Amorphous and Crystallizable Thermoplastic Polyureas Synthesized through a One-pot Non-isocyanate Route

A simple one-pot non-isocyanate route for synthesizing thermoplastic polyureas is presented. In situ urethanization was conducted from the ring-opening reaction of ethylene carbonate with poly(propylene glycol) bis(2-aminopropyl ether) and hexanediamine,m-xylylenediamine, or diethylene glycol bis(3-aminopropyl) ether at 100 °C for 6 h under normal pressure. Melt transurethane polycondensation was successively conducted at 170 °C under a reduced pressure of 399 Pa for different time periods. A series of nonisocyanate thermoplastic polyureas(NI-TPUreas) were prepared. The NI-TPUreas were characterized by gel permeation chromatography,FTIR, 1 H-NMR, differential scanning calorimetry, thermogravimetric analysis, wide-angle X-ray diffraction, atomic force microscopy,and tensile test. NI-TPUreas exhibited Mn of up to 1.67 × 104 g/mol, initial decomposition temperature over 290 °C, and tensile strength of up to 32 MPa. Several crystallizable NI-TPUreas exhibited Tm exceeding 98 °C. NI-TPUreas with good thermal and mechanical properties were prepared through a green and simple one-pot non-isocyanate route.

A Well-defined Hierarchical Hydrogen Bonding Strategy to Polyureas with Simultaneously Improved Strength and Toughness

A well-defined quadruple hydrogen bonding strategy involving dimerization of 2-ureido-4[1H]-pyrimidone(UPy)units is innovatively designed to prepare polyureas with high overall mechanical properties.Three polyureas containing different amounts of UPy units were synthesized by replacing a portion of isophorone diisocyanate(IPDI)with a UPy-derived diisocyanate.The formation of quadruple hydrogen bonds in hard segments via UPy dimers was confirmed by nuclear magnetic resonance(NMR)and Fourier transform infrared spectroscopy(FTIR).The mechanical properties of the polyureas were evaluated by uniaxial tensile testing.Compared to the polyurea without UPy units,remarkable improvements in Young’s modulus,tensile strength,and toughness were simultaneously achieved when UPy units were incorporated.The mechanism behind the strong strengthening effect rooted in the stronger intermolecular forces among hard segments brought by the quadruple hydrogen bonds,which were stronger than the inherent bidentate and monodentate hydrogen bonds among urea groups,and the slower soft segmental dynamics reaveled by both increased Tg and relaxation time of the soft segments.The mechanism behind the strong toughening effect was ascribed to more effective energy dissipation brought by the quadruple hydrogen bonds that served as stronger sacrificial bonds upon deformation.This work may offer new insight into the design of polyurea elastomers with comprehensively improved mechanical properties.

Synthesis and Characterization of Polyureas from Aniline Trimer with TDI, MDI and HDI as pH Sensitive Materials

A series of polyureas were synthesized through the reaction of aniline trimer with toluene-diisocyanate, diphenylmethane-4,4＇-diisocyanate, and hexamethylene-l,6-diisocyanate, respectively. The chemical structure of these polyureas was characterized and verified by FT-IR, ^1H NMR, elemental analysis, UV, XRD and CV. The conductivity of these polyureas ranged from 10^-7 to 10^-6 S/cm measured by four-point-probe instrument. Compared to the standalone aniline trimer, the stability （thermal stability and electrochemical stability）, response range and sensitivity of these polyureas are enhanced. The sensitivity of these polyureas DMF solution to pH value is superior to that of the standalone aniline trimer. The color of the polyureas DMF solution is greatly depended on pH value and the color change process is reversible, whenever from base to acid or from acid to base. These enhance- ments may give these polyureas more opportunities in order to be used as sensor materials.

