Preparation and properties of imide‐containing elastic polymers from elastic polyureas and pyromellitic dianhydride

A new approach to obtain imide‐containing elastic polymers (IEPs) via elastic and high‐molecular‐weight polyureas, which were prepared from α‐(4‐aminobenzoyl)‐ω‐[(4‐aminobenzoyl)oxy]‐poly(oxytetramethylene) and the conventional diisocyanates such as tolylene‐2,4‐diisocyanate(2,4‐TDI), tolylene‐2,6‐diisocyanate(2,6‐TDI), and 4,4′‐diphenylmethanediisocyanate (MDI), was investigated. IEP solutions were prepared in high yield by the reaction of the polyureas with pyromellitic dianhydride in N‐methyl‐2‐pyrrolidone (NMP) at 165°C for 3.7–5.2 h. IEPs were obtained by the thermal treatment at 200°C for 4 h in vacuo after NMP was evaporated from the resulting IEP solutions. We assumed a mechanism of the reaction via N‐acylurea from the identification of imide linkage and amid acid group in IEP solutions. NMR and FTIR analyses confirmed that IEPs were segmented polymers composed of imide hard segment and poly(tetramethylene oxide) (PTMO) soft segment. The dynamic mechanical and thermal analyses indicated that the IEPs prepared from 2,6‐TDI and MDI showed a glass‐transition temperature (T_g ) at about −60°C, corresponding to T_g of PTMO segment, and suggested that microphase‐separation between the imide segment and the PTMO segment occured in them. TGA studies indicated the 10% weight‐loss temperatures (T₁₀) under air for IEPs were in the temperature range of 343–374°C. IEPs prepared from 2,6‐TDI and MDI showed excellent tensile properties and good solvent resistance. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 715–723, 2000     

Synthesis of chromophore‐embedded polyurethanes for electrooptical materials

We carried out the polyaddition of dye‐embedded diols with diisocyanates to obtain novel nonlinear optical (NLO) polyurethanes, where the NLO units were embedded in the polymer backbone. The obtained polymers showed high glass‐transition temperatures (138–184 °C) and thermal stability (temperature of 10% weight loss under nitrogen = 227–287 °C). The λ maximum of the polymers was 521–556 nm. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2620–2624, 2001     

First Principle Simulations of Ethylene Glycol Addition to Diisocyanates

The reaction of addition of ethylene glycol to diisocyanates was studied with the B3LYP method to gain an insight into the mechanism of polyurethane synthesis. It was found that the functional basis set should contain at least one diffusion function for the simulation in order to properly describe thermo‐chemical features of the model reaction. Using the B3LYP/6‐31+G** level the values of Gibbs free energy were estimated for the addition reaction of ethylene glycol to toluene‐2,4‐diisocyanate, toluene‐2,6‐diisocyanate, diisocyanate‐[5‐isocyanato‐1‐(isocyanatomethyl)‐1,3,3‐trimethylcyclohexane], 1,6‐diisocyanatohexane, 4,4′‐methylenebis(cyclohexyl isocyanate) and methylenebis(phenyl isocyanate). Both the gaseous phase and the benzene environment were taken into consideration. Spontaneity of the reaction proved to be dependent on both substrate type and product isomeric configuration. The trans‐urethane isomer has been found to be a more stable product. Considering the values of activation energy the minor dependence on the structure of diisocyanate was observed. This confirmed Flory's postulate to be valid for the polyurethane synthesis. The highest value of activation energy was found for the first stage, which consists of ethylene glycol approach and simultaneous proton transfer to the isocyanate group. For that reason the first stage has been estimated as that limiting the general rate of the urethanisation reaction.

