The formation of polyimides from anhydrides and isocyanates

The addition of water to the reaction of isocyanates with carboxylic acid anhydrides has been observed to increase markedly the rate of formation of the corresponding imide. This effect has been observed with both monofunctional and difunctional reagents as well as in different solvents. Evidence is presented which suggests that water hydrolyzes the isocyanate either to the corresponding urea or amine.     

Kinetic study of the urethane and urea reactions of isophorone diisocyanate

Kinetic studies of the catalyzed urethane reactions between isophorone diisocyanate (IPDI) and alcohols and of the urea reactions between an isocyanate‐terminated prepolymer [IPDI–PPG2000–IPDI, where PPG2000 is poly(propylene glycol) with a number‐average molecular weight of 2000 g/mol] and water in the bulk state were performed with Fourier transform infrared (FTIR) spectroscopy. Dibutyltin dilaurate was used as the catalyst for the urethane reaction, and various tertiary amines were used as catalysts for the urea reactions. The reactions were followed through the monitoring of the change in the intensity of the absorbance band for NCO stretching at 2270 cm^?1 in the FTIR spectra; the activation parameters were determined through the evaluation of the kinetic data obtained at various temperatures (within the range of 30–60°C). The kinetic data indicated that the catalyzed isocyanate/alcohol and isocyanate/water reactions both followed second‐order kinetics during their initial stages but later followed third‐order kinetics resulting from the autocatalytic effects of hydrogen bonding between the hydroxyl groups and the newly formed urethane and urea groups. Furthermore, activation energies of 64.88 and about 80 kJ/mol for the isocyanate/alcohol and isocyanate/water reactions, respectively, indicated that the urea‐forming reactions were more sensitive to the reaction temperature than the urethane‐forming reactions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Interfacial studies of crosslinked urethanes: Part II. The effect of humidity on waterborne polyurethanes; a spectroscopic study

In this study we examined isocyanate crosslinking reactions at the film-air (F-A) and film-substrate (F-S) interfaces of waterborne two-component (2K) urethanes as a function of depth and relative humidity (RH) using attenuated total reflectance (ATR) FTIR spectroscopy. Analysis of water/isocyanate reactions revealed urea formation which further interacts with water via H-bonding. Quantitative analysis of isocyanate consumption showed that the rates of film formation for waterborne polyurethanes are faster than equivalent solvent-borne polyurethanes. These studies showed that isocyanate consumption increases at high relative humidities. Examination of isocyanate consumption as a function of depth from the F-A and F-S interfaces showed that the isocyanate concentration increases when going from 0.65 to 1.14 μm. Part I of this paper was published in the September 1997 issue of theJournal of Coatings Technology. Department of Polymers and Coatings, Fargo, ND 58105.     

The chain extension of anionic prepolymers in the preparation of aqueous poly(urethane–urea) dispersions

Anionic polyurethane prepolymers end‐capped with isocyanate groups were dispersed and chain‐extended in aqueous media using three different extension agents: hydrazine, 1,2‐ethylene diamine (EDA) and 1,2‐propylene diamine (PDA). Two types of prepolymer were used. The first was prepared from isophorone diisocyanate (IPDI), α,α‐dimethylol propionic acid (DMPA) and poly(propylene oxide) diol (PPO) and the second from α,α,α′,α′‐tetramethyl‐1,3‐xylylene diisocyanate (m‐TMXDI), poly(caprolactone) diol (PCL) and DMPA. The colloidal particles which formed in the dispersion process and the constituent poly(urethane–urea) chains were characterised by a combination of dynamic and static light scattering, gel permeation chromatography and FTIR spectroscopy. Using EDA as the extender, a study was made of how the degree of extension depended on the molar ratio of amine to isocyanate groups, [NH₂]/[NCO] (= R_{A, I}). It was found that using a stoichiometric balance of isocyanate and amine groups did not lead to high degree of extension, and better chain extension was obtained at lower R_{A, I} values. In a comparative study using stoichiometric balances of isocyanate and amine groups, the degrees of extension obtained using PDA and EDA were approximately the same, while hydrazine was the least effective. Force–extension studies were carried out on samples prepared from films cast from the aqueous poly(urethane–urea) dispersions in order to assess the influence of chain‐extender type and stoichiometry on bulk properties; values of Young's modulus, tensile strength and maximum extension are reported. Copyright © 2003 Society of Chemical Industry     