NMR Analysis to Identify Biuret Groups in Common Polyureas

Polyureas （PU） are well known as a class of high impact engineering materials, and widely used also in emerging advanced applications. As a general observation, most of them are only soluble in a very limited number of highly protonic solvents, which makes their chemical structure analysis a great challenge. Besides the presence of abundant hydrogen bonding, the poor solubility of PU in common organic solvents is often ascribed to the formation of biuret crosslinking in their molecular chains. To clarify the presence of biuret groups in PU has been of great interest. To this end, two samples, based on hexamethylene diisocyanate （HDI） and toluene diisocyanate （TDI） respectively, were synthesized by precipitation polymerization of each of these diisocyanates in water-acetone at 30℃. Their chemical structures were analyzed by high resolution magic angle spinning （HR-MAS） NMR, and through comparison of their NMR spectra with those of specially prepared biuret-containing polyurea oligomers, it was concluded that biuret group was absent in all the PU prepared at 30 ℃. In addition, this NMR analysis was also applied to a PU obtained by copolymerization of TDI with ethylene diamine （EDA） and water at 65 ℃ in EDA aqueous solution. It was confirmed that biuret unit was also absent in this PU and that EDA was more active than water towards TDI. The presence of EDA was crucial to the formation of uniform PU microspheres. This study provides therefore a reliable method for the analysis of PU chemical structure.

Experimental investigation on weak shock wave mitigation characteristics of flexible polyurethane foam and polyurea

In recent years,explosion shock wave has been considered as a signature injury of the current military conflicts.Although strong shock wave is lethal to the human body,weak shock wave can cause many more lasting consequences.To investigate the protection ability and characteristics of flexible materials and structures under weak shock wave loading,the blast wave produced by TNT explosive is loaded on the polyurethane foam with the density of 200.0 kg/m3(F-200)and 400.0 kg/m3(F-400),polyurea with the density of 1100.0 kg/m^(3)(P-1100)and structures composed of the two materials,which are intended for individual protection.Experimental results indicate that the shock wave is attenuated to weak pressure disturbance after interacting with the flexible materials which are not damaged.The shock wave protective capability of single-layer materials is dependent on their thickness,density and microscopic characteristics.The overpressure,maximum pressure rise rate and impulse of transmitted wave decrease exponentially with increase in sample thickness.For the same thickness,F-400 provides better protective capability than F-200 while P-1100 shows the best protective capability among the three materials.In this study,as the materials are not destroyed,F-200 with a thickness more than10.0 mm,F-400 with a thickness more than 4.0 mm,and P-1100 with a thickness more than 1.0 mm can attenuate the overpressure amplitude more than 90.0%.Further,multi-layer flexible composites are designed.Different layer layouts of designed structures and layer thickness of the single-layer materials can affect the protective performance.Within the research range,the structure in which polyurea is placed on the impact side shows the optimal shock wave protective performance,and the thicknesses of polyurea and polyurethane foam are 1.0 mm and 4.0 mm respectively.The overpressure attenuation rate reached maximum value of 93.3%and impulse attenuation capacity of this structure are better than those of single-layer polyurea and polyurethane foam with higher areal density.

Explosion resistance performance of reinforced concrete box girder coated with polyurea:Model test and numerical simulation

To study the anti-explosion protection effect of polyurea coating on reinforced concrete box girder,two segmental girder specimens were made at a scale of 1:3,numbered as G(without polyurea coating)and PCG(with polyurea coating).The failure characteristics and dynamic responses of the specimens were compared through conducting explosion tests.The reliability of the numerical simulation using LS-DYNA software was verified by the test results.The effects of different scaled distances,reinforcement ratios,concrete strengths,coating thicknesses and ranges of polyurea were studied.The results show that the polyurea coating can effectively enhance the anti-explosion performance of the girder.The top plate of middle chamber in specimen G forms an elliptical penetrating hole,while that in specimen PCG only shows a very slight local dent.The peak vertical displacement and residual displacement of PCG decrease by 74.8% and 73.7%,respectively,compared with those of specimen G.For the TNT explosion with small equivalent,the polyurea coating has a more significant protective effect on reducing the size of fracture.With the increase of TNT equivalent,the protective effect of polyurea on reducing girder displacement becomes more significant.The optimal reinforcement ratio,concrete strength,thickness and range of polyurea coating were also drawn.

