Rubber Seed Oil-Based UV-Curable Polyurethane Acrylate Resins for Digital Light Processing (DLP) 3D Printing

Novel UV-curable polyurethane acrylate (PUA) resins were developed from rubber seed oil (RSO). Firstly, hydroxylated rubber seed oil (HRSO) was prepared via an alcoholysis reaction of RSO with glycerol, and then HRSO was reacted with isophorone diisocyanate (IPDI) and hydroxyethyl acrylate (HEA) to produce the RSO-based PUA (RSO-PUA) oligomer. FT-IR and ¹H NMR spectra collectively revealed that the obtained RSO-PUA was successfully synthesized, and the calculated C=C functionality of oligomer was 2.27 per fatty acid. Subsequently, a series of UV-curable resins were prepared and their ultimate properties, as well as UV-curing kinetics, were investigated. Notably, the UV-cured materials with 40% trimethylolpropane triacrylate (TMPTA) displayed a tensile strength of 11.7 MPa, an adhesion of 2 grade, a pencil hardness of 3H, a flexibility of 2 mm, and a glass transition temperature up to 109.4 °C. Finally, the optimal resin was used for digital light processing (DLP) 3D printing. The critical exposure energy of RSO-PUA (15.20 mJ/cm²) was lower than a commercial resin. In general, this work offered a simple method to prepare woody plant oil-based high-performance PUA resins that could be applied in the 3D printing industry.     

Preparation and properties of hollow silica tubes/bismaleimide/diallylbisphenol A composites with improved toughness,dielectric properties,and flame retardancy

New high performance insulating composites based on hollow silica tubes (mHST) and bismaleimide/diallylbisphenol A (BDM/DBA) resin, which exhibit improved toughness, dielectric properties, and flame retardancy, were successfully developed. The effect of the amount of mHST on the properties of composites was systematically studied. Results show that the impact strength of the composite with 0.5 wt% mHST is about 2.2 times that of BDM/DBA resin. In addition, compared with BDM/DBA resin, the composites show lower and stable dielectric constant, better frequency stability of dielectric loss, significantly improved flame retardancy, and similarly outstanding thermal resistance. The reasons behind these attractive integrated properties are discussed from the view of structure–property relationship. Copyright © 2011 John Wiley & Sons, Ltd.     

Antimicrobial Thiol–ene–acrylate Photosensitive Resins for DLP 3D Printing

Designing digital light processing (DLP) 3D printable photosensitive resins with antibacterial properties is especially vital because of their potential applications in various biomedical fields. In this contribution, a thiol–ene–acrylate ternary system with reduced volume shrinkage and fast photopolymerization rate was chosen as the antibacterial 3D printing matrix resin. Two quaternary ammonium salt‐type antibacterial agents (QAC and SH‐QAC) with different molecular weight were designed and prepared, which can participate in the curing of matrix resin to achieve contact antibacterial effect. The effects of antibacterial agent content on the photopolymerization kinetics and on thermal and mechanical properties were discussed in detail. When the amount of added QAC is 4wt%, the antibacterial rate is almost 100% for Escherichia coli and Staphylococcus aureus, and when the amount of SH‐QAC is 10wt%, the antibacterial rate against S. aureus is also essentially 100%. Both antibacterial photosensitive resins have been successfully applied in DLP technology to fabricate tooth model with high precision.     

A bio-based epoxy resin derived from p-hydroxycinnamic acid with high mechanical properties and flame retardancy

Recent advances in epoxy resins have been forward to achieving high mechanical performance, thermal stability, and flame retardancy. However, seeking sustainable bio-based epoxy precursors and avoiding introduction of additional flame-retardant agents are still of increasing demand. Here we report the synthesis of p-hydroxycinnamic acid-derived epoxy monomer (HCA-EP) via a simple one-step reaction, and the HCA-EP can be cured with 4,4′-diaminodiphenylmethane (DDM) to prepare epoxy resins. Compared with the typical petroleum-based epoxy resin, bisphenol A epoxy resin, the HCA-EP-DDM shows a relatively high glass transition temperature (192.9 °C) and impressive mechanical properties (tensile strength of 98.3 MPa and flexural strength of 158.9 MPa). Furthermore, the HCA-EP-DDM passes the V-1 flammability rating in UL-94 test and presents the limiting oxygen index of 32.6%. Notably, its char yield is as high as 31.6% under N₂, and the peak heat rate release is 60% lower than that of bisphenol A epoxy resin. Such findings provide a simple way of using p-hydroxycinnamic acid instead of bisphenol A to construct high-performance bio-based thermosets.     

