interaction between ionomer molecule itself. For the fluorescent dye‐based PU ionomer molecule system, the average particle size of the fluorescent dye‐based PU ionomer molecule in water increases with increasing concentration of the fluorescent dyes, as a result of increased free volume of the ionomer molecules. Our experimental results also illustrate that the tensile strength of self‐cured film made by the fluorescent dye‐based PU ionomer appears to increase with an increase in the concentration of DYE‐A. This is the result of increased intermolecular interaction between ionomer molecules. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2723–2737, 2003     

Fluorescence from fluorescent dye based polyurethane ionomer(III)

A series of reactive fluorescent dyes were successfully synthesized and their structure was proven by IR spectra, NMR spectra, elemental analysis, and mass spectra. The fluorescence performance 6‐amino‐2(‐3‐phenyl‐propyl)‐benzo[de]isoquinoline‐1,3‐dione and 2‐benzyl‐6‐hydroxy‐benzo[de]isoquinoline‐1,3‐dione appears at around 276 and 437.4 nm, respectively, and their quantum yields are 0.662 and 0.562, respectively. It is important to indicate that the fluorescence performance is better for 6‐amino‐2(‐3‐phenyl‐propyl)‐benzo[de]isoquinoline‐1,3‐dione than for as a result of more electron donating groups linked to the 6‐amino‐2(‐3‐phenyl‐propyl)‐benzo[de]isoquinoline‐1,3‐dione molecule. These fluorescent dyes further react with toluene diisocyanate and other additives to form fluorescent dye based polyurethane (PU) ionomer molecules, and their structures are demonstracted by IR spectra. In aqueous solution, the fluorescence performance appears to be better for 6‐amino‐2(‐3‐phenyl‐propyl)‐benzo[de]isoquinoline‐1,3‐dione based PU ionomer than for 6‐amino‐2‐phenyl‐ethyl‐benzo[de]isoquinoline‐1,3‐dione based PU ionomer. For the fluorescent dye based PU ionomer molecule system, the number‐average particle sizes of the fluorescent dye based PU ionomer molecules in water increase with increasing concentration of the fluorescent dye, as a result of the increased free volume of the ionomer molecule. This may be the result of increased intermolecular interactions between ionomer– molecules themselves. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 455–465, 2005     

水泥嵌缝用聚氨酯密封胶

在甲苯二异氰酸酯中加入脱水聚醚N210,约2h滴加完毕后,将油浴温度升高到(78±2)℃,继续反应2.5～3.0h,可制备水泥嵌缝用聚氨酯密封胶。结果表明,水泥嵌缝用聚氨酯密封胶的—NCO/—OH摩尔比的最佳值为1.30∶1.00;提高—NCO/—OH摩尔比,可使试样的拉伸强度增加,扯断伸长率降低,邵尔A型硬度增大。     

A study of polyurethane ionomer dispersant

Anionic polyurethane ionomers as the dispersant in water‐soluble acrylic baked paint were successfully synthesized at our lab and these ionomer structures have been proven by infrared spectra. In aqueous solution, the surface tension for polyurethane ionomer molecules with different ionics was found to increase with increasing the concentration of ionics, as a result of the hydrophobics of ionomer molecules adsorbed at the air–water interface becoming even more ordered. It was also found that the viscosity is higher for polyurethane ionomer with L ‐2,5‐diaminovaleric acid hydrochloride than for polyurethane ionomer with sodium 4,4‐dihydroxy‐l‐butane sulfonate (DS200) or with dimethylol propionic acid (DMPA) in water. For the wettability and dispersion of titanium dioxide pigment present in water‐soluble acrylic baked paint, the polyurethane ionomer molecules with respective sodium 4,4‐dihydroxy‐L ‐butane sulfonate, DMPA, DS200 containing 3% 1,3‐propane sultone (ES200) and DMPA containing 3% ES200 are considered to be better dispersants. The titanium dioxide pigment was found to become finer, as the agitation time and the ionic concentration of anionic polyurethane ionomer were increased. In addition, the system with DS200 or dimethylol propionic acid will make the dispersion of titanium dioxide pigment stable in water‐soluble acrylic paint. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 103–111, 2005     

Preparation of water-soluble polyurethane surfactants

A novel series of water-soluble polyurethane surfactants has been prepared by the addition polymerization of 2,4 and 2,6-toluene diisocyanate 80 : 20%, respectively (TDI) to polyethylene glycol (PEG) and/or castor oil and ethylene glycol (EG). These water-soluble polyurethane surfactants have been found to exhibit excellent surface active properties including surface tension, foaming and wetting tendency, and formation of stable emulsions. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1531–1536, 1998     

A recycling model of excess toluene diisocyanate isomers in the preparation of polyurethane prepolymer