Preparation of Polyurea Elastomer with Flame Retardant, Insulation and Thermal Conductivity Properties

By using 6,6-((sulfonylbis(4,1-phenylene)bis(azanediyl))bis(thiophen-2-ylm-ethylene))bis6H-di-benzo[c,e][1,2]oxaphosphinine 6-oxide(DOPO-N)as phosphorus-nitrogen flame retardant,the polyurea(PUA)with flame retardant properties(PUA/DOPO-N)was prepared.In addition,organically modified montmorillonite(OMMT)and magnesium hydroxide(MH)were used as co-effectors respectively,and the flame retardant PUA(PUA/DOPO-N/OMMT and PUA/DOPO-N/MH)were also prepared.Thermal properties,flame retardant properties,flame retardant mechanism and mechanical properties of PUA/DOPO-N,PUA/DOPO-N/OMMT and PUA/DOPO-N/MH were investigated by thermogravimetric(TG)analysis,limiting oxygen index(LOI),UL 94,cone calorimeter test,scanning electron microscopy(SEM),and tensile test.The results show that the LOI value of PUA/20%DOPO-N,PUA/18%DOPO-N/2%OMMT and PUA/15%DOPO-N/5%MH are 27.1%,27.7%,and 28.3%,respectively,and UL 94 V-0 rating is attained.Compared with PUA,the peak heat release rate(pk-HRR),total heat release(THR)and average effective heat combustion(av-EHC)of PUA/20%DOPO-N,PUA/18%DOPO-N/2%OMMT and PUA/15%DOPO-N/5%MH decrease significantly.SEM results indicate that the residual chars of PUA/20%DOPO-N,PUA/18%DOPO-N/2%OMMT and PUA/15%DOPO-N/5%MH are completer and more compact.The complex of DOPO-N/OMMT and DOPO-N/MH have synergistic flame retardancy.The mechanical properties of PUA can be improved by the addition of DOPO-N,DOPO-N/OMMT and DOPO-N/MH,respectively.The insulation performance test shows that the volume resistivity of PUA/20%DOPO-N is 6.25×10^(16)Ω.cm.Furthermore,by using modified boron nitride(MBN)as heat dissipating material,the complex of PUA/MBN was prepared,and the thermal conductivity of PUA/MBN was investigated.The thermal conductivity of PUA/8%MBN complex coating at room temperature is 0.166 W/(M·K),which is a 163%improvement over pure PUA.

Preparation and Properties of Spray Polyurea Elastomer for Aquaculture Foam Floating Balls

[Objectives] This study was conducted to develop a polyurea elastomer which can be sprayed on the surface of expanded polystyrene (EPS) floating balls, so as to improve the surface strength and service life of the floating balls. [Methods] The effects of the types and amounts of isocyanate, chain extenders and polyether polyols on the gelation rate, adhesion and wear resistance of polyurea elastomer were investigated, and it was finally determined the preparation process of polyurea elastomer using liquid isophorone diisocyanate (IPDI) and amino-terminated polyether (D2000) as the main raw materials, dimethylthiotoluene diamine (E300) as the chain extender and silica as the wear resistance modifier through two-step solution polymerization of prepolymerization and chain extension. [Results] The physical properties and chemical resistance tests of spray polyurea elastomer showed that it had good physical properties and acid and alkali resistance, and could meet the requirements of spraying and protection of EPS floating ball surface in marine environment. [Conclusions] Polyurea elastomer coating can improve the aging resistance, wear resistance and acid and alkali resistance of EPS floating balls, and prevent them from being fragile and floating randomly to form marine floating garbage which results in "white pollution".

Synthesis and Characterization of Microcapsules with Chlorpyrifos Cores and Polyurea Walls

Microcapsules with chlorpyrifos cores and polyurea walls were synthesized with 2,4-tolylene diisocyanate as an oil-soluble monomer and ethylenediamine as a water-soluble monomer via an interracial polycondensation reaction. The products were characterized by means of Fourier transform infrared spectrometry, ^13C NMR spectrometry and ^31p NMR spectrometry. The morphology, the particle size and the particle size distribution, and the thermal properties were also evaluated. The prepared microcapsules exhibit clear and smooth surfaces and have a mean diameter of 28. 13 μm. These microcapsules also have a good thermal stability for long-term use, and have potential applications in minimizing the toxicity of chlorpyrifos through controlled release.