Effect of temperature and volume on the tensile and adhesive properties of photocurable resins

Knowing the mechanical properties of UV‐curable resins at cryogenic conditions is important to ongoing fusion‐energy research and to emerging aerospace applications. The tensile and interfacial shear strengths of two commercially available UV‐curable resins were measured at room‐temperature and cryogenic conditions for both bulk and reduced (subnanoliter) specimen volumes. The tensile properties of cured specimens are remarkably sensitive to both testing temperature and specimen size. For one type of resin, the cold (?150 °C) tensile strength of subnanoliter specimens is ～9× larger (179 ± 19 MPa) than bulk values at room temperature. The interfacial shear strength between SiC fibers and small volumes of resin volumes is comparable to the bulk, room‐temperature tensile strength, but it varies over a wide range at ?150 °C (15–53 MPa). All resins were fully cured, and an analysis of fractured surfaces revealed microstructural features. The enhanced strength in microscopic specimens may be related to inhomogeneous stress fields that develop during cure. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 936–945     

Preparation of high performance foams with excellent dielectric property based on toughened bismaleimide resin

In order to meet the increasing demands on high performance foams with excellent dielectric property by modern industries, a new type of high performance foams based on diallyl bisphenol A modified bismaleimide (BDM/BA) resin is first developed in this paper. The effects of processing parameters such as prepolymerization time and temperature, foaming temperature and time as well as the content of blowing agent on the properties and morphology of resultant foams are intensively investigated from the view of processing–property–morphology relationship. Results show that compared with BDM/BA resin, the optimum condition of prepolymerization is 140°C for 60 min, and that of foaming is 160°C for 35 min. Foams based on BDM/BA resin with 9 wt% AC135 have uniform cell distribution, and greatly improved dielectric property. Copyright © 2010 John Wiley & Sons, Ltd.     

Rheological study on structural transition in polyethersulfone‐modified bismaleimide resin during isothermal curing

The structural transition in the polyethersulfone (PES)‐modified bismaleimide resin, 4,4′‐bismaleimidodiphenylmethane (BDM), during isothermal curing was studied by using rheological technique, different scanning calorimetry (DSC), and time resolved light scattering (TRLS). Comparing with the cure of neat bismaleimide, two separate tan δ crossover points were observed because of the phase separation during curing the blends of PES/BDM. These two structural transitions stemmed from the fixing of phase structure of the system and the chemical crosslinking of bismaleimide, respectively. The effect of curing temperature and the PES content on structural transition was discussed and found that the occurrence of two structural transition exhibited the different dependency of curing temperature and PES content. The relaxation exponent n and gel strength S were also found to be temperature‐dependent and composition‐dependent. Moreover, the relaxation exponent n of the second structural transition is much lower than that of the first structural transition in the PES/bismaleimide blends. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3102–3108, 2006     

Cure behavior and thermal stability of an epoxy: new bismaleimide blends for composite matrices

A new bismaleimide (BMI) resin was synthesized to formulate epoxy(tetraglycidyl diaminodiphenyl methane; TGDDM) – bismaleimide thermoset blends for composite matrix applications. 4,4′-diaminodiphenyl methane (DDM) was used as an amine curing agent for the TGDDM. A Fourier transform infrared (FTIR) spectroscopy was employed to characterize the new BMI resin. Cure behavior of the epoxy–BMI blends was studied using a differential scanning calorimeter (DSC). DSC thermograms of the thermoset blends indicated two exothermic peaks. The glass transition temperature of the thermoset blends decreased with BMI content. Thermogravimetric analysis (TGA) was carried out to investigate thermal degradation behavior of the cured epoxy–BMI thermoset blends. The new BMI resin reacted partially with the DDM and weak intercrosslinking polymer networks were formed during cure of the thermoset blends.     