Reaction kinetics of dropwise addition of trimethylolpropane (TMP) to toluene diisocyanate (TDI‐80) at various temperatures and initial stoichiometry was studied. The progress of the polymerization reaction was monitored by measuring the concentration of isocyanate groups and TDI isomers by means of backtitration and high performance liquid chromatography (HPLC), respectively. The kinetics of dropwise addition method, compared with the conventional one‐shot method, was well described by a second order equation. This procedure was optimized by comparing the deviations between experimental data and theoretically calculated data. The effects of temperature, initial stoichiometry and TDI isomers on the amount of excess 2,4‐TDI and 2,6‐TDI were investigated. Three commercially available TDI mixtures, 65 : 35, 80 : 20, and 100 : 0 ratio of 2,4‐TDI/2,6‐TDI, respectively, were used. A recycling model of unreacted TDI isomers and solvent was established to reach a stable process and yield polyurethane prepolymer with good reproducibility. This model has been applied in the chemical plant to prepare polyurethane prepolymer with precisely defined chemical compositions in a continuous process. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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。     

PTMG型聚氨酯预聚体的研制

以聚四亚甲基醚二醇（PTMG）和甲苯二异氰酸酯（TDI）为原料，研究了TDI/PTMG的摩尔比和制备工艺条件，制备出了聚氨酯预聚体。结果表明，当TDI/PTMG的摩尔比为1.80-1.85，且在将PTMG分批加入TDI中的制备工艺条件下可制得相对分子质量分布窄，游离TDI质量分数低，黏度小，稳定性及可操作性能好的聚氨酯预聚体。     

R值对PTHF型聚氨酯胶粘剂性能的影响

用PTHF(聚四氢呋喃)与TDI(甲苯二异氰酸酯)合成了PU(聚氨酯)胶粘剂。在合成过程中保持其它相关条件不变的情况下,仅改变R值(异氰酸指数)来制备系列胶膜,测试了R值与胶膜的拉伸强度、断裂伸长率、耐水性、预聚体邵氏硬度及粘度(常温)的关系,同时还运用了红外光谱法对所合成的PU胶粘剂进行了表征。实验结果表明,PU胶粘剂中已成功地引入了硅链节;较佳的R值为1.3,合适的反应时间(预聚体)为3 h。     

乙二胺后扩链TDI型聚氨酯水分散体的过程

以甲苯二异氰酸酯（TDI）、聚氧化丙烯二醇和二羟甲基丙酸等为主要原料制备了聚氨酯水分散体,研究了水、扩链温度、原料的-NCO/-OH摩尔比及扩链比对乙二胺（EDA）后扩链TDI型聚氨酯水分散体过程的影响。FT-IR测试表明,分散体中的H₂O可通过与聚氨酯中残留异氰酸酯基团（-NCO）的竞争反应影响EDA的后扩链过程。分子量及粒径与zeta电位测试表明,H₂O扩链导致分散体失稳;低扩链比时,H₂O对EDA的后扩链过程影响明显,但高扩链比时,后扩链聚氨酯的分子量降低;扩链温度升高,经EDA后扩链聚氨酯的分子量降低,而分散体粒径增大。当原料的-NCO/-OH摩尔比为1.20、扩链温度为30℃、扩链比为60%时,可有效降低H₂O对EDA后扩链聚氨酯过程的影响。     

Effect of toluene diisocyanate index on morphology and physical properties of flexible slabstock polyurethane foams

The effect of toluene diisocyanate (TDI) index on the physical properties, structure, and morphology of flexible slabstock polyurethane foams was investigated. Foams based on a 2700 molecular weight triol, 6 pph water, and varying amounts of an 80/20 mixture of 2,4- and 2,6-TDIs were characterized using a number of physical property and morphological measurements. Extraction experiments using dimethyl formamide (DMF) showed that increasing the index increased the level of covalent crosslinking with perhaps a maximum being reached at an index ca. 100. Viscoelastic measurements also supported the claim of increased crosslinking with TDI index. The initial load in load relaxation experiments at 65% strain systematically increased with increasing TDI while the percent decay in a 3-h period decreased. Temperature and/or humidity “plasticized” the load relaxation behavior in all the foams studied, indicating that the hard segment domain physical “crosslinks” play a significant role in the properties of these materials. Interestingly, compression set measurements appeared to be independent of the index, likely due to some level of hard segment continuity, but the induced recovery of the compression set at elevated temperatures was indeed sensitive to the index. The amount of recovery systematically increased with increasing TDI index due to the more enhanced “recoverable” covalent network. Scanning electron microscopy (SEM) studies of the foams showed that the cellular structure was not significantly affected by the index. However, SEM also showed that the structure of the high index foam was not greatly altered by the extraction process while the lowest index foam's cellular structure was severely disfigured. The fine structure of the foams was found to be influenced by the TDI index. Small angle X-ray scattering, differential scanning calorimetry, and dynamic mechanical analysis all provided evidence that an increase in the TDI index promoted some phase mixing of the soft and hard segments. FTIR showed that the short-range ordering within the hard segment domains displayed a maximum at an index of 100. This was attributed to the concentration of hard segment domains being lower at a lower index and their ordering being disrupted at higher indexes due to more extensive covalent crosslinking prior to completion of phase separation. Wide angle X-ray scattering results also confirmed that for the highest index level, the short-range ordering of the TDI moieties was decreased. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2395–2408, 1997     