Polyurea coating for foamed concrete panel:An efficient way to resist explosion

Autoclaved aerated concrete(AAC) panels have ultra-light weight,excellent thermal insulation and energy absorption,so it is an ideal building material for protective structures.To improve the blast resistance of the AAC panels,three schemes are applied to strengthen the AAC panels through spraying 4 mm thick polyurea coating from top,bottom and double-sides.In three-point bending tests,the polyurea-coated AAC panels have much higher ultimate loads than the un-coated panels,but slightly lower than those strengthened by the carbon fiber reinforced plastics(CEFRPs).Close-in explosion experiments reveal the dynamic strengthening effect of the polyurea coating.Critical scaled distances of the strengthened AAC panels are acquired,which are valuable for the engineering application of the AAC panels in the extreme loading conditions.Polyurea coatings efficiently enhance the blast resistance of the bottom and double-sided polyurea-coated AAC panels.It is interesting that the polyurea-coated AAC panels have much more excellent blast resistance than the CFRP reinforced AAC panels,although the latter have better static mechanical properties.

Investigating the dynamic mechanical behaviors of polyurea through experimentation and modeling

Polyurea is widely employed as a protective coating in many fields because of its superior ability to improve the anti-blast and anti-impact capability of structures.In this study,the mechanical properties of polyurea XS-350 were investigated via systematic experimentation over a wide range of strain rates(0.001-7000 s^-1)by using an MTS,Instron VHS,and split-Hopkinson bars.The stress-strain behavior of polyurea was obtained for various strain rates,and the effects of strain rate on the primary mechanical properties were analyzed.Additionally,a modified rate-dependent constitutive model is proposed based on the nine-parameter Mooney-Rivlin model.The results show that the stress-strain curves can be divided into three distinct regions:the linear-elastic stage,the highly elastic stage,and an approximate linear region terminating in fracture.The mechanical properties of the polyurea material were found to be highly dependent on the strain rate.Furthermore,a comparison between model predictions and the experimental stress-strain curves demonstrated that the proposed model can characterize the mechanical properties of polyurea over a wide range of strain rates.

Mechanical behavior and failure mechanism of polyurea nanocomposites under quasi-static and dynamic compressive loading

Polyurea is an elastomeric material that can be applied to enhance the protection ability of structures under blast and impact loading.In order to study the compressive mechanical properties of SiC/polyurea nanocomposites under quasi-static and dynamic loading,a universal testing machine and split Hopkinson pressure bar(SHPB)apparatus were used respectively.The stress-strain curves were obtained on polyurea and its composites at strain rates of 0.001e8000 s1.The results of the experiment suggested that increase in the strain rates led to the rise of the flow stress,compressive strength,strain rate sensitivity and strain energy.This indicates that all of the presented materials were dependent on strain rate.Moreover,these mechanical characters were enhanced by incorporating a small amount of SiC into polyurea matrix.The relation between yield stress and strain rates were established using the power law functions.Finally,in order to investigate the fracture surfaces and inside information of failed specimens,scanning electron microscopy(SEM)and micro X-ray computed tomography(micro-CT)were used respectively.Multiple voids,crazes,micro-cracks and cracking were observed in fracture surfaces.On the other hand,the cracking propagation was found in the micro-CT slice images.It is essential to understand the deformation and failure mechanisms in all the polyurea materials.

An experimental study on shock wave mitigation capability of polyurea and shear thickening fluid based suspension pads

The present experimental study investigates shock wave mitigation capability of potentially new personal protective equipment(PPE) suspension pads made from polyurea and shear thickening fluid(STF).The shock tube test results show that when placed behind Twaron fabric systems with thickness ranging from 2 mm to 18 mm, the replacement of conventional flexible foam pad with STF and STF-infused foam pads with the same thickness of 20 mm greatly reduces the normalized peak pressure(by about 72% for each pad). However, this benefit is partially offset by a large increase in the normalized impulse(by about78% for the STF pad and 131% for the STF-infused foam pad) which may cause the shock wave mitigation performance of these two pads to become less effective. Interestingly, the use of 4 mm thick polyurea pad can greatly reduce the normalized peak pressure and impulse as well(by about 74% and 49%, respectively). These results reveal that among the potentially new suspension pads tested, the polyurea pad displays the best shock wave mitigation performance. Therefore, polyurea has potential for use as a suspension pad in personal protective equipment requiring shock wave mitigation capability such as fabric ballistic vests, bomb suits and combat helmets.