Mechanically strong waterborne poly(urethane-urea) films and nanocomposite films

A series of transparent waterborne poly(urethane-urea) (PUU) films and nanocomposite films were prepared using isocyanate excess (5–50 mol% excess relative to the hydroxyl groups) and omitting the common chain-extension step in the acetone method of the preparation. The surplus isocyanate groups were converted into urea and eventually biuret linkages via the reaction with water during the last phase inversion step. Nanocomposites were prepared by the direct mixing of the PUU nanoparticles in water with aqueous nanosilica or montmorillonite powder followed by slow water evaporation. Variable urea/biuret content is responsible for substantially different tensile properties; the neat organic films show elongation-at-break values of 100%–1120%, tensile strength values of 0.07–22.1 MPa, and energy-to-break of 0.1–85 mJ × mm⁻³. All of the materials can be potentially used as soft-to-hard topcoats, depending on the specific demands. The most promising materials are films prepared at 30 and particularly 40 mol% isocyanate excess.     

Moisture curing kinetics of isocyanate ended urethane quasi‐prepolymers monitored by IR spectroscopy and DSC

The study of the kinetics of the curing of isocyanate quasi‐prepolymers with water was performed by infrared spectroscopy and differential scanning calorimetry. The influence of the free isocyanate content, polyol functionality, and of the addition of an amine catalyst (2,2′‐dimorpholinediethylether) in the reaction kinetics and morphology of the final poly(urethane urea) was analyzed. A second‐order autocatalyzed model was successfully applied to reproduce the curing process under isothermal curing conditions, until gelation occurred. A kinetic model‐free approach was used to find the dependence of the effective activation energy (E_a) with the extent of cure, when the reaction was performed under nonisothermal conditions. The dependence of E_a with the reaction progress was different depending on the initial composition of the quasi‐prepolymer, which reveals the complexity of the curing process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Emulsion of polyurethane having thermosetting properties. II. Relation between the mechanical properties of film and the polyurethane structure

A self-emulsifiable polyurethane emulsion having thermosetting property was prepared by the following procedure: the polyurethane–urea–amine was first prepared by the reaction of diethylene–triamine with a prepolymer containing terminal isocyanate groups in a ketone solvent, and then the primary amino group in the polyurethane–urea–amine was reacted with epichlorohydrin. The mixture was neutralized with an aqueous acid, and finally the ketone solvent was removed by distillation in vacuo. In the polyurethane, polytetramethylene glycol (PTMG) was the base polymer functioning as the soft segment. The present paper reports the effects of the following variables on the mechanical properties of the film prepared from the polyurethane emulsion, i.e., the M _n of PTMG, the molar ratio of diethylene–triamine (DTA) to prepolymer containing terminal isocyanate groups, the structure of the isocyanate end group and the molar ratio of tolylene diisocyanate (TDI) with PTMG. The best elastomer property was realized when M_n of PTMG was 2000, TDI/PTMG molar ratio was 2.0, and prepolymer/DTA molar ratio was 0.85.     

13C NMR investigation of the reaction in water of UF resins with blocked emulsifiable isocyanates

A solid state ¹³C NMR study of hardened networks obtained by the reaction of blocked and nonblocked isocyanates (pMDI) with urea‐formaldehyde (UF) resins in water showed different results according to the temperature of the reaction. At high temperature, in water, both a nonblocked or an emulsifiable, blocked isocyanate, appear to crosslink with UF resins through the formation both of traditional methylene bridges connecting urea to urea and of urethane bridges. The latter have been confirmed by ¹³C NMR to form in water by reaction of the isocyanate ? N?C?O group with the hydroxymethyl groups of the UF resin. At ambient temperature, UF/pMDI resins where the pMDI is a emulsifiable blocked isocyanate, do not appear to form urethanes to any great extent but rather to crosslink through the usual UF resin urea to urea methylene bridges. Even in this case, when urethane bridges appear to be absent, evidence of crosslinking in water through reaction of the isocyanate with the ? NH₂ and ? NH? amide of the UF resin has not been observed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 589–596, 2006     

