The annulus oxygen material of more than 90% is to be based on double phenolic A (BPA) the reaction with annulus oxygen chloric propane, the aether of 2 shrink glycerine that produces double phenolic A (DGEBA) . Double phenolic A is a kind of petro-chemical compound, it is a kind of estrogen suffers body Jie to fight an agent. Accordingly, BPA is lured to change to cause cancer by classify agent and again noxiousness material (CMR) , get in a lot of countries the tie of restricted code. Empty spaceflight of dedicated Yu Hang and space apply, well-known, the data of hot solid sex that uses in these domains is had good thermomechanical function, fight as hygroscopic, good as substrate and fibrous compatibility to wait.
Study train of thought:
1, sweetgrass alcohol aether of 2 shrink glycerine is mixed a benzene 3 phenol monomer of 3 annulus oxygen and 6 hydrogen - benzene of 4- methylic adjacent anhydride of 2 formic acid or methylic naphthalene cross-linking of 2 acid anhydride, reaction by Zun of 1- methylic Mi (1MIM) or 2- second base - Zun of 4- methylic Mi (2E4M) cause.
2, devise a simple solidify plan, this means low aggregate temperature, expanding to industrial dimensions is feasible.
Study content:
1, former stock
2, annulus oxygen / the solidify behavior of acid anhydride system
The main purpose that DSC studies is the optimal parameter of the solidify after the solidify that devises a recipe certainly is mixed. According to the research that already reported, the solidify temperature interval that the epoxy resin in aerospace application makes is in 120 to 135°C between, can raise 180°C. Compare with recipe photograph with what contain DGEVA, the reaction of the recipe that is based on TGPh and MNA or HMPA acid anhydride is initial temperature is inferior, it is 60−75°C about. In the meantime, with DGEVA recipe (ΔTreaction ～ 80°C) photograph comparing, the recipe that is based on TGPh has bigger solidify temperature interval (ΔTreact ～ 160°C) . These results likelihood and TGPh ～ 3.6 with DGEVA ～ the functionality with 2 taller than having photographs is concerned. To TGPh and DGEVA system, the solidify behavior of the recipe that causes by 1MIM appears the complex and radiative peak that has humeral department, and in the recipe that causes by 2E4M, the feature that cross-linking reacts is individual and radiative peak. The existence of ministry of the shoulder in main and radiative peak but the annulus oxygen that ascribe accompanies copolymerization all gets together. Accordingly, 2E4M is helpful for annulus oxygen optionally here / reaction of acid anhydride copolymerization, form the polyester that takes dominant place to heat up solid sex colophony.
Another related to the reactivity of compound important parameter is the T peak value of DSC radiative peak; Tpeak cost is lower, the reactivity of mixture is taller. To TGPh and DGEVA recipe, with the solidify of HMPA acid anhydride the reaction of reaction comparing and MNA acid anhydride provides reactivity slightly. The ΔH that studies a system undertakes through the area that leaves to radiative peak integral will decide. Still can see, the reaction enthalpy of mixture gets rarely normally the influence of initator property, besides DGEVA−HMPA system, among them 2E4M is mixed in taller ΔH, lower T peak value ΔT action aspect is more significant.
3, the thermodynamic function of hot solid of oxygen of biology radical annulus
TGPh system conducts the same trend of segment of shorter cable length between more concentrated cross-linking, and the feature of DGEVA material is rub the network with the extract with Er higher quality and smaller density. Accordingly, annulus oxygen functionality is right advocate the formation of the chroma of catenary, network and final structure are having main effect.
The cross-linking density of polymer network also with damp factor (Tanδ ) amplitude concerns: Peak value amplitude is smaller, the tigidity of material is bigger. Tanδ and macroscopical Tg change are concerned, depend on all sorts of mix physico-chemically mechanical element. The photograph of colophony of hot solid sex that develops with use DGEVA is compared, TGPh heats up solid sex colophony to have higher Tanδ cost, have lower peak value amplitude and wider curve. With duplex DGEVA element photograph is compared, the 3 functions sex of TGPh brought about the development of more compact network, the catenary between cross-linking paragraph inferior, but overshoot there also are more blames in Cheng too in α- time of even relax comfort.
