The Curing for Modified Vinyl Ester Resin by Hexamethylene Diisocyanate and Its Influence on Performances

The commercial vinyl ester resins(VER)was modified by diphenylmethane diisocyanate(MDI)to enhance its toughness,which is called MVER.Hexamethylene diisocyanate(HDI),a common curing agent for polyurethane(PU),was found to be a reactive agent for MVER and can contribute to the toughness of MVER.Based on present experiment results,the crosslinking mechanism of MVER and HDI system is very similar to that of PU.The FTIR result shows the-NCO of HDI can react with the-OH of MVER.The microstructure of material prepared by MVER and HDI was characterized by NMR,and it was revealed that the unique microstructure leads to the good performances.The different content of HDI has an influence on the microstructure,and the microstructure gradually reduces the toughness and mechanical performances of the MVER cured with increasing concentration of reactive curing agent(HDI).This feature is consistent with a maximum in toughness as a function of the additive(HDI)content,followed by a rapid deterioration in toughness at higher concentrations.The toughness exhibits the maximum at such an HDI concentration(20wt%).Therefore,the special curing agent(HDI)and reactive mode is very important to the microstructure and mechanical properties of material.Furthermore,there should be other reactions which contribute to the curing and microstructure of the material,which needs the further research.

Preparation of Environmentally Friendly Urea-Hexanediamine-Glyoxal(HUG)Resin Wood Adhesive

Using non-toxic,low-volatile glyoxal to completely replace formaldehyde for preparing urea-glyoxal(UG)resin adhesive is a hot research topic that could be of great interest for the wood industry.However,urea-glyoxal(UG)resins prepared by just using glyoxal instead of formaldehyde usually yields a lower degree of polymerization.This results in a poorer bonding performance and water resistance of UG resins.A good solution is to pre-react urea to preform polyurea molecules presenting already a certain degree of polymerization,and then to condense these with glyoxal to obtain a novel UG resin.Therefore,in this present work,the urea was reacted with hexamethylene diamine to form a polyurea named HU,and then this was used to react it with different amounts of glyoxal to synthesize hexamethylenediamine-urea-glyoxal(HUG)polycondensation resins,and to use this for bonding plywood.The results show that the glyoxal can well react with HU polyuria via addition and schiff base reaction,and also the HUG resin exhibits excellent bonding strength and water resistance.The shear strength of the plywood bonded with this HUG at 160°C hot press temperature as high as 1.93 MPa,2.16 MPa and 1.61 MPa,respectively,which meets the requirement of the China national standard GB/T 9846-2015(≥0.7 MPa),and can be a good choice as a wood adhesive for industrial application.

Zn-Co bimetallic supported ZSM-5 catalyst for phosgene-free synthesis of hexamethylene–1,6–diisocyanate by thermal decomposition of hexamethylene–1,6–dicarbamate

A set of mono-and bimetallic（Zn-Co） supported ZSM-5 catalysts was first prepared by PEG-additive method. The physicochemical properties of the catalysts were investigated by FTIR, XPS, XRD, N2adsorption-desorption measurements, SEM, EDS and NH3-TPD techniques. The physicochemical properties showed that the Zn Co2O4 spinel oxide was formed on the ZSM-5 support and provided effectual synergetic effect between Zn and Co species for the bimetallic catalyst. Furthermore, bimetallic supported ZSM-5 catalyst exhibited weak, moderate and strong acidic sites, while the monometallic supported ZSM-5 catalyst showed only weak and moderate or strong acidic sites. Their catalytic performances for thermal decomposition of hexamethylene–1,6–dicarbamate（HDC） to hexamethylene–1,6–diisocyanate（HDI） were then studied. It was found that the bimetallic supported ZSM-5 catalysts,especially Zn-2Co/ZSM-5 catalyst showed excellent catalytic performance due to the good synergetic effect between Co and Zn species, which provided a suitable contribution of acidic sites. HDC conversion of 100% with HDI selectivity of 91.2% and by-products selectivity of 1.3% could be achieved within short reaction time of 2.5 h over Zn-2Co/ZSM-5 catalyst.

