Studies on polyoxymethylene dimethyl ethers production from dimethoxymethane and 1,3,5-trioxane over SO_(4)^(2-)/ZrO_(2)-TiO_(2)

Polyoxymethylene dimethyl ethers(OMEs)with physical properties similar to those of diesel has received significant attention as green additives for soot emission suppression.Herein,series of SO_(4)^(2-)/ZrO_(2)-TiO_(2)catalysts were developed for OMEs production from dimethoxymethane(DMM)and1,3,5-trioxane through sequential formaldehyde monomer insertion into C-O bond of DMM.Not Lewis but Bronsted acid sites were identified to be active for the decomposition of 1,3,5-trioxane into formaldehyde unit,however,both of them are effective for the chain propagation of DMM via formaldehyde unit insertion into C-O bond.Kinetic studies indicated each chain growth step exhibited the same parameters and activation barrier on corresponding Bronsted and Lewis acid sites due to the same reaction mechanism and very similar chemical structure of OMEs.Also,the catalytic stability investigation suggested the deactivation behavior was derived from the carbon deposition,and the decay factor could be exponentially correlated with the amount of coke accumulation.

Mechanism of chain propagation for the synthesis of polyoxymethylene dimethyl ethers

Polyoxymethylene dimethyl ethers(PODE)were synthesized from the reaction of paraformaldehyde with dimethoxymethane(DMM)over different acid catalysts at different conditions.Products were found to follow the Schulz-Flory distribution law.The chain propagation proceeds through the insertion of an individual segment of CH2O one by one,while the simultaneous insertion of a few CH2O segments or their assembly is unlikely.Due to the restriction of this law,it is difficult to increase the selectivity to the desired products(e.g.,PODE3 4).

Chemical equilibrium controlled synthesis of polyoxymethylene dimethyl ethers over sulfated titania

The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers （DMMn） were investigated over sulfated titania in order to reveal the decisive factor controlling the reaction. The results showed that the molar ratio of adjacent DMMn products in equilibrium solution had the same value, which depended absolutely on the reaction temperature. Meanwhile, the reactions had the same DMMn products distributions under varied reaction conditions. The equilibrium constants of the related step-wise reactions for DMMn formation were equal, which were calculated based on the bulk compositions of the reaction solution. And thus, the selectivity to DMMn was mainly controlled by the chemical equilibrium, i.e., thermodynamic control. In brief, the present results provide some guidance for future synthesis of DMMn.

A Synthesis, Process Optimization, and Mechanism Investigation for the Formation of Polyoxymethylene Dimethyl Ethers

Polyoxymethylene dimethyl ethers(DMM_n) are promising diesel additives. The synthesis of DMM_n from methylal(DMM) and paraformaldehyde over the NKC-9 acidic ion-exchange resin catalyst was investigated. Many unrecyclable by-products such as methyl formate, dimethyl ether and formic acid were produced in the reaction. To increase the selectivity of the desired products DMM_(3-6) and reduce the amount of unrecyclable by-products, the effects of reaction temperature, time, pressure and the molar ratio of the raw materials were evaluated through a series of single factor experiments. Experiments revealed that trace amount of water could suppress the formation of unrecyclable by-products, and the optimum initial water content(less than 2 wt%) was investigated. In addition, the synthetic process needs to go through the polyoxymethylene hemiformals intermediate stage, and then the DMM_n were obtained when polyoxymethylene hemiformals reacted with methanol. Ultimately, a possible mechanism is proposed to describe the formation of DMM_n from polyoxymethylene hemiformals in detail, in which it is revealed that the formation of carbocation intermediates is important in the reaction processes.