Abrasion test of flexible protective materials on hydraulic structures

In this study, several kinds of flexible protective materials sprayed with polyurea elastomers （hereinafter referred to as polyurea elastomer protective material） were adopted to meet the abrasion resistance requirement of hydraulic structures, and their abrasion resistances against the water flow with suspended load or bed load were studied systematically through tests. Natural basalt stones were adopted as the abrasive for simulation of the abrasion effect of the water flow with bed load, and test results indicate that the basalt stone is suitable for use in the abrasion resistance test of the flexible protective material. The wear process of the polyurea elastomer protective material is stable, and the wear loss is linear with the time of abrasion. If the wear thickness is regarded as the abrasion resistance evaluation factor, the abrasion resistance of the 351 pure polyurea is about twice those of pure polyurea with a high level of hardness and aliphatic polyurea, and over five times that of high-performance abrasion-resistant concrete under the abrasion of the water flow with suspended load. It is also about 50 times that of high-performance abrasion-resistant concrete under the abrasion of the water flow with bed load. Overall, the abrasion resistance of pure polyurea presented a decreasing trend with increasing hardness. Pure polyurea with a Shore hardness of D30 has the best abrasion resistance, which is 60 to 70 times that of high-performance abrasion-resistant concrete under the abrasion of the water flow with bed load, and has been recommended, among the five kinds of pure polyurea materials with different hardness, in anti-abrasion protection of hydraulic structures.

Experimental investigations on small-and full-scale ship models with polyurea coatings subjected to underwater explosion

Nowadays, the mitigation of damage to a ship caused by the underwater explosion attracts more and more attention from the modern ship designers. In this study, two kinds of scale tests were conducted to investigate the effects of polyurea coatings on the blast resistance of hulls subjected to underwater explosion. Firstly, small-scale model tests with different polyurea coatings were carried out. Results indicate that polyurea has a better blast resistance performance when coated on the front face, which can effectively reduce the maximum deflection of the steel plate by more than 20% and reduce the deformation energy by 35.7%-45.4%. Next, a full-scale ship(approximately 50 m × 9 m) under loadings produced by the detonation of 33 kg of spherical TNT charges was tested, where a part of the ship was coated with polyurea on the front face(8 mm + 24 mm) and not on the contrast area. Damage characteristics on the bottom were statistically analyzed based on a 3D scanning technology, indicating that polyurea contributes to enhancing the blast protection of the ship. However, damage results of this test were different from those of the small-scale tests. Moreover, the deformation area of the bottom with polyurea was greatly increased by 40.1% to disperse explosion energy, a conclusion that cannot be drown from the small-scale tests.

Preparation and characterization of hexadecane microcapsule with polyurea-melamine formaldehyde resin shell materials

This paper gives a brief report of the preparation of hexadecane microcapsule with polyurea-melamine formaldehyde resin shell materials(HMPM).The sealing performance and thermal stability of HMPM was enhanced much more effectively than that of microcapsule with polyurea shell material(HPM).The results of microscopical imaging analysis system,DSC,TG,and laser particle analyzer were briefly introduced.