     

Functional Polymers. LVII. Electronic Absorption Spectra of Benzotriazole Derivative/Electron Acceptor Systems

The electronic absorption spectra of charge-transfer complexes (CTC) of benzotriazole derivatives including 2(2H-hydroxyphenyl)2H-benzotriazole-containing copolymers with various electron acceptors were investigated. While no charge-transfer interaction was observed with weak acceptors, strong acceptors such as trinitrofluorenone and pyromellitic anhydride exhibited an absorption of the contact charge-transfer type with these donors. When the very strong acceptor tetracyanoethylene was used as acceptor, new peaks of a CTC type appeared at longer wavelengths. From the wavelengths of the absorption maxima and the equilibrium constants of the CTC, the electron-donating ability of several related (2(2-hydroxyphenyl)2H-benzotriazole derivatives was estimated as follows: 2(2-Hydroxy-5-methylphenyl)2H-benzotriazole > 2H-benzotriazole > 2(4-hydroxyphenyl)2H-benzotriazole > 2(2-acetoxy-5-methylphenyl)2H-benzotriazole > copolymers containing 2(2-hydroxyphenyl)2H-benzotriazole groups.     

Preparation and chromatographic characteristics of a novel 2,6-dimethyl-β-CD bonded HPLC chiral stationary phase

A novel 2,6-dimethyl-b-CD bonded and silica based HPLC chiral stationary phase（CSP） was prepared.The diphenylmethane diisocyanate（MDI） was applied for the first time in the immobilization of 2,6-dimethyl-b-CD onto the surface of aminized silica gel under mild conditions. The composite materials obtained were used as the CSP for chiral separation processes and this kind of CSP exhibits good enantioselectivity for a variety of chiral compounds under reversed-phase conditions.     

IPDI的NMR数据解析

用NMR对异氟尔酮二异氰酸酯（IPDI）的两种立体异构体进行结构表征，包括¹H、¹³C、DEPT135、HMBC、HMQC谱，并详细解析图谱. 此外对这两种异构体在不同温度下的稳定性进行了研究.      

Study of slabstock flexible polyurethane foams based on varied toluene diisocyanate isomer ratios

The morphological features of three flexible slabstock polyurethane foams based on varied contents of 2,4 and 2,6 toluene diisocyanate (TDI) isomers are investigated. The three commercially available TDI mixtures, that is, 65:35 2,4/2,6 TDI, 80:20 2,4/2,6 TDI, and 100:0 2,4/2,6 TDI were used. The foams were characterized at different length scales with several techniques. Differences in the cellular structure of the foams were noted with scanning electron microscopy. Small‐angle X‐ray scattering was used to demonstrate that all three foams were microphase‐separated and possessed similar interdomain spacings. Transmission electron microscopy revealed that the aggregation of the urea phase into large urea‐rich regions decreased systematically on increasing the asymmetric TDI isomer content. Fourier transform infrared spectroscopy showed that the level of bidentate hydrogen bonding of the hard segments increased with the 2,6 TDI isomer content. Differential scanning calorimetry and dynamic mechanical analysis (DMA) were used to note changes in the soft‐segment glass‐transition temperature of the foams on varying the diisocyanate ratios and suggested that the perfection of microphase separation was enhanced on increasing the 2,6 TDI isomer content. The preceding observations were used to explain why the foam containing the highest content of the symmetric 2,6 TDI isomer exhibited the highest rubbery storage modulus, as measured by DMA. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 258–268, 2003     

Slightly Cross‐Linked Polyrotaxanes Made by Linking α‐Cyclodextrins Entrapped in Polyrotaxanes Using Hexamethylene Diisocyanate

In this study polyrotaxane (PR)‐based triblock copolymers were first synthesized via the atom transfer radical polymerization (ATRP) of N‐isopropylacrylamide initiated with the self‐assembly of a distal 2‐bromoisobutyryl end‐capped Pluronic 17R4 with a varying amount of α‐cyclodextrins (α‐CDs) in the presence of CuCl/PMDETA at 25°C in aqueous solution. The α‐CDs entrapped on the copolymer chain were then linked with hexamethylene diisocyanate to give rise to novel slightly cross‐linked polyrotaxanes (SCPRs) in DMF at 45°C. The structures of the PR‐based triblock copolymers and SCPRs were characterized by ¹H NMR, ¹³C CP/MAS, GPC and TGA analyses. The number‐average molecular weight of the resulting SCPRs was nearly three and five times of their precursor after linking with a low polydispersity index range of 1.08–1.28. The thermo‐responsive transition of both PR‐based supramolecular polymers in aqueous solution was demonstrated by turbidity measurements and the self‐aggregated morphologies were also evidenced by TEM observations.