Brφsted-acidic ionic liquids as efficient catalysts for the synthesis of polyoxymethylene dialkyl ethers

Acetalation of formaldehyde(HCHO)with dialkyl formal or aliphatic alcohol to prepare polyoxymethylene dialkyl ethers(RO(CH2O)nR,n≥1)catalyzed by Br?nsted‐acidic ionic liquids has been developed.The correlation between the structure and acidity activity of various ionic liquids was studied.Among the ionic liquids investigated,1‐(4‐sulfonic acid)butyl‐3‐methylimidazolium hydrogen sulfate([MIMBs]HSO4)exhibited the best catalytic performance in the reaction of diethoxymethane(DEM1)with trioxane.The influences of ionic liquid loading,molar ratio of DEM1to HCHO,reaction temperature,pressure,time,and reactant source on the catalytic reaction were explored using[MIMBs]HSO4as the catalyst.Under the optimal conditions of n([MIMBs]HSO4):n(DEM1):n(HCHO)=1:80:80,140°C,and4h,the conversion of HCHO and selectivity for DEM2?8were92.6%and95.1%,respectively.The[MIMBs]HSO4catalyst could be easily separated and reused.A feasible mechanism for the catalytic performance of[MIMBs]HSO4was proposed.

Enhancement in Thermal Stability of Polyoxymethylene (POM)-Based Biopolymer Blend Materials

In this study, we demonstrate the enhancement in thermal stability of polyoxymethylene (POM)-based biopolymer blend materials. Polyoxymethylene (POM)/Polylactic acid (PLA) blends have been used as alternative biopolymer materials for supporting environmental problems with thermal stability feature. The effects on POM biopolymer blend materials with a controlled PLA amount in their compositions under various injection conditions, were investigated by thermogravimetric analysis, dynamic mechanical analysis, and differential scanning calorimetry. The POM/PLA biopolymer blend materials showed POM phase acted as a homogeneous nucleating site for increasing PLA crystallization, which improves storage modulus of the blend materials. The decomposition temperatures of POM/PLA biopolymer blends tend to shift around 30˚C - 50˚C lower compared to the decomposition temperatures of PLA. Thus, the decomposition temperature behavior of POM/PLA blends seems to be closer to POM. The suitable ratio in POM70/PLA30 resulted in the high strength of the blend materials. The POM/PLA biopolymer blend material was tested at various injection speeds and good miscibility was obtained at an injection speed of 100 mm/s. This enhancement of thermal stability in POM/PLA blend materials should be useful in the development of high-performance bio-based thermoplastic materials.

Controllable synthesis of polyoxymethylene dimethyl ethers by ionic liquids encapsulated in mesoporous SBA-16

The promising combustion and emission properties of polyoxymethylene dimethyl ethers(PODEn)are of significant interest.However,the synthesis of PODEn products with desired chain lengths is still a problem facing synthetic PODEn.Herein,a series of unique IL@SBA16Cx solid catalysts are prepared by encapsulation of ionic liquids(ILs)within the nanocage of SBA16 through a silylation method.The structure of the encapsulated catalyst was characterized by UVvis spectra,Fourier transform infrared(FTIR),N2 adsorptiondesorption isotherms,Powder Xray diffraction(XRD),Transmission electron microscopy(TEM)and Elemental analysis.The encapsulated catalysts show similar catalytic activity to the homogeneous counterparts and display higher selectivity to the targeted PODE35 products than their homogeneous counterparts in the synthesis of PODEn from methanol(MeOH)and trioxymethylene(TOM).The encapsulated catalysts exhibit a superior PODE35 selectivity and could be the promising catalysts for PODEn synthetic reaction.

The Friction Wear Properties and Application of Thermoplastic Polyester Elastomer and Polyoxymethylene

The experiment of injection molding, Dais-simulating test, morphological structure investigation(Scanning Electron Microscopy, SEM),X-ray photoelectron spectroscopy(XPS)were performed on mini-automobile spherical seat which was made of thermoplastic polyester elastomer(TPEE)and oiled polyoxymethylene(POM),respectively. The friction-wear properties between the frictionl pair of polymer spherical seat and metallic(iron)spherical pin were studied. The test results indicate that the antifriction property of TPEE is superior to that of POM, while its surface chemical effect is inferior to that of POM.

