氨酯反应喷射模塑工艺——新颖、先进的FRP船成型工艺

本文简要介绍了氨酯反应喷射模塑(RSM)工艺概况,聚氨酯(PUR)的种类、聚酯/PUR混杂系统材料,RSD的主要工艺参数、生产设备、制品实例等。

Recent advances in fixation of CO_(2) into organic carbamates through multicomponent reaction strategies

Carbon dioxide(CO_(2)) is the main greenhouse gas and also an ideal C1 feedstock in organic synthesis because it is abundant,nontoxic,nonflammable,and renewable.The synthesis of organic carbamates using CO_(2) as a phosgene alternative has attracted extensive attention because of the importance of carbamates in organic synthesis and in the pharmaceutical and agrochemical industries.In recent decades,many multicomponent reaction strategies have been designed for constructing different types of organic carbamate molecules.Most of these methods rely on the in situ generation of carbamate anions from CO_(2) and amines,followed by reactions with other coupling partners.Synthetic strategies for acyclic carbamates include nucleophile‐electrophile coupling,nucleo‐phile‐nucleophile oxidative coupling,difunctionalization of unsaturated hydrocarbons,and C–H bond functionalization.Strategies for the synthesizing cyclic carbamates include carboxylative cyclization of in situ‐generated unsaturated amines and difunctionalization of unsaturated amines with CO_(2) and other electrophilic reagents.This review summarizes the recent advances in the synthesis of organic carbamates from CO_(2) using different multicomponent reaction strategies.Future perspectives and challenges in the incorporation of CO_(2) into carbamates are also presented.

Synthesis of Waterborne Polyurethane Modified by Nano-SiO_2 Silicone and Properties of the WPU Coated RDX

A series of nano silica/silicone modified waterborne polyurethane(WPU) have been synthesized from polytetramethylene glycol and isophorone diisocyanate, dihydroxymethyl propionic acid and triethylamine, ethylenediamine, trimethylolpropane, nano-SiO2 and the silane coupling agent KH550. The effect of the dosage of nano-SiO2 on the WPU-Si membrane and the coated RDX(cyclotrimethylenetrinitramine) particles have been studied in terms of their surface properties, mechanical properties, and thermal stability. The results showed that with the increase of Si content, the stability of the emulsion reduced gradually. The material with more Si content displayed an increased thermodynamic stability, an increased high temperature resistance, an increased tensile strength and a decreased elongation at break. With the increase of Si content, the surface tension of the material decreased, the bibulous rate reduced, and the contact angle increased gradually, so that the surface tension of the polyurethane and RDX are close to each other which could improve the performance of coating.

Kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to1,6-hexamethylene diisocyanate

The kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to 1,6-hexamethylene diisocyanate was studied. A consecutive reaction model was established and the reaction orders for the two steps were confirmed to be 1 and 1.3 by the integral test method and the numerical differential method, respectively. The activation energies of the two steps were （56.94 4±5.90） kJ·mol^-1 and （72.07±3.47） kJ·mol^-1 with the frequency factors exp（ 12.53±1.42） min^- 1 and （ 14.254±0.84） tool^-0.33. L^0.33·min^-1, respectively. Based on the kinetic model obtained, the progress of the reaction can be calculated under given conditions.

An efficient and facile synthesis of N-Cbz-β-aminoalkanesulfonamides

An efficient method for the synthesis of N-Cbz-β-aminoalkanesulfonamides was described.N-Cbz-β-aminoalkanesulfonamides were readily prepared in good yields from a variety of amino alcohols,including optically active ones,via N-Cbz protection with benzyl chloroformate,Mitsunobu esterification reaction with thiolacetic acid,N-chlorosuccinimide oxidation,and ammonolysis process.

Some recent advances in transition-metal-catalyzed ortho SP^2 C–H functionalization using Ru, Rh, and Pd

In the past decade,transition-metal-catalyzed C–H functionalization by weak coordination has emerged as a practical and powerful tool to access many valuable chemicals.Two classes of weakly coordinating directing groups,commonly occurring functional groups,and easily removable auxiliaries,have been found to be efficient and practical for C–H activation reactions.This mini-review contains examples of recent research advances on transition-metal-catalyzed SP2 C–H functionalization via weak coordination,using Ru,Rh,and Pd.A number of weakly coordinating functional groups(e.g.,ketone,ester,carbamate,tertiary amide,ether,thioether,alcohol,and some others)are covered.As the field of transition-metal-catalyzed C–H functionalization continues to develop and more synthetically useful chemo-,regio-,and enantioselective reactions catalyzed by transition metal via weak coordination are discovered,this promising and attractive strategy will play a more important role in modern organic synthesis.

In-depth study on aminolysis of poly(ε-caprolactone): Back to the fundamentals

The aminolysis can effectively introduce primary amine （- quent surface fiiofunctionalization reactions. However, less NH2） groups onto polyester materials, enabling a variety of subse- attention has been paid to the basic knowledge of aminolysis reac- tion in terms of reaction kinetics and its influences on materials properties. In this study, taking the widely used poly（e-caprolactone） （PCL） as a typical example, the influences of diamines and solvent property on the surface -NH2 density are firstly assessed by using X-ray photoelectron spectroscopy （XPS） and colorimetric analysis. Results show that smaller dia- mine molecules and nonpolar alcohols could accelerate the reaction. The reaction kinetics with 1,6-hexanediamine is further investigated as a function of temperature, reaction time, and diamine concentration. During the initial stage, the reaction shows a 1^st order kinetics with the diamine concentration and has an activation energy of 54.5 kJ/mol. Ionization state of the -NH2 groups on the PCL surface is determined, revealing that the pKa of -NH3^＋ （〈5） is much lower than that of the corresponding diamine molecules in solution. After aminolysis, surface hydrophilicity of PCL membrane is significantly enhanced, while surface elastic modulus and average molecular weight are decreased to some extent, and others such as weight, surface mor- phology and bulk mechanical strength are not apparently changed. The introduced -NH2 groups are found to be largely lost at 37 ℃, but can be mostly maintained at low temperature.

SmI_2-promoted imino-Reformatsky reaction for facile synthesis of enantioenriched β-amino acid esters

A facile and efficient method for the stereoselective synthesis of β-amino acid esters via SmI2-promoted imino-Reformatsky reaction is described.Asymmetric addition of tert-butyl bromoacetate to N-tert-butanesulfinyl aldimines afforded β-amino acid esters in moderate to high yields with excellent diastereoselectivities.The synthetic utilities of the tert-butyl β-amino acid esters were expanded by the preparation of β-lactams and 3-aminoindan-1-ones derivatives.

Enantioselective synthesis of β-amino esters bearing a quinazoline moiety via a Mannich-type reaction catalyzed by a cinchona alkaloid derivative

The cinchona alkaloids catalyzed the direct asymmetric Mannich reactions of 1, 3-dicarbonyl compounds with acyl imines to produce novel β-amino ester derivatives containing a quinazoline moiety. The adducts were isolated with high enantiomeric excess （up to 99%）.