Experimental Design Optimization of Acrylate—Tannin Photocurable Resins for 3D Printing of Bio-Based Porous Carbon Architectures

In this work, porous carbons were prepared by 3D printing formulations based on acrylate–tannin resins. As the properties of these carbons are highly dependent on the composition of the precursor, it is essential to understand this effect to optimise them for a given application. Thus, experimental design was applied, for the first time, to carbon 3D printing. Using a rationalised number of experiments suggested by a Scheffé mixture design, the experimental responses (the carbon yield, compressive strength, and Young’s modulus) were modelled and predicted as a function of the relative proportions of the three main resin ingredients (HDDA, PETA, and CN154CG). The results revealed that formulations containing a low proportion of HDDA and moderate amounts of PETA and CN154CG gave the best properties. Thereby, the optimised carbon structures had a compressive strength of over 5.2 MPa and a Young’s modulus of about 215 MPa. The reliability of the model was successfully validated through optimisation tests, proving the value of experimental design in developing customisable tannin-based porous carbons manufactured by stereolithography.     

Studies on thermal, mechanical and morphological behaviour of caprolactam blocked methylenediphenyl diisocyanate toughened bismaleimide modified epoxy matrices

Diglycidyl ether of bisphenol A epoxy resin (DGEBA, LY 556) was toughened with 5%, 10% and 15% (by wt) of caprolactam blocked methylenediphenyl diisocyanate (CMDI) using 4,4′-diaminodiphenylmethane (DDM) as curing agent. The toughened epoxy resin was further modified with chemical modifier N,N′-bismaleimido-4,4′-diphenylmethane (BMI). Caprolactam blocked methylenediphenyl diisocyanate was synthesized by the reaction of caprolactam with methylenediphenyl diisocyanate in presence of carbon tetrachloride under nitrogen atmosphere. Thermal properties of the developed matrices were characterized by means of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), heat distortion temperature (HDT) and dynamic mechanical analysis (DMA). Mechanical properties like tensile strength, flexural strength and impact strength were tested as per ASTM standards. The glass transition temperature (T_g) and thermal stability were decreased with increase in the percentage incorporation of CMDI. The thermomechanical properties of caprolactam blocked methylenediphenyl diisocyanate toughened epoxy resin were increased by increasing the percentage incorporation of bismaleimide. The values of impact strength for epoxy resin were increased with increase in the percentage concentration of CMDI. The homogeneous morphology of CMDI toughened epoxy resin and bismaleimide modified CMDI toughened epoxy resin system were ascertained from scanning electron microscope (SEM).     

Thermal Properties Improvement of Bismaleimide Resin by a New Phosphorus‐containing Polycyclic Bismaleimide

A new phosphorus‐containing polycyclic bismaleimide resin (BMPI) was prepared by the reaction of bis(3‐maleimidophenyl) methylphosphine oxide (BAMP) with benzene‐1,2,4,5‐tetracarboxylic dianhydride (BTD) and maleic anhydride (MA). BMPI was confirmed by infrared (IR), ¹H‐ and ¹³C‐NMR spectroscopies. Its thermal properties were carried out by a differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) that revealed that the polymers have excellent thermal properties in the high temperature region and a high char yield of up to 53～65%. Furthermore, three conventional bismaleimide resins were prepared from different phosphorus‐free bismaleimides for comparison, e.g. 4,4′‐bismaleimidodiphenylmethane (BDM), 4,4′‐bismaleimidodiphenylether (BDE), 4,4′‐bismaleimidodiphenylsulfone (BDS).     

超支化聚硅氧烷改性双马来酰亚胺树脂的研究

将共聚改性与端氨基超支化聚硅氧烷(HBPSi(N))的合成一步完成,建立了一步法制备改性双马来酰亚胺树脂(记为B/D/H(N))的方法.以N,N′-4,4′-二苯甲烷双马来酰亚胺(BMI)、二烯丙基双酚A(DBA)组成的体系(记为B/D)为对比,探讨了HBPSi(N)含量对B/D/H(N)树脂性能的影响.研究结果表明,HBPSi(N)含量对B/D/H(N)树脂的性能有重要影响.少量HBPSi(N)的加入不仅可以显著提高固化物的韧性,而且能有效加快树脂的凝胶时间,同时大幅度提高固化树脂的耐热性、介电性能和耐湿性.这些性能的改善主要缘于HBPSi(N)的加入改变了交联网络的分子结构.B/D/H(N)体系优异的综合性能使之在制备先进树脂基复合材料、胶黏剂方面显示出很大的应用潜力.     