Study on the Miscibility and Phase Behavior of Polyoxymethylene with Novolak

The miscibility and phase behavior of the blends of polyoxymethylene (POM)/Novolak were investigated by the cloud point method, which showed that the POM/Novolak blends exhibited a lower critical solution temperature. The melting point of POM decreased when diluted with Novolak. From the melting temperature depression of POM, a negative interaction parameter (x) between POM and Novolak was obtained. The IR spectrum revealed that the miscibility between POM and Novolak was caused by the specific interaction between the OH groups of Novolak and the ether oxygen atoms of POM. The morphology of the blends investigated by polarized light microscopy showed that the size of spherulites of POM was sharply decreased by its mixing with Novolak. This suggests that Novolak be used as a compatibilizer for POM.

Formation kinetics of polyoxymethylene dimethyl ethers from methylal and trioxane with little water

Polyoxymethylene dimethyl ethers(CH_(3)-O-(CH_(2)O)_(n)-CH_(3),PODE_(n),n>1)can be added to diesel to reduce air pollution caused by incomplete combustion.Driven by this need,a cost-effective and efficient synthetic route is presented and investigated by this work for the production of PODE_(n),which are formed from methylal and trioxane with low water content(<10%(mass))over HZSM-5 catalyst in a batch slurry autoclave at the temperature from 353.15 K to 393.15 K.The reaction rate laws including the PODE_(n) and byproducts of polyoxymethylene hemiformals(HF_(n)),polyoxymethylene glycols(MG),methanol(MeOH)and methyl formate(MF)are developed.The rate constants of propagation step(k_(6))and depolymerization step(k_(-6))are assumed independent on polymerization degree of PODE_(n).The rate of reaction is proportional to the content of the catalyst(Wcat)for the catalytic reaction within the scope of the study.All kinetic parameters were estimated by combining genetic algorithm and least square regression to fit experimental data well.This work is valuable for process optimization and reactor design.

Polyoxymethylene dimethyl ethers synthesis from methanol and formaldehyde solution over one-pot synthesized spherical mesoporous sulfated zirconia

The synthesis of polyoxymethylene dimethyl ethers as an ideal diesel fuel additive is the current hot topic of modern petrochemical industry for their expedient properties in mitigating air pollutants emission during combustion.In this work,a series of spherical sulfated zirconia catalysts were prepared by a one-pot hydrothermal method assisted with surfactant cetyltrimethylammonium bromide(CTAB).The prepared sulfated zirconia catalysts were used to catalyze PODEn synthesis from methanol and formaldehyde solution.Various characterization(XRD,BET,SEM,TGA,NH_(3)-TPD,FTIR,and Py-IR)were employed to elaborate the structure–activity relationship of the studied catalytic system.The results demonstrated that S/Zr molar ratio in precursor solution played an effective role on catalyst morphology and acidic properties,where the weak Brønsted acid sites and strong Lewis acid sites were favorable to the conversion of methanol and formation of long-chain PODEn,respectively.The reaction parameters such as catalyst amount,molar ratio of FA/MeOH,reaction time,temperature and pressure were optimized.The speculated reaction pathway for PODEn synthesis was proposed based on the synergy of Brønsted and Lewis acid sites,which suggested that Brønsted and Lewis acid sites might be advantageous to the activation of polyoxymethylene hemiformals[CH_(3)(OCH_(2))_(n)OH]and methylene glycol(HOCH_(2)OH),respectively.

Investigation of the Thermal Decomposition Properties of Polyoxymethylene

By testing the melt index （MI）, tensile strength and breaking extension ratio, the thermal ageing rate of polyoxymethylene （POM） was analyzed and compared. The surface morphology and type of function group of POM surface were observed and analyzed by SEM and XPS. The results show that the MI value increases gradually with the ageing time at 120℃, indicating that the thermal oxidation decomposition occurrs slowly. The effect of 20-day thermal ageing on the tensile strength and breaking extension ratio of POM is not obvious, showing that the ageing of POM is quite a long process. After 105-day, thermal ageing cracking and powdering occurr on the POM surface. XPS determination shows the Cls spectra of samples before and after ageing include two peaks of C-C and C-O, while after ageing the content of C-C decreases and the content of C-O increases, indicating that the thermal ageing of POM is mainly the breaking and decomposing of C-C bond. The Ols/Cls ratio of original samples is 56.98% and after 105-day thermal ageing the ratio is 72.92%.