Cyclotrimerization of isocyanate groups. II. Catalyzed reactions of phenyl isocyanate in the presence of 1-butanol or butyl-N-phenylurethane

Cyclotrimerization of phenyl isocyanate at 30–50°C in the presence of 1-butanol or butyl-N-phenylurethane and catalysts of tertiary amine, quaternary ammonium salt, or carboxylate types in 1,4-dioxane was studied by reverse-phase liquid chromatography. Urethane, allophanate, urea, biuret, isocyanurate, and isocyanate model compounds were found in the system. Stability of all reaction products was also examined. The time dependence of evolution of various products depends on the catalyst type and temperature. The overall reaction scheme was proposed. © 1994 John Wiley & Sons, Inc.     

Interphase Reaction of Isocyanates with Epoxy Resins Containing Functional Groups of Different Reactivity

Interphase reactions between cured epoxy resins and isocyanates are investigated. The epoxy resins contain secondary hydroxyl groups as reactive groups only or secondary hydroxyl plus amine. The isocyanate diffuses into the epoxy resin forming an interphase with a thickness of some micrometers. Depending on the functional groups available in the epoxy resin, urethane and urea groups are formed in the interphase. If a monofunctional isocyanate is used, no difference between both kinds of epoxy resin could be detected regarding the formation of urethane. If the epoxy resins react with bifunctional isocyanates a crosslinked interphase is formed. Due to the higher reactivity between amine and isocyanate compared to hydroxyl and isocyanate, the urea is formed first. The resulting cross‐links restrict the further diffusion of isocyanate into the epoxy resin. The consequence is a lower urethane content in the interphase and a thinner interphase compared to the epoxy resin containing hydroxyl only. If a prepolymer with isocyanate end groups is used as isocyanate the formation of the interphase is slower compared to the low molecular weight isocyanate. This is due to the reduced mobility of the prepolymer.     

聚脲交联改性丙烯酸酯弹性乳液的制备与性能研究

为了在性能上对聚脲交联改性后的丙烯酸酯乳液(PUA)和纯丙乳液(以)进行比较,文章以丙酮为溶剂,通过端氨基聚醚和甲苯二异氰酸酯的缩合反应合成了端异氰酸酯基聚脲预聚物,由于丙酮与胺基的可逆缩合反应,降低了胺基与异氰酸酯基反应的活性,从而可以更好地控制反应速度,降低副反应的发生几率.聚脲预聚体经丙烯酸羟乙基酯双键封端制备了含有2个双键的聚氨酯脲大单体,以其为外交联剂,通过与甲基丙烯酸甲酯、丙烯酸丁酯的乳液共聚反应制备了聚氨酯脲改性的纯丙弹性乳液,对乳液涂膜进行了FT-IR,DSC和TGA的表征.研究表明:PUA涂膜比PA涂膜具有更好的热稳定性、机械性能、耐低温性以及耐溶剂性.     

有机硅改性热反应型水基聚氨酯

用氨丙基聚硅氧烷与PU预聚体反应生成合硅氧烷的PU预聚体,通过NaHSO3封闭NCO基,并在水中分散制得有机硅改性热反应型水基聚氨酯乳液。考察了有机硅含量对封闭率和解封速率以及乳液粒径的影响。     

Graft copolymerization of unsaturated segmented polyurethanes with 2-hydroxyethyl methacrylate

Relatively high molecular weight unsaturated segmented polyurethane synthesized from poly(ethylene glycol), methylene bis(4-phenyl isocyanate), cis-2-butene-1,4-diol, and butane-1,4-diol was modified by graft copolymerization reaction. 2-Hydroxyethyl methacrylate (HEMA) monomer was grafted onto the unsaturated segmented polyurethane using 2,2′-azobisisobutyronitrile (AIBN) as initiator in N,N-dimethylformamide (DMF) as solvent. The graft copolymers were isolated by selective solvent extraction in a Soxhlet apparatus. The effect of reaction time, initiator concentration, reaction temperature, and monomer concentration on the graft yields has been examined. The graft yields were enhanced by increased monomer concentration and reaction temperature.     