聚氨酯涂料中游离甲苯二异氰酸酯(TDI)单体的测定方法

研究了在GB/T18446-2001方法基础上改变内标物(使用无毒性记录的十二烷代替毒性大的1,2,4-三氯代苯)测定样品中游离TDI的方法。该方法简捷、快速、准确度高、精确度高、更环保。本方法的适用范围同GB/T18446-2001。     

A structure–property study of IPDI-based polyurethane anionomers

Polyurethane (PU) anionomers were prepared as aqueous dispersions and as solutions in tetrahydrofuran or absolute ethanol using dimethylol propionic acid (DMPA) as the stabilizing moiety, isophorone diisocyanate, polytetrahydrofuran, and cyclohexane dimethanol. The structure–property relationships were investigated for these PUs, cast as films, at similar and differing chain-extension levels. Comparisons were made with respect to the mechanical and viscoelastic properties and solvent resistance. Finally, the consequences of DMPA incorporation into the PU backbone were determined for two solvent-borne compositions of similar structure with and without DMPA. Dynamic mechanical thermal analysis, tensiometry, solvent spot tests, and swelling studies were employed for the characterization of the materials. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1437–1448, 1998     

具有反射近红外功能浅色粉体的合成

采用水溶液共沉淀法合成了具有近红外反射功能的浅色氧化铟锡粉体材料。实验结果表明,最佳反应条件为：三氯化铟浓度0.25 mol/L,反应温度90℃～95℃,陈化时间2 h,陈化温度50℃,煅烧时间2 h,煅烧温度700℃～800℃,沉淀剂为尿素。     

Phase inversion and its effect on the properties of polyester polyurethane cationomers

Polyester polyurethane cationomers are prepared using polyester polyol of molecular weight 2000 as soft segments, N-methyl diethanolamine as chain extender, glycolic acid as quaternization agent, methyl ethyl ketone as solvent, and 4,4'-diphenylenemethylene diisocyanate (MDI) as diisocyanate. Properties of the films cast from solutions and emulsions are studied by infrared spectroscopy, dynamic mechanical analysis, thermogravimetric analysis, differential scanning calorimetry, and tensile-elongation testing. Ionization can cause phase separation and produces increased cohesion in the hard domains. The dispersion process can be divided into three stages involving a separation of hard segment aggregates due to adsorption of water on their surface, water entering into hard segment microionic lattics, and finally a rearrangement of agglomerates to form microspheres. The dispersion can disrupt the order in the hard domains and an increased phase separation.     

1H nuclear magnetic resonance study of polyurethane prepolymers from toluene diisocyanate and polypropylene glycol

Polyurethane prepolymers prepared from toluene 2,4‐diisocyanate, toluene 2,6‐diisocyanate, and polypropylene glycol with a ratio between the isocyanate and hydroxyl groups equal to 2 were analyzed by ¹H nuclear magnetic resonance (NMR) spectroscopy in acetone‐d₆. Different temperatures and concentrations were used. Toluene 2,4‐dimethylurethane and toluene 2,6‐dimethylurethane were synthesized and used as model compounds to assign prepolymers signals. Measurements of spin–lattice relaxation time T₁ by “inversion recovery” experiments were carried out on toluene 2,4‐diisocyanate, toluene 2,6‐diisocyanate, toluene 2,4‐dimethylurethane, toluene 2,6‐dimethylurethane, and polyurethane prepolymers. Differences in T₁ times were used to interpret prepolymers spectra, by means of the strong observed effect on protons due to the presence of adjacent isocyanate groups. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 347–357, 2003     

甲苯二氨基甲酸甲酯催化分解反应的研究

对甲苯二氨基甲酸甲酯（TDC）热分解制备甲苯二异氰酸酯（TDI）进行了研究,考察了溶剂、温度、压力、催化剂浓度及热载体和催化剂重复利用对TDC液相分解性能的影响。最佳反应条件为：邻苯二甲酸二辛酯（DOP）为溶剂,反应温度260℃,反应压力5.4 kPa,冷凝柱顶温度165℃,TDI的最高收率为99%;邻苯二甲酸二辛酯、...     

一种新型聚乙烯醇氨基甲酸酯胶粘剂的研究──甲苯二异氰酸酯对聚乙烯醇胶粘剂的改进

本研究是用甲苯二异氰酸酯（ＴＤＩ）为交联剂，对聚乙烯醇胶粘剂改性．讨论其反应原理、合成方法、粘结强度（木／木），以及耐水性能等．本实验结果获得一种新型的聚乙烯醇氨基甲酸醋水乳胶．