Experimental investigation on anti-penetration performance of polyurea-coated ASTM1045 steel plate subjected to projectile impact

In this study,the anti-penetration performance of polyurea/ASTM1405-steel composite plate subjected to high velocity projectile was analyzed.Two kinds of modified polyurea material(AMMT-053 and AMMT-055)were selected and a ballistic impact testing system including speed measuring target system and high-speed camera was designed.This experiment was conducted with a rifle and 5.8 mm projectile to explore the effects by the polyurea coating thickness,the polyurea coating position and the glass-fiber cloth on the anti-penetration performance of polyurea/ASTM1405-steel composite plate.The result showed that the effects of polyurea coating position were different between two types of polyurea,and that the effects of glass-fiber position were disparate between two types of polyurea as well.For AMMT-053 polyurea material,it was better to be on front face than on rear face;whereas for AMMT-055 polyurea,it was better to be on rear surface although the difference was very subtle.Additionally,formulas had been given to describe the relationship between the effectiveness of polyurea and the thickness of polyurea coating.In general,AMMT-055 had better anti-penetration performance than AMMT-053.Furthermore,five typical damage modes including self-healing,crack,local bulge,spallation and local fragmentation were defined and the failure mechanism was analyzed with the results of SHPB test.Additionally,the bonding strength played an important role in the anti-penetration performance of polyurea/steel composite plate.

Evaluation of effectiveness of polymer coatings in reducing blastinduced deformation of steel plates

Incorporating elastomers such as polymers in protective structures to withstand high energetic dynamic loads,has gained significant interest.The main objective of this study is to investigate the influence of a Polyurea coating towards the blast-induced response in steel plates.As such,Polyurea coated steel plates were tested under near-field blast loads,produced by the detonation of 1 kg of spherical nitromethane charges,at a standoff distance of 150 mm.Mild steel(XLERPLATE 350)and high-strength steel(BIS80)plates with thicknesses of 10 mm were Polyurea coated with thicknesses of 6 mm and 12 mm on either the front(facing the charge)or the back face.The deformation profiles were measured using 3D scanning.Numerical simulations were performed using the non-linear finite element code LS-DYNA.The strain-dependent behaviour of the steel and Polyurea were represented by Johnson-cook and Money-Rivlin constitutive models,respectively.The numerical models were validated by comparing the plate deflection results obtained from the experiments and were then used in the subsequent parametric study to investigate the optimum thickness of the Polyurea coating.The results indicate that back face coating contributes towards an approximately 20%reduction in the residual deformation as well as the absence of melting of the Polyurea layer,while the front-face coating can be used a means of providing additional standoff distance to the steel plates.

Blast response of clay brick masonry unit walls unreinforced and reinforced with polyurea elastomer

Clay brick masonry unit(CBMU) walls are widely used in building structures,and its damage and protection under explosion loads have been a matter of concern in the field of engineering protection.In this paper,a series of full-scale experiments of the response characteristics of 24 cm CMBU walls unreinforced and reinforced with polyurea elastomer subjected to blast loading were carried out.Through setting 5.0 kg TNT charges at different stand-off distances,the damage characteristics of masonry walls at different scaled distances were obtained.The reinforcement effect of different polyurea coating thicknesses and methods on the blast resistance performance of masonry walls under single and repeated loads were also explored.Five failure grades were summarized according to the dynamic response features of masonry walls.Based on the stress wave propagation pattern in multi-media composite structures,the internal stress distribution of masonry walls were analyzed,and the division basis of the masonry walls’ failure grades was then quantified.Combined with Scanning Electron Microscope(SEM)images,the deformation characteristics of soft and hard segments of polyurea and effects of detonation products on microstructures were revealed respectively,which provides an important reference for the design and application of polyurea in the blast resistance of clay brick masonry walls.

NOVEL SULPHONATED POLYSILOXANE POLYUREA-URETHANE IONOMERS

A series of novel polysiloxane polyurea-urethane blockcopolymers based on methylene bis(p-phenylisocyanate (MDI), sodium-s-1,2-dihydroxy propyl sulphonate (SDPS) and aminopropyl-terminated polydimethylsiloxane (ATPS) was synthesized with varying length of soft segments and neutralizing cation. The effect of the chemical composition and the cation on the morphology and mechanical properties of the samples were studied. It was found that the SDPS chain extender based samples have definite chemical structure (-MDI-SDPS-MDI-ATPS-). As the length of the soft segment increases, an improvement of phase separation was observed. In addition, when SO3Na was translated into SO3H or the sulphonic acid groups were neutralized with different charge cations (Na+, Zn2+ and Al3+), the morphology and mechanical properties changed greatly.