Hydrogen bonding effects on aspartate ester reactions

Michael addition reactions were utilized to form AB₂ type monomers and esterified to form polyaspartate esters (PASPE). FTIR and NMR spectroscopic methods indicate that a relatively linear architecture was produced that contrasts with an expected hyperbranched (HB) structure. Linear chains formed due to a reactivity difference between the hydrogen bonded (H-bonded) and non-H-bonded esters. The esterification reaction was directed toward the H-bonded ester as shown by 2D NMR correlation spectroscopy. A model is proposed to explain the observed increase in reactivity of the H-bonded ester. Hydrogen bonding (H-bonding) in both the monomeric and polymeric aspartate (ASP) esters was analyzed by 2D NMR spectroscopy. The difference in chemical shifts of the methylene protons before and after reaction was attributed to the geometrical effects of the five-membered ring formed from H-bonding. Monomeric aspartate esters (ASPE) were found to have the greatest difference in chemical shift, while the in-chain H-bonded protons of the PASPE were observed to have the least difference in chemical environments. Internal H-bonding in the ASPE affected its reaction with an aliphatic isocyanate (NCO) due to varying reactivities of the primary hydroxyl (OH) compared to the secondary amine (NH). Internal hydrogen bonding of the OH groups with the amine may also explain unexpected relative reactivities with isocyanates. Both NMR and FTIR spectroscopy indicated that the OH group was exclusively consumed with no NH reaction product detected. A lack of hydantoin ring formation upon further heating the NCO/ASPE reaction product proved that the OH group was more reactive. In an equimolar reaction of ASPE with cyclohexyl isocyanate, NMR and FTIR measurements showed quantitative formation of the urethane adduct instead of the expected urea.     

尿素羰化法绿色合成间苯二亚甲基二氨基甲酸酯

间苯二亚甲基二氨基甲酸酯(XDC)是非光气绿色合成特种异氰酸酯间苯二亚甲基二异氰酸酯(XDI)的关键中间体.本工作以TiO2作为催化剂,以尿素、间苯二甲胺(XDA)和乙醇为原料绿色高效合成XDC.通过气质联用,分析了 XDC合成的主副反应,推测了主反应路径,并优化了反应工艺条件.结果表明,以TiO2作为催化剂时,催化剂...     

Preparation of propylene carbonate by alcoholysis of urea from the perspective of homogeneous reaction: Influence of dissolution and precipitation of metal oxide catalysts

The dissolution process of metal oxide catalysts in the alcoholysis of urea by 1, 2-propylene glycol (PG) to the synthesis of propylene carbonate (PC) was investigated. It was found that the reaction was mainly catalyzed by homogeneous catalysts. The metal oxide reacted with ammonia and isocyanate acid, the decomposition products of urea, to form a complex and dissolved into the reaction system. The dissolved amount of catalyst was positively correlated with the PC yield by using different oxides and salts as catalysts. The Fourier-transform infrared spectroscopy (FTIR) result of the catalysts reacting with urea showed that the dissolution-precipitation process of the catalysts was related to the decomposition of urea. The results of catalytic test indicated that both the dissolved amount of catalysts and the structure of the complex affected PC yields. A reaction mechanism was proposed based on the results. From the mechanism, a complex catalyst with at least two ammonia ligands is better for this reaction.     