Photosensitizer conjugate-functionalized poly(hexamethylene guanidine) for potentiated broad-spectrum bacterial inhibition and enhanced biocompatibility

Pathogen infection is the main cause of human morbidity and death.Traditional antibiotics usually sterilize bacteria in chemical ways,which tends to develop serious antibiotic resistance.Cationic polymers exhibit good bacterial inhibition with less resistance,but often face severe cytotoxicity toward normal cells.The optimization of polymeric antimicrobials for enhanced bactericidal capacity and improved biocompatibility is quite meaningful.In addition,photodynamic therapy(PDT) is a therapeutic modality with less susceptibility to develop resistance.Herein,a typical commercial polymeric antimicrobial,polyhexamethylene guanidine(PHMG) was selected for current proof-of-concept optimization due to its excellent bactericidal capacity but moderate biocompatibility.Eosin-Y(EoS)was copolymerized to afford EoS-labeled polymer conjugates,poly(2-(dimethylamino) ethyl methacrylate-co-eosin),P(DMAEMA-co-EoS),which was conjugated with PHMG to afford a novel polymeric antimicrobial,P(DMAEMA-co-EoS)-b-PHMG-b-P(DMAEMA-co-EoS),noted as PEoS-PHMG.It could efficiently kill broad-spectrum bacteria by physical damage and photodynamic therapy.Compared with PHMG,the bacterial inhibition of PEoS-PHMG was potentiated after the functionalization.Furthermore,PEoS-PHMG exhibited low cytotoxicity and minimal hemolysis,which was demonstrated by cell viability assays toward LO2 cells and RAW 264.7 cells as well as hemolytic assays against red blood cells.These results confirmed that the resultant PEoS-PHMG could act as promising alternative antibacterial materials with excellent broad-spectrum bacterial inhibition and favorable biocompatibility.

LIQUID CRYSTALLINE PROPERTIES OF POLY (PHENYLENE TEREPHTHALATE-COHEXAMETHYLENE TEREPHTHALATE)

One of the most attractive recent developments in polymer chemistry is the observation of liquid crystallinity in aromatic polyesters and polyamides. The aromatic polyesters showing thermotropic behavior offer important utility in the

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 Pluronie 17R4 with a varying amount of a-cyclodextrins （a-CDs） in the presence of CuCI/PMDETA at 25 ℃ in aqueous solution. The a-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 ℃. The structures of the PR-based triblock copolymers and SCPRs were characterized by 1H NMR, 13C CP/MAS, GPC and TGA analy- ses. 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.

Surface Modification of Commercial Aromatic Polyamide Reverse Osmosis Membranes by Crosslinking Treatments

Crosslinking treatments for a commercially available aromatic polyamide reverse osmosis membrane were carried out to improve its chlorine resistance.The crosslinking agents including 1,6-hexanediol diglycidyl ether,adipoyl dichloride and hexamethylene diisocyanate ester with long flexible aliphatic chains and high reactivity with N-H groups were used in the experiments.Attenuated total reflective Fourier transform infrared spectra verified the successful preparation of highly crosslinked membranes by crosslinking treatments.It was suggested that the crosslinking agents were connected to membrane surface through the reactions with amine and amide Ⅱ groups,which is confirmed by surface charge measurements.Based on contact angle measurements,crosslinking treatments decreased membrane hydrophilicity by introducing methylene groups to membrane surface.With increasing amount of crosslinking agent molecules connected to membrane surface,the hydrolysis of unconnected functional groups of crosslinking agent produced polar groups and increased membrane hydrophilicity.The highly crosslinked membranes showed higher salt rejections and lower water fluxes as compared with the raw membrane.Since the active sites(N-H groups) vulnerable to free chlorine on membrane surface were eliminated by crosslinking treatments,the chlorine resistances of the highly crosslinked membranes were significantly improved by slighter changes in both water fluxes and salt rejections after chlorination.

Aberrant expression of nuclear matrix proteins during HMBA-induced differentiation of gastric cancer cells

AIM: To investigate the aberrant expression of nuclear matrix proteins in human gastric cancer cells before and after hexamethylene bisacetamide (HMBA) treatment.METHODS: Proteomics analysis of differential nuclear matrix proteins was performed by two dimensional electrophoresis polyacrylamide gel electrophoresis and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.The expression levels of three nuclear matrix proteins were further confirmed by Western blotting and their locations in nuclear matrix filament were observed by quantum dots-based immunofluorescence.RESULTS: Proteomics analysis showed that 43 protein spots were significantly changed due to HMBA treatment.Fifteen proteins were identified in the HMBAinduced differentiation of gastric tumor cells.Eight proteins spots were down-regulated while seven were up-regulated.Among these proteins,prohibitin,nucleophosmin and hnRNP A2/B1 were significantly decreased in HMBA-treated human gastric cancer cells,and their locations in nuclear matrix were altered by HMBA.Our results proved the alteration of specific nuclear matrix proteins during the differentiation of human gastric cancer cells.And the aberrant expressions of nuclear matrix proteins were of significance in revealing the regulatory mechanism of tumor cell proliferation and differentiation.CONCLUSION: The aberrant expressions and intracellular redistributions of nuclear matrix proteins before and after HMBA treatment indicated that nuclear matrix proteins play a pivotal role in the differentiation of gastric cancer cells.