Between Tanδ and Tg result first-rate dependency, tg is worth resinous of sex of TGPh hot solid very tall, it is 180−210°C about. Compare with these colophony photographs, the material that use DGEVA develops shows inferior Tg value, limits is in 96 to 108°C between.
4, the thermal stability of annulus oxygen condensate
Normally, the first pace of degradation is decomposed with what small element measures constituent about, be like MNA/HMPA stiffening agent or 1MIM/2E4M initator. The thermal stability material and the cross-linking behavior connection that DSC studies rise, can observe, the recipe that contains HMPA shows excel to contain the reaction enthalpy of the recipe of MNA, this be related is solid besides chemical structure, affect the little difference with initiative hot degradation possibly still. Main degradation move occurs inside the 250 temperature limits to 540°C. Peak value of rate of the biggest degradation can be in TGPh resinous 369−379°C left and right sides observes, and the Tdmax of DGEVA system can observe below 399−409°C, this depends on the property of acid anhydride. The first phase represented main degradation step, heat up solution namely, MNA is 60% to 70% , HMPA is the 72% quality loss per cent to the material of 84% . In this one measure, network structure produces hot solution, adipose catenary ruptures, young member loss. Quality caustic break an appointment happens in 560°C above for the phase of the 2nd degradation of 15−35% , this is the feature that key of fragrant annulus, C−C and other and luscious group heat up oxidation degradation.
5, the biology that annulus oxygen heats up solid sex material base carbolic content (BCC) with bibulous rate
Content of biology radical carbon (BCC) it is affirmatory on the research foundation of the person such as Pan, calculated in the first pace among them the carbolic per cent of every kinds of compound, calculated next the biology of all recipes base charcoal content. The article monomer of oxygen of two kinds of annulus is by but the benzene between second birth compound 3 phenol and sweetgrass aldehyde alcohol and biology base annulus oxygen chloric propane (it is with glycerine but second birth raw material is produced) shrink glycerine changes complex compound, accordingly they are 100% biology base, and HMPA and MNA also are 100% petrifaction base compound. The live thing that designs a system base organic carbon (BOC) data rank is expressed 4 in. To the material of all development, the value that can see BCC is more adjacent, limits is in 55% to 61% between. 25% what foregone biology pledges plastic the smallest acceptability percentage is material gross weight about actually. Accordingly, the TGPH of the design and sex of DGEVA hot solid are plastic and contented what require a level.
The WAs of material reachs saturated level after immersing about 300 hours. Bibulous value is in 1.5% and 1.95% between, besides TGPh-MNA_2E4M matrix, its achieve the water content balance of about 2.8% after immersing 15 days.
Study conclusion:
1, came true TGPh and DGEVA monomer have the acid anhydride from the powerful latent capacity that can acquire in renewable resources with two kinds, 6 hydrogen - benzene of 4- methylic adjacent anhydride of 2 formic acid and methylic naphthalene copolymerization of 2 acid anhydride. The recipe of all tests shows tall reactivity in DSC, the initiative temperature limits of TGPh recipe is 35 to 60°C, DGEVA recipe is 70 to 90°C, highest reaction temperature is 115−150°C about. These solidify parameter are brought about designed to upgrade feasibly plan.
2, the Chu Nengmo value of a quantity that data of obtains hot solid sex issues in 30°C is between 2.7~3.1GPa. The Tg value of the material that is based on DGEVA is in 96 to 108°C between, the Tg value of the material that is based on TGPh is in 189 to 210°C between. Shore D hardness checks the tall hardness that confirmed these data, acquisition value is 80−89 SD, can classify is exceed hard data.
3, after immersing for long in water, develops material shows particularly good moistureproof sex, the biggest water absorption after 15 days is about 2.8% . Material of designs hot solid sex also shows tall gel content, the gel content of almost all system > 99% . 4, be designed successfully and developed come from biology radical and but of renewable resources have good mix physico-chemically thermomechanical the new-style colophony of function. These material become what replace fossil data in the essential industry such as car, naval, aerospace and spaceflight to be able to await select material to expect continuously.
Document information:
Roxana Dinu, ugo Lafont, olivier Damiano, and Alice Mija, high Glass Transition Materials From Sustainable Epoxy Resins WithPotential Applications In The Aerospace And Space Sectors. ACS Appl. Polym. Mater. 2022, 4, 3636−3646DOI: 10.1021/acsapm.2c00183