纳米Al_2O_3改性双酚A型环氧丙烯酸酯的制备与性能研究

选用硅烷偶联剂KH570对纳米Al_2O_3进行表面改性处理,并用改性后的Al_2O_3对双酚A环氧丙烯酸酯进行复合改性,研究了纳米Al_2O_3含量(1%(wt)~5%(wt))对树脂性能的影响。结果表明:改性纳米Al_2O_3质量分数为5%时的复合材料的体积收缩率最小,为6.48%;粒子质量分数为2%时,树脂的凝胶率最大,为88.3%;热失重测试结果表明,改性纳米Al_2O_3提高了树脂的热稳定性;拉伸性能显示,随着改性纳米Al_2O_3质量分数的增加,复合材料的拉伸强度先升高后下降,当改性纳米Al_2O_3质量分数为3%时,复合树脂拉伸强度最大,为34.74MPa,与未改性树脂相比,拉伸强度提高了108.27%。本文所制备的改性光敏树脂可适用于3D打印环境。     

Enhanced thermal properties and flame retardancy from a thermosetting blend of a phosphorus‐containing bismaleimide and epoxy resins

Epoxy resins modified by an organosoluble phosphorus‐containing bismaleimide (3,3′‐bis(maleimidophenyl) ­phenylphosphine oxide; BMPPPO) were prepared by simultaneously curing epoxy/diaminodiphenylmethane (DDM), and BMPPPO. The resulted epoxy resins were found to exhibit glass transition temperatures as high as 212 °C, thermal stability at temperatures over 350 °C, and excellent flame retardancy with Limited oxygen index (LOI) values around 40. Incorporation of BMPPPO into epoxy resins via the thermosetting blend was demonstrated to be an effective way to enhance the thermal properties and flame retardancy simultaneously. Copyright © 2003 John Wiley & Sons, Ltd.     

Novel high performance RTM bismaleimide resin with low cure temperature for advanced composites

A novel performance matrix, coded as LCRTM, with low cure and post‐cure temperature (≤ 200°C) for fabricating advanced polymer composites via resin transfer molding (RTM), was successfully developed, made up of 4,4′‐bismaleimidodiphenylmethane (BDM) and N‐allyl diaminodiphenylether (ADDE). Investigations show that the stoichiometry of BDM and ADDE has great effect on the processing and performance parameters of the resultant resins. In the case of the optimum formulation (the mole ratio of BDM and ADDE is 1:0.55), the injection temperature range is between 70–82°C, and the pot life at 80°C is 300 min, moreover, the cured resin has desirable thermal and mechanical properties after being cured at 200°C for 6 hr, reflecting a great potential as high performance matrices for fabricating advanced composites via the RTM technique. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis,cure, and composite properties of mixed allyl/propargyl cyclopentadiene resins

A series of thermosetting resins were synthesized via phase transfer reaction of allyl chloride and propargyl bromide with cyclopentadiene in the presence of a strong base. Feed ratios of 1 : 1, 3 : 1, and 5 : 1 allyl chloride to propargyl bromide were used to give resins with varying amounts of propargyl and allyl functionality. In all cases the resins could be thermally cured, without added catalyst, at temperatures below 275°C to give black, glassy, brittle materials with densities of 1.15. TGA evaluation of the resins, with heating to 1000°C, resulted in carbon yields ranging from 48 to 66% with increasing propargyl functionality causing increased values. Physical mixtures of ACP and PCP resins were also made and evaluated. Cure of the mixed materials also occurred below 275°C, and carbon yields were comparable to the corresponding APCP resin. APCP/carbon fiber composites gave good mechanical properties with flexural modulus values of 115–130 GPa and flexural strength values of 1000 MPa. Carbonization of 1 : 1 APCP/carbon fiber composites provided materials with interlaminar strength values of approximately 1.14 MPa. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2869–2876, 1998     