Curing reaction and mechanism of phenol-formaldehyde novolac resins for foundry

In this study on the curing dynamics of phenol-formaldehyde novolac resins(PFNR) and hexamethylene tetramine(HMTA), two typical commercial PFNR were selected as examples and the curing reactions of the resins with HMTA were studied by differential scanning calorimetry(DSC). Based on the data calculated by the Kissinger equation and the Crane equation, a thermocuring dynamic model was established, from which the process conditions, activation energy, reaction kinetics equation and a f irst-order reaction of the curing reactions were derived.

Effects of Plasticizers,Antioxidants and Burning Rate Modifiers on Aging Performance of the HTPB/HMDI Composite Solid Propellant

The effects of plasticizers,antioxidants and burning rate modifiers on the aging performance of the composite solid propellant based on hydroxyl-terminated polybutadiene(HTPB)/hexamethylene diisocyanate(HMDI)were explored by apply-ing an accelerated aging program for 90 day at 70 ℃. The HTPB propellant matrix with the diisooctyl sebacate(DOS)as plasti-cizers and diisooctyl azelate(DOZ), antioxidants as N,N ′-Diphenyl-p-phenylenediamine(AO) and 2,2′-methylenebis(4-methyl-6-tert-butylphenol)(cyanox 2246)and burning rate modifiers as barium ferrite(BF),copper chromites(CC)and fer-ric oxide(FO)were varied. Results show that sample(S1)which based on DOS decreases the stress value and increases the strain value which considered to be an excellent start for aging program. Sample(S3)containing AO presents the higher resis-tance to oxidation showing the better performance that reflects on increasing the shelf life of the composite solid propellant mo-tor. Sample(S5)which based on BF enhances the ballistic performance among over the other tested two samples. The accelerat-ed aging program allowed us to estimate the motor in-service lifetime.

A ONE-STEP SURFACE MODIFICATION PROCEDURE TO PEG-GRAFTED NANO-TITANIA

PEG （Polyethylene Glycol）-grafted nano-titania has been obtained in a one-step procedure using hexamethylene diisocyanate as the coupling agent and dibutyltin dilaurate as the catalyst in toluene at 80℃ and characterized qualitatively by FTIR and quantitatively by elemental analysis and thermogravimetric analysis. A comparison of nano-titania with two other commonly used inorganic nanoparticles, nano-silica and nano-alumina, is made, revealing that reactivity order is nano- silica 〉 nano-alumina 〉 nano-titania in view of PEG grafting. Possible mechanism of PEG grafting is also discussed.

Synthesis and Characterization of HDI/MDI-Polycarbonate Urethanes

A novel polycarbonate urethane was synthesized by the two-stage solution process of diisocyanates with polycarbonate diols(PCDL),in which PCDL,1,4-butanediol(BD) and mixture of 4,4 -methylenediphenyl diisocy-anate and hexamethylene diisocyanate(HDI) were soft segment,chain extender and rigid segment,respectively.The structures were characterized by using FTIR and 1H-NMR.The thermoanalysis and mechanical properties of products were measured by means of DSC,TG and other systems.The result shows that an import...

The Influence of Aziridine on the Aging of Composite Solid Rocket Propellant

Aging of a solid composite propellant containing HTPB/AP/AL was performed in order to validate the conformance of the accelerated aging data to the Arrhenius law. The main objective of the work was to examine the influence of the aziridine bonding agents family on the propellant aging. Aging of the prepared propellant samples was conducted as follows: 1. Four samples, one free of bonding agents, and three containing aziridine based bonding agents MAPO,HX-752, MAT4 were aged at 65°C. 2. Another four samples based on HX-752, MAT4 with different curing agents were aged at 65°C. The measured mechanical properties of the free bonding agent propellant samples were very far from the specifications and this illustrates the importance of the bonding agents in both the preparation and the aging phases.The prepared bonding agent 'MAT4' gave remarkable improvements of the mechanical properties comparing with HX-752 and MAPO. The aziridine bonding agents family inhibited the rate of decomposition of the propellant during the aging periods and supported the propellant matrix against decomposition at the elevate temperatures. Using of HMDI as curing agent gave slight better mechanical properties to the IPDI.