Mechanical and Morphological Properties of Polypropylene/Polyoxymethylene Blends

This work studies the mechanical and morphological properties of polypropylene (PP)/polyoxymethylene (POM) blends. The PP/POM blends were prepared by melting-blend with an internal mixer. The contents of PP were used at 10%, 20%, 30%, 70%, 80% and 90% by weight. The phase morphology of the blends was observed by scanning electron microscope (SEM) due to the mechanical properties depended on the phase morphology. The results show the decrease of the impact strength, Young’s modulus and tensile strength of POM/PP blends with increasing of PP content up to 30 wt% and then increase again with a high PP content. The percent strain at break of the blends increases after adding PP in a range of 70 - 90 wt%. SEM study reveals that the POM/PP blends clearly demonstrate a two-phase matrix-particle microstructure. The results also show that the domain size of dispersed PP or POM phase increases with increasing PP or POM content. The POM domain size is smaller than the PP domain size which leads to a little change of mechanical results of PP.

Investigation on combustion and emission characteristics of diesel polyoxymethylene dimethyl ethers blend fuels with exhaust gas recirculation and double injection strategy

As a kind of renewable and high oxygen content fuel,polyoxymethylene dimethyl ether(PODE)can be added in diesel to realize energy saving and emissions reduction.To evaluate the combustion and emission characteristics of a diesel engine fueled with diesel and diesel/PODE mixtures,exhaust gas recirculation(EGR)and main-pilot injection strategies with various injection timings were applied.PODE was blended with diesel by volume to form mixtures which were marked as D100(pure diesel),D90P10(90%diesel+10%PODE),and D80P20(80%diesel+20%PODE).The results showed that the ignition delay(ID)and combustion duration(CD)of D80P20 were the shortest because of the highest cetane number(CN)and high oxygen content of PODE,indicating more concentrated heat release.At low and medium loads,D80P20 achieved the highest peak heat release ratio(PHRR)and peak combustion temperature(PCT)among the three fuels,and it was 14.3%and 3.6%higher than those of D100.PODE blending with diesel can significantly reduce particulate matter(PM)and D80P20 has the lowest PM emissions at all loads.Compared with D100,both PM and nitrogen oxide(NO_(x))emissions of PODE blends decreased simultaneously with 20%EGR at all loads.With the increase of pilot-main interval,the ID and CD of all test fuels increased,while the NO_(x)and PM emissions decreased.The conclusions of the present research provide a state of the application in light-duty engines fueled with diesel/PODE blends in future work.

Optical investigation on polyoxymethylene dimethyl ethers spray flame at different oxygen levels in a constant volume vessel

In this paper,high-speed imaging and spectrometry diagnostics were used to study the spray flame structures and emission spectra of polyoxymethylene dimethyl ethers(PODE)in an optical constant volume vessel.The effects of oxygen volume fraction(15%to 80%)on some typical combustion characteristics such as spatially integrated natural intensity,flame propagation speed,lift-off length and the distribution of flame emission spectra were investigated.The results show that the PODE spray flame mainly exhibits blue chemiluminescence,which is different from the diesel yellow diffusion flame dominated by soot radiation.As the oxygen concentration increases,the flame natural luminosity and propagation speed increases,the position of lift-off region and flame tip move towards the injector nozzle,and the flame width becomes narrower.According to the spectral results,the blue chemiluminescence generated by carbon monoxide oxidation dominates the PODE flame luminescence,suggesting that no soot is formed.The increase in oxygen concentration leads to enlarged intensity and gradient of PODE flame radiation.In summary,the combination of PODE and oxygen-enriched combustion shows no soot formation and promotes the oxidation of carbon monoxide and unburned hydrocarbon.This study can provide more insights into PODE spray combustion,and offer guidelines for achieving efficient and clean combustion.