Viscoelastic phase separation in polyethersulfone modified bismaleimide resin

The polymerization-induced phase separation process of polyethersulfone (PES) modified bismaleimide resin, 4,4′-bismaleimidodiphenylmethane (BDM), was investigated by time resolved light scattering (TRLS) and scanning electronic microscopes (SEM). At the blends with 10 wt% and 12.5 wt% PES, a phase inversion structure was found by SEM. TRLS results displayed clearly the spinodal decomposition (SD) mechanism and the exponential decay procedure of scattering vector q_m, which followed Maxwell-type relaxation equation. The characteristic relaxation time τ for the blends can be described by the Williams-Landel-Ferry equation. It demonstrated experimentally that the phase separation behaviors in these PES modified bismaleimide blends were affected by viscoelastic effect.     

Curing characteristics of o-cresol novolac epoxy resin modified by bismaleimide

Curing characteristics of o-cresol novolac epoxy resin modified by 4,4-diaminodiphenylmethane bismaleimide (DDM-BMI) using FTIR were investigated and the glass transition temperature was measured. With the addition of DDM as hardener, the relative curing reaction conversion of DDM-BMI increased with equivalent weight ratio [R₁ = (equiv wt summation of epoxy and DDM-BMI)/equiv wt of DDM] and weight ratio of epoxy and DDM-BMI (R₂ = wt of epoxy resin/wt of DDM-BMI). Using phenol novolac resin (PN) as hardener, the curing reaction conversion of DDM-BMI was hardly changed, but the variation of that in the epoxy resin was observed with R₂ change. © 1996 John Wiley & Sons, Inc.     

Flame retardancy and flame retarding mechanism of high performance hyperbranched polysiloxane modified bismaleimide/cyanate ester resin

A novel kind of modified bismaleimide/cyanate ester (BCE) resins by copolymerizing with hyperbranched polysiloxane including high content of phenyl (HBPSi) was first reported. The effect of HBPSi on the curing mechanism, and that on the dielectric properties and flame retardancy of cured networks were systemically investigated. Results show that compared with BCE resin, HBPSi/BCE resin has obviously different cross-linked structure, and thus leading to simultaneously improved dielectric properties and flame retardancy. The reactions between HBPSi and the decomposition structure of BCE resin change the thermo-oxidative degradation mechanism of the first step in the thermo-oxidative degradation; in addition, the presence of HBPSi in BCE resin also significantly reduces the mass loss rate (MLR) and increases char yield at 800 °C under an air atmosphere. Therefore, the positive effect of HBPSi on improving the flame retardancy is attributed to the condensed phase mechanism. On the other hand, HBPSi/BCE resins exhibit improved dielectric properties (including decreased dielectric constant and loss) with increasing the content of HBPSi. More importantly, this investigation demonstrates that designing new polysiloxane with suitable chemical structure is important to develop high performance resins with attractive flame retardancy and dielectric properties.     

Facile synthesis of bio-based phosphorus-containing epoxy resins with excellent flame resistance

The development of high-performance biomass-derived epoxy thermosets with excellent flame resistance is vital to various applications (i.e., composites, coatings and adhesives). Herein, a difunctional epoxy monomer bis(2-methoxy-4-(oxiran-2-ylmethyl)phenyl) phenyl phosphate (BEU-EP) was synthesized from abundant and biobased eugenol. In addition, BEU-EP was cured by 4,4′-diaminodiphenyl methane (DDM) and the cured resin diglycidyl ether of bisphenol A (DGEBA)/DDM was used as a reference. Results indicated that BEU-EP/DDM not only showed a 58.1%, 28.8% and 35.1% increase in residual char (at 700 °C), flexural and storage modulus (at 30 °C) compared with DGEBA/DDM, but also exhibited excellent flame resistance and smoke suppression. BEU-EP/DDM passed V-0 rating (in UL-94 testing) with limiting oxygen index (LOI) of 38.4% and greatly decreased the peak heat release rate (pHRR) and total smoke production (TSP) by 84.9% and 80.5%, respectively. The mechanism analysis confirmed that the phosphorus-containing group and aromatic structure from BEU-EP contributed both the gas and condensed-phase flame retardation of BEU-EP/DDM network. This work provides an efficient and scalable route for synthesizing biobased epoxy thermosets with high integrated performance and superior flame resistance.