油脂基聚氨酯改性脂肪胺水性环氧固化剂的合成及性能

以高级脂肪醇聚氧乙烯醚（OE-6）、甲苯二异氰酸酯（TDI）为原料,物料比n(TDI)∶n(OE-6)= 1.05∶1、温度45℃、反应2.5 h合成了端异氰酸酯预聚体,再将其与多元胺按照摩尔比n (多元胺)∶n (预聚体)=1.2∶1、温度40℃、反应3 h扩链,得到油脂基聚氨酯改性脂肪胺水性环氧固化剂（UFAWECAOF）。用红外光谱、 13C-NMR表征了UFAWECAOF的结构。粒径分析表明目标产物具有乳化液体环氧树脂的功能,其与环氧树脂EPON828复配制备的双组分水性涂料涂膜固化物,柔韧性达1 mm、铅笔硬度达3 H、耐冲击性达50 kg/cm。     

Novel water-dispersible glycidyl carbamate (GC) resins and waterborne amine-cured coatings

Water-dispersible glycidyl carbamate (GC) functional resins were synthesized and crosslinked using a water-dispersible amine to form coatings. GC functional resins are synthesized by the reaction of an isocyanate functional compound with glycidol to yield a carbamate (urethane) linkage (–NHCO–) and reactive epoxy group. The combination of both functionalities in a single resin structure imparts excellent mechanical and chemical properties to the coatings. Previous studies on the development of GC coatings have focused on solvent-borne coating systems. In this study, GC resins were modified by incorporating nonionic hydrophilic groups to produce water-dispersible resins. To determine the influence of the content of hydrophilic groups on dispersion stability, aqueous dispersions were made from a series of hydrophilically modified GC resins and characterized for particle size and dispersion stability. The composition of a typical, dispersed GC resin particle was predicted using Monte Carlo simulations. Stable GC dispersions were used to prepare amine-cured coatings. The coatings were characterized for solvent resistance, water resistance, hardness, flexibility, adhesion, and surface morphology. It was observed that GC resins were able to be dispersed in water without using any surfactant and by minimal mixing force (hand mixing) and produced coating films with good properties when crosslinked with a compatible waterborne amine crosslinker.     

Platelet adhesion on a polyurethane surface grafted with a zwitterionic monomer of sulfobetaine via a Jeffamine spacer

A possible approach to improve the blood compatibility of poly(ether urethane)s (PU) involves the covalent attachment of key molecules on its surface. The purpose of the present study was to design and synthesise a novel non‐thrombogenic biomaterial by modifying the surface of the PU with a zwitterionic monomer of sulfobetaine via a Jeffamine spacer. In this study, sulfobetaine was grafted onto a PU surface through the following reaction steps: (1) The PU surface was activated with hexamethylene diisocyanate (HDI) in toluene at 50 °C in the presence of di‐n‐butyltin dilaurate (DBTDL) as a catalyst. The extent of the reaction was measured by ATR‐FTIR spectra; a maximum number of free NCO groups was obtained after a reaction time of 90 min. (2) One cap of Jeffamine was reacted with isocyanate groups bound on the surface, so Jeffamine was introduced. (3) The PU surface terminated by Jeffamine was recoupled with isocyanate groups by HDI. (4) The hydroxyl groups of 4‐dimethylamino‐1‐butanol (DMAB) or 2‐dimethylaminoethanol (DMAE) were allowed to react with the isocyanate groups capped on Jeffamine. (5) Sulfobetaines were constructed on the surface through the ring‐opening reaction between tertiary amine and 1,3‐propanesultone (PS). It was confirmed by ATR‐FTIR and XPS that the grafted surfaces were composed of sulfobetaine. The results of the contact‐angle measurements and water absorption showed that they were strongly hydrophilic. The results of this platelet adhesion experiment as a preliminary test showed that PU grafted with sulfobetaine has good blood compatibility featured by the low platelet adhesion. Copyright © 2004 Society of Chemical Industry     

双组分水性聚氨酯的成膜过程

双组分水性聚氨酯的成膜过程主要考虑挥发物(水)的挥发、多元醇和多异氰酸酯粒子的聚结、多异氰酸酯与多元醇和水的反应这3个因素的影响。本工作从双组分水性聚氨酯的甲、乙两组分混合中的粒子聚结、混合相中异氰酸酯的反应、水的蒸发和粒子聚结3个方面概述了成膜的具体过程，初步探讨了成膜机理。