An experimental and modeling study on polyoxymethylene dimethyl ether 3(PODE_(3))oxidation in a jet stirred reactor

Polyoxymethylene dimethyl ether(PODE n,n≥1)is a class of oxygenated fuels containing unique carbon-oxygen chain structure and a promising alternative fuel for diesel engines.In this study,low-temperature oxidation characteristics of PODE_(3) were studied experimentally and numerically.Experiments were performed in a jet-stirred reactor(JSR)at equivalence ratios of 0.5,1.0 and 2.0,in the temperature range of 500 to 950 K,and at atmospheric pressure.Mole fractions of PODE_(3),O_(2),H_(2),CO,CO_(2),CH_(3) OH and C_(1)-C_(2) hydrocarbons were measured by gas chromatograph(GC).Experimental measurements were compared with the simulation results based on two literature low-temperature oxidation models,denoted as the He model and the Cai model,respectively.Good agreement was obtained between the measured and simulated fuel consumption profiles,while a deviation was observed between the experimental and simulation results on the mole fractions of O_(2) and intermediate products at medium temperatures.Reaction pathway analyses based on the two models were performed,revealing that the second O_(2)-addition reaction pathway is more significant in the prediction by the Cai model than that by the He model.Sensitivity analyses pointed out that the most important reactions affecting fuel consumption are the H-abstraction reactions of PODE_(3),and the decomposition of H_(2) O_(2) and the consumption of CH_(2)O become more sensitive at medium temperatures.

聚甲醛的耐候改性及其光稳定性研究

以受阻胺光稳定剂和紫外线吸收剂对聚甲醛(POM)进行光稳定化耐候改性,并对制得的耐候POM的力学性能和人工加速老化行为进行了测试和评价。结果表明,经氙灯人工加速老化1000h后,试样的拉伸强度保持率、断裂伸长率保持率和缺口冲击强度保持率分别达到103%、76.2%和84.4%,色差由7.6减小至0.8,远优于未经光稳定化处理的POM的相应性能。

Semi-analytical calculation model for friction of polymers on the example of POM|PE-UHMW and steel|PE-UHMW

In this paper,a semi-analytical calculation model for the coefficient of friction(COF)of single spherical protrusions is presented.It allows the prediction of the deformative friction part(μ_(def))and adhesive friction part(μ_(def))of the friction pairings steel|polyethylene with ultra-high molecular weight(PE-UHMW)and polyoxymethylene(POM)|PE-UHMW.The experimental studies included unlubricated friction tests,which served to determine the total COF(μ_(def)),as well as tests being lubricated with silicone oil,from whichμ_(def)is obtained.Based on the verification tests,it could be shown that both states of lubrication result in the same deformation and that the relationship between the rear angle(w)andμ_(def)postulated in the calculation model is valid.Therefore,friction tests with segmented spheres were carried out,which allow a specific variation of thew.It can be concluded that for both pairings theμ_(def)is generally of minor significance(approx.1/3μ_(tot))and the influence of theμ_(adh)predominates(approx.2/3μ_(tot))the friction process.Furthermore themtot decreases with increasing contact pressure especially in the low pressure range and depends on the form of motion(continuous and discontinuous).

A calculation method for friction coefficient and meshing efficiency of plastic line gear pair under dry friction conditions

A calculation method for the friction coefficient and meshing efficiency of plastic line gear(LG)pair under dry friction conditions was studied theoretically and experimentally,taking a polyoxymethylene parallel line gear pair(POM PLGP)as an example.Firstly,the geometric and mechanical models of PLGP were built by considering the effects of misalignment and loaded deformation under the actual operating condition.Then,the friction coefficient of POM specimens was obtained via the ball-on-disk experiment,of which the value varies between 0.35 and 0.45 under the experimental conditions.The calculation formula for the friction coefficient of POM LG pair was obtained by fitting the friction coefficient of the POM specimens,and the meshing efficiency of POM LG pair was calculated based on the calculation formula for friction coefficient and the meshing efficiency calculation approach.Finally,the meshing efficiency of POM PLGP specimens was measured using a homemade gear meshing efficiency test rig.The experimental results validated the feasibility of the proposed calculation method for the friction coefficient and meshing efficiency of the plastic LG pair.This study provides a method for the calculation of the friction coefficient and meshing efficiency of plastic gear pairs under dry friction conditions.It also provides the basis for the wear calculation of plastic LG pair under dry friction conditions.